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Petro Mohyla Black Sea National University, Ukraine


University of the West of England, United Kingdom

WATER SECURITY
MONOGRAPH

edited by
Olena Mitryasova
Chad Staddon

Bristol – Mykolaiv 2016


UDC 502.171:556] : 005.336.4 (100)

Reviewers:
Prof., Dr.Sc.Yaroslav Movchan, Head of the National Ecological Center of
Ukraine, National Aviation University;
Prof., Dr.Sc. Oleg Aleksandrowicz, Director of the Institute of Biology and
Environment Protection, Pomeranian University in Slupsk, Poland;
Dr.Sc. Volodymyr Beglytsya, Vice-rector for scientific work of the PMBSNU.

Approved for publication by the Academic Council of Petro Mohyla


Black Sea National University, Ukraine

Water Security: Monograph. – Mykolaiv: PMBSNU – Bristol: UWE, 2016. – 308 p.

Editors: prof. Olena Mitryasova & prof. Chad Staddon

ISBN 978-617-7421-13-8

The monograph is devoted to problems of water services economics and policy, water
usage, sewerage, management, quality and pollution of waters, monitoring, measures to
improve the state of water objects, quality of water, system and technology of sewage
treatment.
The monograph was published with the support of British Council in the joint project
of internationalization of higher education.
The book is written for scientists, lecturers, postgraduate students, engineers and
students who specialize in the field of environmental researches, where the object of study
is water.

Publishers:
Petro Mohyla Black Sea National University, Ukraine
10, 68-Desantnykiv St., Mykolaiv, 54003, Ukraine
tel.: +380512765568
e-mail: rector@chdu.edu.ua; http://www.chdu.edu.ua
University of the West of England, United Kingdom
Frenchay Campus, Coldharbour Lane, Bristol, BS16 1QY, UK
tel.: 01173283214
http://www.uwe.ac.uk

Printed by: FOP Shvets V.M., Phone: +38 (0512) 500448;


Certificate subject publishing MK №5078 from 01.04.2016
© Petro Mohyla Black Sea National University, Ukraine, 2016
© University of the West of England, United Kingdom, 2016
All rights reserved. No part of this publication may be reproduced, stored in retrieval system or
animated or transmitted in any form or by any means, electronic, mechanical, photocopying,
recording or otherwise without the prior permission of the publisher.
Water Security: Monograph 3

CONTENTS

Foreword 5
Water Ecosystem Ecological Safety Assessment by the Determination
of Energy Flow Sustainability
Viacheslav Andrieiev, Yevhen Bezsonov, Nataliia Andrieieva 7
Assessment of Water Pollution by Bioindication Method
Vitalii Ishchenko, Sergey Kvaternyuk, Oksana Styskal 21
Increases in Removal of Phosphorus Compounds During Biological
Treatment of Urban Wastewater in Constructions Without Zoning
Valentina Iurchenko, Olena Bryhada 31
Using a Photocatalytic UV-nano-ТіО2-K2Cr2O7 System to Determine
COD in Water Analysis
Svitlana Kel’ina, Jury Dedkov 43
Analysis of the Theoretical and Practical Aspects of Water Pollution
Caused by Motor Transport
Olena Kofanova, Oleksii Kofanov 56

Investigation of Co-Utilization of Meat Processing Wastewater Sewage


and Rice Husk by Anaerobic Digestion
Galyna Krusir, Heinz Leuenberger, Olesia Chernyshova 66

Anaerobic Treatment of Wastewater from Wineries


Galyna Krusir, Alfred Zikalo, Oleksiy Harkovych, Maria Madani,
Valentina Zakharchuk 76

Technological Aspects of the Pre-treatment of Leachate, Stored at the


Retention Ponds of the Grybovychi Landfill, Lviv Region, Ukraine
Myroslav Malovanyy, Volodymyr Zhuk, Mykola Oducha, Vira Sliusar,
Andriy Sereda 88

Valuation Hydroecological and Sanitary-Hygienic Condition of the


River Network of Pokutsko-Bukovinian Carpathians
Andrew Masikevych, Yuri Masikevych, Valentyn Myslytsky, Ivan Burdeniuk 98

New Technologies for Automated Control of Water


Maryna Mikhalieva, Volodymyr Pohrebennyk 108
Environmental Status of Surface Water Resources in Mykolaiv Region
Olena Mitryasova, Andrii Mats 121
Multispectral Methods and Means of Water Pollution Monitoring by
Using Macrophytes for Bioindication
Vasyl Petruk, Sergii Kvaternyuk, Olga Bondarchuk, Roman Petruk,
Igor Vasilkovsky 131
4 Water Security: Monograph

Improving the Accuracy of Operative Control Parameters of Water Environment


Volodymyr Pohrebennyk 142
Evaluation of Impact of Mining and Chemical Enterprise on Ecological State
of the Water Environment
Volodymyr Pohrebennyk, Elvira Dzhumelia 155
Impact of Lviv Municipal Solid Waste Landfill on Water Bodies
Volodymyr Pohrebennyk, Iryna Podolchak 170
Efficiency of Wastewater Treatment in a Mountainous Area of Poland
Grzegorz Przydatek, Anna Kochanek , Volodymyr Pohrebennyk 182
Balanced Mineral Composition of Drinking Water as an Influence on the Public
Health at the Urban Agglomerations of the Northwestern Black Sea Region
Tamerlan Safranov, Kateryna Husieva 192
Safety Study of Wastewaters from Bakery Enterprises Using Biotest Organisms
of Different Trophic Levels
Katherine Savvova, Irina Kondratenko, Lyudmila Lobotskaya, Bondar Sergey,
Elena Sevastyanova 208
Environmental Assessment of Wastewater Treatment Technologies for the Dairy
Industry
Roman Shevchenko, Anna Kiriyak, Mariya Korotkevich, Ivan Krestinkov,
Tatyana Shpirko 217
Wastewater Treatment of Company «Ternopil Milk Plant»
Alla Shybanova, Volodymyr Pohrebennyk, Olena Mitryasova, Roman Politylo 227
The Environmental Quality Evaluation of the Surface Water Resources of the
Inhul River within Mykolaiv Region
Victor Smyrnov, Sviitlana Smyrnova 242
Water Resources Landscape Ecosystems of River Valleys of the Central
Bug Region
Svitlana Sovgira 251
Socio-cultural Drivers of Water Demand in Student Residential
Accommodation
Chad Staddon, Deirdre Toher, Karen Simpson, Fabia Jeddere-Fisher 267
Establishing the Optimal Frequency of the Sewage Water Processing by Means
of Different Kinds of Cavitation Generators
Volodymyr Starchevsky, Volodymyr Pohrebennyk, Nataliya Bernatska 278
Formation of New Deltas in Large Water Reservoirs
Volodymyr Starodubtsev 289
Oil Pollution Monitoring by Satellite Photography Analysis
Andriy Volkov 299
Water Security: Monograph 5

FOREWORD

Water was given a magic power to become the force of life on Earth
Leonardo da Vinci
Water stands alone in the history of our planet. There is a natural body, which
could be compared to her influence on the course of fundamental, most ambitious
geological processes. Not only the surface but deep-scale biosphere-part of the
planet are most significant in its ramifications, its existence and its properties
Volodymyr Vernadsky

Water resources are one of the vital components of the planet and the prerequisite
for socio-economic development of society, the satisfaction of basic human needs,
activities in the field of food production, preservation of ecosystems.
Ecologically destructive models of a development in many countries of the
world have led to the degradation of water resources, which is reflected in their
volume and quality. The need arises to ensure the optimal use of water, protection
of fresh water resources, monitoring of water resources, the search for new
technologies and methods of wastewater treatment, the investigation of the quality
of drinking water.
Over the past decades in water management in many countries use an ecosystem
approach. Ecosystem water management is carried out by the state and society
through a basin management based of paid water use. Basin principle is this method
of water management, which basic unit is the area of the river basin, where the latter
is a system of established environmental and socio-economic connections. Now the
river basin approach enables to foresee the effects of anthropogenic activities for
early warning of environmental catastrophe.
Among the methods of wastewater treatment is more effective and promising
biological methods that have shown good results in the water preparation.
The urgency of the problems of management, monitoring and forecasting of
water resources in conditions of intense water use, drinking water quality are the
issues related to technology, methods of wastewater treatment, biological and
biochemical aspects of municipal and industrial wastewater treatment i.e. a wide
range of scientific research subjects, where an object is the water has caused the
publishing of collective monograph under the general name «Water Security».
The main thematic modules of the monograph:
• Water services economics and policy.
• Water use and sewerage.
6 Water Security: Monograph

• Water management.
• Quality and pollution of waters.
• Water monitoring.
• Measures to improve the state of water objects.
• Quality of drinking water and its impact on health.
• System and technology of sewage treatment.
The release of the book became possible in the framework of the International
project, through 2016 under the auspices of the British Council in Ukraine between
the Petro Mohyla Black Sea National University (Ukraine) and the University of
the West of England (United Kingdom).
The project would be impossible without the support of the Government of the
United Kingdom in the framework of the global partnership. On the pages of
monographs filed work of scientists from Ukraine, United Kingdom, Poland, Russia
and Switzerland. There is especially the wide geography of Ukrainian scientists.
The monograph is the result of the scientific achievements of scientists, leading
specialists from universities and organizations: Petro Mohyla Black Sea National
University; University of the West of England; Vinnytsia National Technical
University; Moscow State Regional University; Lviv Polytechnic National
University; State Higher Technical School in Nowy Sacz, Odessa National Academy
of Food Technologies; Kharkov National University of Construction and
Architecture; University of Applied Sciences and Arts Northwestern Switzerland
FHNW; Odessa National Economic University; Lviv City Communal Enterprise
«Lvivvodokanal»; Chernivtsi Faculty of the National Technical University «Kharkiv
Polytechnic Institute»; Bukovinian State Medical University; Hetman Petro
Sahaidachnyi National Army Academy; Odessa State Environmental University;
Mykolaiv National University Named after V.O. Sukhomlynsky; Pavlo Tychyna
Uman State Pedagogical University; National Technical University of Ukraine «Igor
Sikorsky Kyiv Polytechnic Institute»; National University of Life and
Environmental Sciences of Ukraine.
We express our sincere thanks to all the authors, esteemed colleagues, who in a
short time presented the own, original, interesting researches on the problems of
water security, contributing to this book was published.
In the future we hope that the scientific expertise is on the pages of this edition
will find a creative affiliate cooperation through a successful joint implementation
of actual ideas, proposals, scientific and practical developments.

Prof. Olena Mitryasova & Prof. Chad Staddon


Mykolaiv & Bristol
November 2016
Water Security: Monograph 7

WATER ECOSYSTEM ECOLOGICAL SAFETY ASSESSMENT


BY THE DETERMINATION OF ENERGY FLOW SUSTAINABILITY

As. Prof., PhD. Viacheslav Andrieiev1


Postgraduate Yevhen Bezsonov2
Postgraduate Nataliia Andrieieva1
1
Petro Mohyla Black Sea National University, e-mail: avi@chdu.edu.ua,
Ukraine
2
Petro Mohyla Black Sea National University, e-mail: xaxa1990@yandex.ru,
Ukraine

ABSTRACT
In this paper the causes of deterioration to the majority of water bodies in
Ukraine, including the ecosystem of the Southern Bug River, are analyzed. A
method of assessing the ecological safety of the Southern Bug aquatic ecosystem is
proposed, which is based on the study and uses the main energy aspects of the river.
It can be applied to any natural water body. The main elements of the assessment in
this case are the indicators of productivity measured in units of energy or biomass.
The main tool of the proposed method is a diagram of the food chain or their
combination. The evaluation by this scheme will be more objective than the existing
system for monitoring anthropogenic impacts on the environment, which cannot
objectively assess the real state of natural systems today. It better captures real
conditions, because it takes into account the full range of existing external factors,
including the phenomenon of synergy action. In this paper, it is proved that water
resources in most cases are underestimated in terms of their material and energy
capacity and that this causes the majority of ecological problems in the aquatic
ecosystem.
Keywords: ecological safety, water ecosystem, energy, productivity.

INTRODUCTION
Each year, water resources, especially freshwater, are becoming increasingly
important as food and environmental problems are aggravated around the world,
including in Ukraine. In almost every corner of the world there are currently
environmental problems related to water, depletion of groundwater, excessive
regulation, physical and chemical water pollution and others, which are significantly
8 Water Security: Monograph

underestimated. If these phenomena are complemented by processes of quantitative


and qualitative impoverishment of hydrocoles, there will not be any doubt that these
problems needs to be urgently tackled.
Narrowing the scope of the problem to the local level (in this case – to the
Mykolaiv region of Ukraine) adds a number of local problems to the total list. The
region has one of the highest drinking water resources deficits per inhabitant,
according to indices and, owing to weather conditions, it belongs to the zone of
risky agriculture with a low density of hydrographic nets.
Considering this, it is important to find the cause of the Southern Bug’s
ecological crisis, which is the subject of this research. The research almost
completely covers the territory of the region, and objectively assesses its condition.
Recently thoughts have increasingly appeared which consider that the normative
approach of assessing human impact on the environment does not objectively assess
condition, which greatly affects water ecosystem management processes.

METHODOLOGY OF RESEARCH
At the stage of forming the theoretical framework of the proposed evaluation
method, it will be important to determine the content of the key elements of
conceptual and categorical apparatus, which determines further the action algorithm
and trains of thought. These concepts are ‘ecological safety’, ‘ecological system’
and ‘ecosystem services’.
The majority of authors interpret ‘ecological system’ almost identically. A new
version of its interpretation is: a spatially defined aggregate of functionally related
biotic and abiotic components of the environment that interact among themselves
by flows of matter, energy and information. Particular attention in the future will
be made for energy, because it is a universal measure regardless of the historical
period and can describe livelihoods of any element of ecological systems, taking
into account complex acting factors.
The term «ecosystem services» that is widely used by the UN, is understood as
"the benefits that people receive from ecosystems. They include providing, such as
food and water; regulating, such as regulation of floods, drought, land degradation
and diseases; supporting, such as soil formation and nutrient circulation; and cultural,
such as recreational, spiritual, religious and other intangible benefits" [14].
The majority of discussions are mainly concerned with the interpretation of the
‘ecological safety’ concept. The UN documents determine ecological safety as “the
minimum level of ecological resources (environmentally safe residue), that
providing a sustainable flow of ecosystem services” [2]. In other words, it is
proposed that we should protect the minimum required renewable resources of the
natural system, and take the rest. But another definition of ‘ecological safety’ is to
“secure access to natural and other resources, personal safety and protection from
natural and anthropogenic disasters” [15]. Again, the main object for which the ‘safe
Water Security: Monograph 9

access’ is provided is considered to be a human. In general, we could affirmatively


talk about the anthropocentric orientation of these interpretations, given their priority
of the inherent human needs over the ecological systems’ needs.
Among Ukrainian scientists the problem of interpreting the ‘ecological security’
concept is studied by Dobrovolskyi V. V. [16; 17], Kachynskyi A. B. [18],
Nekos V. Y. [19], Shmandii V. M. [20; 21] etc. The Law of Ukraine
"On Environmental Protection", which is acknowledged as one of the most
progressive in the world, defines ecological safety as a state of the environment that
prevents deterioration of the environmental condition and associated risks to human
health.
There are also some differences in the use and interpretation of words
‘ecological’ or ‘environmental’, ‘security’ or ‘safety’ and their combinations in
English scientific literature. But in general, the issue of conceptual and categorical
apparatus unification is poorly investigated.
If it is difficult to distinguish ecological safety’s form and content, the following
may be considered: the object of the ecological safety (something that is affected)
is a human, territory or settlement of people; the environment or its individual
components, artificial structures and so on. It should be noted that the assessment
of ecological safety is justified only in relation to something – security of life,
territory and state. The subject of action (that is the source of negative impact)
should be assessed only from the point of danger. In a state of ‘security’ deterioration
must be prevented and spatial and functional integrity of any element of the
biosphere should be provided.
The focus of study is the Southern Bug River which flows into the Black Sea.
Its watershed is located in the south-western part of Ukraine. Based on the analysis
of hydrological and energy characteristics, a way to assess the safety of aquatic
ecosystems will be offered, which seems to be more objective and comprehensive
than the existing approach.
Scientific novelty of the proposed method of environmental assessment is that
it is conducted on indicators of productivity of elements in the food chain. In this
case, living organisms are the integrated indicators (receptors). This allows the full
range of existing environmental factors to be accounted for, more accurate
determination of the current productive capacity of the ecosystem and minimization
of certain subjective aspects of evaluation.

RESULTS OF RESEARCH
In conditions of extremely rapid technological progress and increasing consumer
needs of people, the preservation and rational use of water resources should occupy
a central place in the system of ecological systems safety management. This view
has been repeatedly emphasized at international level by the United Nations [1; 2;
3; 4] and in various works of scientists [5; 6; 7; 8].
10 Water Security: Monograph

This approach is explained with several reasons. Firstly, it is well known that
people can hardly survive a day without water. Drinking water is a basic biological
need for the majority of living organisms of the biosphere, including humans. Thus,
deficit or absence of drinking water considerably affects the well-being of a
particular species or functional integrity of ecological systems.
Secondly, it is difficult to overestimate the contribution of aquatic ecosystems
in supporting and accelerating the circulation of materials, energy and information
that they carry out on the Earth. This aspect of water’s value, in the context of global
biogeochemical cycles, has been thoroughly investigated in the works of
V. I. Vernadskyi [9].
Thirdly, any natural water body, when rationally managed, is to some extent a
‘hive’, which can serve the needs of human society in terms of biological, industrial
or cultural aspects over many decades. In Western literature such needs are
summarized by the term ‘ecosystem services’; a quantitative description of
ecosystem services for the purposes of this research will be given later.
Generally, it should be noted that the environmental safety of water systems
largely determines the level of a region or locality’s development.
But why is the condition of water resources in each region of the world
becoming worse, despite the thoughts of this paper being based on well-established,
synthesized and available research? Legislation in most countries is sustained at a
high level, therefore, the problem occurs in practice.
The first reason for worsening water resources is the system used for assessing
anthropogenic impacts on the environment, which is based on using of ‘maximum
allowable value’ (MAV). This is a term for negative factor, and does not ensure the
objectivity of the results, regardless of the database of 1000 normative indicators.
It is known that in the environment any object interacts simultaneously with other
factors and with varying intensity. However, the assessment system does not take
into account the availability of synergetic interaction. The overall conclusion in this
case is an illustrative one [10], which states that the development of computer
technology facilitates the spread of mathematical models aimed at the most adequate
consideration of the object by expanding the number of investigated processes and
their more detailed descriptions. However, this leads to the fact that the
mathematical models sometimes include hundreds of variables and parameters, are
becoming cumbersome and expensive, and their creation is possible only on the
basis of long-term studies by large groups of scientists. There is a typical situation
of the ‘curse of dimensionality’. Focus on a more accurate consideration of
ecosystems is increasing the number of discounted factors and processes. But the
more indicators that a model contains, the harder it is to work and to confirm its
adequacy. These models produce errors resulting from the accumulation of purely
computational errors and inaccuracies in measurements of parameters and initial
conditions, and these mistakes can lead to catastrophic inconsistencies in model
projections.
Water Security: Monograph 11

Furthermore, it is important to emphasize that the norms of environmental


impact are anthropocentric, in other words, they are calculated according to the
properties of the human body, although it is known that members of the Homo
sapiens species today are among the most adaptable to external factors. From this
perspective, the normative evaluation system is inadequate.
The second reason for worsening water resources is excessive regulation of river
flow. Today the rethinking processes about the expediency of creating reservoir and
ponds in the watershed occur too slowly.
It should be noted that in Ukraine the issue of riverbeds regulation is very
important in view of the water quality deterioration, increasing periods of water
eutrophication, and specific and quantitative depletion of aquatic biological
resources, including fish.
According to [11], pressure on water resources could arise in cases where the
amount of fresh water consumption exceeds 10% of the volume of renewable fresh
water, and could significantly increase when the amount of water consumption
exceeds 20%. Any country through dams, reservoirs and intake structures can take
an average of no more than one third of the annual runoff of its rivers. The problem
that "water consumption is so large that several major rivers’ flow decreases
downstream, causing deficient of water resources for water users and ecosystems
downstream and affects both the river and the adjacent coastal areas" is clear.
Along with the priority of human water needs, paragraphs 8, 32, 119 of the
document [11] , focus on the fact that the consumer approach is unsatisfactory and
should be reoriented to "ensure the normal functioning of aquatic ecosystems" and
support "necessary hydrological regime of swamps, lakes, rivers and coastal areas",
"the normal functioning of the natural complex on which human society is built".
Investigating the regulation problem of the Southern Bug watershed has shown
an absolute lack of control, systematic and sustainable river water usage.
The growth dynamics of the total intake of hydraulic structures in the river
watershed is shown in fig.1.
According to analyzed data [12], about 9900 artificial reservoirs, with a total
volume of more than 1,5 km3 have been created in the watershed.
The analysis of more than 14,000 actual data of daily water flow in the Southern
Bug River in the hydrological post Оlexandrivka showed that the average runoff
from the river for 1999-2015 is 2,8 km3. That is, the economic complexity of human
consumption takes about 50% of river runoff each year. But the main danger appears
in dry years. For example, in 2007 and 2009, river runoff was 1,8 km3 (83% was
taken). In 2012 the runoff was 1,44 km3 (100% was taken, water flow in the river
during low water levels were at 2 m3/s, with normal – 30-40 m3/s), and in 2015 it
was 1,3 km3 (a situation similar to 2012).
12 Water Security: Monograph

Such hydrological situations in the watershed affects the number of key


indicators, which, ultimately, express certain environmental problems, but with a
general cause. For example, in recent decades, when the riverbed was not cleaned
by technical methods, it became rapidly silted and overgrown with reeds. In other
words, the river essentially loses one of its major properties – it stops flowing. Fig.2
graphically presents this aspect of the overall problem.

Figure 1. Growth of created reservoirs and pond volumes


in the Southern Bug’s watershed

Figure 2. Declined water flow extremes in the Southern Bug

Current regulation of flow processes have destroyed the natural spring-flood-


cleaning mechanisms of the river. In the near future this will result in full siltation
of water bodies, or to extremely high costs and energy usage for clearing and partial
recovery.
Water Security: Monograph 13

In addition, the total overlapping of the riverbed by dams has destroyed the
natural migration paths of all the region’s diadromous fish species (sturgeon, beluga,
stellate sturgeon, shemaya, Black Sea roach and many others).
Due to the decrease in flow velocity and turbulent mixing of the riverbed water
column, decay processes and eutrophication that cause mortality of fish and other
aquatic organisms have become far more intense and longer.
Summarizing the scope of the problem, we note that it is stated in the source
[13] that there were 115 times of the MAV being exceeding in the watershed during
2015. However, apart from ascertaining this fact, according to these data it is
difficult to determine the cause and actual damage thresholds of such effects on the
water body.
Therefore, the logical conclusion is that there is a need to develop a simple and
objective methodology for assessing human impact on aquatic ecosystems.
The source [22] indicates that man in relation to abiotic environmental factors
is a pronounced eurybiont. The breadth of adaptation to different conditions and the
widest dispersal across the planet have been achieved through the ability to adapt
to the environment through technological methods and by creating favorable
microclimates. It is therefore obvious today that the principles of anthropocentrism
cannot form the methodological basis of ecological safety at this stage of human
development.
Energy, in contrast to economic or physical indicators, is a unique value with a
constant dimension (or weight) over time. It is also known that amplification, deletion
or modification of one or more abiotic factors on the ecosystem will necessarily affect
the structure and quantitative indicators of biotic diversity. Based on the fact that the
most important thing for human existence is productivity of ecological systems (in
energy or biological aspect), it is proposed that energy losses in the food chain to the
end user (i.e. humans) are used to determine the ecological safety assessment (fig.3).
In this case, the link that is the most affected will be monitored clearly and the
negative factors and causes of their appearance will be tracked faster.

Figure 3. The scheme of material and energy flows in ecological systems


(P – producers; C1, C2, C3 – consuments of the first, the second and the third order

The conclusion that the total biomass of a stable ecosystem is relatively constant
formed the basis of the proposed approach [22; 23]. That is why historical data from
these studies (including qualitative and quantitative nature) become so valuable for
analyzing the causes of deterioration to ecological safety in any ecological system.
14 Water Security: Monograph

It is known that during the transition from one trophic level to another (fig. 3),
part of the available energy is not perceived: some of it is lost as heat, excrements,
and some is spent as breath. On average, total energy decreases by about 10 times
("10% rule") in the transition from one trophic level to another.
The longer the food chain is, the less available energy remains in the end.
Therefore, the number of trophic levels is never too high. It should also be noted that
the components C2 and C3 are not a graphical representation of one type of organism
in the food chain, and may include a system with two or three species. Therefore
horizontal links of Fig. 3 in a more expanded form will be seen as follows (1):
P → C1 → C2 → … → Cn → D (1)
In this case, a number of elements from C1 to Cn will respond to each species
(individuals) in the food chain.
It is advisable to note that according to the law of distribution of organic matter
degradation between different groups of organisms for large consuments it is
permissible to withdraw less than 1% of the annual production of the biosphere
("1% rule"). Humanity has exceeded the natural "norm" many times over, and the
technosphere circulation of substances is significantly open-circuited in quantitative
and qualitative terms. Because anthropogenic mass transfer is a significant part of
the global cycle of matter, its open-circuiting violates the required high degree of
biotic isolation which developed in the long process of evolution and is the most
important condition of a sustainable steady state in the biosphere. This means that
we are experiencing a very serious violation of biosphere balance, as evidenced by
today's global environmental crisis [23].
Therefore, the use of an ecological safety assessment methodology for
ecosystems, built on energy circulation, is a relevant and expedient task. At the same
time, the productivity of each species, populations or body affects the whole range
of environmental factors. As for the maximum permissible concentration, it is a
well-known fact that in nature the effect of harmful substances, the concentration
of which does not exceed the norm, may be strengthened by other environmental
factors and adversely affect elements of ecological systems [17].
Considering that, the evaluation method should be simple in practical application,
and the results representative and objective, the assessment of the ecological safety
of aquatic ecosystems through a relevant index is proposed as follows:

Under such conditions, ESIe is reduced to a dimensionless value and falls inside
the limits 0 ˂ IEB ˂ 1, and allows quick characterization of results. The closer the
index value is to 1, the better (safer) is the state of the studied ecological system.
The closer it is to 0 – the worse the state. If the ratio is > 1, then we take it equal to
"1" in a formula.
Water Security: Monograph 15

According to the proposed algorithm for ecological safety assessment, we note


that values from E1 to En characterizes the modern number or density indicators of
certain species and living components in the ecosystem. Values from E01 to E0n are
historically documented and accepted by the "etalon" values of the number (density)
of certain species and living components in the ecosystem. The solid lines on fig. 3
show the direction of matter and energy movement in the ecological system, while
the dotted line shows the negative effect of human activity on biota, the environment
and the functioning of each of the previous trophic groups. Because of human
impact on the volume (usually reduced), the production of organic products plants
P is changing and as a result its flows in the overall structure of a particular food
chain for each subsequent level En are also changing. An example of such a negative
actions on the various components of the food chain is fish mortality caused by a
reduction in the water column’s light transmission properties and light absorbance
(that immediately affects the volume of reservoir Autotrophs primary production).
These changes are in the basis of the version of the natural system ESIe
definition, if stenobiont species are unknown [24]. Based on historical data, when
environmental systems were not violated by humans, the etalon of energy capacity
E0 is elected and then the calculation continues. The living matter conversion into
energy unit is proposed using numerous data for the energy capacity of food
materials found in the literature.
In case the value of En is not known, the current index productivity, expressed
by summary or specific values, the environmental characteristics of organisms
should be defined. Knowing or having studied the ecological characteristics of
species or populations in relation to the current negative anthropogenic factors in
the investigated area could determine the number or biomass of studied organisms
and these indicators could be used in the evaluation of the formula (2).
Feasibility of calculations in this way explains that energy, unlike money, is a
universal evaluation criterion, which does not lose its importance over time. In other
words, 1 kilogram of honey contained the same amount of energy in 1700 as it did
in 2015. In [22] on this matter, it is indicated that the value of the natural capacity
of the production areas and environmental technovolume territory can be expressed
in terms of the weight of a substance for the standardized hazard (toxicity), and in
energy or monetary terms. In general, the model estimates the preferred energy
approach.
Therefore, it is seems to use the total data (quarterly, half year, year) for resource
extraction or dynamic changes in it density in the environment. For example, about
nine thousands tons of fish were caught in 1980 in the Dnipro-Bug estuary [25], while
from 1995 to 2012 – an average of only 3-4 thousand tons were caught [26]. During
1951-1955 in the same aquatic body, according to [27], about 20 thousand tons of fish
were caught, 160 tons of it constituted diadromous fish species. In 1976-1979 – the
amount of fishing declined to 31 tons and in the late 1980s, most of these species were
endangered (sturgeon, beluga, stellate sturgeon, alosa sapidissima). It should be added
to the abovementioned fact that the trend in the reduction of the catch and the number
16 Water Security: Monograph

of fish in the water ecosystem is mostly associated with unsustainable models and
management approaches based on these.
Substituting data found in the literature with factual data of Dnipro-Bug estuary
aquatic organisms, we could determine the index of ecological safety for the lower
reaches of the Southern Bug and Dnipro rivers:
4 2,2 1,1
ESIe = __ . __ . __ = 0,2 . 0,23 . 0,5 = 0,023
20 9,5 2,1
The value 4 refers to the number (thousand tons) of fish caught in 2012. 20
refers to the number (thousand tons) in 1950; 2,2 is the average biomass of
zooplankton in the estuary in 2012 in g/m3, which was 9,5 g/m3 in 1951-1952; 1,1
and 2,1 refer to amphipod biomass (g/m2) in 2012 and 1967 respectively.
According to the results, we can assert that the crisis of the ecological state of
the Southern Bug River aquatic ecosystem is in its lower reaches.
For comparison, the normative index of water pollution (IWP) for the studied
ecosystem is 1,05–2,12 on average, which corresponds to the category of moderate
contamination water or the III quality class [28].

DISCUSSION
Obtained results are presented exclusively in energy units as follows (3):
Dec = (Cpast – Clast year) . Q, (3)
where, Dec – ecological damage, kilocalories;
Cpast – j extracted water bioresources for any previous year (advisable to choose
indicators of catching from older years, which will be considered as "etalon");
Clast year – extracted water bioresources in the last year;
Q – the average energy value range of commercial fish list, which is adopted
annually by the governance, kilocalories/kg.
The nomenclature for industrial species from the list of commercial fish catches
is obtained from [29], and the sources from [30, 31]. The nutritional value for each
type of fresh fish in kilocalories/kg is totalled and then averaged for the entire list.
Thus, the average energy value of the modern list is about 857,2 kilocalories/kg. It
is difficult to find aggregated data for each aquatic region. This approach is more
advisable for use in the calculation of the proposed formula, where Cpast and Clast
year are also generalized statistical indicators.
From sources [19] we find out that in 2012 the volume of caught bioresources
was 2780,5 tons. Substituting the known values in the formula (3) we get:
Dec = (9160000 – 2780545,9) . 857,2 = 5,5.109 (kcal/kg)
Water Security: Monograph 17

The same amount of energy is contained, for example, in the winter wheat grain
weight of 183,17 thousand tons (if crop yield of this agriculture at 35 kg/ha, and it
is necessary to sow an area of about 52,3 thousand ha).
Economic aspects are easier to calculate – the actual difference in water
bioresources caught should be multiplied by the average price for this type of
product so we determine the share of the GDP. Thus, at a very rough assessment,
(average price for a kilogram of fish from the list [21] is 39 UAH/kg), the total value
of fish resources and crayfish lost over the year 1980 is 248,8 million UAH.
If the energy production aspect (through the wheat) is assessed, the realization
of 183,17 thousand tons of it at the lowest price in 2014 (from 3500 UAH/t), the
economic side of the issue will amount to 641,095 million UAH – a fifth of the
Mykolaiv region’s budget in the same year.
And this is without taking into account the value of water bioresources from the
positions of vitamins, macro- and micronutrient content. In general, the usefulness
of this calculation is seen to show the indissoluble unity of the economic sector and
the environment, and how relationships between them affect the safety of humans
and ecosystems.
Therefore, the assessment confirms that management of natural resources which
ignores the laws of ecosystem functioning worsens the current condition of any
region, especially in social and economic terms. This is because the lost volume of
fishery resources today is covered by imports of raw materials and finished products,
for which we need to pay.
Consider another variant of assessing water’s significance for the economy,
using the example of the Dnipro-Bug estuary.According to some Ukrainian
scientists [32; 33] annual total photosynthetic active radiation (PAR) in the Northern
Black Sea (Odessa, Mykolaiv and Kherson regions) is about 2600 MJ/m2.
The square of the Dnipro-Bug estuary is about 1006,3 km2 [27]. So we can
calculate the total PAR it absorbs as:
2600 MJ/m2 . 1006,3 . 106 м2 = 2616,4 . 109 MJ = 2616,4 . 1015 J
Considering that the average efficiency of photosynthesis in algae (mainly
phytoplankton) is higher than in terrestrial plants at approximately 2%, it is possible
to calculate the primary production that can be formed in the estuary:
2616,4 . 1015 J . 0,02 = 52,328 . 1015 J
Compare the resulting value of primary production of the aquatic ecosystem
with annual capacity, for example, of the South Ukrainian Nuclear Power Plant.
According to data posted on the website of the company it produces about
19 . 109 kW.h a year, equal to about 68,4 . 1015 J.
Thus, if in the case of nuclear power plants considerable energy are costed at
the stage of construction and, especially, decommissioning, and ‘profit’ for about
18 Water Security: Monograph

30 years, the estuary does not require any efforts from humans to produce a similar
amount of energy for centuries – only proper management of available resources.
A striking example of sustainable resource management is beekeeping, which
in the author's research [24] provides about 3% of gross regional product in Ukraine.
In general, these calculations are indicative only in terms of power, as in this
case, we can better see the potential of aquatic ecosystems. But it will not be correct
to compare the final products each of the research objects due to the fact that they
produce different kinds of energy.

CONCLUSIONS
The paper suggests a way to assess environmental safety of natural systems,
which is considered as alternative to normative approach, and is based on the use
of biological indicators or energy productivity of the latter. In this way, a greater
level of objectivity in evaluation results is achieved.
It proves the discrepancy in normative assessment methods of anthropogenic
impacts on the aquatic ecosystem in the real world on water bodies.
The calculations highlight the crisis in the ecological status of the Southern Bug
aquatic ecosystem, which is caused mainly by two factors: the excessive extent of
river runoff regulation and contamination of domestic sewage.
The modernization of existing systems of wastewater treatment is a long and
expensive process, as is the development and introduction of new systems..
Therefore, the primary goal today is to produce an inventory of all the reservoirs
and ponds in the river watershed in order to decommission those that do not fulfill
their intended purpose, or which violate environmental legislation.

REFERENCES

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https://sustainabledevelopment.un.org/content/documents/Agenda21.pdf.
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/rio20_outcome_document_complete.pdf.
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T. J., Acuña, V. (2016). Placing ecosystem services at the heart of urban water systems
management. Science of The Total Environment, 563–564, 1078–1085.
Water Security: Monograph 19

6. Grizzetti, B., Lanzanova, D., Liquete, C., Reynaud A., Cardoso, A. C. (2016).
Assessing water ecosystem services for water resource management. Environmental Science
and Policy, 61, 194–203.
7. Zagonari, F. (2016). Using ecosystem services in decision-making to support
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8. Barboura, E. J., Holzc, L., Kuczerad, G., Pollinoe, C .A., Jakemana, A. J., Loucksf,
D. P. (2016). Optimization as a process for understanding and managing river ecosystems.
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9. Vernadskyi, V. I. (1933). History of nature waters. Leningrad: Goshimtehizdat.
(in rush.)
10. Serdiutskaia, L. F. (2009). System analysis and mathematical modeling of ecological
processes in aquatic ecosystems. Мoscow: Librokom. (in rush.)
11. Report of the Secretary-General. Comprehensive assessment of the freshwater
resources of the world. Retrieved 29/10/2016, from: http://www.un.org/spanish/esa/sustdev/
documents/docs_csd5.htm.
12. The annual report "About the activities of Southern Bug Water Resources Basin
Department on the management, use and reproduction of water resources by 2012". (2013).
Vinnitsa, Ukraine. (in ukr.)
13. The regional report "About the state of the environment in the Mykolaiv region in
2015". Retrieved 29/10/2016, from: http://ecolog.mk.gov.ua/store/ files/1473057744.pdf
(in ukr.)
14. Millennium Ecosystem Assessment. (2005). Ecosystems and human well-being: a
framework for assessment. Washington, DC: World Resources Institute.
15. Millennium Ecosystem Assessment. (2005). Ecosystems and human well-being:
synthesis. Washington, DC: World Resources Institute, Island Press.
16. Dobrovolskyi, V. V. (2006). Fundamentals of the ecological systems theory. Kiev:
"Professional". (in ukr.)
17. Dobrovolskyi, V. V. (2010). Ecological risk: assessment and management
(Екологічний ризик: оцінка і управління). Mykolaiv: Petro Mohyla Black Sea State
University. ISBN 978-966-336-208-3. (in ukr.)
18. Kachynskyi, A. B. (2001). Ecological safety of Ukraine: a systematic analysis of
prospects for improvement (Екологічна безпека України: системний аналіз перспектив
розвитку). Кiev: The National Institute of Strategic Studies. (in ukr.)
19. Nekos, V. Yu. (2011). General Ecology and Neoecology. Kharkiv: Kharkiv National
University of V. N. Karazin. (in ukr.)
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(theoretical and practical aspects. Kharkiv: Kharkiv National University of V. N. Karazin.
(in ukr.)
21. Shmandii, V. M., Nekos V. Yu. (2008). Ecological safety. Kharkiv: Kharkiv National
University of V. N. Karazin. (in ukr.)
20 Water Security: Monograph

22. Akimova, T. A., Haskin V. V. (1999). Ecology. Мoscow: YUNITI. (in rush.)
23. Odum, Yu. (1975) Fundamentals of ecology (Основы экологии). Мoscow: Мir.
(in rush.)
24. Bezsonov, Ye. M., Andreev V. I. (2016) Justification and formalization of approach
to regional ecological safety evaluation. Eastern-European Journal of Enterprise
Technologies, 2/10(80), 9-18. Doi: 10.15587/1729-4061.2016.64843. (in ukr.)
25. Zabolotnyi, V. Z., Lisetskyi M. F., Molodetskyi A. Ye. (1997). Mykolaiv region:
geographical dictionary directory. Mykolaiv. (in ukr.)
26. The regional report "About the state of the environment in the Mykolaiv region in
2012". Retrieved 29/10/2016, from: http://www.duecomk.gov.ua/data/nac_dop/19.pdf.
(in ukr.)
27. Zhukinskii, V. N., Zhuravleva, L. A., Ivanov, A. I. et al. (1989). Dnieper-Bug estuary
ecosystem. Kiev, Naukova Dumka. ISBN 5-12-000803-8. (in rush.)
28. Maniushko, M. M. Water quality evaluation of hydrochemical indicators for the
Northwest shelf of the Black Sea. Retrieved 29/10/2016, from:
http://sibnigmi.ru/GidroCongress/%D1%E5%EA%F6%E8%FF%203%20%CF%F0%EE%E
1%EB%E5%EC%FB%20%EA%E0%F7%E5%F1%F2%E2%E0%20%E2%EE%E4,%20%
EE%F5%F0%E0%ED%FB%20%E2%EE%E4%ED%FB%F5%20%EE%E1%FA%E5%EA
%F2%EE%E2%20%E8%20%E8%F5%20%E2%EE%F1%F1%F2%E0%ED%EE%E2%EB
%E5%ED%E8%FF/35.pdf. (in rush.)
29. On approval limits and acceptable example of the special use of water biological
resources of national importance for 2015. Retrieved 27/10/2016, from:
http://zakon3.rada.gov.ua/laws/show/z1432-14. (in ukr.)
30. Fish and seafood. Table of foods calories. Retrieved 27/08/2016, from: http://health-
diet.ru/base_of_food/food_1515. (in rush.)
31. Caloric content of fish and seafood. Retrieved 27/08/2016, from:
http://gotovimka.ru/kalorijnost/ryba-i-moreprodukty.html. (in rush.)
32. Gudz, V. P., Shuvar I. A., Yunyk A. V., Ryhlivskyi I. P., Mishchenko Yu. G. (2014).
Adaptive farming systems. Кiev: Center of educational literature. (in rush.)
33. Tkachenko, T. G. (2015). Agrometeorology. Kharkiv: Kharkiv National Agrarian
University. (in ukr.)
Water Security: Monograph 21

ASSESSMENT OF WATER POLLUTION BY BIOINDICATION


METHOD

Ass.Prof., PhD. Vitalii Ishchenko


Ass.Prof., PhD. Sergey Kvaternyuk
Assistant Oksana Styskal
Vinnytsia National Technical University, e-mail: ischenko.v.a@vntu.edu.ua,
Ukraine

ABSTRACT
The quality of polluted water was assessed using a bioindication method based
on the identification of changes in algal reproduction due to the influence of toxic
substances contained in the aquatic medium. This makes it possible to assess the
influence not only from the concentration of pollutants, but also by final effect, i.e.
their toxic action on living organisms. The investigation was carried out using the
example of water pollution by chlorination by-products and batteries. The results
show the high reliability of the bioindication method for water pollution assessment.
In addition, the method of monitoring water objects was improved. This method is
based on the identification of phytoplankton particles, which is achieved by
comparing array multispectral images using the Bayesian Classifier based on
Mahalanobis distance.
Keywords: water, pollution, bioindication, phytoplankton.

INTRODUCTION
Since water is the main factor supporting human life, then ensuring water quality
must be a priority for every country. Increased pollution of natural water bodies and
the impossibility of providing high quality of drinking water with outdated sewage
treatment technologies make health risks of water consumption very high.
Chlorination by-products and substances contained in batteries are among the
most widespread water pollutants.
There are many toxic by-products formed during water disinfection by chlorine
(sodium hypochlorite, etc.) [Nikolaou]: trihalomethanes, haloacetic acids,
halogenated aldehydes, halogenated ketones, haloacetonitrils, chloropicrin,
22 Water Security: Monograph

chlorophenols. They cause a chronic impact on humans if orally ingested, inhaled


or absorbed through the skin [Villanueva]. Some of these organochlorine
compounds are carcinogenic, mutagenic (break DNA chains, causing birth defects
such as interventricular septum defects and obstructive urinary tract defects), or
teratogenic, according to [Morris, King, Kasim, Sharma]. However, regulatory
limits are established only for a few substances. For example, there are no limits
for toxic and carcinogenic haloacetic acids and carcinogenic and mutagenic
haloacetonitrils in many countries, although the World Health Organization and the
US Environmental Protection Agency (USEPA) have established limits for some
substances from these groups.
According to [Recknagel, Moreno-Merino], heavy metal content in many
batteries is over limit values. Therefore, batteries pose a serious danger to the
environment. Since methods of non-hazardous waste utilization are unsuitable for
battery processing, heavy metal release to water is totally uncontrolled [Moreno-
Merino].
Due to the potential toxic effects of chlorination by-products and heavy metals,
it is necessary to evaluate their impact on living organisms. Phytoplankton is known
to be useful test-object. Bioindication is used in environmental research as a method
of identifying anthropogenic influences on ecosystems. This method is based on
investigation of variable factors which influence different characteristics of
biological objects and systems. The biological systems or organisms which are the
most sensitive to investigated factors are used as bioindicators [Styskal]. The
objective of this study is to investigate how batteries influence living organisms
using a bioindication method.
In addition, the theoretical and practical aspects of automated control of water
ecosystems are not developed enough due to the relativistic approach and
subjectivity of integral indicators used for quality assessing. The main parameter
of polydisperse mediums is concentration of phytoplankton particles. The
quantitative correlation between the concentrations of these particles is the criteria
of water quality assessment, including indices of biodiversity, ecological balance,
integrated bioindicators of the human and industrial impact of various pollutants,
and others.

METHODOLOGY OF RESEARCH
For well and river water chlorination by different doses of sodium hypochlorite
solution (SHS), the mass concentration of active chlorine in SHS was defined. For
this purpose, potassium iodide was added to SHS and the solution was titrated by
sodium thiosulfate. After chlorination, free residual chlorine in the investigated
samples was measured using a method of titrating by methyl orange.
Investigations of the toxic impact of water chlorination by-products and heavy
metals of batteries were carried out using a bioindication method. Chlorella and
Water Security: Monograph 23

Scenedesmus were used as bioindicators. Eleven samples were prepared by mixing


an equal volume (100 ml) of well and river water disinfected with different SHS
doses and a phytoplankton solution. The same was done for a non-disinfected well,
river and tap water. The samples were placed in a sunny spot for 90 days.
Additionally, water with bioindicators was divided up into 20 samples by adding
10 different types of batteries (2 batteries of each type: damaged and undamaged),
and one control sample without batteries. The batteries were prepared so that one
battery had undamaged casing and another (of the same type) was damaged. This
enabled direct contact between the investigated water medium and the battery’s
content. These samples were placed in a lit spot for 14 days. Measurements of the
samples’ pH and visual observation of changes were carried out during the 14 days.
Visual investigation of the samples was carried out at the end of experiment using
a microscope, DCM-300 (400x zoom).
In addition, the method of measuring television multispectral environmental
control of water bodies was used for water quality assessment, which was based on
identifying the qualitative and quantitative composition of microalgal cells. Data
were compared to normalized values, by performing multispectral television flow
analysis of phytoplankton particle, where images of particles flowing in the
measured cell received at characteristic wavelengths of phytoplankton pigments
with a microscope and CCD-TV camera are compared with images from the
database of phytoplankton particles in certain specialized processors in real time
using the Bayesian optimal Сlassifier with a solved function based on Mahalanobis
distance.

RESULTS OF RESEARCH AND DISCUSSION


Assessment of water pollution
Visual analysis of the investigated samples was conducted (see fig. 1–6).
The results indicate reduced phytoplankton activity with increasing SHS doses
for both underwater and river water. In addition, more phytoplankton was found in
the samples of good water compared to the samples of river water with the same
SHS dose. This confirms the theory that chlorination by-products increase with
increasing organic substances in the water (river water contains far more organic
compounds than good water). Some samples were of special interest. These were
samples of normal well water and good water chlorinated with 0,49 g/l of SHS. They
both had a gray-white taint of unknown origin (fig. 1 and 2). One can assume that
this is probably due to the development of pathogenic microflora caused by a lack
of disinfectant. Such a phenomenon was not observed in other samples with larger
SHS doses. Also, there were yellow-white clusters noticed in the sample of tap water
with phytoplankton (fig. 3). These could be precipitated salts – carbonates etc.
The residual chlorine content of 0,3 mg/l is considered normal according to
Ukrainian standards. Therefore, theoretically well water chlorinated by an SHS dose
24 Water Security: Monograph

of 0,49 g/l and river water chlorinated by an SHS dose of 3,7 g/l can be consumed
by humans without risk. But according to fig.2 and assumptions mentioned above,
the SHS dose of 0,49 g/l does not remove all pathogens and drinking such water
can be dangerous to health.

Figure 1. Well water with phytoplankton Figure 2. Well water with phytoplankton
and SHS dose of 0,49 g/l

Figure 3. Well water with phytoplankton Figure 4. Distilled water with


and SHS dose of 3,7 g/l phytoplankton

The largest impact of batteries on the bioindicator was found in the samples with
alkaline batteries, while the lowest influence was in the samples with 9V block
batteries of the 6F22 type (fig. 5–6). Importantly, all the samples with damaged
batteries were characterized by higher levels of mortality to organisms in
comparison with the samples with the undamaged batteries of the same type.
Comparison of pH dynamics of the samples with undamaged batteries showed that
the sample with the most similar dynamics to control sample was the sample containing
Li-Ion battery of the CR2032 type. This was probably either due to the lowest weight
of this type battery among all investigated batteries or due to a less aggressive chemical
composition. Similar pH dynamics were also noticed for the sample containing the
Ni-Cd rechargeable battery. Therefore, one can assume that the result of this sample
was similar to the result of the control sample due to absence of contact between the
sample’s water medium and battery content during the experiment.
Water Security: Monograph 25

Figure 5. Sample with a zinc-carbon Figure 6. Sample with a alkaline battery


battery of a 6F22 type at 400x zoom of a LR20 type at 400x zoom

The most significant pH changes occurred in the samples containing zinc-carbon


batteries. Additionally, one of these samples was the single one where an acid
environment was noticed at the end of experiment despite its pH increasing due to
the presence of algae. It is most likely that this result was caused by the much greater
weight of the battery in this sample (zinc-carbon battery of R20 type) in comparison
to the majority of the other investigated batteries. Therefore, more hazardous
substances could potentially come to the sample’s water medium. The last
assumption can indirectly prove the instability of zinc-carbon batteries’ casing.
High pH values for some samples with undamaged batteries could be the
consequence of the influence of a few factors: the instability of zinc-carbon battery
casing that, in turn, could cause the release of electrolytes with ammonium ions into
the water medium, potentially leading to their binding by ions of Fe and Zn (for
example, to insoluble forms).
The analysis of the pH dynamics of the samples with damaged batteries has
shown a larger dispersion of pH values in comparison to the samples with
undamaged batteries. The samples can be divided into several groups by pH
dynamics. The changes in pH that were most similar to the control sample were
noticed in the samples containing damaged batteries. The samples with undamaged
batteries demonstrated pH values similar to those in control sample.
The smallest pH deviation from values in control sample were in the sample
with Li-Ion battery of the CR2032 type. It should be noted that other above-
mentioned samples (which correspond to the majority of alkaline batteries and to
one type of rechargeable batteries) were characterized by dramatic increases in pH
(to over 12) at the beginning of experiment followed by reduction to control values.
This can be explained by alkaline electrolyte release from damaged batteries to the
water medium as previously described.
The sample with damaged alkaline battery of the LR20 type had the highest pH
value (almost 13) from the first day of the experiment due to its large electrolyte
26 Water Security: Monograph

volume (a battery of such type has larger dimensions compared with majority of
other batteries). The sample with a damaged zinc-carbon battery of the 6F22 type
had the lowest pH value (below 5 at the end of the experiment) as it was also in the
case of undamaged batteries. But there was no temporary pH increase observed in
the samples with damaged batteries.
The same dynamics were noticed for other samples where pH gradually fell to
neutral or acid values. These were the samples containing zinc-carbon batteries and
the rechargeable phone battery. Therefore, potential pH increases due to electrolyte
influence in abovementioned samples could be neutralized by the act of other
substances from a given type of battery. For example, chloride in the electrolytes
of zinc-carbon batteries can cause pH reduction due to hydrochloric acid formation.
Similar pH values were observed in some samples with the same batteries types,
one of which was damaged and another one was undamaged. They include a zinc-
carbon battery of a R20 type, an alkaline battery of a LR03 type, a Li-Ion battery of
a CR2032 type and a rechargeable battery of a KR6 type. These could have be
influenced by several factors: the low content of substances able to change pH or their
instability, the neutralization of such substances by the bioindicator (algae), the low
hermeticity of the metal casing of the battery or its self-damage during the experiment.
The most significant pH change took place on the first day which demonstrates
the intensity of the batteries’ impact. Generally, pH changes correspond to the type
of substances contained in batteries regardless of whether they were damaged or
undamaged. Comparing the samples with damaged and undamaged batteries of the
same type showed nearly identical pH dynamics. In the case of zinc-carbon and
rechargeable phone batteries, the samples with damaged batteries had constantly
lower pH values and, conversely, in the case of other batteries types they had higher
pH values. Naturally, this is explained by the chemical composition of batteries,
including the electrolyte type.
The level of bioindicator death was the highest in the samples which had pH
values similar to the control (almost all alkaline batteries, the Li-Ion button and
rechargeable batteries), as well as in the sample with a highly alkaline environment
(an alkaline battery of an LR20 type). These are the battery types containing the
largest quantity of mercury. Alternatively, the samples with pH values different from
the control sample (all zinc-carbon batteries and the damaged Li-Ion rechargeable
phone battery) had the lowest level of algal death, except for the samples with zinc-
carbon batteries of the R20 type.
Therefore, one can assume that pH change during contact between sample
medium and battery content is not a reliable indicator for defining the degree of
batteries’ impact on the environment. In turn, the metals contained in batteries affect
ecosystems without any pH change. For example, the level of algal death is
considerable in the samples with batteries containing nickel and cadmium,
especially in the sample with the damaged battery, although its pH was similar to
values in the control sample.
Water Security: Monograph 27

Method of controlling the phytoplankton concentration


The proposed method for controlling the concentration of phytoplankton
particles uses comparable array spectral polarimetric images of particles obtained
in vitro using the CCD camera developed in the controls (fig. 7). The volume
concentration and quantitative correlation between certain types of particles are
determined from characteristic wavelengths of pigments in the specified positions
and angles of a polarizer analyzer, which allows their identification more reliably
[Petruk].

Figure 7. Block diagram of the automated means of phytoplankton


concentration control
28 Water Security: Monograph

Theautomated tool works as follows. Water particles with different sizes of


phytoplankton enter the mixer 26 and share a set of filters with pores of different
diameters 271 ... 27n on the flow of particles of a certain size, which are received
in the flow measuring cell 13 corresponding to measuring channel 281... 28n.
Radiation from a light source enters the monochromator 2, the wavelength is fixed
by stepper motor 3 according to the values of the characteristic wavelength
pigments in phytoplankton particles. Then radiation passes through the fiber-optic
waveguide 4, 5, and polarizer compensator 8, the rotation angles for rotary device
(6, 9) are set, which rotate by stepper motors (7; 10). After that, radiation runs
through measuring cuvette 13 with a thin layer of phytoplankton. Before the
experiment, flow measuring cuvette 13 standard solution is washed by flushing
pump 11.
Flow measuring cuvette 13 is placed on the stage of the microscope 14 and can
be moved by stepper motors (15; 16) in the directions X and Y. To ensure stability
and repeatability of test flow measuring, cuvette 13 is placed in thermostat 17.
Radiation then passes through the analyzer 18, the rotation angle is set for rotary
device 19 by stepper motor 20. Increases to the size of spectral-polarimetric images
of phytoplankton particles are achieved by using an optical microscope system 21.
Autofocus microscope is achieved by means of AF 22 and stepper motor 23. Control
unit 24 of stepping motor provides the necessary control signals for stepper motors.
A magnified image of particles is fixed by photodetector (CCD-camera) 25 and
transferred to computer 29. Computer 29, using means of specialized software,
compares the received image with a spectral-polarimetric sample and determines
the correlation between particles of different species. The obtained correlation
between particles of different species of phytoplankton allows assessment of its
condition. The number of measuring channels 281 ... 28n and filters 271 ... 27n is
defined by the condition of accordance of the sharpness depth of images with
particle size and with liquid thickness in the measuring cuvette. Thus, if the
concentration of particles with the size dmin.... dmax needs to be controlled in
polydisperse aqueous medium, one should use a certain number of measuring
channels where the conditions by sharpness depth of particle images and their
resolution has to be provided in each.

CONCLUSIONS
Investigation of the impact of chlorination by-products and heavy metals from
batteries on water quality using phytoplankton has resulted in new assumptions.
Chlorinated water, in particular by-products of chlorination, indeed affect the
phytoplankton activity according to following trends. Increasing SHS doses causes
a reduction in the amount of phytoplankton at the end of experiment. In addition,
the fact that more phytoplankton were found in the samples of well water compared
to the samples of river water with the same SHS dose confirms the theory that
chlorination by-products increase with increasing organic substances in the water.
It was also experimentally studied that an SHS dose of 0,49 g/l providing free
Water Security: Monograph 29

residual chlorine content in the normal range does not remove all pathogens.
Therefore, the main objective of water disinfection cannot be achieved in this case.
The research results have also shown that all batteries, including undamaged
batteries, affect living organisms when they enter the environment. They change
environmental characteristics very quickly. The most significant pH change took
place on the first day of the experiment which demonstrates the intensity of the
batteries’ impact. Batteries with undamaged casing also cause destruction to living
organisms, possibly due to gradual damage of the casing in an aggressive
environment.
Different types of batteries can provide alkaline or acidic environments. This
partly depends on the electrolytes used. But this research has shown the ambiguity
of this parameter’s influence on living organisms. A much larger impact is caused
by hazardous heavy metals (mercury, nickel, cadmium and others) contained in the
batteries. When analyzing the impact of the potentially most hazardous batteries
containing mercury, nickel and cadmium, the authors noticed the most negative
reaction of bioindicator in such samples. These batteries include nickel-cadmium
rechargeable batteries and all alkaline batteries. Therefore, one can assume that pH
change during contact between the sample medium and battery content is not a
reliable indicator for defining the degree of batteries’ impact on the environment.
In turn, the metals contained in batteries affect ecosystems without pH change.
Consequently, the additional research into the impact of heavy metals on living
organisms is needed.
The proposed method of using multispectral images and an appropriate device
can efficiently control the concentration of phytoplankton in photo-bioreactor
wastewater treatment plants, and can be used to assess the state of water and
complex human impacts on aquatic ecosystems using bioindication by
phytoplankton.

REFERENCES
1. Nikolaou, A.D., Kostopoulou, M.N., & Lekkas, T.D. (1999). Organic by-products of
drinking water chlorination, Global Nest. – Greece, 1(3), 143-156.
2. Villanueva, C.M., Cantor, K.P., Grimalt, J.O., & others (2006). Bladder Cancer and
Exposure to Water Disinfection By-Products through Ingestion, Bathing, Showering, and
Swimming in Pools. American Journal of Epidemiology, 165(2), 148-156.
3. Recknagel, S., Radant, H., & Kohlmeyer, R. (2014). Survey of mercury, cadmium and
lead content of household batteries. Waste Management, 34(1), 156-161.
4. Moreno-Merino, L., Emilia Jimenez-Hernandez, M., de la Losa, A., & Huerta-Munoz,
V. (2015). Comparative assessment of button cells using a normalized index for potential
pollution by heavy metals. Science of the Total Environment, 526, 187-195.
5. Styskal, O.A., & Petruk, V.G. (2015). Danger of chlorination by-products in dinking
water for live systems. Environmental studies, 9, 154-161.
30 Water Security: Monograph

6. Petruk, V.G., Kvaternyuk, S.M., Ivanov, A.P., & Barun V.V. (2010). Device for control
of polydisperse biological fluids based on a spectral polarimetric images of particles. Patent
of Ukraine №52754.
7. Morris, R.D., Audet, A.M., Angelillo, I.F., Chalmers, T.C., & Mosteller, F. (1992).
Chlorination, chlorination by-products, and cancer: a meta-analysis. American Journal of
Public Health, 82(7), 955-963.
8. King, W.D., Marrett, L.D., & Woolcott, C.G.. (2000). Case-Control Study of Colon
and Rectal Cancers and Chlorination By-Products in Treated Water. Cancer Epidemiologic
Biomarkers Prevention, 9, 813-818.
9. Kasim, K., Levallois, P., Johnson, K.C., Abdous, B., & Auger, P. (2006). Chlorination
disinfection by-products in drinking water and the risk of adult leukemia in Canada. American
Journal of Epidemiology, 163(2), 116-126.
10. Sharma, R.N., & Goel, S. (2007). Chlorinated drinking water, cancers and adverse
health outcomes in Gangtok, Sikkim, India. Journal of environmental science & engineering,
49(4), 247-254.
Water Security: Monograph 31

INCREASES IN REMOVAL OF PHOSPHORUS COMPOUNDS DURING


BIOLOGICAL TREATMENT OF URBAN WASTEWATER IN
CONSTRUCTIONS WITHOUT ZONING

Prof., Dr.Sc. Valentina Iurchenko1


PhD. Olena Bryhada2
1
Kharkov National University of Construction and Architecture, e-mail:
yurchenko.valentina@gmail.com,
2
Kharkov National University of Construction and Architecture, e-mail:
ebrigada@gmail.com, Ukraine

ABSTRACT
Indicators of biological treatment of urban wastewater from the compounds of
nutrients (nitrogen and phosphorus) during processing in aeration tanks (aerotanks)
without zoning of the traditional scheme «primary clarifier aerotank secondary
settling tank» were studied. Research was carried out at the existing wastewater
treatment plants of Kharkov and in laboratory experiments. It was established that
the concentration of nutrients in the incoming wastewater to the treatment plant
exceeds the admissible concentration. Treatment processes in the studied plants
include ammonification and nitrification, while the denitrification process does not
occur. The concentration of mineral nitrogen compounds in the effluent, as a rule,
does not exceed the regulatory limits at Kharkov’s biological wastewater treatment
plant. The concentration of phosphate in wastewater after the secondary settling
tank exceeds the regulatory limits for these facilities. It was found that after settling
in the secondary settling tank the phosphate concentration in the wastewater
increases, on average, by 110%. For the inhibition of water phosphatizing in the
secondary settling tank nitrates were used and an inhibition constant process was
installed using 25 mg.l–1 nitrate. To prevent pollution of wastewater by phosphates
in the secondary settling tank during the regulatory 2 hour settling period, the nitrate
concentrations in wastewater have to be above 35 mg.l–1.
Keywords: biological wastewater treatment, nutrient removal, phosphating,
inhibition, nitrates.

INTRODUCTION
The eutrophication of natural sources of drinking water has become a global
problem and so the implementation of highly efficient removal techniques for
32 Water Security: Monograph

biogenic elements (nitrogen and phosphorus) is necessary. In countries where supply


of potable water relies on surface waters (Central Europe, Northern America and
Southern Africa) pollution by nitrogen and phosphorus compounds (eutrophication)
is one of the most acute problems for maintaining ecological safety (Lubchenko et
al., 1996; EPA, 2009). To prevent eutrophication of water bodies and to restore the
quality of the aquatic environment it is necessary to minimize emissions of biogenic
elements into receivers. Until recently, these elements were mostly discharged from
agricultural areas (as surface runoff), however, domestic (municipal) and industrial
wastewaters are becoming important sources as well.
Generally, nitrogen and phosphorus compounds are partially removed from
municipal wastewater during a conventional biological treatment process performed
in activated sludge tanks (aerotanks) or in biofilters. Unfortunately, such processes
are not efficient enough, and do not achieve admissible concentrations for
wastewater discharged into natural reservoirs. Such efficiency also does not satisfy
modern requirements for protecting natural reservoirs against eutrophication.
Application of modern technologies which increase the efficiency of treatment
processes at municipal treatment construction – nitrogen and phosphorus compound
removal – is considered as a viable option.
The biological methods of nitrogen compound removal are based on
microbiological processes with the use of the active sludge, and are considered as
the most effective and safe for the environment (Henze et al., 1999; Choubert et
al., 2005; Yagov, 2008; Gujer, 2010). Transformation of nitrogen compounds during
traditional biological treatment process includes the following stages:
microbiological assimilation, ammonification, and partial nitrification. During
advanced nitrogen removal, additional advanced nitrification and denitrification are
introduced. Microbiological nitrification is a chemoautotrophic process occurring
in two phases. The ammonium oxidizing bacteria carry out the first phase of
nitrification in aerobic conditions, oxidizing ammonium to nitrites (eq. 1):
(1)
In the second phase of nitrification – nitrite bacteria oxidizes nitrites to nitrates
in aerobic conditions, as per equation 2:
(2)
To remove nitrites/nitrates from wastewater, a denitrification process is applied
(more precisely, dissimilation denitrification). The dissimilation denitrification is a
catabolic process of the heterotrophic microbiological reduction of nitrites/nitrates
by protons of organic substrates under anaerobic conditions (eq. 3):
(3)
The biological phosphorus removal during the traditional biological treatment
process is based only on the microbiological assimilation according to the BOD
(biochemical oxygen demand): P = 100: 1. The Enhanced Biological Phosphorus
Water Security: Monograph 33

Removal (EBPR) mechanism is based on the following key facts (Kulakovskaja,


T. et al., 2014; Phosphorus and nitrogen removal from municipal wastewater:
principles and practice. 1991; Henze et al., 2004):
1) phosphate accumulating microorganisms (PAM) are capable of storing excess
amounts of phosphorus as polyphosphates;
2) these bacteria are capable of removing simple fermentation substrates
produced in the anaerobic zone and assimilating them into storage products within
their cells. This process involves the release of phosphorus;
3) in the aerobic zone, energy is produced by the oxidation of storage products
and polyphosphate storage in the cell increases.
One term used to descride the anaerobic zone is that it is a ‘biological selector’
for phosphorus-storing microorganisms. This zone provides a competitive advantage
for the phosphorus-storing microorganisms, since they can take up substrates in this
zone before non-phosphorus storing bacteria can. Thus, this zone allows the
development or selection of a large population of phosphorus-storing organisms in
the system which take up significant levels of phosphorus and are removed from
the system via the waste sludge. (Phosphorus and nitrogen removal from municipal
wastewater: principles and practice. 1991).
At biological phosphorus removal the activated sludge must be exposed to two
alternating conditions; an anaerobic (neither oxygen nor nitrate) environment with
readily biodegradable substrate and an aerobic environment. In a sequential process
this occurs in two phases. In the first phase, the sludge releases phosphate and the
concentration of dissolved phosphorus increases (phosphatizing of water), while
the soluble COD (chemical oxygen demand) decreases. During the aerobic phase,
the sludge takes up phosphate and the concentration of dissolved phosphorus
decreases (dephosphatizing of water), normally to a lower value than at the
beginning of the cycle (Henze et al., 1999).
Biological phosphorus removal involves design or operational modifications to
conventional treatment systems that result in the growth of a biological population
that has a much higher cellular phosphorus content. Such systems incorporate an
anaerobic operating phase somewhere in the process, and the waste sludge’s overall
phosphorus content is typically in the range of 3-6 percent. This diverts more
phosphorus to the waste solids and yields lower effluent phosphorus concentrations.
Thus, for high-efficiency removal of nitrogen and phosphorus compounds, it is
necessary to alternate anaerobic and aerobic treatment of wastewater by activated
sludge (EPA, 2009). In the anaerobic step treatment the biological transformation
of nitrogen and phosphorus compounds compete for the organic substrate. During
biological wastewater treatment a change of aerobic and anaerobic conditions is
carried out due to a consecutive passage of the sludge through anaerobic and aerobic
zones of the activated sludge tanks (aerotanks) (division of oxygen modes in space)
or due to change of anaerobic and aerobic periods of processing in the same reactor
34 Water Security: Monograph

of full mixture (division of oxygen modes in time). Reactors in which aerobic


conditions (created by pneumatic aeration) and anaerobic conditions (created by
stirring) are performed within a single reactor are called the sequencing batch
reactors (SBR) (Gujer et al., 2010; Choubert et al., 2005). Many technological
schemes have been designed for the efficient removal of nitrogen and phosphorus
compounds in the alternation of anaerobic and aerobic treatment zones (Henze, et
al., 1999; Gmur, 2003; Henze et al., 2004)
In Ukraine, the majority of wastewater biological treatment plants work under
the traditional scheme of ‘primary clarifier aerotank secondary settling tank’, which
is based on the normative documents developed 30 years ago (SNaR 2.04.03-85
"Canalization. External networks and constructions”). These documents are based
on the kinetics and efficiency of organic carbon removal (COD, BOD).
Nevertheless, the efficiency of nitrogen and phosphorus compound removal during
the wastewater biological treatment in such constructions can be improved.
The purpose of this work is efficient management of wastewater from
phosphorus compounds in the processing of biological wastewater treatment plants
operating under the traditional scheme.

METHODOLOGY OF RESEARCH
Investigations on working wastewater treatment plants in Kharkov city focused
on: i) determination of nitrogen compound concentrations (ammonium nitrogen,
nitrites and nitrates) and phosphorus compound concentrations (orthophosphate) by
standard techniques according to requirements of Ukraine’s normative documents;
ii) determination of Kjeldahl nitrogen concentrations according to recommendations
from literature (Lurie, 1971; Perelik, 1997). Also, data from various stages of
biological treatment are presented. In vitro investigations were focused on
determining nitrate and phosphate concentrations in purified wastewater in
sedimentation dynamics (a simulation of processes in the secondary settling tank).
There are two wastewater treatment plants in the Kharkov city with a total
capacity of 1.1 million m3 per day. The sequence of treatment processes at these
facilities includes mechanical and biological processes, disinfection and sludge
processing (fig. 1). The following study presents results for one of the treatment
plants (Kharkov biological wastewater treatment plant, Kharkov WWTP, with
capacity of 300 000 m3) where municipal and industrial wastewaters are delivered.
Construction of the biological reactor at the Kharkov WWTP has been presented
in fig. 2.

RESULTS OF RESEARCH
Kharkov city is a big industrial center of Ukraine. The rivers in this region are
shallow and contaminated with ammonium nitrogen and orthophosphate received
from surface runoff and discharges of untreated wastewater.
Water Security: Monograph 35

Figure 1. Wastewater Treatment scheme at the Kharkov WWTP: 1 – lattice , 2 – sand


trap , 3 – primary clarifier, 4 – aerotаnk, 5 – secondary settling tank, 6 – disinfection
installation, 7 – sludge compactor, 8 – sludge fields, 9 – installation of mechanical
dewatering, 10 – sand fields.

Figure 2. Construction of the plug-flow biological reactor (the aerotank) at the Kharkov
WWTP (arrows designate the direction of movement of a liquid)

Indicators of wastewater treatment from biogenic elements in the aeration tank


during the dynamics processing are presented in fig. 3, 4. As presented in fig. 3,
concentrations of N-NH4 steadily decline, but particularly rapidly in the first corridor.
Nitrite concentrations are constantly minimal. Concentrations of nitrates start to
increase in the second corridor of the biological reactor, and reach maximum values
at the exit from the biological reactor (the end of fourth corridor). This demonstrates
that high activity of the nitrification process, where not only N-NH4, present in
36 Water Security: Monograph

wastewater, is oxidized actively, but also that this form of nitrogen is formed as a
result of the mineralization of Nоrg. The residual concentration of Nоrg remains high
at the exit from the biological reactor in comparison with EU specifications for
wastewater discharged in natural reservoirs. This can be explained by a partial
resistance of nitrogen incorporated into organic compounds to the biological
oxidation (Henze et al., 1999). Calculation of balance for oxidized and reduced forms
of nitrogen in the entrance and exit from the biological reactor testifies, that in the
investigated biological reactor, the denitrification process of nitrates and nitrites
practically does not occur. As can be seen, the nitrate concentration at the outlet of
the aerotank exceeds the allowable 7,9 mg.l-1 N-NO3. However, analysis of the data
for the year of work has shown that the average nitrate concentration in the
wastewater after treatment in aeration tanks was << 7,9 mg.l-1.
The concentration of Р-РО4 in the incoming wastewater (fig. 4) exceeds the
allowable requirements for the Kharkov WWTP (2 mg.l-1).

Figure 3. Transformations of different nitrogen compounds during processing treatment


in biological reactor at the Kharkov city WWTP (points: 0 entering wastewater, 1 – 2nd
corridor, 2 – 3rd corridor, 3 the end of 4th corridor)

As can be seen, the concentration of Ptotal and Р-РО4 in the wastewater, treated
in the aerotank, steadily decreases, reaching values at the outlet of the aerotank of
2,0 and 1,9 mg.l-1, respectively.
The results of the survey of the system ‘aerotank- secondary settling tank’ show
that the phosphate concentration in wastewater after settling steadily increases
(fig. 5).
Water Security: Monograph 37

Figure 4. Transformations of phosphorus compounds during processing treatment in


biological reactor at the Kharkov city WWTP (points: 0 entering wastewater,
1 – 2nd corridor, 2 – 3rd corridor, 3 the end of 4th corridor)

Figure 5. Monthly average concentrations of P-PO4 in wastewater at treatment stages:


1 – wastewater after aerotаnk, 2 – wastewater after secondary settling tank

The presence of nitrates in the treated wastewater is a positive development as


evidence of the passage of a full biological treatment with nitrification. It is known
that nitrates inhibit phosphatizing of water, but the quantitative characteristics of
the process according to different authors vary greatly. In addition, the nitrate
concentration in the effluent discharged into a natural water source has a limited
MPC (maximum permissible concentration) of 30-45 mg.l-1. As shown the results
of laboratory research into the process of settling reveal that the concentration of
effluent phosphate increased steady (table 1).
38 Water Security: Monograph

Table 1
The effect of the duration of the sedimentation of sludge liquid on the
concentration of phosphates and nitrates in wastewater
Settling time Phosphates, mg.l-1 Nitrates, mg.l-1
0 11,56 47,7
20 11,76
30 15,84
60 16,0
120 16,2 39,2
180 16,5
210 18,0 30,9

In experiments with settling of wastewater with different concentrations of


nitrates, obtained data revealed a relationship shown in fig. 6. From the data of
fig. 6 it is clear that with increasing nitrate concentrations from 0 to about 45 mg.l-1
the phosphatizing speed falls in a linear relationship.

Figure 6. Influence of nitrate concentrations in treated wastewater on their phosphatizing


during settling

DISCUSSION
Required treatment efficiency is based on standards for treated effluent discharged
into water bodies. Different values of admissible nitrogen and phosphorus
concentrations are presented in table 1. In EU countries, only the total concentration
of nitrogen and total concentration of phosphorus in wastewater are standardized,
and in eutrophication sensitive areas, they should not exceed 15 mg.l-1 and 2 mg.l-1
Water Security: Monograph 39

(respectively) for wastewater from settlements with up to 100 thousand person


equivalents (PE), and 10 mg.l-1 and 1 mg.l-1 (respectively) for wastewater from
settlements with over 100 thousand PE. In Ukraine, only soluble mineral nitrogen
and phosphorus forms are under scrutiny. For fish farming reservoirs the admissible
concentration of mineral soluble nitrogen is 9,55 mg.l-1 and standardization of
phosphorus compounds concentrations is absent. For reservoirs used for drinking
supply the admissible concentration of mineral soluble nitrogen is 13,16 mg.l-1 and
the admissible concentration of mineral soluble phosphorus is 1,14 mg.l-1.
Concentrations of organic nitrogen and organic phosphorus are not supervised, and
the absence of this control parameter extremely complicates the rational organization
of wastewater treatment process, and also diminishes the efficiency of the
eutrophication protection measures.
Changing N-NH4, N-NO2, N-NO3 and Nоrg concentrations in wastewater in the
aeration tank during processing proves high activity of the nitrification process,
where not only N-NH4, present in wastewater, is oxidized actively, but also that this
form of nitrogen is formed as a result of the mineralization of Nоrg. The
concentration of Ntotal = N-NH4+ N-NO2+ N-NO3+Nоrg in the treatment
wastewater at the exit from the biological reactor exceeds EU specifications for
wastewater discharged into natural reservoirs. Calculations of the balance of
oxidized and reduced forms of nitrogen in the entrance and exit from the biological
reactor testifies that in the investigated biological reactor the denitrification process
of nitrates and nitrites practically does not occur. Concentrations of N-NO3 in the
treated wastewater sometimes exceeds admissible concentration for Kharkov
WWTP (7,9 mg.l-1 or 35 mg.l-1 nitrates). Because concentrations of BOD5 in
wastewater exceeds 110 mg.l-1 at the entrance to the biological reactor,
denitrification of more than 28 mg.l-1 N-NO3 is possible through partial recycling
of treated wastewater at the entrance to the biological reactor.
The P-PO4 concentration in the incoming wastewater is up to 70% of the Ptotal
content. The concentration of P-PO4 in the incoming wastewater exceeds the
admissible concentration for Kharkov WWTP (2 mg.l-1). The share of P-PO4 in the
treated wastewater increases, reaching an average of 85% Ptotal. This indicates that
the removal of phosphorus compounds extends deeply, and its residual compounds
are inorganic biologically non-degradable substances. Aerotank residual
concentrations of P-PO4 in most cases (fig. 5) exceed allowable standards for
Kharkov WWTP (0,7 mg.l-1). After treatment of wastewater in the secondary
settling tank (fig. 4) the concentration of P-PO4 increases from 0 to 233% (on
average by 110%). In laboratory experiments that simulate the processes in the
secondary sedimentation tanks, the concentration of phosphates in wastewater after
the normative duration of settling (2 hours) increased by 42% with a parallel
decrease in the nitrate concentration. This corresponds with data in scientific
literature about the migration of phosphates in system activated sludge - wastewater
under anaerobic conditions (Henze et al., 2004; Phosphorus and nitrogen removal
from municipal wastewater: principles and practice. 1991; EPA, 2009; Yurchenko,
V. et al., 2015).
40 Water Security: Monograph

Table 2
Admissible concentrations of nitrogen and phosphorus in wastewater
Country Sources of wastewater Controllable Admissible
parameter concentration
(mg.l-1)
European Wastewater from settlements up to Total nitrogen 15
Union 100 thousand PE Total phosphorus 2
countries
Wastewater from settlements above Total nitrogen 10
100 thousand PE
Total phosphorus 1
Ukraine Reservoirs at fish-farms N-NH4 0,5
N-NO2 0,02
N-NO3 9,03
P-PO4 absent
Reservoirs of drinking water N-NH4 2,0
N-NO2 1,0
N-NO3 10,16
P-PO4 1,14

From the obtained dependence (fig. 5), the inhibition constant of phosphatizing
of treated wastewater in a secondary settling tank by nitrates can be installed – the
nitrate concentration at which the inhibition of the phosphatizing rate occurs is 50%.
This constant has a value of 22 mg.l-1 nitrates or 5,0 mg.l-1 N-NO3. During settling
the nitrate concentration decreases at a rate 4.8 mg.(l.h)-1, i.e. after the normative 2
hours settling – to 9,6 mg.l-1 or 2,2 mg.l-1 N-NO3. If the regulatory allowable
concentration of nitrate in the effluent is not more than 35 mg.l-1 or 7,9 mg.l-1
N-NO3 (the admissible concentration for Kharkov WWTP) after 2 hours settling
their residual concentration is not more than 26 mg.l-1 or 5,7 mg.l-1 N-NO3. Based
on this concentration phosphatising in a secondary settling tank has to be suppressed
by at least 50%. Considering the reduction of the nitrate concentration in the
secondary settling tank after 2 hours of settling, settling tank water will have a
concentration of N-NO3 = 7,9 + 2,2 = 10,1 N-NO3 mg.l-1 or 44,7 mg.l-1 nitrate. In
the secondary settling tank phosphatising will be inhibited by almost 100%.
A residual concentration of nitrate will not exceed regulatory requirements.

CONCLUSIONS
The current study based on the Kharkov WWTP allowed us to draw the
following conclusions:
Water Security: Monograph 41

- The total load of ammonium nitrogen and organic nitrogen on the biological
reactors is extremely high due to the concentration of ammonium nitrogen
exceeding allowable levels;
- Treatment processes in the biological reactors with active sludge include deep
nitrification, while the denitrification process does not occur at all;
- The most effective way to increase efficiency of the nitrogen and phosphorus
compounds removal is to the increase time of the aerobic treatment to allow
advanced oxidation of organic compounds and to improve the nitrification process
(decrease of residual ammonium nitrogen concentration);
- The concentration of P-PO4 in the incoming wastewater exceeds the allowable
requirements for Kharkov WWTP.
- To prevent pollution of treated wastewater by phosphates in the secondary
settling tank, the retention time of settling must consider the nitrate concentrations
in wastewater. Phosphatizing of the water is minimal at the nitrate concentration
above 35 mg.l-1 and retention time of settling 2 hours.
- Modernization of the investigated facility shall also point out the necessity of
improving of standardization for nitrogen and phosphorus compound concentrations
in Ukrainian wastewaters.

REFERENCES
1. Choubert, J.-M., Racault, Y., Grasmick, A., Beck, C., Heduit, A. (2005). Maximum
nitrification rate in activated sludge process at low temperature: key parameters, optimal
value. E-Water official Publication of the European Water Association (EWA), 1–13.
2. EPA 2009 Nutrient Control Design Manual. State of Technology Review Report.
Environmental Protection Agency. (EPA/600/R-09/012), Cincinnati, OH 45268.
3. Gmur, N.S. (2003). Tehnologicheskie i biohimicheskie procesy ochistki stochnyh vod
na soorugeniyah s aerotenkami. (Technological and biochemical processes of wastewater
treatment on constructions with aerotanks). AKVAROS. Moskva. (in rush.)
4. Gujer, W. (2010). Nitrification and me a subjective review. Water Resources, 44 (1),
1–19.
5. Henze, M., Gujer, W., Mino, T., Matsuo, T., Wentzel, M.C., Marais, G.R., Loosdrecht,
M.C.M. (1999). Activated Sludge Model No.2d. ASM2d. Wat. Sci. Tech., 39 (1), 165–182.
6. Henze, M., Armoes, P., Lya-Kur-Yansen, Y., Arvan, E. (2004). Ochistka stochnyh vod.
Mir. Moskva. (Wastewater treatment). (in rush.)
7. Kulakovskaja, T., Lichko, L., Rjazanova, L. (2014). Raznoobrazije phosphornyh
rezervov mikroorganizmov (A variety of phosphate microorganisms reserves). Uspehi
biologicheskoj chimii. (Advances of Biological Chemistry). 54. 385-412. (in rush.)
42 Water Security: Monograph

8. Lubchenko, O.A., Mogilevich, N.F., Gvozdyak, P.I. (1996). Mikrobnaya nitrifikaciya


i ochistka vody. Himiya i texnologiya vody (Microbic nitrification and water treatment.
Chemistry and technology of water). 18 (1), 98–112. (in rush.)
9. Lurie, Y.Y. (1971). Unificirovannye metody analiza stochnyh vod. (Standardized
methods for analysis of wastewater). Chimiya. Moskva. (in rush.)
10. Perelik atestovanyh tymchasovo doputchenyh do vykorystannya metodyk
vyznachennya skladu, vlastyvostey ta zabrudnyuyuchyh rechovyn prob pryrodnych ta
stichnyh vod. (List of certified provisionally permitted to use techniques of composition,
properties and pollutant samples of natural and wastewaters). Uzgodzeno lystom
Dergstandartu Ukrainy № 1864/5-3. (in Ukrainian).
11. Phosphorus and nitrogen removal from municipal wastewater: principles and practice.
(1991). Richard l. Sedlak, editor.-2nd ed. NY.
12. Yagov, G.V. (2008). Kontrol soderganiya coedineniy azota pri ochistke stochnyh vod.
Vodosnabgenie i sanitarnaya tehnika. (Control of the content of nitrogen compounds in
wastewater treatment. Water Supply and Sanitary Technology). 7, 1–6. (in rush.)
13. Yakovlev, S.V., Karyuhina, T.A. (1980) Biohimicheskiye procesy v ochistke stochnyh
vod. (Biochemical processes in wastewater treatment). Stroyizdat. Moskva.
14. Yurchenko, V., Smyrnov, O., Bakhareva, A. (2015). Vlijanije redox potentciala sredy
na migratciju phosphora v ilovoj smesi (Influence of redox potential of migration phosphorus
in activated sludge system). Eastern-European Journal of Eenterprise Technologies. 6/6 (78).
78-84. (in rush.)
Water Security: Monograph 43

USING A PHOTOCATALYTIC UV-nano-ТіО2-K2Cr2O7 SYSTEM


TO DETERMINE COD IN WATER ANALYSIS

Ass. Prof., PhD. Svitlana Kel’ina1


Prof., Dr.Sc. Jury Dedkov2
1Petro Mohyla Black Sea National University, e-mail:sk21@rambler.ru,
Ukraine
2Moscow State Regional University, e-mail: j13021936@yandex.ru, Russia

ABSTRACT
The results of a study of a photocatalytic system which uses UV-nano-TiO2-
K2Cr2O7 is described. The oxidation process was conducted in a specially designed
photo reactor. Glucose (a readily oxidizable compound and standard substance in
the arbitration method for chemical oxygen demand (COD)) and acetic acid (a hard
to oxidize substance) were used to optimize oxidation conditions. The effects of
irradiation time and intensity, acidity, the amount of the catalyst and electron
scavengers were investigated. The effect on oxidation of organic substances and its
causes from the amount of scavengers K2Cr2O7 was studied and is explained. The
oxidation of many organic compounds − hydrocarbons, alcohols, ketones, organic
acids and their derivatives, amino acids, aromatic compounds, nitro compounds,
surfactants and others, which are the most common organic pollutions in waters in
optimal conditions were investigated. The UV-nano-TiO2-K2Cr2O7 system was
applied in the methods of determining the COD for clean waters and wastewaters.
The results were in good agreement with those from conventional CODCr methods.
Keywords: photocatalytic oxidation, nano-TiO2 catalyst, potassium dichromate,
chemical oxygen demand

INTRODUCTION
Conventional COD evaluation methods have several disadvantages, such as
extreme conditions of determination, a long period of analysis (2-4 h), high
probability of errors due to complex procedures dependent upon the operator’s skill,
the duration of the procedure for determining distorted results of the analysis due
to the presence of certain salts, and the consumption of expensive (Ag2SO4) and
toxic reagents (K2Cr2O7 and HgSO4) [1]. Therefore, a scientific task is the search
for new oxidation conditions for determining the oxidability of water.
44 Water Security: Monograph

In recent years much attention has been paid to a process for photocatalytic
oxidation (mineralization) of organic substances in water [2]. Much research has
investigated the oxidizing abilities of systems which use a heterogeneous
photocatalyst – a semiconductor nano-TiO2. Nano-TiO2 has a number of advantages
as a catalyst − it is ecologically safe, chemically inert and sufficiently stable in
composition and structure under ordinary conditions, and is relatively inexpensive
[3−5]. In analytical practice nano-TiO2 was first proposed to determine the total
organic carbon (TOC) [6], and then − for the determination of COD. Scavengers
of electrons (electron absorbers) have been used as common chemical oxidants −
potassium dichromatе and potassium permanganate, Ce(IV) [7−10]. Photocatalytic
oxidation of glucose and potassium hydrogen phthalate have been examined in these
studies (standard substances which are used in the arbitration method for
determination of COD) and methods have been developed for determining the COD
for certain types of water. The results were validated through comparison with
results obtained by known methods.
In our opinion, these authors have not discovered any significant patterns of
behavior in photocatalytic systems. For example, they have not explained the initial
concentration of the K2Cr2O7, boundaries that determine the amount of COD, the
influence of sorption of dichromate ions on the catalyst on the accuracy of the
analysis’s results, or the effect of methods used to separate the photocatalyst. Some
recommendations of the authors are difficult to perform, for example, measuring the
pH of 0,5 with high precision using a common pH-meter. In addition, a significant
decrease in the initial concentration of dichromate ions greatly reduces the potential
for absorption of electrons process, so at high COD values (500-600 mg)
stoichiometric ratios between the components of the process are violated, which
greatly affects the reproducibility of the results.
Our aim was to conduct a detailed study of all the factors that affect the
completeness of oxidation and optimization of conditions for photocatalytic
mineralization of organic impurities in reducing agents.

METHODOLOGY OF RESEARCH
Device
The process of destruction in a specially
designed photo reactor was carried out. It
consisted of a quartz reaction flask 100 cm3 (4),
a UV-lamp (3), mounted on the base (2). The
lamp was placed directly in the flask. The
reaction mixture was kept in suspension and
heated with a magnetic stirrer (7). The
temperature was measured by a thermometer
(1). The flask was placed in a water jacket (5)
Figure 1. Photoreactor with thermal insulation (6). (fig. 1).
Water Security: Monograph 45

Lamp’s (OSRAM) characteristics: HNS mercury lamp low pressure type,


C-band, λ = 253,7 nm, capacity 9 W, the total capacity of the UV flux − 1,9 W.
The spectrophotometric measurements were carried out using the
spectrophotometer Beckman DU 520.
The acidity was measured by a pH-meter P-160 MI.
Reagents and solutions
The catalyst was nano-TiO2, grade P25, produced by Degussa− it was a non-
porous powder mixture of anatase and rutile in a ratio of 70:30, with a surface area
of 55 ± 15 m2.g−1 and a crystallite size of 30 nm to 0,1 micron diameter particles
[11].
All chemicals were of analytical reagent grade:
Potassium dichromate, K2Cr2O7, a standard solution of 0,25 N; sulfuric acid,
concentrated and diluted at a ratio of 1:10; d-glucose, a standard solution,
corresponding to 1000 mg.l−1 COD, was prepared by dissolving 0,9372 g of d-glucose
in distilled water and diluted to 1: l with distilled water. Appropriate dilutions gave
solutions of different COD values [7]; Mohr's salt, 0,25 N and 0,05 N.; ferroin
(prepared by mixing batches of 1,485 g of 1,10-phenanthroline and 0,695 g
FeSO4.7H2O and subsequent dissolution in 100 cm3 of distilled water); silver
sulphate.
Organic compounds used were: hexane, heptane, octane, decane; methanol,
ethanol, propanol, 2-butanol, 1-butanol, ethyleneglycol, glycerol, mannitol, benzyl
alcohol; phenol, resorcinol; acetone, acetylacetone, methyl-ethyl ketone; tartaric
acid, oxalic acid, acetic acid, lactic acid; potassium hydrogen phthalate; dioxane,
amyl acetate, ethyl acetate; glucose, lactose, saccharose; aniline, nitroaniline,
ethanolamine; glycine, alanine, valine, leucine, phenylalanine, proline, leucine,
serine, asparagine, glutamine, histidine, arginine; acetamide, urea, thiurea,
dimethylformamide; benzene, nitrobenzene, toluene, ethylbenzene; sodium lauric
sulphate, cetyl pyridinium bromide; chloroform; benzotriazole.
These solutions were prepared by dissolving (or emulsifying) a certain amount
of sample substance in 100 cm3 distilled water. The concentration of substances was
0,125 mol eq.dm−3.
Experimental procedure
A volumetric flask of 50 cm3 was injected in stages with: a potassium dichromate
solution, sulfuric acid, a d-glucose solution or other organic reductant and distilled
water to the mark. The resulting solution was transferred to the reaction flask of
100 cm3 which was placed weighted mass of catalyst. The solution was heated to
the desired temperature. Oxidation of the substances began to occur with intensive
mixing, when the UV-lamp was turned on, and was accompanied by an increase in
the concentration of Cr(III) produced by the photocatalytic reduction of Cr(VI).
After a certain time of irradiation reaction, the aqueous samples were centrifuged
46 Water Security: Monograph

at 800 rpm (using photocolometry). The registration of the results of experiments


carried out in two ways − titrimetric and photometric.
RESULTS OF RESEARCH AND DISCUSSION
In this research COD measurement by a photocatalytic oxidation method using
nano-TiO2 was studied [11]. It is known, that by irradiation with UV light C-band in
the nano-oxide electrons valence band (ē) pass in the conduction band, leaving
positively charged vacancy − holes (h+) in the valence band, which are strong oxidants
(their potential amount +3,5 V) [12,13]. The high oxidizing ability of such systems is
also associated with the formation of various oxygenated radicals (e.g. ∙OH), which
are formed on the surface of TiO2 illuminated by ultraviolet light [3]:
TiO2 → hν
h+ + ē;
h+ + H2O → ∙OH + H+;
∙OH + R→∙ ∙ ∙→ CO2 + H2O;
h+ + R→∙ ∙ ∙→ CO2 + H2O.
where R − organic radical.
Simultaneously, the process of photogeneration leads to the undesirable
recombination of electron-hole pairs. To prevent this occurring, different chemical
oxidizing agents − electron scavengers are used [14-17]. The potassium dichromate,
K2Cr2O7 (φ0(Cr2O72−) = 1,36 V) was used in our studies.
It is known [7; 8] that the amount of reduced absorber and oxidized reductant
are stoichiometric. Indeed, the electrons that enter the valence band are absorbed
by the chemical oxidant, thus it is recovered quantitatively. The remaining positive
holes oxidize stoichiometric reducing agents present in the system.
Overseeing the process of photooxidation can determine the amount of the
oxidized or reduced form of dichromate ions.
To optimize the heterogeneous photooxidation process, glucose was used
because it is a standard substance in the arbitration method of determining CODCr.
The effect of acidity, temperature, time, weight of the catalyst and the initial
concentration of dichromate ions were studied.
Effect of acidity
It is known that the isoelectric point of nano-TiO2 P-25 is at pH 6,25 [14]. At
pH < 6,25 the catalyst’s surface becomes electropositive, which favors adsorption
of Cr(VI) anions and therefore the degree of oxidation of organic substances
increases with decreasing pH. The greatest oxidative capacity among the forms of
Cr(VI) are dichromate ions Cr2O72−, which exist in a highly acidic environment.
The direct oxidation of organic substances by potassium dichromate in the system
at a pH ~ 0 does not occur, because it is a weaker oxidant than holes.
It was found that the presence in the system of 2,4 cm3 of 1:10 of diluted solution
of sulfuric acid (рН ~ 0,75) allows the oxidation of glucose at COD 100 mg O.dm−3
Water Security: Monograph 47

95-100%. These figures match – and are therefore confirmed by – theoretically


calculated values of COD and obtained experimental data. Of this, 0,17 cm3 is
consumed directly by the oxidation of glucose per 100 mg O.dm−3, and the remainder
is necessary to maintain the oxidation potential of dichromate ions.
Temperature effect
The process speed increases with increasing temperature up to the boiling point
of the solution. According to the rule of Vant Hoff, the function v = f(t) is non-linear.
However, in our case we are seeing a straight line. In [2] it is shown that the linear
form of this dependence is determined by the Langmuir-Hinshelwood mechanism,
which takes into account not only the chemicals, but also physical processes
(sorption, processes in the semiconductor, etc.).
It should also be noted that increased evaporation occurs at temperatures around
the boiling point of the solution, which leads to a decrease in reproducibility.
Therefore, the temperature range was chosen as 85-90 °C.
Effect of time
The time of the process greatly affects the degree of reduction of dichromate
ions. The optimal time for glucose oxidation is 15-20 minutes.
Dosage of the photocatalyst nano-TiO2
The degree of glucose oxidation increases with the concentration of TiO2 to
4 g.dm−3. A further increase in the concentration of the catalyst decreases the
efficiency of photooxidation, which can be explained by the weakening of
penetrating radiation in a suspension.
Selection of the initial concentration of K2Cr2O7 and their adsorption on the
catalyst
In [7] the proposed initial concentration of Cr(VI) is 0,01 mol.dm−3. The authors
believe that at high concentrations the process is stabilized and explains the
maximum adsorption of Cr2O72− on the catalyst.
We have found that this relationship is more complex. On the one-hand, the
absorber should be sufficient to ensure destruction of the process, especially for
water with a high content of impurities (COD > 100 mg O.dm−3). On the other hand,
dichromate ions strongly absorb in the UV-range, almost at the same level as with
the lamp-conductive radiation range. Therefore, most will reduce the amount of
energy used for photocatalysis and, in general, a useful reaction yield is significantly
reduced. A COD range of of 0 − 100 mg O.dm−3 was thus determined and the
necessary amount of scavengers with a slight excess (~ 15%) was calculated. Given
the excess, to determine the COD unit 100 under the described conditions, 7,5.10−4
equivalents of dichromate ion must enter the reaction flask.
Studying the influence of adsorption of dichromate ions on the catalyst in the
absence of glucose revealed that dichromate ions in the system are spent almost
48 Water Security: Monograph

exclusively on the absorption of photoelectrons and they adsorbed only ~ 2,7 %.


These data confirm the stoichiometric heterogeneous photocatalysis processes.
The degree of recovery of dichromate ions on the amount of glucose was studied
as a function νeq(K2Cr2O7)use = f(COD) and the data were compared with the
theoretical COD. The method of calculation of this index is given in [18].
Registration of experimental results
The titration method was chosen for better comparison with the results obtained
by the arbitration method definition of COD. The amount of glucose oxidized and
accordingly, COD, was determined by the potassium dichromate concentration
difference before and after the photooxidation process of Mohr salt titration in the
presence of a ferroin indicator [1].
Ions Cr(VI) and Cr(III) are colored, so that a more precise and express
photometric method can be used for the determination of COD.
It is advisable to determine the content of the ions Cr(III), because their spectrum
has a peak at 610 nm and is more intensive with equal concentrations of the two
forms of chromium ions.
To determine completeness of the recovery of ions Cr(VI) various concentrations
of the reaction mixture are plotted in coordinates A − f(CCr3+), which were used in
determination of the concentration of Cr(III) after photooxidation.
Removal of the catalyst
When using photometric methods for determining COD, a significant problem
is the removal of nano-TiO2 from the system. In [19-22] it is suggested that
precipitation and centrifugation are carried out, and the catalyst used is immobilized
in solid support, such as glass, metal, quartz, etc. We used centrifugation.
Positive results of glucose oxidation have allowed a number of experiments on
the mineralization of substances of other classes, to confirm the optimal conditions.
Table 1
The oxidation of organic substances in the UV-nano-TiO2-K2Cr2O7
system under optimized conditions for glucose

Substance Oxidability, % Substance Oxidability, %


Ethanol 37 Oxalic acid 37
Isobutanol 32 Tartaric acid 71
Glycerin 100 Acetic acid 21
Resorcinol 99 Amyl acetate 38
Mannitol 100 Glycine 63
Acetone 21 Lauryl sulfate 33
Glucose 100 Benzene 28
Water Security: Monograph 49

The table shows that the conditions chosen for the glucose (an easily oxidized
substances) [22], are not optimal for the oxidation of many other substances, and
should be optimized for conditions with compounds that are hard to oxidize.
One of these substances is acetic acid. It is known as an intermediate in the
catalytic oxidation of many organic substances and participates in the metabolism
of a variety of biological systems. Therefore, to test the oxidative ability of the UV-
nano-TiO2-K2Cr2O7 system, we chose acetic acid.
As shown by previous experiments, the oxidation of acetic acid is 21% in the
previously selected conditions. Therefore, we studied the ability of the system to
oxidize hard-to-oxidize substances.
The experimental procedure is analogous to the method of using glucose.
To optimize the process of oxidation of acetic acid we also investigated the effect
of the initial concentration of dichromate ion, acidity, time and temperature.
The influence of the initial concentration of K2Cr2O7.
We conducted a study of oxidation of acetic acid with a wide range of
concentrations of potassium dichromate.
Table 2
Dependence of the degree of oxidation of acetic acid on the concentration
of dichromate ions

C0(Cr2O72−), C0(Cr2O72−),
ω (С2Н4О2), % ω (С2Н4О2), %
mol.dm−3 mol.dm−3
0,0025 32 0,01 18
0,0033 28 0,0133 16
0,0042 24 0,0166 13
0,005 21 0,02 3
0,0066 19

It was found that under the conditions proposed by the authors of [6], oxidation
of acetic acid is only 11 %, therefore, we assume that dichromate ions absorb the
most of amount of energy. For the oxidation of acetic acid, COD ≤ 100 mgO.dm−3
is optimal with an initial concentration of C0(Cr2O72−) = 0,0025 mol.dm−3.
Effect of acidity
It has been found that the previously set (for glucose) acidity at a pH order of
0,75 is insufficient to oxidize the acetic acid.
At pH ~ 0,5, which is achieved by introducing 5 cm3 of sulfuric acid diluted to
1:10 into the reaction mixture ensured oxidation COD acid at 100 mgO.dm−3 at
60-62% (subject to the other, previously established conditions). Lowering the
50 Water Security: Monograph

degree of oxidation of acetic acid at pH < 0,5, we explained difficulties in sorption


of dichromate ions on the photocatalyst due to the shielding effect of protons.
Temperature effect
The degree of oxidation of acetic acid by the temperature has the same pattern
as that for the oxidation of glucose. When the temperature reached 85 °C, the degree
of oxidation was 60 % and did not increase further. Therefore, an optimum
temperature of 85 °C was chosen.
Dependence of time
The time of process significantly influenced the degree of reduction of
dichromate ions. As expected, for the oxidation of acetic acid longer exposure to
UV-radiation is needed. The optimal time of exposure to acetic acid oxidation is 60
minutes.
Thus, the optimized conditions of photocatalytic oxidation of acetic acid are as
follows: C0(Cr2O72−) = 0,0025 mol.dm−3 , m(TiO2) = 4 g.dm−3 , time of experiment
τ = 60 min, the temperature t = 85 °C, the volume of H2SO4 (diluted 1:10), V =
5,00 cm3.
In new optimized conditions the oxidizing ability of the system has been studied
for a variety of organic substances, which have been selected and classified
according to different functional groups. Moreover, most of them are representative
of pollutants in wastewater.
Methods of experiment
A volumetric flask of 50 cm3 was injected in stages with: a solution of potassium
dichromate − 1,5 cm3, a sulfuric acid − 5 cm3, the organic substance − 5 cm3,
distilled water − to label.
The results of photocatalytic mineralization of organic substances are shown the
table 3. For comparison, the literature data and some of our data (marked with *),
obtained under the conditions of the arbitration and acceleration methods are also
shown.
Table 3
Comparison of oxidation of organic compounds in various oxidation systems
Water Security: Monograph 51
52 Water Security: Monograph

1 − Oxidation under the arbitration method without catalyst,%


2 − Oxidation in the conditions of the arbitration method with the catalyst
Ag2SO4 ,%
3 − Oxidation in a photocatalytic mineralization%
* − Our results of arbitration method
** − Results based on the oxidation of the amino group to molecular nitrogen.

The table 3 shows that in a UV-nano-TiO2-K2Cr2O7 system under optimized


conditions all classes of organic compounds are well oxidized.
The results of the study of oxidation of organic compounds and the
determination of optimal photocatalysis conditions enabled the development of
methods for determining COD in natural waters and wastewaters. To verify the
results of the method in parallel with the photocatalyst, COD was determined by
an accelerated arbitration procedure described in [1] using the catalyst Ag2SO4
(tab.4) or photometrically.
To verify the results from the photocatalytic method, COD was determined by
arbitration and accelerated methods, described in [1] using the catalyst Ag2SO4 or
photometrically.
Water Security: Monograph 53

Characteristics of the working solution and photocatalytic systems for COD for
relatively pure waters (1) and wastewaters (2) are as follows:
(1) V(K2Cr2O7) = 1,5 dm−3 (0,5 N), V(sample) = 30…40 dm−3,
V(H2SO4,1:10) = 2,4 dm−3, Vsol = 50 dm−3, m (TiO2) = 0,2 g , UV-irradiation, 9 W,
λ = 253,7 nm, τ = 30 min, t = 85ºC ± 2ºС, stirring with a magnetic stirrer
~ 800 rpm.
(2) V (K2Cr2O7) = 1,5 dm−3 (0,5 N), V (sample) = 30…40 dm−3,
V (H2SO4,1:10) = 5 dm−3, Vsol = 50 dm−3, m (TiO2) = 0,2 g, UV-irradiation, 9W,
λ = 253,7 nm, τ = 60 min, t = 85ºC ± 2ºС, stirring with a magnetic stirrer ~ 800 rpm.
The results of the analysis of waters and wastewaters are shown in table 5.
As can be seen from table 5, the results of determining COD in wastewater using
a photo-catalytic method correlate well with the values of CODCr using an arbitrage
method for 11 samples of water. The linear regression equation and correlation
coefficient were: y = 1,0054x + 0,7063 and 0,9756 (n = 6), respectively, where x
and y are the results obtained by the arbitration and the proposed methods.
Table 5
The results of the determination of COD for different types of water
54 Water Security: Monograph

CONCLUSIONS
The purpose of this work was to investigate the oxidative capacity of the
photocatalytic UV-nano-TiO2-K2Cr2O7 system, optimization of conditions of
oxidation using glucose and acetic acid, develop a method for monitoring COD
when applying this system and validating the results of the determination in real
water in comparison to existing methods. In this system K2Cr2O7 stoichiometrically
interacts with photoelectrons in the conduction band and improves the
photocatalytic degradation of organic compounds. Thus, the COD of the sample of
water can be assessed by determining the concentration of Cr(III), resulting in the
reduction of chromate ions.
The optimization of operational conditions were studied. This method of
determination of COD in different waters have a number of significant advantages
− a short time of analysis, accuracy, sensitivity, simplicity, and absence of expensive
and toxic reagents. These results correlate well with results obtained by other
methods.

REFERENCES
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8. Jiaqing Li, Luoping Li, Lei Zheng, Yuezhong Xian, Litong Jin L. (2006).
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9. Lihua Zhu, Yu’e Chen, Yinghui Wu, Xiurong Li, Heqing Tang. (2006). A surface-
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10. Yihao Chai, Hongchun Ding, Zhonghai Zhang, Yuezhong Xian, Zhensheng Pan, Litong
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12. Hoffmann, M.R, Martin, S.T., W. Choi, Bahnemann D.W. (1995). Environmental
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13. Halyavka, T.A., Kapinys, T.A., Strelko, V.V., Shimanovskaya, V.V. (2000).
Photocatalytic degradation of cetylpyridinium chloride on titanium dioxide in aqueous solutions.
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14. Fu H.Е., Lu G.X., Li S.B. (1998). Adsorption and photo-induced reduction of Cr (VI)
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56 Water Security: Monograph

ANALYSIS OF THE THEORETICAL AND PRACTICAL ASPECTS OF


WATER POLLUTION CAUSED BY MOTOR TRANSPORT

Prof., Dr.Sc. Olena Kofanova


Postgraduate Oleksii Kofanov
National Technical University of Ukraine «Igor Sikorsky Kyiv Polytechnic
Institute», e-mail: alexina555@gmail.com, Ukraine

ABSTRACT
The investigation explores the main theoretical and practical aspects of water
pollution caused by motor transport in Ukraine and other countries. Today roads,
vehicles and parking facilities are a source of serious water pollution and hydrologic
disruptions.
Water pollution comes from sources including road deicers, crankcase oil drips and
leaking underground storage tanks. Hydrologic impacts of this pollution include loss
of wetlands, increased flooding and concentrated runoff andharmful shoreline
modifications. This research analysed the pollution indexes of various countries and
cities including Ukraine and Kyiv. The most polluted and unpolluted places of the
European region are described. It was found that vehicles contain substances that are
toxic to humans, plants and animals fluids, such as antifreeze, gasoline, motor oil, air-
conditioning refrigerants, as well as brake, hydraulic, transmission and windshield
wiper fluids. Oil products and other vehicle toxins kill plants, animals, fish and other
aquatic life. Runoff from roads and parking lots has a high concentration of toxic
metals, suspended solids and hydrocarbons. Methods for the reduction of the harmful
impact of the vehicles on the water environment are proposed.
Keywords: water pollution, water quality, pollution index, motor transport,
urbanization problems, sustainable development.

INTRODUCTION
Water is an important natural resource with unique properties and is extremely
essential for maintenance of life on our planet. Like all other creatures, humans need
water for their developmental activities. Thus, people use water not only for drinking,
but also for transportation, washing, irrigation, waste disposal, etc. At first glance, there
is a lot of water on the Earth, but nearly 97,4 % is salty and only 2,6 % is fresh. It
Water Security: Monograph 57

should also be noted that 1,98 % of the freshwater is locked up in the polar ice and just
0,6 % of it is available [1].
The problem is also complicated by the fact that global distribution of water
resources is quite uneven and depends on several geographic factors – tropical
rainforest areas receive maximum rainfall while deserts occur in dry zones with
descending air and receive very little rainfall [1]. That is why water is so precious for
us. And today because of anthropogenic pollution and rapid population growth, the
problem of water supply is becoming even greater.
Water is an extremely important resource not only for humans, but also for other
living beings, in particular because of the fact that it is their habitat. The freshwater
environment is more variable than the sea. Its chemical composition is affected by the
rock type on which a lake has formed or over which the river flows.
In places with a rich supply of nutrients there is a large number and variety of
animals. Nutrient-rich water is described as eutrophic and this condition can be caused
by various human activities, including different forms of pollution. Non-productive
waters are called oligotrophic and in most cases they can be found in highland areas
and over hard rocks that do not erode easily. This water is clear and rich in oxygen but
has poor aquatic life [2]. Freshwater ecosystems have low concentrations of salt (less
than 1 %). They support 700 species of fish, 1200 species of amphibians, and a variety
of insects and mollusks [3].
Many years ago in urbanized parts of the world, water-based systems for the sewage
discharge were implemented. Previously, wastewater was disposed of into nearby rivers
and lakes but, because of population growth, it was not a good solution and natural
reservoirs became overloaded with waste. This situation has led to development of
more active treatment systems and in most countries this problem has been solved [4].
But today, when automobiles contaminate air, water and soil, we face another new
serious problem, which may cause even greater harm to the environment.

METHODOLOGY OF RESEARCH
In this research a complex of scientific methods were used. The required theoretical
level was ensured with the help of the methods of synthesis and interpretation of the
obtained results. The analysis method was used for theoretical and practical analysis
of vehicle pollution’s impacts and consequences, as well as for the estimation and
interpretation of the pollution indexes for various countries and cities, including
Ukraine and Kyiv.

RESULTS OF RESEARCH
The research analysed the pollution indexes (PI) of various countries and cities
based on the Numbeo data [5; 6] with the help of bar charts, shown in fig. 1 and fig. 2.
The pollution index is a result of the estimation of the overall pollution in a country or
58 Water Security: Monograph

city. The greatest significance is given to air pollution, over water accessibility and
pollution, and smaller significance is given to other types of pollution. High values of
the PI correspond to the most polluted places, while low values correspond to the most
unpolluted places.
In fig. 1 (a), ten countries of the European region with the highest pollution indexes
are shown. In contrast, in fig. 1 (b), ten countries of the European region with the lowest
pollution indexes are shown. As we can see on the bar chart in fig. 1 (a), the most
polluted country in Europe is Monaco with a pollution index of 85,60, while Ukraine
is in fifth place with a pollution index of 68,58.
According to fig. 1 (b), the least polluted country in Europe is Iceland with a
pollution index of 10,44. Thus, the difference between Ukraine’s pollution index and
the index of the most polluted country is 17,02. The difference between the Ukrainian
index and the index of the least polluted country is 58,14. This means that Ukraine has
serious environmental problems not only in terms of air quality but also in terms of
water quality because these two indicators have the greatest significance in pollution
index estimation.
The detailed analysis of cities in the European region based on the Numbeo data
[5; 6] has also been conducted. In fig. 2 (a), we can see the ten cities with the highest
pollution indexes while in fig. 2 (b) we can see the ten cities with the lowest pollution
indexes. The bar chart in fig. 2 (a) shows that the most polluted city in Europe is Bitola
in Macedonia with a pollution index of 85,02, while the least polluted city in Europe
is Trondheim in Norway with a pollution index of 9,24 (fig. 2 (b).
The capital of Ukraine, Kyiv, is the fourth most polluted city with a quite high
pollution index of 75,54 (fig. 2 (a)). This means that air and water quality in Kyiv, as
well as some other environmental indicators, are dangerous. According to [7], the water
pollution index in Kyiv is 63,68. In the most eco-friendly city, Trondheim, this index
is very low – 15,91. The drinking water pollution and inaccessibility index in Kyiv is
74,06, while in Trondheim it is 0,00. Thus, if we compare indexes in Kyiv and
Trondheim, we can see that their value in Kyiv is extremely high – and it is really
dangerous. The only low environmental index in Kyiv is “dissatisfaction with green
space and parks in the city” [7] with the value 33,96. In Trondheim this index is 8,33.
This means that it is still necessary to increase the amount of green space in Kyiv − it
is essential to create more parks and gardens.
It should be noted that water contamination rates vary by country. For example,
most people in the United States and European countries don’t even think whether the
drinking water is safe or not. However, in developing countries people have to take
this environmental aspect into account.
It is estimated that 80 % of sickness in the world is due to the improper quality and
quantity of drinking water. So, it is important to provide drinking water which is free
from various toxic substances. Thus, such water must be free from pathogens and toxic
chemicals, have all required salts but at the same time should not contain high
concentrations of organic matter and minerals [1].
Water Security: Monograph 59

Water has the property to dissolve many substances which means that it can easily
become polluted. Pollution of water can be caused by point sources (industries,
underground coal mines, power plants, etc.) or non-point sources (overflowing small
drains, atmospheric deposition, etc.). Previously, scientists thought that groundwater
is quite pure compared to surface water. However, contemporary research shows that
even groundwater is contaminated by various harmful substances [1].

Figure 1. Pollution index for countries of the European region (2016, mid year) [5; 6]

We can distinguish several potential sources of groundwater pollution. Industry,


transport and mining are responsible for irreversible groundwater contamination. It
should be noted that groundwater pollution with heavy metals, arsenic compounds,
fluorides and nitrates pose very serious health hazards. The major sources of surface
water pollution are sewage, industrial effluents, synthetic detergents, agrochemicals,
oil and even waste heat. Various pathogens, as well as nitrogen, phosphorus and other
toxic compounds, are among the most dangerous water pollutants [1].
60 Water Security: Monograph

Figure 2. Pollution index for cities of the European region (2016, mid year) [5; 6]

Today many scientists agree that roads, vehicles and parking facilities are a source
of water pollution and hydrologic disruptions. Sources of water pollution include road
deicer, crankcase oil drips and disposal, leaking underground storage tanks, etc.
Hydrologic impacts include loss of wetlands, increased flooding and concentrated
runoff, harmful shoreline modifications, various construction activities along
shorelines, etc. Water quality impacts are highly related to vehicle maintenance and
use. Hydrologic impacts are proportional to lane miles and parking supply. Roads and
parking facilities have serious hydrologic impacts, because they concentrate storm
water and then cause increased flooding and siltation, reduce surface and groundwater
recharge, which lowers dry season flows, and also create physical barriers for fish.
Water temperatures can also be increased. All these impacts degrade surface water
quality, reduce wildlife habitat and contaminate drinking water. Hydrologic impacts
can be extremely harmful to the natural environment [8].
Water Security: Monograph 61

Vehicles are among the main contributors to non-point pollution sources, because
small quantities of various pollutants are emitted during their usage [9]. Vehicles are
also among the most dangerous sources of water contamination, in particular, because
they contain various fluids, including antifreeze, gasoline, motor oil, air-conditioning
refrigerants, as well as brake, hydraulic, transmission and windshield wiper fluids. All
of these fluids are very toxic to humans, plants and animals; if they leak from a car or
are recycled incorrectly, they can seriously pollute waterways. A lot of vehicle fluids
are exposed to oxygen and heat, while an engine is running, and can therefore undergo
chemical changes [10]. These fluids also pick up various heavy metals from the
engine’s wear and tear and become even more toxic to the natural environment.
Some scientists think that waste from the operation of motor vehicles contribute
heavily to non-point sources and groundwater contamination. According to them,
pollutants from motor vehicles, as well as from the transport infrastructure, include
various sediments (for example, from erosion or construction), grease and oils (from
leaks or improperly recycled used oil), heavy metals (from worn tires, car exhausts,
engine parts, brakes, and also from used antifreeze), road salts, herbicides, pesticides,
fertilizers (for example, used alongside roads). According to the US Environmental
Protection Agency, up to half of the suspended solids and a sixth of the hydrocarbons
reaching streams originate from motorways. In some cases heavy metals can make
roadway runoff chronically toxic to the receiving waters but they are not necessarily
toxic because toxicity depends on the chemical form and availability to the various
aquatic organisms. Brake wear is the largest contributor to copper loading (47 %) in
urban runoff while tire wear contributes 25 % of zinc loading, the second greatest
contributor after buildings [9].
Various investigations show that oil products and other vehicle toxins kill plants,
animals, fish and other aquatic life and, in some cases, even people. According to
scientists, one quart of oil pollutes thousands of gallons of water because it does not
dissolve. Harmful substances, heavy metals and toxins pollute water and can cause
serious illnesses, because they are absorbed by aquatic creatures and, thereby, can
poison people who eat them or just drink poisonous water [11]. Furthermore, nitrogen
and phosphorus cause explosive growth of algae that leads to the depletion of oxygen
in water and to the death of fish and other aquatic creatures. It has been estimated by
experts that, each year, millions of gallons of improperly recycled used motor oil
contaminate coastal areas, rivers and lakes. But not all pollutants that can be found in
roadway runoff originate from transport activities, because roads collect pollutants
from other sources, such as wind-blown contaminants from energy production and
manufacturing facilities, agricultural runoff, etc. [9].
Runoff from roads and parking lots also has a high concentration of toxic metals,
suspended solids and hydrocarbons, which originate largely from automobiles.
Contamination levels in road runoff waters (μg/dm3) based on the [8] data are shown
in fig. 3. The analysis of the bar charts in fig. 3 shows that pollution levels in the
road runoff waters are the highest in urban areas, while in rural areas they are
relatively low. But according to [9], non-urban roadway runoff shows greater
62 Water Security: Monograph

concentrations of pesticides, total suspended solids and ammonia, which points to


various agricultural sources.
Many pollutant loadings have seasonal variations. For example, winter brings high
concentrations of sulfates and chlorides. During the long dry season pollutants
accumulate on road surfaces and reach receiving waters during the first storm. Some
scientists think that regular street sweeping can help to solve this problem. Storm-water
runoff also generates a serious public health concerns. Wetlands, vegetative controls,
infiltration systems and wet detention basins are measures for controlling runoff .
Additionally, vehicles are a significant source of carcinogens in water bodies, for
example, of polycyclic aromatic hydrocarbons [9]. Therefore, used oil is the main
source of hydrocarbons to runoff.
Road runoff carries thousands of tons of oil. Additionally, improperly recycled
used oil filters may account for 5 % of used oil in the natural environment and thus,
used oil is the largest environmentally unsafe recyclable material. Refined products,
such as gasoline and motor oils, are more toxic than crude oils and can have even
more serious impacts on aquatic life. They disperse more readily in water and in
some cases they are absorbed more easily. Used motor oil often contains added
chemicals to boost engine performance, as well as compounds produced during
engine operation and mixed wastes. It should be also noted that large quantities of
petroleum are released during extraction, processing, and distribution from leaks
and spills [8].The environmental impacts of used oil depend on its characteristics,
temperature, weather and geographic features. Whilst wave action can disperse an
oil spill relatively quickly in open waters, oil pollution in calm waters can persist
for years, so natural recovery times can vary considerably [9]. Another source of
pollution, antifreeze, typically consists of 95 % ethylene glycol, a highly toxic
liquid. In the USA, for example, millions of gallons of antifreeze are sold each year
but only 12 % are recycled. Engine antifreeze can also contribute high biochemical
oxygen demand levels to storm-water.
Operating motor vehicle disc brakes emits heavy metals. Disc brakes are exposed
to the environment, so each time semi-metallic brake pads squeeze against the rotors
of the wheels, small amounts of metal dust (copper and sometimes zinc and lead) are
deposited along the roadway and washed into water bodies with the help of
precipitation. While used oil and antifreeze pollution mostly affects surface waters,
gasoline spills from leaking underground storage tanks are a major source of
groundwater pollution. Although severe leaks can create fire hazards, primary
environmental concerns include volatile organic compounds, such as dissolved-phase
benzene, toluene, ethylbenzene and xylene. Previously, in many countries most gasoline
underground storage tanks were made of bare steel, which corroded over time. With
increasing awareness of the environmental and economic costs of gasoline leaks, the
installation of unprotected steel tanks was banned. However, many leaks remain
undetected because monitoring is inadequate and many tanks are abandoned and
inactive. It should be noted that leaking underground storage tanks are a significant
environmental problem, because many countries rely on groundwater sources [9].
Water Security: Monograph 63

Figure 3. Levels of the contamination in the road runoff waters (μg/dm3) [8]

Some ways to reduce the impacts of the water pollution caused by vehicles are
known. Most of them are [12]: recycle oil; recycle antifreeze; return used batteries;
keep the car tuned up; use commercial car washes; substitute shoveling for salt; repair
leaks; drive less; check tire pressure; use up paints, polishes and cleaners, etc.
64 Water Security: Monograph

DISCUSSION
The research shows that there are serious environmental problems with water
quality in Kyiv and in Ukraine. Water quality is extremely important for the sustainable
development of our nation, so it is necessary to pay serious attention to such issues as
vehicle pollution of surface water and groundwater.
Vehicles contaminate water with large amounts of toxic substances that can harm
people or other living beings. The conducted analysis shows that Iceland, Norway,
Sweden, Switzerland, Finland and other eco-friendly countries have very low pollution
indexes. Ukraine has to use their experience to implement the tools of the green
economy and sustainable development to improve not only the ecology of the country,
but also its socioeconomic conditions. In the future, it can be useful to conduct
additional investigations aimed at creating an algorithm for the improvement of the
water environment in Ukraine and, in particular, in Kyiv and other megalopolises. This
is extremely serious issue must be solved in the nearest future to prevent the
consequences of ecological crises.

CONCLUSIONS
The comparison of the pollution indexes of the countries shows that the most
polluted country in Europe is Monaco with the PI = 85,60. The least polluted country
in Europe is Iceland with the PI = 10,44. The analysis shows that Ukraine is in fifth
place with the pollution index of 68,58, thus it has serious environmental problems not
only in terms of air quality but also in terms of water quality because these two
indicators have the greatest significance in pollution index estimation. The analysis
also shows that the most polluted city in Europe is Bitola in Macedonia with the
pollution index 85,02, while the least polluted city in Europe is Trondheim in Norway
with the PI = 9,24. Our capital − Kyiv −is on the fourth place with quite a high pollution
index of 75,54. The comparison of the water pollution index, as well as drinking water
pollution and inaccessibility index, in Kyiv and Trondheim has confirmed that water
quality in Kyiv is dangerous. The only low environmental index in Kyiv is
dissatisfaction with green space and parks in the city with a value of 33,96.
It was also found that roads, vehicles and parking facilities are a source of water
pollution and hydrologic disruptions. Vehicles contain fluids that are very toxic to
humans, plants and animals. These fluids also pick up various heavy metals and become
even more toxic for the natural environment. In some cases heavy metals can make
roadway runoff chronically toxic to receiving waters but they are not necessarily toxic
because toxicity depends on the chemical form and availability to the various aquatic
organisms. The investigation also shows that used oil and antifreeze pollution mostly
affects surface waters. Gasoline spills from leaking underground storage tanks are a
major source of groundwater pollution.
Runoff from roads and parking lots contains a high concentration of toxic metals,
suspended solids and hydrocarbons. The analysis of contamination levels in the road
Water Security: Monograph 65

runoff waters has shown that they are highest in urban areas, while in rural areas they
are relatively low.

REFERENCES
1. Kaushik, A., & Kaushik C. P. (2010). Basics of Environment and Ecology. − New Delhi:
New Age International (P) Limited, Publishers.
2. Ecology (2005). London, New York, Munich, Melbourne, and Dilhi: Eyewitness.
3. Ecology (2010). Chicago, London, New Dilhi, Paris, Seoul, Sydney, Taipey, Tokio:
Britannica Illustrated Science Library.
4. Ecosystem Ecology (2009). Ed.-in-Chief Sven Erik Jørgensen. − Amsterdam: Elsevier.
5. NUMBEO (2016). Europe: Pollution Index 2016 Mid Year. Retrieved 4/11/2016, from
https://www.numbeo.com/pollution/region_rankings.jsp?title=2016-mid&region=150
6. NUMBEO (2016). Europe: Pollution Index by Country 2016 Mid Year. Retrieved
4/11/2016, from https://www.numbeo.com/pollution/rankings_by_country.jsp?title=2016-
mid&region=150
7. NUMBEO (2016). Pollution Comparison Between Trjndheim and Kiev. Retrieved
4/11/2016, from https://www.numbeo.com/pollution/compare_cities.jsp?country1=Norway&
country2=Ukraine&city1=Trondheim&city2=Kiev&tracking=getDispatchComparison
8. Transportation Cost and Benefit Analysis II – Water Pollution (2015) Victoria Transport
Policy Institute. Retrieved 4/11/2016, from http://www.vtpi.org/tca/tca0515.pdf
9. Nixon, H., Saphores, J.-D. (2016) Impacts of Motor Vehicle Operation on Water Quality
in the United States - Clean-up Costs and Policies. India Waterportal. Retrieved 4/11/2016, from
http://hindi.indiawaterportal.org/%20Impacts-of-Motor-Vehicle-Operation-on-Water-Quality-
in-the-United-States-Clean-up-Costs-and-Policies
10. How Does Car Pollution Affect the Environmental & Ozone Layer? SFGATE. Retrieved
4/11/2016, from http://homeguides.sfgate.com/car-pollution-affect-environment-ozone-layer-
79358.html
11. Non-Point Sourse Pollution. Automobile Pollution. Retrieved 4/11/2016, from
http://protectingwater.com/automobile.html
12. Johnson,C., UW-Extension (1999). Car Care for Cleaner Water. A Series of Water Quality
Fact Sheets about Stormwater Runoff. CWQ019. The University of Wisconsin–Extension in
cooperation with the Wisconsin Department of Natural Resources. Retrieved 4/11/2016, from
http://www.uwgb.edu/Facilities/documents/GWQ019.pdf
66 Water Security: Monograph

INVESTIGATION OF CO-UTILIZATION OF MEAT PROCESSING


WASTEWATER SEWAGE AND RICE HUSKS BY ANAEROBIC
DIGESTION

Prof., Dr.Sc., Galyna Krusir1


Prof., Dr. Heinz Leuenberger2
Postgraduate Olesia Chernyshova1
1
Odessa National Academy of Food Technologies, krusir.onaft@gmail.com,
Ukraine
2
University of Applied Sciences and Arts Northwestern Switzerland FHNW,
Switzerland

ABSTRACT
The main position of Environmental Protection Policy strategy provides a
comprehensive solution to the problems of sustainable development of the economy
and improvement of the environment. The current rate of development of grain-
processing and meat-processing industries makes effective and cost-effective waste
disposal more actionable. The re-processing of waste from the meat processing
industry, which includes waste water, formed directly in the production of meat and
from cattle manure, requires special attention. Biotechnological methods of
processing are considered a promising form of recycling food production wastes.
One such method is anaerobic digestion, which is a continuous multi-component
process that transforms organic material into finished products, such as biogas
containing methane, water vapor and carbon dioxide, through microbial activity.
The aim of this study was to investigate the joint utilization of rice husks, manure
and sewage from a meat processing plant by anaerobic digestion in a laboratory
anaerobic batch bioreactor (Upflow Anaerobic Sludge Blanket reactor - UASB) for
10 days. During the study, parameters of influence of the substrate composition on
the efficiency of decomposition of organic matter, biogas and methane yield were
identified. A series of experiments investigating anaerobic fermentation of substrates
was carried out with different weight ratios of manure, waste water and rice husks
at mesophilic temperature conditions (36 ± 1°C). To determine the optimal weight
proportions of components in mixed waste as a substrate for fermentation in an
anaerobic bioreactor, we assessed the degree of organic matter degradation in
manure, rice husks and waste waters and estimated the negative impact of volatile
fatty acids on anaerobic reactions. After benchmarking fermentation mono-
Water Security: Monograph 67

substrates and mixtures, the use of mixed substrates for methane was proved to
increase the degree of biodegradability of organic substance waste.
Keywords: wastewater, anaerobic sludge, rise husk, cattle manure, biogas.

INTRODUCTION
Requirements of the modern market dictate the implementation in production
processes of technologies with low power, resource-and capital intensity. Such
technologies enable high-quality and competitive products. One of the strategic
directions of development in the food and processing industry is providing the
population with food products in a necessary quantity, while also actively
greening the industry. Today, upgrades of production capacities in the move
towards closed cycle production is considered as one of the fundamental
directions to take in solving the problems of rational use of natural raw material
resources and environmental protection. Gradually, producers are considering
their accumulated world experience of waste recycling, understanding that it
creates by-products, and thereby provides an additional source of financial
income and also improves their ecological image. Given world growth rates in
the prices of raw materials for food, questions of further reduction and effective
utilization of food waste and the emergence of processing industries acquire
increasing relevance in ecological and economic plans. Manufacturers pay
considerable attention to these aspects as their products are oriented to the
European consumer market with strict requirements for environmental
protection. The choice of methods for waste recycling considers the physical and
chemical parameters of waste, the features of the manufacturer, and indicators
of water and energy efficiency.
In this work, the joint recycling of meat-processing waste and waste from rice
cleaning is considered. For the period 2014-2016, 3884 thousand cattle a year were
produced in Ukraine’s livestock industry. Around 192 thousand were reared in the
Odessa region [1]. Manure waste from cattle production for nongrazing time (220-
240 days) in Ukraine and the Odessa Region amounts to 34,9 million tons and 1,7
millin tons respectively. Wastewater from the meat-processing entities amounts to
188 800 000 m3 and 3 760 000 m3 a year for Ukraine and Odessa, respectively.
Manure is the mix of excrement and urine from animals mixed with a straw or
peat layer. Manure can be categorised as either covering (solid) or bespodstilochny
(liquid) manure. The composition of manure depends on parameters such as the
breed and age of animals, the type of feed and type of a layer. The second object of
the research is wastewater from the meat-processing industry. This wastewater has
many components and high level of COD (chemical oxygen demand), content of
the weighed substances and fats, increased content of biogenous elements, neutral
рН values, temperature within 20-30 ºC, and organic substances are in both colloidal
and soluble forms.
68 Water Security: Monograph

According to a statistical year-book of public service of statistics of Ukraine in


recent years [1] the productivity of rice in Ukraine was 50 centners per 1 hectare.
For Odessa region for the period of 2014-2016, on average 4,5 thousand tons of
rice a year were imported by processing plants. This leads to theformation of rice
husk waste amounting to 828 tons annually, on average. The rice husk is a by-
product of grain cleaning. The husk is characterized by a considerable content of
cellulose and mineral substances. There are three main methods of treating rice
husks: burning, creating special dumps and conversion to produce silicon. As rather
small amounts of rice are cultivated and converted in Ukraine, burning remains by
the dominant method of waste treatment of rice and does not conform to modern
requirements for low-waste and wasteless technologies. Therefore, to improve the
profitability of the grain processing and meat-processing industries, effective waste
recycling with the subsequent generation of by-products is the priority direction of
development of policy for these industries.
Anaerobic fermentation is considered one of the most efficient paths of utilization
of multicomponent effluent. Biochemical and microbiological aspects of the process
of anaerobic fermentation depend on the composite conditions. According to the
commonly used scheme, anaerobic fermentation consists of four phases: hydrolysis,
acidogenesis, acetogenesis and methanogenesis. Courses of each of these phases
provide corresponding development of a microbiological community. Bacterial
activity results in various products of disintegration of the complicated molecules
which are a substrate for microorganisms for the following phase. The bacteria for
the reactor are divided into three common groups [2]. The first group includes
hydrolytic bacteria, referred to as acidogenic, and which provide initial hydrolysis
of a substrate to low-molecular organic acids and other small molecules. The second
group is represented by heteroacetogenic bacteria which produce ethanoic acid and
Hydrogenium. The third group includes metanogenic bacteria which form a methane.
The last group can be divided into subgroups: consumers of Hydrogenium –
lithotrophs, and consumers of ethanoic acid – acidtrophs. Synergism of these groups
occurs, for example, various growth rates can be explained by common cultivation
and appear as a result of interaction between trans-species type of hydrogen transfer.
Substrates, which are partly Sulfur and Nitrogen, can cause increases in two
additional groups of microorganisms: sulfate-reducing bacteria and denitrifying
bacteria [2]. These symbiotic microbial communities can change the characteristics
of fermentation, and function as self-regulating systems which maintain рН value,
redox potential and thermodynamic equilibrium at optimum levels for growth,
thereby providing stability of fermentation.
Courses of anaerobic reactions substantially depend on environmental
temperature because of the sensitivity of bacteria to temperature jumps of an
anaerobic system. There are three various temperature ranges which affect
functioning (activity) of anaerobic bacteria: psychrophilic (18−20 °C), mesophilic
(25−40 °C), and thermophilic (50−70 °C). It is known that when keeping a
psychrophilic temperature regime, the process of a substrate’s fermentation takes
place very sluggishly and does not provide a sufficient degree of destruction of
Water Security: Monograph 69

organic matter. During the mesophilic mode, stable growth of the metanogenic
bacteria occurs, and the biomass increases. This mode positively influences
biodegradation of substrate components. Keeping a thermophilic temperature
regime stimulates a more intensive course of processes of anaerobic fermentation
in the reactor. However, expenses on energy for heating and maintaining a
thermophilic temperature regime are not compensated in full.
Activity of bacteria depends on рН level as each group of microorganisms has
specific levels of рН for optimum growth. Monitoring of the рН parameter is
fundamental to maintaining optimum bacterial growth. It is known that
accumulation of volatile fatty acids in the bioreactor causes sharp jumps in рН level,
which causes serial atrophy in methanogenic bacteria [3]. It, in turn, leads to a
decrease in the effectiveness of removal of pollutants and formation of biogas. For
acidogenic bacteria the optimum рН level is from 5,2 to 6,5 рН units, while the
optimum рН level for metanogen is in the range of 7,5 to 8,5 рН units. Low рН
values promote restitution of a proton to Hydrogenium, then its restitution into
methane. A wide range of types of acidogenic bacteria entering the hydrolytic group
provide their resistance to changes of conditions of cultivation, partly becoming
acidophilic. It is known that the mean time of regeneration for such bacteria is 2-3
hours, which is a rather short time term for anaerobic processes [4]. However, this
group of bacteria is negatively influenced by low рН values and a redox potential.
In the conditions of a sharp increase of Hydrogenium concentration, microorganisms
choose the alternate metabolic path for Hydrogenium removal, thereby regulating
its concentration [2]. In cases of increased substrate concentrations in the reactor, a
bacterium immediately reacts by formation of an excess amount of Hydrogenium
and ethanoic acid, thereby reducing the oxidizing potential and рН. If this process
continues further, then the substrate in the reactor "turns sour" and finishes the work.
However, acidogenic bacteria use feed-back and choose alternate metabolic paths,
such as formation of propionic and butane acids that helps to restore the stability of
operation of the reactor. The role of Hydrogenium in management of emergence
and consumption of the intermediate products explains the formation of some long-
chain fatty acids which leading to accumulation or an expenditure of Hydrogenium.
An important aspect in regulating the operation of the bioreactor is availability
of nutrients which are important for efficient anaerobic microorganisms’ growth
[5]. In addition to the main content of macronutrients, organization of a
microbiological community demands availability of micronutrients and minerals,
such as Nitrogen, Phosphorus, Sulfur, Potassium, Calcium, Magnesium, Iron,
Nickel, Cobalt, Zincum and Copper for ensuring optimum microbial growth. These
nutrients have to be present at very low concentrations, however, their absence
general negatively influences microbial growth and activity of microorganisms.
Existence of ions of ammonium plays an important role in anaerobic fermentation.
For an optimum process of anaerobic fermentation the level of ions of ammonium
have to be supported at the level of 80 mg/l. It is known from research that a stable
course of anaerobic fermentation processes needs the maintenance of ammonium
ions at the level of 50-150 mg/l under mesophilic conditions. Higher concentrations
70 Water Security: Monograph

of ammonium lead to serious violations of reactor operation because of the resulting


decrease in growth rates and specific activity of methanogenic bacteria [6]. In
addition, a sulfide concentration is necessary for stable methanogenic organisms’
growth, but it should be noted that depending on the рН level of the reactionary
environment, sulfides can show toxic properties. Numerous research has shown that
sulfide toxicity in relation to methanogenic bacteria, namely acetate consumers and
H2 consumers, inactivates and suppresses transformations of the intermediate
products. This process depends on accumulation of volatile fatty acids that cause a
decrease in the exit of methane.
From literary data it is known that the presence of heavy metals on a substrate
in many cases causes toxic or inhibiting effects on the process of anaerobic
fermentation. However, despite this, their presence at a very low («trace»)
concentration is necessary for microorganisms’ growth. The toxicity of heavy metals
(Cadmium, Chlorine, Copper, Nickel and Zincum), have been estimated through
results of research. It has been revealed that acidogenic, acetogenic and metanogenic
microorganisms are characterized by different resistances to the toxic influence of
heavy metals [7].

METHODOLOGY OF RESEARCH
The laboratory tests are executed by fermentation of a substrate in a UASB
bioreactor (Upflow Anaerobic Sludge Blanket reactor) of periodic action with a volume
of 50 dm3 (figure 1, image 1). We investigated anaerobic substrate fermentation with
different weight ratios of components in mesophilic conditions with a temperature
regime of 36±1°C and рН units of 6-7±5. During the laboratory tests we controlled the
amount of the emitted biogas, methane and degree of biodegradation of organic matters
on an index of the chemical oxygen demand (COD) and рН. Considering design
features of the anaerobic reactor, it should be noted that the effectiveness of the process
will be affected by the generation rate of easily settling bacterial floccules. Thus, the
waste of rice purification is used as a biological additive in anerobic process of sewage
fermentation [8]. At the beginning of each cycle a component of a substrate was moved
into the reactor, then the crane was hermetically closed. Working mix substrates were
heated to 35-37 °C automatically. A stable temperature of working mix substrates was
provided by a water-jacket with a temperature sensor. Hashing of a substrate was carried
out by an automatic mixer. Biogas was gathered and measured in a water gasholder
with a total amount of 13 dm3.
The pH meter Hanna HI2210 was used to determine pH units. The pH range was
from -2 to 16±0,01 units pH, and the temperature range was -0,9 to 120±0,5 °C. The
amount of methane in biogas was determined using the Signalling-explosimeter
thermochemical device CTX-17-90, and measurements range from 00,0 to 99,9%.
The COD indicator was determined according to standard gain 211.1.4.021-95.
"Methods of determining the chemical oxygen demand (COD) in surface water and
wastewater". The amount of total nitrogen was determined according to the standard
Water Security: Monograph 71

gain 211.1.4.031-95 "Methods titration determination of total nitrogen in


wastewater". The quantity of VFA (volatile fatty acids) was determined in
accordance with "Methods of measuring fat mass concentrations by thin layer
chromatography (TLC) ".
The aim of this work was anaerobic digestion of wastewater from meat
processing enterprises with different substrate weight ratios of components
(table 1). The first three samples were monosubstrates (S1, S2, S3).The first sample
consisted of meat processing wastewater after the mechanical treatment stage, the
second consisted of cattle manure and the third was rice husks produced as a

Figure 1. Equipment-technological scheme of


anaerobic digestion of sewage, where
1 – supply of waste water; 2 – flow of
sewage; 3 – bioreactor; 4 – electric mixer;
5 – heating element; 6 – water-jacket; 7 –
sludge effluent; 8 – capacity to collect the
sludge; 9 – temperature sensor; 10 – biogas
stream; 11 – water gasholder.

Image 1. Photo of laboratory scale anaerobic bioreactor


72 Water Security: Monograph

by-product of rice cleaning. The other substrates were mixtures and consisted of
various components and weight ratios of manure and rice husks as follows: 3:1 (S4),
1:1 (S5), 1:3 (S6).
Each substrate was added to 0,5 l of excess sludge from the previous anaerobic
digestion of cattle manure with the addition of ordinary water, which contains the
necessary microbial community to start fermentation and decomposition of organic
matter. The temperature of the mixture was maintained at 35-36 °C in the tests. The
value of the redox potential fluctuated in the range of -260-140 mV; conditions for
anaerobic transformation of organic matter below this range are not optimal [9].
Fermentation of each of the substrates was carried out for 10 days.
Table 1
Characteristics of substrates

RESULTS OF RESEARCH
According to the research, fluctuations in pH during anaerobic digestion of
different substrates occurred in the range of 6,2 pH units in the substrate S2 (cattle
manure) to 7,3 pH units in the substrate S1 (waste water). All substrates were
characterized by optimum pH levels for microbial community functioning.
After the 10 day cycle of fermentation, substrates were observed to decrease in
dry matter content by about 2 times the biggest indicator of removal of solids
reported in the substrate S1 (sewage) – 56% and in mixed substrate S6 (1m : 3r.h.)
– 54%. There was also a marked decrease in COD of substrates before and after
fermentation, reflecting the degree of decomposition of organic matter. Figures for
COD decrease were as follows: S1 (sewage) – 42%, S2 (manure) – 58%, S3 (rice
husk) – 37%, S4 (3m : 1r.h.) – 66%, S5 (1m : 1r.h.) – 64% and S6 (1m : 3r.h.) –
65%.
The amount of total nitrogen in the substrates after anaerobic digestion did
decreased slightly, by 5-10% in all substrates. The content of VFA after anaerobic
digestion of substrates for S2 (manure), S4 (3m : 1r.h.), S5 (1m : 1r.h.) аnd S6 (1m
: 3r.h.) decreased by 49%, 55%, 61% and 54%, respectively. In substrates S1
(sewage) and S3 (rice husk) VFA accumulation was observed, ie their number
Water Security: Monograph 73

increased by 5% and 20%, respectively, indicating a slowing of reactions in


anaerobic digestion. Changes in the physical and chemical parameters for the
investigated substrates before and after digestion in an anaerobic reactor are given
in table 2.
DISCUSSION
According to the dynamics of the intensity of production for biogas, the substrate
samples S4 (3m : 1r.h.) аnd S2 (cattle manure) showed the highest level of bacterial
activity on the first day, and the production of biogas was 8,04 dm3 and 6,43 dm3,
respectively.
The low levels of activity of bacteria in fermentation were noted on the first day
for S1 (sewage) – which produced 1,22 dm3 of biogas, and S3 (rice husk), which
produced 0,33 dm3 of biogas.Other substrates with a significant share of cattle
manure contained methanogenic bacteria (Methanococcus, Methanobacteriales,
Methanomicrobiales, Methanosarcina and Methanosaeta) [10].
Table 2
Physical and chemical properties of substrates before and after anaerobic digestion

The best biogas production results I during the 10 day period were S4 (3 m:1r.h.)
– 8,04 dm3 on the first day, S2 (manure) – 8,03 dm3 on the third day, S5 (1m : 1r.h.)
– 6,76 dm3 on the third day, and S6 (1m : 3r.h.) – 6,52 dm3 on the third day of
fermentation. The total amount of biogas produced over the entire period for each
substrate was (in order of size): S2 (manure) – 52,53 dm3, S4 (3m : 1r.h.) –
43,54 dm3, S5 (1 m:1r.h.) – 38,9 dm3, S6 (1 m:3r.h.) – 32,2 dm3, S1 (sewage) –
17,38 dm3, S3 (rice husk) – 16,86 dm3.
The results of the tests of the dynamics of biogas formation from various
substrates are shown in figure 2 a). The volume of methane in biogas for the period
of study was: S2 (manure) – 35,9 dm3, S4 (3 m : 1r.h.) – 35,2 dm3, S5 (1m : 1r.h.)
74 Water Security: Monograph

– 32,1 dm3, S6 (1m : 3r.h.) – 26,7 dm3, S1 (sewage) – 14,8 dm3, S3 (rice husk) –
7 dm3. The dynamics of the intensity of methane as a result of methanogenic bacteria
during anaerobic digestion are shown in fig. 2 b).

2 a) 2 b)
Figure 2. a) dynamics of intensity of the production of biogas,
b) dynamics of intensity of the production of methane in biogas,
formed from substrates S1, S2, S3, S4, S5, S6.

CONCLUSIONS
The aim of the work was to investigate the impact of rice husks on the anaerobic
digestion process of industrial meat processing wastewater and cattle manure for
10 days. Changes in the physical-chemical characteristics of substrates showed that
the pH during substrates fermentation remained within optimal conditions for
methanogenic microorganisms. Dry organic matter content after fermentation in all
samples decreased by 2 times, and the amount of total nitrogen in the substrates
decreased by 5-10%. A slight accumulation of intermediate components of
fermentation wre also noted – volatile fatty acids in the substrates S1 (sewage) –
5% and S3 (rice husk) – 20%, which indicated a failure in the phase change of
anaerobic digestion process.
Substrate fermentation was characterized by varying degrees of organic matter
decomposition, which depended on the components of the substrate. The quantity
of biodegradable organic matter ranged from 37% in the substrate S3 (rice husk) to
66% in substrate S4 (3m : 1r.h.). According to the results of the investigation into
substrates’ gas-forming properties, during the period of fermentation the largest
amount of biogas production was noted for substrates S2 (manure) – 52,53 dm3 and
S4 – 43,54 dm3. Total methane content in biogas samples was S2 – 35,9 dm3 and
S4 – 35,2 dm3.
The results of comparative analysis of indicators before and after the
fermentation of mixed substrates with different weight ratios of cattle manure and
rice husks (S4 – 3:1, S5 – 1:1, S6 – 1:3) show that the effectiveness of organic matter
Water Security: Monograph 75

biodegradation in all three substrates was 65 ± 1%; the amounts of collected biogas
were: S4 (3m : 1r.h.) – 43,54 dm3, S5 (1m : 1r.h.) – 38,9 dm3, S6 (1m : 3r.h.) –
32,2 dm3. The amounts of methane in the collected biogas were: S4 (3m : 1r.h.) –
35,2 dm3, S5 (1m : 1r.h.) – 32,1 dm3, S6 (1m : 3r.h.) – 26,7 dm3. Thus, the joint
fermentation results of rice husk and meat production wastewater in an anaerobic
bioreactor demonstrate the significant efficiency of this recycling method which
provides high rates of organic substance decomposition and biogas formation with
high methane content.

REFERENCES
1. Statistichnij shhorіchnik Ukraїni, 2014 [Tekst] : statistichnij shhorіchnik / Derzhavna
sluzhba statistiki Ukraїni / O. A. Vishnevs'ka. – K.: Derzhanalіtіnform., 2015. – 585 s.
2. Forster, C.F., and D.A.J. Wase, Eds. (1987). Environmental Biotechnology. Ellis
Horwood, Chichester, U.K.
3. Samir S.Sofer, Oskar R.Zaborsky (1981). Biomass Conversion Processes for Energy
and Fuels, Plenum Press, New York.
4. Wang, Q.; Kuninobu, M.; Ogawa, H.; Kato, Y. (1999). Degradation of volatile fatty
acids in highly efficient anaerobic digestion. Biomass Bioenergy, 16, 407–416.
5. Rajeshwari K.V., Balakrishnan M., Kansal A., Kusum Lata and Kishore V.V.N., (2000)
State-of-the-art of Anaerobic Digestion Technology for Industrial Wastewater Treatment,
Renewable and Sustainable Energy Reviews, X,Vol. 4, 135-156.
6. V. ReginattoI, R. M. TeixeiraI; F. PereiraI; W. SchmidellI; A. Furigo JrI; R. MenesII;
C. EtchebehereII; H. M. Soares (2005). Anaerobic ammonium oxidation in a bioreactor
treating slaughterhouse wastewater, Brazilian Journal of Chemical Engineering, vol.22 no.4,
doi: 10.1590/S0104-66322005000400012.
7. Viet, N.T. (1999). Sustainable Treatment of Rubber Latex Processing Wastewater-the
UASB-System Combined with Aerobic Post-Treatment, Thesis, The Wageningen University,
Wageningen, The Netherlands, 1-17.
8. Krussir, G.V., Heinz Leuenberger, Chernyshova O.O. (2016). Investigation of joint
utilization of meat processing waste and rice husk by anaerobic digestion, Grain Products
and Mixed Fodder’s, 62(2) DOI: http://dx.doi.org/10.15673/gpmf.v62i2.140.
9. Malashenko, Y.R. (1989). Medium redox-potential during cultivation of mehtanogenic
community. In: Symposium on biotechnology for fuel and chemicals. Colorado-Sprinm,
USA, 1989.
10. Sharon McHugh, Micheal Carton, There'se Mahony, Vincent O’Flaherty (2003).
Methanogenic population structure in a variety of anaerobic bioreactors; FEMS Microbiology
Letters 219. doi:10.1016/S0378-1097(03)00055-7.
76 Water Security: Monograph

ANAEROBIC TREATMENT OF WASTEWATER FROM WINERIES

Prof., Dr. Sc. Galyna Krusir1


Prof., Dr. Sc. Alfred Zikalo1
Ass. Prof., PhD. Oleksiy Harkovych1
Ass. Prof., PhD. Maria Madani1
Ass. Prof., PhD. Valentina Zakharchuk2
1
Odessa National Academy of Food Technologies, e-mail: krussir_65@mail.ru,
Ukraine,
2
Odessa National Economic University, e-mail: zakharchukv@yahoo.com,
Ukraine

ABSTRACT
This study analysed wastewater from primary wine production and determined
its chemical composition. There are two types of biological processes used for
purifying water: аerobic processes, in which microorganisms use oxygen dissolved
in wastewater by aeration for oxidation of organic matter (OM); anaerobic
processes, in which microorganisms mineralize carbon to form biogas which
contains 50-80% methane and 20-50% carbon dioxide, without oxygen.
Based on the analysis of its chemical composition, methanogenesis was
proposed as the most efficient method of wastewater treatment which also provides
the possibility of biogas production.
Laboratory studies of the process of anaerobic fermentation of waste water were
conducted using the laboratory biogas installation BU-1. BU-1 consists of a methane
tank, where methane fermentation takes place, and a gas-holder intended for biogas
collection. The optimal parameters for anaerobic fermentation of wastewater for
maximum cleaning efficiency and biogas production intensity were defined.
Keywords: biological waste water treatment, anaerobic methane fermentation.

INTRODUCTION
The food industry, including wine producers, is one of the most intensive water
consumers among industries in terms of water consumed per unit of produce. On
average, producers of primary wine discharge up to 20,000 m3 of wastewater per
Water Security: Monograph 77

year which poses a serious threat to the environment. The problem of cleaning,
disinfection and disposal of wastewater is therefore particularly relevant.
When processing 1 ton of grapes, 1,08 m3 of wastewater (including recycle water
system) is produced. Of this, the share of manufacturing water is 0,28 m3, municipal
water — 0,02 m3 and 0,78 m3 is relatively clean. For every 1 decalitre of grape must
produced, 0,19 m3 of wastewater is discharged [1]. Due to the absence of a
comprehensive waste-free technology for waste water treatment at industrial
winemaking enterprises, there is a violation of ecological balance, because the low
technical level of waste recycling is accompanied by waste discharged into the
water, which leads to a degree of contamination that exceeds the established norms.
The concentration of contaminants in waste water from primary production
enterprises changes throughout the year due to the seasonality of grapes processing.
For example, in winter the amount of waste water produced is over 31 m3/day, but
in the off-season period not more than 21 m3/day is produced.
The predominant trend in modern water management in the food industry is to
reduce water consumption as an effective preventative measure to reduce the associated
burden on the environment. In concept "Cleaner Production" concept, [2] the solution
to the water consumption problem is to create conditions that reduce the formation of
waste water through the development of an efficient water recycling system (figure 1).
This provides for the separation of waste water flows and local cleaning together with
traditional measures that help reduce the formation of waste water.

Figure 1. The balance of water in the water recycling system

As water is not a component of wine, circulated (technical) water can be used


for technological needs. Thus, a system of water recycling at primary winemaking
enterprises will reduce the amount of wastewater generated, and as a result, the load
on the environment.
78 Water Security: Monograph

METHODOLOGY OF RESEARCH
Biological treatment methods are currently the most widespread forms of
treatment in the processing of industrial waste. They are based on the ability of
different types of microorganisms to mineralize organic pollution [3].
There are two types of biological processes used for water purification:
1. Aerobic processes, in which microorganisms use oxygen dissolved in
wastewater by aeration for oxidation of the organic matter (OM).
2. Anaerobic processes, in which microorganisms mineralize carbon and form
biogas which contains 50-80% methane and 20-50% carbon dioxide, without
oxygen [4].
Degradation of OM during methanogenesis is a multistep process in which
carbon bonds are gradually destroyed by different groups of microorganisms.
Anaerobic transformation of any complex OM into biogas goes through four
successive stages [5].
Waste water from primary winemaking enterprises consists of wash and flush
water, which contain pollutants, such as stems, leaf residue, particles of grapes, etc.
In addition, the wash water contains marc and grape must, which enters the water
when presses are washed. When processing wine materials with gelatin and yellow
prussiate of potash, colloids form, which contain proteins in the form of sludge. To
remove metal compounds, such as lead, from grape must and for clarification, red
prussiate of potash is used. Waste water is produced in primary winemaking
enterprises mainly as a result of washing equipment, such as pipelines and
production facilities. Due to the fact that most wineries practice joint runoff, the
total amount of waste water also contains municipal waste water (fig. 2) [6].

Figure 2. The balance of water in the water recycling system


Water Security: Monograph 79

The concentration of contaminants in waste water varies throughout the year


due to the seasonality of grape processing. For example, in the autumn-winter period
the amount over 31 m3 day of wastewater is produced per day, while in the off-
season period not more than 21 m3/day is produced. Characteristics of winery waste
water are presented in table 1.
Table 1
Characteristics of wineries waste water.
(n = 3, P≥0,95)
№ Indicator Values
1 рН 6,5
2 Chemical oxygen demand, gO2/l 9,1
3 Biochemical oxygen demand(BOD5), gO2/l 5,6
4 Suspended solids, g/l 1,0
5 Nitrogenous substances, mg/l 26,0
6 Sulfates 250,0
7 Chlorides 250,0

RESULTS OF RESEARCH
Based on the characteristics of the waste water’s chemical composition, it may
be concluded that waste water has significant indicators of BOD5 and COD, which,
in turn, are grounds for using methanogenesis as the most effective method of
treating highly-concentrated waste water [7].
It is known that the intensity of the process of methane fermentation, as well as
purification efficiency and the formation of biogas, depend on several factors,
namely, the humidity of the substrate, the ratio of C/N, pH, temperature, exposure
of fermentation and the type of microbial communities that are used in the methane
tank[8].
The humidity of sewage sludge is 92%, which is the best value for effective
methane fermentation.
The optimum C: N ratio is between 20:1 and 100:1. These values were
maintained by introducing crushed grape stems in to the waste water (hydromodule
10).
The optimum pH medium level for steady methane formation is 6,5-7,5. Primary
winemaking enterprise waste water is characterized by weak alkalinity of pH 7,4.
Methane formation processes can proceed within the following temperature
ranges: psychrophilic – 10-15 °C, mesophilic – 33-37 °C and thermophilic –
53-55 °C. It is known that the higher the temperature, the faster the biochemical
processes, which is why thermophilic processes are typically 2-3 times more
intensive than mesophilic ones. However, thermophilic processes have a significant
80 Water Security: Monograph

drawback: a significant power intensity of the process. So, the next stage of research
was to determine the optimum temperature for anaerobic fermentation of
wastewater, the results of which are shown in fig. 3.

Figure 3. The dependence of biogas output at the temperature conditions


1–55 °C, 2–40 °C, 3–15 °C

The research results, presented in the graph, show that an increase in


fermentation temperature leads to an increase in biogas output. The maximum
biogas output at 55 °C is 9,32 dm3/day. At 40 °C 5,65 dm3/day is produced and at
15 °C 2,6 dm3/day is produced.
The dependence of efficiency of reduction in chemical oxygen demand (COD)
values on different temperature conditions is presented in figure 4.

Figure 4. Dependence of efficiency of decrease of COD value in% on the fermentation


temperature, where 1–55 °C, 2–40 ° C, 3–15 °C.
According to the present graph, the efficiencies of the COD decrease at
thermophilic and mesophilic temperatures are almost identical; with the
thermophilic mode the maximum reduction in COD is observed on the third day
and constitutes 91%, while with the mesophilic mode the maximum reduction in
COD is observed on the fourth day and equals 90%. Thus, the mesophilic regime
Water Security: Monograph 81

[1] was considered to be the optimum temperature process for methanogenesis, and
is characterized by significantly lower energy costs and a more diverse composition
of microflora. The efficiency of COD reduction with the mesophilic mode does not
differ much from that of the thermophilic mode.
Results of the efficiency in reduction of COD values for the mesophilic mode
are shown in figure 5.

Figure 5. Change of COD reduction efficiency at 40 °C, where 1 – COD inf. (influent
– incoming contaminated waste water) gO2/dm3; 2 – COD eff. (effluent – outgoing
treated waste water) gO2/dm3; 3 – COD efficiency,%.
According to the present graph, the efficiency of waste water treatment reaches
92% on the fourth day of methanogenesis.
Figures for biogas formation under the selected conditions are shown in figure 6.

Figure 6. The formation of biogas and methane content at 40 °C, where 1 – biogas
yield, 2 – methane content.

DISCUSSION
The results of the research show that the formation of biogas begins 22 hours
after the substrate loading. At that point, methane is missing in the gas phase during
82 Water Security: Monograph

fermentation. The process of biogas induction is accompanied by an increase in


methane content of the gas mixture. The maximum biogas yield is observed after
21 days and amounts to 5,65 dm3/day, while the methane content in the gas mixture
reaches 67% [4].
Thus, the study of rational parameters of anaerobic fermentation of winery
sewage allows the development of optimum operating conditions for liquid waste
treatment technologies in winemaking.
The research results of rational parameters of anaerobic fermentation of
winemaking sewage which form the basis of the waste water treatment process are
presented in figure. 7.

Figure 7. Technological scheme of anaerobic fermentation of waste water treatment.

The technological scheme of waste water treatment involves the following steps:
- waste water with moisture (w = 90-93%), as well as crushed stems, is fed into
a storage tank at a ratio of 1:0,1, respectively. Cattle humus is also added at a ratio
of 1:1,5;
- the produced mass is subjected to anaerobic fermentation within 4 days at a
temperature of 40 °C and pH = 6,5-7,5;
- the formed biogas is sent for drying and then to the cogeneration unit, while
treated waste water is fed to aerobic post-treatment (bioponds).
Water Security: Monograph 83

Laboratory studies of the process of anaerobic fermentation of waste water were


conducted using the laboratory biogas installation BU-1 (fig. 8).

Figure 8. Biogas laboratory installation BU-1 with vertical bioreactor.

BU-1 consists of a methane tank, where methane fermentation takes place, and
a gas-holder intended for biogas collecting. The device for substrate heating and
mixing is an important element of the installation. The basic scheme of the biogas
plant is shown in figure 9.

Figure 9. Basic scheme of biogas plant,


where I – methane-tank; II – gas-holder;
1 – outer casing of methane-tank;
2 - inner casing of methane-tank;
3 – water-jacket; 4 – methane-tank core;
5 – cover; 6–pipe for supplying
biomass; pipe to remove the fermented
biomass; 9 – pipe for supplying water;
10 – pipe to determine the water level in
the water-jacket; 11 – gas pipeline;
12 – pipe for feeding biogas;
13 – gas-holder case; 14 – cylinder
level-gauge; 15 – guideway; 16 – tap,
17 – pipe to drain biogas from the
methane-tank core; 18 – tube for gas
extraction from the gas-holder; 19 –
mixer, 20 – heater.
84 Water Security: Monograph

The methane-tank I consists of an external (1) and an internal (2) case, with the
water jacket (3) between them; it is a container filled with water from the pipe (9)
and which transfers heat from the substrate heater (20). When the water-jacket is
filled with water, air is removed through the pipe (10) and tap (16). To create the
tightness of the methane-tank’s core 4, it has a sealed cover (5). Substrate is supplied
through the pipe 6 into the methane-tank core (4). Pipe 6 almost reaches the bottom
of the bioreactor core (4) enabling fresh substrate to be fed to the bottom of the
reactor core, and thus displacing fermented biomass through pipe 7. To drain all the
biomass, pipe 8 is used. To prevent formation of a crust, as well as to ensure
uniformity of biomass, a mixer (19) is used, which periodically mixes biomass in
the reactor core.
Biogas is supplied from the reactor to the gas-holder (II) through the pipe 17
via the pipeline 11 and further through pipe 12. A ‘wet’ gas-holder is used in this
installation, consisting of two cylindrical containers: a gas-holder case (13) and a
level-gauge (14), as well as a guideway (15). The gas-holder case (13) is filled with
water, with a floating hollow level-gauge (14). Biogas is supplied to the inner cavity
of the level-gauge (14) through the pipe 12. Filled with biogas through the guideway
(15), the level-gauge (14) rises above the gas-holder case that, in turn, determines
the presence and amount of gas in the gas-holder [6].
Technical and technological parameters of the waste water anaerobic
fermentation is represented in table 2.
Based on the data represented in table 2, it can be concluded that there is a high
efficiency of the anaerobic fermentation process, proved by data on the efficiency
of the reduction in the COC index (90,0-92,0%) and high biogas induction
(0,69 m3/day).
According to the developed method of wastewater treatment a pilot sample of
treated wastewater was received , of which such parameters were investigated as
follows: organoleptic, physical, chemical and microbiological ones. The
organoleptic properties of treated waste water are represented in table 3.
Table 2
Technical and technological parameters of anaerobic fermentation of waste water
(n=3, P≥0,95)
Indicator Values
Organic matter load, COD g/l of reactor volume/day 0,93
Hydraulic fermentation time, day 4
COD, g/l:
input 9,1-9,3
output 0,2-0,8
COD reduction efficiency, % 90,0-92,0
Biogas amount, m3/day 0,48-0,69
Methane amount, m3/day 0,18-0,19
Methane content, % 65,0-67,0
Water Security: Monograph 85

Table 3
Organoleptic evaluation of the waste water treatment
Indicator Values
Turbidity Weak opalescent solution

Neutral, very weak, is not immediately detected, but revealed


Smell
through careful study (while heating water)

Foaming None

The next stage of research was to determine the physical and chemical
characteristics of treated waste water (table 4).
Table 4
Physical and chemical qualities of the treated waste water

№ Indicator Values
1 рН 8,0
2 Temperature, °С 32,0
3 COD gО2/l 0,8
4 BOD5 gО2/l 0,3
5 Suspended solids, mg/l 170,0
6 Nitrogenous substances 14,0
7 Sulfates 210,0
8 Chlorides 240,0

On the basis of the characteristics of the waste water’s physical and chemical
composition, it can be concluded that they meet the requirements of Sanitary Rules
and Standards 4630-88 and pose no threat to surface water.
Definition of biogas components, formed as a result of the waste water
fermentation, was carried out by means of a gas analyzer GEM-500. Gas Analyzer
GEM-500 is intended to determine the main components of biogas, namely CH4, CO2
and O2. The results of the biogas component determination are given in table 5.
Table 5
Characteristics of biogas components

Indicator Values
СН4, % 67,0
СО2,% 30,6
O2% 0,4
86 Water Security: Monograph

According to the data presented in table 5, biogas, obtained by the above


method, comprises 67,0% methane, 30,6% СО2, and 0,4% О2; the remainder is
comprised of H2 and H2S, which were not determined because of their low content
in the biogas (less than 2%).
Along with biogas, decomposition products of complex organic substances in
the form of liquid organic fertilizers are formed in the bioreactor. . Research has
established [6] that high-quality organic fertilizers can be obtained through the
process of methanogenesis of organic matter in primary winemaking waste water.
These fertilizers are better absorbed by crops than with mineral fertilizers as
they have good properties of water loss that, in turn, simplify the problem of use
and storage. When using these fertilizers, groundwater contamination and the spread
of disease and weeds are reduced, which, in turn, reduces the cost of chemical
fertilization measures and plant protection.

CONCLUSION
The use of anaerobic fermentation for wine production waste water provides
purified runoff and an additional source of energy, biogas, as well as organic
fertilizers.
The results of the investigation into the chemical composition of industrial liquid
waste, such as sewage, confirm the advisable choice of utilization by anaerobic
fermentation in a methane-tank. The parameters for anaerobic fermentation of
sewage, with maximum process stability, are determined experimentally.
The results of this research demonstrate the high efficiency of the treatment
process on the initial pollution in wastewater (90-92% efficiency) and provides an
experimental ground for theoretical studies.

REFERENCES
1. Sokolova, І.F., Krusіr, G.V., Kіrіyak G.V. (2011). Ecological aspects of winemaking
enterprises. Ecological safety, 2, 128-132.
2. Sokolova, I.F., Krusir, G.V. (2012). Solid waste and ecological aspects of winemaking
enterprises. Ecological safety, 2, 112-115.
3. Sokolova, I.F. Krusir, G.V., Krestinkov I.S. (2013). Index estimation of ecological
danger of wineries. Ecological safety, 1, 96-98.
4. Sokolova, I.F., Krusir, G.V. (2013). Prospects for the use of the wineries yeast
precipitate. Ecological safety, 2, 111-114.
5. Sokolova, I.F., Krusir, G.V., Sevastyanova O.V. (2014). Grounding for developing feed
additive from wine waste, Food. science and technology, 1, 73-79.
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6. Sokolova, I.F., Krusir, G.V., Dubrovin, V.A., Polishchuk, V.N., Dubovik, A.A. (2014).
Research of methanogenesis of primary wine making enterprises waste water. Eastern
European Journal of advanced technologies, 4/10, 43-47.
7. Sokolova, I.F., Krusir, G.V. (2014). Grounding for choice of the anaerobic bioreactor
for sewage treatment of primary wine making enterprises. Scientific Journal «ScienceRise»,
1(1), 22-25.
8. Sokolova, I.F., Polishchuk, V.N., Dubrovin, V.A., Krusir, G.V., Lobodko, M.M. (2014).
Improving the efficiency of biogas production by means of using the wineries waste water.
Collection of Scientific Study «SWorld» (Russia), 4(37), 5-9. (in rush.)
9. Patent for Utility Model 94587 Ukraine IPC (2014) S02F 11/12. Method of anaerobic
fermentation of sewage sludge / Krusir, G.V., Sokolova, I.F. patent owner (Odessa National
Academy of Food Technologies. – № u2014 03878; appl. 04/14/2014; publ. 25.11.2014, Bull.
22.- 4 p.(in ukr.)
88 Water Security: Monograph

TECHNOLOGICAL ASPECTS OF THE PRE-TREATMENT OF


LEACHATE, STORED AT THE RETENTION PONDS OF THE
GRYBOVYCHI LANDFILL, LVIV REGION, UKRAINE

Prof., D.Sc. Myroslav Malovanyy1


Ass.Prof., PhD. Volodymyr Zhuk2
Mykola Oducha1
Ph.D. Vira Sliusar1
Andriy Sereda1
1
Lviv Polytechnic National University, e-mail: mmal@lp.edu.ua, Ukraine
2
Lviv City Communal Enterprise «Lvivvodokanal», e-mail: gteh_lvk@ukr.net,
Ukraine

ABSTRACT
Characteristics of environmental hazardous leachate of the Grybovychi landfill,
Lviv region, are presented. Analysis of modern technologies of landfill leachate
utilization was performed. It was found that for Grybovychi landfill the most
suitable are technologies of local leachate's pre-treatment directly at the landfill
territory with subsequent complete treatment at the municipal wastewater treatment
plant (WWTP). Pre-treatment of leachate should be done in three stages:
1) prolonged biological treatment in the aerobic lagoons, 2) coagulation-flocculation
treatment with sludge separation and its return into the tip of landfill, 3) disinfection.
The second and the third stages can be combined. After pre-treatment leachate
should be diluted with municipal sewages in such proportion, that allows the normal
treatment of this mixture at Lviv WWTP in compliance with the maximum
allowable discharge concentrations. Laboratory scale approbation of the proposed
technology was performed using the natural probes of Grybovychi landfill leachate.
Optimal parameters of proposed technology were defined. Principal technological
scheme of the leachate pre-treatment at Grybovychi landfill is outlined.
Keywords: leachate, aerobic treatment, coagulation, flocculation.

INTRODUCTION
A tip of Grybovychi landfill, Lviv region contains about 12−15 mln tons of
wastes, and now is ecologically dangerous in the area of its influence, that evidenced
in expert opinion of the Ministry of Ecology and Natural Resources of Ukraine. Up
Water Security: Monograph 89

to 1990 at Grybovychi landfill were deposited not only domestic wastes but also
industrial toxic wastes of 1−3 hazard classes. Their quantity reaches of 2 mln tons
for some tentative estimations. Landfill leachate is formed in the waste's tip due to
infiltration of stormwater and as result of complex biochemical processes of
decomposition of organic matter. Utilization of leachate at Grybovychi landfill is
complicated due to the following reasons:
− very large leachate volumes (about 100,000 m3) as a result of their long-term
accumulation in six retention ponds;
− urgency in disposal of leachate in a relatively short time because of the
necessity to start reducing the inclination of the tip slope and other remediation
processes at Grybovychi landfill.
Physicochemical properties of Grybovychi landfill leachate collected at different
periods of the year vary considerably, as shown in table 1.
Table 1
Physicochemical properties of Grybovychi landfill leachate

These two stages are radically different in leachate fluxes must to be treated, its
physical and chemical parameters and time scales. Thus one universal treatment
technology for both stages can not be efficient, as from a technical point of view
(impossible the effective performance of equipment for both stages), so for
90 Water Security: Monograph

economic reasons (significant cost overruns). To choose the optimal strategy of


leachate ecological danger mitigation, the review of modern technologies of landfill
leachate treatment was performed.
Among the recommended in Ukraine [1] the most widespread technologies are:
- reverse osmosis;
- chemical and biological oxidation;
- electron plasma leachate treatment;
- evaporation and drying;
- leachate solidification;
- anaerobic and aerobic biological treatment.
Reverse osmosis technology is used at more than 350 landfills around the world
[2]. Modern reverse osmosis systems allow achieving high treatment efficiency, but
cause the production of about 10% concentrate that should be returned to the landfill
tip.
Chemical and biological oxidation generally comprises such stages [3]: reagent
adsorption; biological treatment in the oxide-anoxide circulation block; gravity
separation of waste sludge; reagent or ultraviolet disinfection of treated wastewater.
This technology is not approved for treating landfill leachate with high flow
discharge.
Electron plasma leachate treatment [4; 5], known since 1990, is very attractive
technology due the high efficiency and low maintenance costs, but up today is not
widespread and there are few commercial proposals concerning electron plasma
industrial installations.
Evaporation and drying of the landfill leachate are not suitable for such huge
leachate volumes, which are stored at Grybovychi landfill, so this technology was
not considered as available one.
Anaerobic technology of the landfill leachate is very promising, but its
successful realization in large scales requires the strict compliance to technological
parameters, that is difficult in realization when the leachate quality is variable.
Our attention was attracted to the treatment technology in aerobic lagoons [6−8].
Experimental experience suggests the availability of this method as the first stage of
leachate pre-treatment at Grybovychi landfill. Coagulation-flocculation should be
considered as the second stage of leachate pre-treatment. After the disinfection leachate
can be outlet into the municipal sewerage system with full treatment at Lviv WWTP.

METHODOLOGY OF RESEARCH
Investigation of aerobic leachate treatment was fulfilled on experimental
installation (fig. 1) using following method. Natural Grybovychi landfill leachate
Water Security: Monograph 91

from retention pond in quantity of 4 dm3 poured into the laboratory flask. A portion
of 10 cm3 of Lviv WWTP activated sludge was added to leachate to enable the initial
microbiological environment. The laboratory aerator compressed air in the bottom
part of the flask with discharge 42 cm3/s. The initial leachate parameters were:
dissolved oxygen − 1,87 mg/dm3, pH=8,64, ammonium anions − 900 mg/dm3, COD
− 11,000 mg/dm3.
Dissolved oxygen concentration was measured by the portative oxygen meter
sensІon6™, the ammonium nitrogen concentration was defined by the photometric
method [9]. COD was obtained by the official method [10], pH value was measured
by the portative potentiometer рН/ISE/mB/°C sensIonтм2 [11].

Figure 1. Laboratory installation for the experimental investigation of the leachate


aerobic treatment

Aeration was performed continuously at the constant temperature 20 °C. After


a certain time period samples were taken, for which the above mentioned parameters
were determined.
Two modes of aerobic leachate treatment were investigated: 1) so called static
mode, as in a batch reactor, without fresh leachate addition; 2) so called dynamic
mode with periodical addition of some portion of fresh leachate instead the same
volume of processed one.
In the static mode the maximum effect of the leachate biological aerobic
treatment was defined at the experimental conditions. In the dynamic mode the
treatment in natural conditions was modeled, considering the constant inflow of the
fresh leachate into the aerobic lagoon so as corresponding outflow of the partially
treated leachate to the next stage of pre-treatment technology. In this research the
daily amounts of inlet and outlet leachate was equal 250 cm3, 350 cm3, 400 cm3 and
500 cm3. Each series of investigation continued until the leachate parameters were
constant within three days; then began a new series.
92 Water Security: Monograph

Leachate influence on the biological treatment process on the Lviv WWTP was
investigated experimentally on the pilot treatment installation (fig. 2). Mixture of
the municipal sewages with leachate was treated in continuous mode on the
experimental aeration tank 1, installed in the polyethylene cylindrical reservoir with
diameter D=1,2 m. At the bottom of tank 1 the aeration tube 2 was installed to
saturate with oxygen and to mix the water−sludge system. Air was supplied by the
compressor station of WWTP. Dissolved oxygen concentration in experimental tank
1 was maintained the same as in natural aeration tanks at Lviv WWTP. Air flow
discharge was adjusted by the valve 3 and the dissolved oxygen rates were
controlled by the portative oxygen meter.
Pilot treatment installation includes two primary clarifiers: the clarifier N1 (4 at
fig. 2) with sewage−leachate mixture and the clarifier N2 (9 at fig. 2) with only
municipal sewages. Sewage−leachate mixture (8 hours per day) and only municipal
sewage (16 hours per day) were continuously pumped into the experimental aeration
tank 1. Homogeneity of the sewage−leachate mixture was ensured by aerator 6.
Flow discharge was controlled by the valves 7 and changing the pressure curve of
frequency regulated pumps 5. The total duration of pilot experimental research in
continuous mode was about 10 days.

Figure 2. Pilot continuous mode treatment installation:


1 − experimental aeration tank; 2, 6 − aeration tubes; 3, 7 − valves; 4 − primary clarifier
N1 with leachate; 5 − circulating pumps UPE 25-40; 8 − ball valves; 9 − primary
clarifier N2 without leachate; 10 − secondary clarifier
Water Security: Monograph 93

Primary clarifier N2 (9 at fig. 2) consists of two hydraulically connected 1 m3


tanks. Municipal sewages from the clarifier 9 pumped into the experimental aeration
tank 1 by means of circulation pump 5. Treated wastewater after the aeration tank
flowed into the secondary clarifier 10. Flow switching between primary clarifiers
N1 and N2 was done by ball valves 8.
At the beginning experimental aeration tank was filled with 1,5 m3 of water-
sludge mixture from the natural aeration tank of Lviv WWTP. Then switched on
the aeration in tanks 1 and 4. Simultaneously the primary clarifiers N1 and N2 were
filled with sewages from the outlet of natural primary clarifiers of Lviv WWTP.
Then Grybovychi landfill leachate was added into the primary clarifier N1 in such
quantity to obtain proportion between sewage and leachate as 500:1. After that
circulating pump H1 was switched on to move the sewage−leachate mixture into
the aeration tank 1. This mixture was aerated for 8 hours. Excessive amount of liquid
from aeration tank 1 continuously flowed out by gravity into the secondary clarifier
2 and then into the sewerage system of WWTP. After the first 8 hours the pump H1
was switching off whereas the pump H2 was switching on to pump sewage without
leachate into the aeration tank 1 for next 16 hours with relatively smaller discharge
compared to pump H1 to account the non-uniformity of sewage discharge at the
inlet of WWTP. This 24 hours cycle was repeated for 10 times. Every day after the
8 hour period of sewage-leachate aeration the 1.5-liter of aerobically treatment
wastewater was sampling to determine its physicochemical properties.

RESULTS OF RESEARCH
The main results of laboratory aerobic biological treatment of leachate in the
static mode are presented on the fig. 3 - fig. 6. Steady state of the leachate at the
laboratory installation was achieved in average through 9-11 days.

Figure 3. Concentration NH4-N in the Figure 4. pH values in the static mode


static mode versus the time of aeration, versus the time of aeration, days

Numerical results of laboratory aerobic biological treatment of leachate in the


dynamic mode are presented at the table 2.
94 Water Security: Monograph

Figure 5. Dissolved oxygen in the static Figure 6. pH values in the static mode
mode versus the time of aeration, days versus the time of aeration, days
Table 2
Results of experimental aerobic leachate treatment in the dynamic mode

Coagulation-flocculation method of Grybovychi landfill leachate treatment was


investigated in 2016 by different researchers. Specialists of the company Liptovský
Hrádok (Slovakia) used in their study coagulant polyaluminiumchlorid (PAC)
together with flocculant PRAESTOL K255L. Specialists of the company Węglostal
(Poland) investigated the influence of the PIX and PAX coagulant and flocculant
Superfloc C446. Analogical experiments but with another chemicals were done by
the scientists of Lviv National University and by specialists of the company Alufinish
(Lviv, Ukraine). Clear phase separation was observed in all cases, some results of
the COD decreasing after coagulation-flocculation are represented in table 3.
Table 3
Effects of experimental COD decreasing after coagulation-flocculation
of Grybovychi landfill leachate

Landfill leachate disinfection is studied deeply enough [12;13] and investigation


of this stage of treatment was not provided in this study.
Water Security: Monograph 95

At pilot aerobic treatment plant (fig. 2) was studied periodical 8-hour biological
treatment process for leachate–sewage proportions 1:10, 1:500, 1:1000, 1:1250,
1:1500.
The results show that only at proportion 1:10 NH4-N and COD values exceed
maximum allowable discharge concentrations for Lviv sewerage system
respectively on 64,3% and 1,32%. At proportions 1:500 та 1:1500 treatment effect
by the ammonium nitrogen was equal respectively 92,6% та 93%. These values are
almost so high, then for the sewage treatment without leachate for the same
conditions (95 %).
DISCUSSION
Analysis of the experimental aerobic treatment of Grybovychi landfill leachate
in the static mode shows, that 16-day continuous aeration leads to almost 2 times
decreasing of COD and more than 3 times − ammonium nitrogen decreasing.
Microbiological analyses showed in aerobically treated leachate a wide range of
aerobic microorganisms, different types from analogical ones in activated sludge
of Lviv municipal WWTP. Detail characteristics of this microbiological culture must
be more deeply investigated. A sharp reduction of dissolved oxygen concentration
after the first 24 hours of aeration can be the evidence of incumbency time of this
microbiological culture.
Results of aerobic treatment in the dynamic mode show the optimal retention
time in the aerobic lagoon for about 8−10 days. As result, the COD is decreasing
almost twice and ammonium nitrogen − on 35%. The influence of the aeration
intensity and environment temperature onto the treatment efficiency should be
investigated. Another important question is the effectiveness of artificial
immobilization media for microbiological culture and dynamics of this process.
Analysis of the results of coagulation-flocculation treatment of leachate reveals
that for different tested combination of chemicals similar phase separation and COD
decreasing can be achieved. The main optimization parameter in this case should
be a minimal maintenance costs. An important fact is, that in all above mentioned
results of the coagulation-flocculation stage were obtained using the raw leachate
without any preliminary treatment. With purpose to realize a multi-stage leachate
pre-treatment technology it is necessary the additional investigation of coagulation-
flocculation treatment effect on the leachate after aerobic stage.
At the pilot pre-treatment plant of continuous action was modeled the 10-days
performance of the Lviv WWTP for the mixture of municipal sewages and
Grybovychi landfill leachate, that was outlet by such schedule: every day for 8 hours
(from 9 am till 5 pm) − treatment of the sewage and leachate mixture in proportion
500:1 and 16 hours (5 pm − 9 am) − sewage treatment without leachate addition.
This schedule is the first approximation of pre-treated leachate discharging onto the
Lviv WWTP. Phase separation of the activated sludge at the pilot treatment plant
increased from 5 min in the first day to 10 min at the end of the experiment. Any
unusual smell or color of activated sludge were not detected. Thus, the dilution of
96 Water Security: Monograph

pre-treated leachate with municipal sewage in the proportion 1:500 was


recommended.
Based on the analysis of this study can be recommended the principal
technological scheme of the Grybovychi landfill leachate pre-treatment, shown at
fig. 7.

CONCLUSION
The mitigation of the ecological danger, caused by the Grybovychi landfill
leachate, can be achieved by two consequent steps: 1) short-term utilization of large
amount of previously stored leachate to enable the landfill remediation process;
2) long-term treatment of relatively small quantities of raw leachate that will leak
from the landfill's tip for decades even after the remediation. These steps are very
different so in leachate discharge, as in the physicochemical properties of leachates
and duration of the process. Thus, the same pre-treatment technology can not be
effective not from technical nor economical point of view. In this study was
proposed three-stage pre-treatment technology of Grybovychi landfill leachate. It
includes the biological treatment in the aerobic lagoons, coagulation-flocculation
and finally disinfection of leachate. Pre-treated leachate should be fully treated at
the Lviv WWTP. Processes of leachate aerobic biological pre-treatment in the static
and dynamic modes so as coagulation-flocculation were investigated at laboratory
scale. Based on experimental investigation on the pilot treatment plant, modeling
the maintenance of Lviv WWTP, were defined the minimum acceptable proportion

Figure 7. Principal technological scheme of the Grybovychi landfill leachate


pre-treatment
Water Security: Monograph 97

of pre-treated leachate dilution by the municipal sewages to ensure the effective


WWTP operation.
ACKNOWLEDGEMENTS
The authors express gratitude to the Lviv City Communal Enterprise
«Lvivvodokanal» for technical and financial support in carring out this research.

REFERENCES
1. Methodical recommendations on collection, utilizations and rendering of filtrate of
grounds of domestic wastes harmless. Ministries of regional development, building and housing
and communal services of Ukraine ratified by an order № 421 November, 21, 2012 (in ukr.).
2. Maslov, V.M. (2002) Recommendable methods of cleaning of filtrate. Research and
information collection the "Sanitary cleaning of cities and communal motor transport", 44–50
(in rus.).
3. Vaisman, Ya. I., Korotaev, V. Y. & Petrov, V. Y. (2001) Management by wastes. Burial
place of hard domestic wastes, Perm: Perm state technical university (in rus.).
4. Gomez, E., Amutha Rani, D., Cheeseman, C.R. & oth. (2009) Thermal plasma technology
for the treatment of wastes: A critical review. Journal of Hazardous Materials, 161, 614–626.
5. Mashal, A., Abu-Daherieh, J., Graham, W. & oth. Landfill leachate treatment using
plasma-Fenton’s process. In: Sixth Jordan International Chemical Engineering Conference.
Amman, Jordan, 2012.
6. Howard, D. Robinson & Grantham, G. (1988) The treatment of landfill leachates in on-
site aerated lagoon plants: experience in Britain and Ireland. Water Research, 22 (6), 733-747.
7. Mehmood, M. K., Adetutu, E., Nedwell, D. B. & Sall, A. S. (2009) In situ microbial
treatment of landfill leachate using aerated lagoons. Bioresource technology, 100, 2741-2744.
8. Maehlum, T. (1995) Treatment of landfill leachate in on-site lagoons and constructed
wetlands. Water Science & Technology Journal, 32(3), 129-135.
9. Methodology of photometric determination ammonium of ions with the reagent of Nessler
in effluents. Leading normative document 211.1.4.030-95, 1995 (in ukr.).
10. Quality of water. Determination of chemical requirement in oxygen (ISO 6060:1989,
IDT). State standard of Ukraine ISO 6060:2003. Kyiv: State consumer standard of Ukraine,
2004 (in ukr.).
11. Firm «Hach» from http://www.hach.com/manual-sension2-portable-ph-ise-meter/
product?id=7640316961#
12. Vronska, N. Y., Malovanyy, M. S. & Popovych, O. R. (2015) Cleaning of effluents by
the method of ultraviolet irradiation. Scientific and production journal "Chemical industry of
Ukraine", 6 (131), 29 – 33 (in ukr.).
13. Vronska, N. Y., Malovanyy, M. S. & Sakalova, H. V. (2015) Research of efficiency of
application of ultraviolet-adsorption technology for sewer water treatment from microbiological
contamination. Scieentific bulletin of Ukrainian National Foresty University, 25.8, 146-149
(in ukr.).
98 Water Security: Monograph

VALUATION HYDROECOLOGICAL AND SANITARY-HYGIENIC


CONDITION OF THE RIVER NETWORK OF POKUTSKO-
BUKOVINIAN CARPATHIANS

Ass.Prof. PhD. Andrew Masikevych1


Prof., Dr.Sc. Yuri Masikevych2
Prof., Dr.Sc. Valentyn Myslytsky2
Senior Lect., PhD. Ivan Burdeniuk2
1
Chernivtsi Faculty of the National Technical University «Kharkiv Polytechnic
Institute», e-mail: ecolawkhpi@meta.ua, Ukraine
2
Bukovinian State Medical University, e-mail: yumasik1957@bsmu.edu.ua,
Ukraine

ABSTRACT
On the basis of conclusions from our own investigations and available data in the
literature, a complex analysis of the hydroecologic and sanitary-hygienic condition
of the Prut River basin in the boundaries of the territory of the Pokutsko-Bukovinian
Carpathians has been carried out. The main challenges to the ecological safety of the
region have been considered Economic activity related to timber has a significant
influence on the state of the water basin of the Carpathians. The data obtained provides
evidence of increase in biological and chemical consumption of oxygen from the river
headwaters to the mouth of the Bily Cheremosh and Siret rivers, and their tributaries.
Contamination of the river increases with washouts of organic matter from the
riverside and water protective zones. Economic activity related to timber has a
significant influence on the state of the water basin of the Carpathians. This tendency
has a distinct seasonal character. Close correlative connection between the sanitary-
hygienic indices of the water and the health of the dwellers of the foothills and
mountain territories of the Chernivtsi oblast has been shown.
Keywords: river network, mountain region, anthropogenic influence, water
quality, population health

INTRODUCTION
Energetic economic activity along the riverbeds and flood plains (the
organization and functioning of open pits along the riverbeds in output of sandy-
gravel mixture, construction of dams against flood and riverbed regulation, bridge
Water Security: Monograph 99

passages, etc.) [20], for the last 50 years, resulted in intensification of riverbed
change in the Pokutsko-Bukovinian Carpathians region. Sketch map of the river
network is visually pesented in fig.1.
The Prut River basin constitutes the basis of the river network in the Pokutsko-
Bukovinian Carpathians. The current ecological state of the rivers Prut, Cheremosh,
Siret and their tributaries is a serious concern. Due to deforestation in the region - from
95% to 53% coverage - and the destruction of bushy areas in the highlands, the forests
have lost their protective function. As a result, cumulative disturbances of the normal
hydrologic regime of the mountain rivers have taken place. Dangerous floods started
to occur more often, and the scale of their negative influence upon the environment
increased. Floods in 2008 and 2010 resulted in human victims and were accompanied
by destruction of hydrotechnical and transport infrastructure, as well as housing [7].

Figure 1. Sketch map of the river network in


the Pokutsko-Bukovinian Carpathians (according
Yushchenko, Pasichnyk, data, 2001 [27])

Thus, the necessity of detailed monitoring of the riverbeds in the Carpathians


region has arisen. Assessment of the degree of the riverbeds’ durability of the small
river pools of the Prut-Dnistrovsk territory was put into practice by the hydrologists’
school of the Chernivtsi National University under the guidance of prof.
Kyryliuk O.V. [27].
Nowadays the Carpathians territory is one of the European regions most at risk
from flooding. On average, 20% of the population will suffer some form of flooding
each year [7]. For example, heavy rains on 24-28 July 2008 caused a flood, which
was classified as having disastrous effects, on the rivers of the Ukrainian
Carpathians. Spring floods cause a lot of damage in the foothills, accompanied by
the flooding of river valleys and the first terrace above the floodplain. In Verkhnii,
100 Water Security: Monograph

Prut spring floods in 1927, 1941, 1948, 1951, 1955, 1957, 1964, 1969, which arose
due to the rains, were similar to the spring flood of 2008 [26].
The basic types of anthropogenic influence on the riverbeds processes on the
rivers Prut, Cheremosh and Siret are: coast protective works, engineering structures
and extraction of sand and gravel from the riverbed [20].
The basin of the Prut river – the basis of the ecological network of the Pokuttya-
Bukovina Carpathians. The basin area is 27500 km2. [7]. The main reason for
contamination of the Prut is a mass inflow of unclean water from private farmsteads,
hotels and recreation complexes [5].
Another serious ecological problem in the Prut basin is the contamination of the
riverbeds with everyday rubbish. Many spontaneous dumps have appeared along
the rivers. Spring floods wash rubbish into the river, worsening the water quality.
The output of the sandy gravel mixture from the riverbed and the effects of
deforestation have negatively affected the ecological river condition. The river gets
shallower, with less water in the riverbed, and higher velocity flows [19].
Cheremosh is the biggest tributary of the Prut (Dunai basin) at 80 km long, and
a basin area of 2,650 km2. It is formed by the junction of Chorny Cheremosh (length
– 87 km, the basin area – 856 km2) and Bily Cheremosh (length – 80 km, the basin
area – 606 km2) near the village Usteriky. It flows on the boundary of the Ivano-
Frankivsk oblast (Verkhovyna, Kosiv, Sniatyn) regions [9].
The river Cheremosh is one of the largest water arteries of the Ukrainian
Carpathians. Its water quality is rated in the upper reaches of all parameters and
standards. Ecological threats to the river’s existence are: (illegal) deforestation
within the limits of the river basin (on the adjacent river slopes), erosion processes,
crucially changing the riverbed and hydrological regime (it is manifested especially
sharply in Bily Cheremosh). Other threats include solid everyday waste products,
housing-communal waste, building waste products, motor transport, output of
sandy-gavel mixture (for building work), and use of water for irrigation or industrial
requirements. The above mentioned reasons have substantial negative influence on
the water ecosystem of the river [4; 8].
Construction of mini hydroelectrostations (HESs) in the upper flow (in the
region of the village Yablunytsia) are a considerable threat to the Cheremosh water
ecosystem. It will lead to a decrease of the attractiveness of the area to tourists
(including making rafting an impossibility), restrict the development of the green
(ecological) tourism (the basis for the economic potential development of this
territory), will create obstacles for fish spawning and hydrobiont migration, and
threaten the distinct ecosystem integrity with by decreasing the level of the subsoil
waters. It should be noted that advantages in the sphere of tourism and recreation
are greater than advantages of mini hydroenergetics. Detailed analyses of the mini
hydroelectrostations’ negative influence on the river network of the Carpathians
region is cited in the work [23].
Water Security: Monograph 101

As a result of economic activity the deterioration in the types of the river process
is seen in Pokutsko-Bukovinian Carpathians. The riverbeds of many rivers, flowing
past densely populated regions, can change irreversibly. The reason for these
changes is the pollution of watercourses due deforestration, plowing, irrigation,
selection of sand and gravel. Changes are discrete downstream. [26].
Studying peculiarities of the dangerous processes spread in the basin systems
of the Ukrainian Carpathians, intensity and development tendencies, causes of
activization, the risk of their origin as well as the influence on ecological state of
the riverbeds is important nowadays. Spring floods, in particular the riverbed
forming and catastrophic ones have a great influence on the planned deformations
of the riverbeds, they can even change the type of the riverbed. Research into these
processes have episodic rather than systematic character, that doesn’t allow in full
measure to use them for the general conclusions. However, modern geo-information
systems and methods of remote sensing of the Earth help to create the methods of
calculation and prediction of the riverbed processes and, especially, horizontal
riverbed deformations. To analyze their intensity, hydromorphological analysis has
been used, which is a totality of the means of studying natural materials in order to
reveal new forms of manifestation of the riverbed processes, their regularities and
connections with the riverbed forming reasons [3; 25].
The basic approaches to the formation of ecological safety of the Carpathians
drains, in the opinion of a number of authors [20; 21], may come to the following:
careful management of the mountain ecosystems; an increase of the area covered
with woods, and optimization of the aged and cenotic structure of the woods’
ecosystems; creation of definite conditions, which maintain the nature - or close to
the natural - balanced functioning of the river; keeping natural ecosystems;
methodological approaches to the regulation of the riverbed deformations; decision
of the problems of the protection and constant use of the natural resources.

METHODOLOGY OF THE RESEARCH


The article is of observation character. Complex analysis of the hydroecological
and sanitary-hygienic condition of the Prut river basin in the boundaries of the
territory of the Pokutsko-Bukovinian Carpathians has been carried out on the basis
of the results of our own investigations and available data from the literature.

RESULTS OF THE RESEARCH AND CONCLUSION


The health of human beings is a result, to some degree, of the dynamic balance
of the human organism and the environment [1]. Investigations, carried out by us,
have shown that the population health of the inhabitants of separate regions of the
Bukovinian Carpathians is a significant element of their steady balanced
development [12].
Quite a few works [6; 22] are devoted to cartographic analysis of morbidity, and
studying the health condition and the sickness rate according to the landscape
102 Water Security: Monograph

complexes. A new direction in scientific investigation is medical geology: studying


the health and life of a person as a function of geological surroundings and how
they reciprocally influence a person [22]. However, the influence population health
on the stability and safety of the natural ecosystems is not sufficiently studied.
The analysis of medico-demographic indices of the mountain and foothills
regions [14; 15; 16], carried out by us, suggests that there is a growth of
demographic burdening in comparison with indices elsewhere in the Chernivtsi
region. It should be mentioned that demographic burden is considered as
generalizing quantitative characteristics of the aged structure of the population,
which shows burdening of the society with unproductive population. Herein, the
demographic burdening index is calculated for persons aged of 15–65 years as ratio
of the general number of persons aged 0–14 years and 65 years and more to the
number of population aged 25–64 years, that can be explained by an increase of the
birthrate indices in the region (table 1).
Table 1
Medico-demographic characteristics of the dwellers of the foothills and mountain
population of the Chernivtsi region

According to the data of the Chief Statistical Board in the Chernivtsi region

Figure 2. Nozological structure of


the population mortality of
Storozhynets region of the
Chernivtsi oblast (average for the
period 1989 – 2004 years)
*according to the data (Gutsuliak,
Nakonechny, 2010)
Water Security: Monograph 103

Analyzing the data presented in fig.1, we see that among the main causes of
mortality of the dwellers of the foothills territory are: cardiovascular diseases (CVD
– 61,8%), oncological diseases (ONCO – 11,6%) and respiratory organs diseases
(ROD – 8,9%).
Water quality is one of the most significant environmental factors determining
the health of the residents of Chernivtsi oblast. Data available in the literature [6]
indicates that, based on bacteriological indices in Chernivtsi oblast, 3,6% of water
from the sources of the centralized water supply didn’t correspond to sanitary-
hygienic standards (in Ukraine – 4,8%); from the decentralized sources, it was 12%
(in Ukraine – 22,7%). For mountain areas further up-catchment this discrepancy
was lower (see table 2).
Table 2
Sanitary-hygienic discrepancy of the water medium quality in the regions of
Chernivtsi oblast (% discrepancy according to bacteriological indices)

Note: C – centralized water supply, DC – decentralized water supply

Economic activity has had a significant influence upon the condition of the
Carpathians water basin in this region. In Bukovyna, the forest areas stored
44,3 mln t of phytomass in Chernivtsi oblast, which constitutes 5,07% of the
energetic potential of the woods of all-Ukraine. Herein, about 21% of commercial
timber stock becomes waste products. Timber waste – produced at stocking up,
manufacturing, rafting of woods materials (bark, sawdust, chip, block, dry branches,
etc.) – is one of the most widespread contaminants of the natural basins. Wood
biomass, not utilized, can create considerable danger to the natural surroundings.
Accumulation of the suspended organic substances, especially sawdust, in
watercourses results in decomposition, accompanied by changes in oxidizing
processes due to which oxygen content in water decreases, increasing its need for
expensive biochemical requirement, organoleptic indices of the water worsen, and
as a result the integrity of the natural ecosystem and its safety is disturbed. This
peculiarity acquires especially weighty significance for the mountain economic
region [10; 11]. Our inspections of the basin of the Bily Cheremosh and Siret Rivers
during 2010–2013 revealed significant accumulations of the timber waste products,
in particular sawdust, in the riverside strip in the region of the Yablunytsia,
104 Water Security: Monograph

Cheremoshna, Dovgopillia settlements as well as others. The above mentioned


sawdust dumps are the main cause of the increase of suspended substances in the
basins This tendency towards worsening sanitary-hygienic indices of the water
quality of the river basin of Bukovinian Carpathians has been evident for the last
five years [13].
The data obtained by us is evidence of an increase of the biological consumption
of oxygen (BCO) along the entire lengths of the rivers Bily Cheremosh, Siret and
their tributaries. Thus, in the upper reaches of the Bily Cheremosh basin (the area
of the junction of Perkalaba and Sarata) the content of the dissolved oxygen was
4,6 mg/dm3 and in the area of the mouth (the place of sampling in the village
Usteriky) it decreased to 2,0 mg/dm3. The indicated tendency is essentially becomes
stronger during the transition from winter-spring to the summer season.
One more index studied by us was water oxidation permanganatic (OP). OP
increase in the river water is a direct index of its contamination. normally, OP of
the river water must be less than 5–6 mg/dm3. In the upper part of Bily Cheremosh
basin, in the area of the junction of the Perkalaba and Sarata rivers, OP was
1,2 mg/dm3, while in the middle part it increased to 9,3 mg/dm3, and at the mouth
it was 12,4 mg/dm3. Clear seasonal conditionality of OP index is also observed in
the mouth part of Bily Cheremosh river. It is explained by rather intensive
contamination of the river water by organic substances, primarily from timber waste
products and everyday waste from the settlements located in Bily Cheremosh basin.
However, a more exact concept about the total contamination is given by another
index:chemical oxygen demand (COD, or dichromate oxidation) – the oxygen
needed for complete oxidation of carbon, hydrogen, sulphur, nitrogen and other
substances.
Indices of closely correlate (r = 0,95) with COD value. Beginning from the
boundary of Yabluchnytsia settlement and heading downstream, there is a clearly
marked tendency of growth of the ChCO index towards a value of 25 mg/dm3,
almost twice permitted values.
The mentioned tendency is essentially increased during the period of transition
from the winter-spring to summer season. Accumulation of timber waste products
in the river network of the Pokutsko-Bukovinian Carpathians results in a sharp
worsening of the hydrochemical regime and basic hygienic indices of the mountain
hydroecosystem.
The whole chain of ecological safety has been compromised by poor
environmental assessment carried out during and building of mini HESs on the
mountain water drains of the Eastern Carpathians [2; 18]. Regardless of the
questions of the state’s energy independence, building of mini HESs without taking
into account the ecological safety requirements should be unconscionable.
Classification of the main challenges for ecological and technogenic safety in
the mountain ecosystem of Pokutsko-Bukovinian Carpathians was conducted on
Water Security: Monograph 105

the basis of many years investigations carried out by us (table 3). Weighty economic
damages have occurred as a direct function of the disturbance of the mountain forest
ecosystems, landscape and biological diversity. The main dangers to forest
ecosystems in the region are: dry vegetation burning in the spring the use of
improper wood harvesting, distribution of pests of spruce forests in mountain areas,
deforestation in violation of the law
Chemical (acid rains), physical (industrial discharges), noise and
electromagnetic contamination of the natural surroundings, chemical contamination
of water arteries with industrial and domestic drainage and agricultural firms cause
significant damage to biological integrity. An extensive network of roads for various
purposes, land erosion in mountainous regions is an obstacle to reproduction and
conservation of flora and fauna.The indicated challenges are universal for the whole
Carpathians region [17].
Table 3
Main challenges for ecological and caused by technological activities of people
safety of the Carpathians region and their consequences

The majority of challenges shown in the table are directly or indirectly connected
with the ecological condition of the mountain water ecosystem.
106 Water Security: Monograph

CONCLUSIONS
Anthropogenic activity has resulted in risks and challenges for water ecosystems
in the Pokutsko-Bukovinian Carpathians – activity that is the main cause of
contamination of the river network of the region under study. Accumulation of timber
waste products in natural drainage channels results in a sharp deterioration of the
hydrochemical regime and the main hygienic indices of the mountain hydroecosystems.
Complex, integrated management of water resources and, at the same time,
optimization of the rivers’ use is a multidimensional ecological-social problem for the
region. The hygienic characteristics of the river network of the region may serve as
one of the important indicators of changes in the ecosystem. The disturbed relations in
the environment – human system has a negatively reinforcing character and is a
regulator of the population health of the local dwellers. The health of the ecosystem
and of the local dwellers are two interdependent sides of the same existence.

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environmental hygiene studies. Environment and Health, 10, 3-5. (in ukr.)
2. Berezhnyj, Ie., Havryliuk, R., Masikevych, Iu., Movchan, Ia., Parchuk, G., Tarasova, O.,
Bolot, K. (2015). Small Hydro Power Stations Development in the Carpathians as a likely
Threat: IA and SEA Aspects. Symposium Abstracts of the 17th International Symposium on
Landscape Ecology: Landscape and Landscape Ecology / [Editors: Martin Boltižiar & Andrej
Bača]; Institute of Landscape Ecology, Slovak Academy of Sciences. Nitra: Slovakia.
3. Bilous, A.M. (1999). The impact of economic activities on water Ukraine.
Environmental technology and resource conservation, 5, 58-61. (in ukr.)
4. Drukman, E.L. (1985). Cheremosh and Prut: putyvodytel. Uzhgorod: Carpathians.
(in ukr.)
5. Dubys, L., Kovalchuk, V.I., Myhnovych, I. (2006). Dangerous processes in the basin
system Ukrainian Carpathians: distribution, intensity of the effect on the ecological state of
the river channel. Hydrology, hydrochemistry, hidroekolohiya, 11, 59-69. (in ukr.)
6. Gutsulyak, V.M., Nakonechny, K.P. (2010). Medical and environmental assessment
landscape Chernivtsi region: monograph. Chernivtsi: Chernivtsi University Press. (in ukr.)
7. Ilchyshyn, J. T. (2012). About the ecological state of water quality mountain rivers of
the Ukrainian Carpathians. Hydrology, hydrochemistry, hydroecology, 1, 156-166. (in ukr.)
8. Klenske Claudia (2011) Physical geography of the Carpathian-Podolsk region of
Ukraine. Chernivtsi: Ruta (in ukr.)
9. Kostenyuk, L.V. (2008). Overall analysis of the hydrological regime of rivers
Cheremosh pool. Hydrology, hydrochemistry and hidoekolohiya, 14, 131-138. (in ukr.)
10. Masikevych, Ju.G., Masikevych, A.Yu. (2011). Prospects for the disposal of waste
wood in Chernivtsi region. Science journal: Environmental safety, 2 (12), 63-66. (in ukr.)
11. Masikevych, Ju.G., Solodkyi, V.D., Masikevych, A.Ju., Myslytskyy, V.F. (2012).
Evaluation of the energy potential of plantations of Chernivtsi region. Herald of the National
Technical University, 39, 129-135. (in ukr.)
Water Security: Monograph 107

12. Masikevych, Ju.G., Solodkyi, V.D., Myslytskyy, V.F. (2012). Public health - an
indicator of the ecological state of Bukovina Carpathians. Clinical and Experimental
Pathology, 11, 1 (39), 199-203. (in ukr.)
13. Masikevych, Ju.G., Masikevych, A.Yu. (2014). Hygienic water quality in the rivers
of Bukovyna as an indicator of environmental safety in the region. Man and the environment.
Problems neoekolohiyi, 3-4, 104-108. (in ukr.)
14. Masikevych, Ju.G., Myslytskyy, V.F. Masikevych, A.Ju. (2015). Population health
Highlanders Chernivtsi region. Clinical and Experimental Pathology, 14, 4 (54), 90-93.
(in ukr.).
15. Masikevych Yuriy, Myslytsky Valentyn, Tkachuk Svitlana, Masikevych Andriy.
(2015). Safe environment-guranty of the population health highlanders. Challenges for
ecological and technological safety of the Carpathian region. Current issues of social studies
and history of medicine: Joint Ukraine-Romanian scientific journal, 4 (8), 72-78. Engl.
16. Masikevych Yuriy, Myslytsky Valentyn, Tkachuk Svitlana, Masikevych Andriy.
(2016). Safe environment – key of helth of higlanders. Announcement II. Sanitary aspects
of environmental safety of mountain regions and population of health of horyan of Chernivtsi
region. Current issues of social studies and history of medicine: Joint Ukraine-Romanian
scientific journal, 2 (10), 78-80. Engl.
17. Masikevych, Ju. G., Masikevych, A.Yu. (2016). Ocnovni conditions and challenges
for environmental safety of mountain areas Pokuts'ka-Bukovina Carpathians. Eastern
European scientific journal, Warszawa (Polska), 1, 1 (5), 128-132. (in ukr.)
18. Masikevych, Ju.G., Masikevych A.Yu. (2016) Risks and challenges for sustainable
development of mountain ecosystems Bukovina Carpathians. Berg -140 years: collections
of the Scientific statey. Bendery: Eco-TIRAS, 178-181. (in ukr.).
19. Obodovskyy, O.G. Hydrological and ecological assessment of channel processes (for
example, rivers Ukraine). Kyiv: Nick Center. (in ukr.)
20. Revera A.Z. (1999). New life Small Rivers. Kyiv: Harvest. (in ukr.)
21. Rozhko I.M.(2000). Recreation evaluation mountain natural-territorial complexes for
tourism purposes (for example, Ukrainian Carpathians) thesis. on competition sciences.
degree candidate. geographer. Sciences specials. 11.00.01 - "Physical geography, geophysics
and geochemistry of landscapes". – Lviv. (in ukr.)
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Academpress. (in ukr.)
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Geography. Tourism, 46, 14-16. (in ukr.)
24. The population of Chernivtsi region 2014: statistical yearbook. Ed. Rotary, A.V.
(2014). Chernivtsi: Department of Statistics in the Chernivtsi region. (in ukr.)
25. Yatsyk, A.V., Byshovets, L.B. (2004). Small river Ukraine. Kyiv:Vintage. (in ukr.)
26. Yavkin, V.H., Kyrylyuk, A.A., Tsependa, M.V. (2006). Osoblyvosti floods and erosion
prouesy vertical Prut river beds pool. Hydrology, hydrochemistry and hidroekolohiya, 11,
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of geo-ecological river corridors. Chernivtsi: Ruta. (in ukr.)
108 Water Security: Monograph

NEW TECHNOLOGIES FOR AUTOMATED CONTROL OF WATER

Ass.Prof., PhD. Maryna Mikhalieva1


Prof., Dr.Sc. Volodymyr Pohrebennyk2
1
Hetman Petro Sahaidachnyi National Army Academy, e-mail: galmih@ukr.net,
Ukraine
2
Lviv Polytechnic National University, e-mail: vpohreb@gmail.com, Ukraine

ABSTRACT
The purpose of the research is to develop methods and ways of using
electroacoustic influences and appropriate measurements for improving the control
of the composition of liquid products. The analysis of the experiment results of
electrical measurements of model liquids under the influence of continuous
ultrasonic field and the electromagnetic field of variable frequency is presented.
Scientific facts are obtained, on the basis of which the method and techniques
of rapid monitoring of quantitative and qualitative control of the composition of
liquid products and objects of the environment are offered. The researches were
conducted for the development of new rapid non-laboratory control methods of
liquids that combine acoustic and electric influences.
The analysis of the research results of model liquids, obtained under the
influence of continuous ultrasonic field and the electromagnetic field of variable
frequency, is presented. On the basis of scientific facts the method of fast qualitative
and quantitative monitoring of liquid objects is proposed.
Keywords: control of liquids composition, electroacoustic measurement, water,
drinking, technical and waste water.

INTRODUCTION
The aqueous mixtures are the most common objects for testing of characteristics
in industry, medicine, agriculture, and environmental monitoring. The possibility
of determining the normalized characteristics of water through measurement of
electrical parameters is suggested as the results of analyzing of the theme, a literary
review of new scientific data and the results of our experimental researches [1].
Water Security: Monograph 109

The standard method for analyzing the composition of the liquid requires a
laboratory, specially trained staff, and a long time. Therefore, the purpose of
scientific research in the field of metrology is the improvement of the standard
methods by speeding up, ensuring high accuracy and the possibility of automation
and non-laboratory testing conditions. This article includes the results of a study of
ultrasound influence on the electrical properties of liquids. Investigations were
carried out with the help of the developed installation. During studies fluid models
were used. According to the study of complex conductivity at different frequencies
the graphics of relation between reactive and active component of the complex
conductivity and the frequency of the electromagnetic field were built and scientific
facts were received that have theoretical and practical significance.
In the developed experimental conditions such interactions of ultrasound and
electromagnetic field on the acoustic and electrical characteristics of the liquid were
installed, which further allows the use of these simultaneous influences for the
improvement of new methods of composition research of liquid objects. Such non-
laboratory methods give us the opportunity to get more information at the expense
of increased sensitivity and selectivity during short period of researches and the
possibility of their automation.

METHODOLOGY OF RESEARCH
With the integration of Ukraine into the EU the new technologies requires
adaptation and metrological support.
For example on the national market there are plants for production of dioxin
chlorine used to disinfect drinking water, waste water and food products. At better
(non-toxic) characteristics, compared to conventional chloride compounds there is
still a need for constant controlling such solute in water. The standard method of
such control is photometrical. In applying of this method, portable devices with
price more than 40 thousand UAH are used.
The reasons of laboratory methods imperfection lie in the fact, that chemical
metrology, as part of Theoretical, Applied and Legal Metrology, that deals with the
ensuring the unity of measurement in quantitative and chemical analysis, has its
own characteristics:
– presence of significant systematic errors that are caused by the dependence of
analysis results on the composition and properties of samples for analysis;
– multistage and complexity of the measurement process, which leads to an
increase in the total measurement error;
– chemical information about composition of the surrounding environment is
very important, but even all the analytical methods are not able to cover the
functional diversity of pollutants [2].
In order to expand the list of controlled substances of different electrical
properties, to increase the selectivity, precision and promptness of analysis it is
110 Water Security: Monograph

necessary to improve the methods, in which the established electrical parameters


are used corresponding to the normalized concentrations of components of
multicomponent fluids.
Modern researches in this area are intended to develop new improved methods
to control hazardous substances. This is due to the fact that ISO standards recommend
to replace laboratory methods of controlling of hazardous substances with production
methods, i.e., with rapid methods which can be used in automated systems.
The meaning of instrumental methods of analysis is constantly increasing and
is caused by the requirements of science and industry. For example, there is a
tendency to use material that contains a small amount of the desired product and
also remove items from of production wastes where these elements are found in
small quantities. In addition, highly purified substances and composite materials,
to which the high standards are presented, specifically, conservation of components
concentrations (metallurgy, semiconductor equipment), are increasingly used.
Constantly growing rationalization and automation of production and the associated
with them rapid production output lead to the need for using sensitive, accurate and
rapid analytical methods. Speed of the analysis is especially important factor
because it is economically profitable and safer to control manufacturing process in
"real-time" for its regulation and the adoption of the necessary solutions in process
management (control of food products, monitoring of waste water).
There are famous schools of acoustical research products and objects of the
environment, where researches are being conducted to establish the dependence of
the acoustical properties and the composition of fluids [3–9].
There are famous schools of electrical research of products and objects of the
environment, where researches are being conducted to establish the dependence of
the electrical properties and the composition of fluids [10–11].
In conductometric studies the magnetic and dielectric constant almost remain
constant, only the electrical conductivity changes. In these studies, the sample
solution is plugged into an electrical oscillating circuit, the electrical properties
changes of which are used to indicate immitance and its changes. The advantage of
research methods of liquids on alternating current is elimination of noise caused by
polarization resistance [12].
Because this method involves the use of high-frequency field, the value of
alternating current always includes the value of active (or real) and reactive
components:
Z = R + jX
G = GW + jGB, (1)
where: R – аctive resistance;
X – reactive resistance;
GW – active conductivity;
GB – reactive conductivity;
j – imaginary unit.
Water Security: Monograph 111

Usually active or reactive component is measured. Dependence of the active


component on concentration is different than the reactive component. In the first
case we get typical curve that is like bell and in second – "s"-like. Dependence of
the active component on the electrical conductivity and on concentration of
electrolytes (when it is considered that all the ions dissociate) has similar view.
If in constant voltage, for example, an active component of conductivity
capacitive cell is measured, we receive:
, (2)

for reactive component:


, (3)

There are developed methods and techniques to monitor substances and their
concentrations relying on the parameters of immittance, namely on the measured
values of active and reactive components of the conductivity [13-20]. In laboratory
conditions frequency of measurement and the values of the complex conductivity
for the development of methods of conductometric rapid control of multicomponent
fluids are established. Such methods are fast and simple.
Ultrasound as a branch of science and technology gets particularly rapid
development in the last three or four decades. This is due to the overall progress of
acoustics as a science and, in particular, with the formation and development of its
sections as nonlinear acoustics and quantum acoustics, and the development of solid
state physics, electronics, and especially with the birth of quantum electronics.
The fluid is viscous homogeneous material. Ultrasound is acoustic vibrations,
the frequency of which is greater than the high-frequency limit of audible sound
(over 20 000 Hz). Ultrasound emission is widely used physical effect in many areas,
which used the dependence of composition on the intensity of its absorption of
acoustic signal. Development of improved techniques of using of ultrasonic
emissions with new electrical appliances will simplify and speed up the control of
the composition of the liquid objects. Therefore, the research topic is relevant.
The object of this study is the process of measurement of acoustic and electrical
signals passing through the model fluids.
The subject of research is the model fluid of known composition.
The novelty of the experimental conditions is to combine the influence of
ultrasound and electromagnetic fields of different frequencies (50 Hz to 100000 Hz)
on liquid.
The purpose of research is the study of ultrasound influence on acoustic and
electric properties of liquids. Therefore, we faced with such task: in elaborated
experimental conditions to establish the relationship of ultrasound and
112 Water Security: Monograph

electromagnetic field on the acoustic and electrical characteristics of the fluid.


Further it allows the use of these simultaneous influences for improving new
methods of the research of liquid object's composition by increasing its sensitivity
and selectivity and performing an analysis in short time.

RESULTS OF RESEARCH
For research the following measuring system was designed: the glass of the test
model fluid; conductivity electrodes (which create an electromagnetic field); glass
plate with a microphone; ultrasound stand. The converter is connected to both RLC
meter and installation of generating and recording the acoustic signal. The novelty
of the experimental conditions is to combine the influence of ultrasound and
electromagnetic fields of different frequencies (50 Hz to 100000Gts) on liquid. In
these experiments the frequency of ultrasound is 2,6 MHz. Admittance was
measured before, during and after influence of ultrasound. Acoustic characteristics
were measured before, during and after influence of ultrasound and electromagnetic
field. Model fluids: salt of electrolytes: 1) sodium chloride and 2) copper sulfate
with the same concentration 1,203 g/L. In a glass of primary converter during two
separate studies of model liquid we pour the same volume – 10 ml (for fixing the
working area of the electrodes and a microphone). For observations without pointing
the temperature influence on the informative parameters its change was considered
as not significant (duration of the experiment is 2 sec). Observation is performed
using the results of measurements of equal accuracy (3-4 experiments) for fixing
the mistakes and the objectivity of the results.
Comparing the results for equally accurate measurements we showed that under
the influence of ultrasound and electromagnetic field on liquid (within certain
frequency intervals) an asymptotic approximation of the admittance values, which
improved by increasing the time of exposure to these fields, is observed. For us,
one of the working explanation of received fact is the special orientation of the
particles in the electromagnetic and acoustic fields, which is more ordered with time
impact. It was also found that temperature and ultrasound do not effect on the set
parameters of control. Such parameters are the coordinates of the intersection point
of plots obtained in studies of multicomponent fluids with variable concentration
of controlled substance (with the help of model solutions). But it found that these
coordinates may be established in experimental effecting of ultrasonic, that
simplifies the development of appropriate methodises.
Studies of the ultrasound effects on frequency dispersion of electrolyte
solutions immitance shown that ultrasound increases the value of both active and
reactive component and does not effect on the coordinates of qualitative point.
In addition, the effect of ultrasound had a residual effect, after the six minutes
of influence the source of ultrasound was switched off, i.e. graphic dependences
of eight-minute and ten-minute analyzing were obtained without its impact
fig. 1 (a) and (b).
Water Security: Monograph 113

Analysis of fig. 1 (a) and (b) leads to the conclusion that in the research the
proposed methods should consider this influential factor too.

Figure 1. Dependences of active (a) and reactive (b) component of the conductivity of the
electrolyte solution on frequencies by the effects of ultrasound in time
(from 2 to 10 minutes)

Under the influence of ultrasound and electric field on the liquid individual
graphic form of admittance does not change (that are inherent to a particular
composition) fig. 2 (a) and (b).
Comparing the results for equally accurate measurements it was found that under
the influence of ultrasound and electromagnetic field to a liquid (at known intervals
frequency) for admittance it is observed the asymptotic approximation, which
improved by increasing the exposure time of fields (fig. 3).
114 Water Security: Monograph

Figure 2. Dependences of active (a) and reactive (b) component of frequency


for copper sulfate
Water Security: Monograph 115

Figure 3. Dependences of active (a) and reactive (b) components of the conductivity on
the frequency of the electromagnetic field in different conditions:(21a-24a) – without the
influence of ultrasound; (21y-14y) – with the influence of ultrasound; (21y10-24y10) –
with 10-minutes ultrasound influence

For us, one of the working explanations of received fact is the special orientation
of the particles in the electromagnetic and acoustic fields, which is more ordered
with time impact.
As a result of experiments it was found that under the influence of ultrasound
importance of active and reactive component (for various periods of frequency
values (fig. 4) conductivity increases.
116 Water Security: Monograph

a)

b)
Figure 4. Dependences of active (a) and reactive (b) component of the conductivity of the
electrolyte solution on frequencies by the effect of ultrasound in time
(from 2 to 10 minutes)
Now we propose to compare the effect of temperature on admittance (fig. 5).
The motivation for this comparison is based on the individual essence of
ultrasound influence and temperature on the kinetic energy of particles – liquid
components. Usually the residual effect of increasing values admittance during
cooling of fluid is not observed.
It was also found that ultrasound and temperature have no effect on the set
parameters of control.
These parameters of control are the coordinates of control point of intersection
of graphic dependences obtained in studies of multicomponent fluids with varying
concentrations of controlled substances (through model solutions).
Water Security: Monograph 117

Experimental investigations have established that when using the impact of


ultrasound and electromagnetic fields of different frequencies from the spectral
dependences of the reactive component of frequency and conduction we can quickly
identify a substance in a liquid and to set a concentration, that is to perform
qualitative and quantitative analysis.

a)

b)
Figure 5. Experimental results of effects of temperature and composition on the active
(a) and reactive (b) components of model fluid conductivity
Fig. 6–8 shows dependencies of the values of the reactive component of the
conductivity and frequency of the electromagnetic field for water solutions of copper
sulfate, chlorine dioxide and sodium chloride. Ultrasound effects on the solutions
for 2 minutes.

Figure 6. Solution of copper sulfate with concentration 0,09 g/l under the action of
ultrasound (or electromagnetic field)
118 Water Security: Monograph

A method, that is proposed, works as follows.


For the sample liquid that falls into converter under the influence of ultrasound
and electromagnetic fields dependence of the reactive component of the
conductivity and frequency is measured. On obtained several dependencies
frequency is observed, in which the value of the reactive component is unchanged.
As a result of comparing the experimentally obtained atlases of dependencies (for
example, fig. 6–8) and the value of frequency intersection of the plots for
measurement objects in a multi-component fluid the presence of a controlled
substance (qualitative analysis) and the concentration by the value of the reactive
component (quantitative analysis) are set.
The temperature on informative parameters of control does not effect. A
composition of the solvent (matrix) does not significantly affect [13].

Figure 7. Solution of chlorine dioxide with concentration of 0.12 g/l under the action of
ultrasound (or electromagnetic field)

Figure 8. Solution of sodium chloride with concentration of 0.23 g/l under the action of
ultrasound (or electromagnetic field)
Water Security: Monograph 119

CONCLUSIONS
In the article an analysis of research of fluids by electro-optical methods based
on the principles of conductometric and potentiometric methods is presented.
As the result of analysis of the received experimental data and literature sources
the following conclusions are done:
by comparing the results for equally accurate measurements it was found that
under the action of ultrasound and electromagnetic field on liquid (within certain
frequency intervals) an additive effect on admittance and its asymptotic
approximation, which is improved by increasing the time of exposure of these fields,
was observed. For us, one of the working explanation of received fact is the special
orientation of the particles-components in the electromagnetic and acoustic fields,
which is more ordered with time impact.
It was also found that ultrasound and temperature do not effect on the set
parameters of control. These parameters are the coordinates of the intersection point
of graphic dependences obtained in studies of multicomponent fluids with varying
concentrations of a controlled substance (in studies of a large number of model
solutions). But it found that these coordinates may be established in experimental
effecting of ultrasonic, that simplifies the development of appropriate methodises.
As a result of researches of simultaneous effects of ultrasound and
electromagnetic fields of different frequencies, their additive effect to amplify the
informative signal was set.
The introduction of this method creates the conditions for the transition from
the laboratory conditions of control to the operational and allows us to solve the
problem of increasing the reliability of the control, to save material resources and
to ensure minimal impact on human health.

REFERENCES
1. Pokhodylo, Ye.V. (2012). Immittance Control of Quality: monograph, Lviv. (in ukr.)
2. Lure, Yu.Yu. (1973). Unified methods of analysis of water, Moscow: Chemistry.
(in rush.)
3. Krylovich, V.I. (1985). Ultrasonic frequency-phase research methods and non-
destructive testing. Pod. red. A.G. Shashkova, Minsk: Science and Technology.
4. Jakovlev, V.F., Kushlyk, R.V., Mykytenko, O.V., Kushlyk, R.R. (2009). Ultrasound
rapid method to control the presence of water and fuel in the oil fractions, Metody ta prylady
kontrolyu jakosti, 22, 33–36. (in ukr.)
5. Barwiez, A. (1989). Electronic measurement structure for ultrasonic analysis of
solution, IEEE Instrum. and Meas. Technol., Washington, 25–27 Apr., New-York, 139–140.
6. Patent Japan no. 62-35063. (1988). The ultrasonic method and apparatus for measuring
the concentrations of the solutions, Tarymo, K.K.
120 Water Security: Monograph

7. Patent Ukraine no. 33870A. (2001). Method of ultrasonic testing the chemical
composition of the environment and device for its implementation, Sochenko, P.S., Zelenkov,
O.A. and Zubchenko, О.М. (in ukr.)
8. Pohrebennyk, V.D. (2011). Operative measure of integrated parameters of water
environment and bottoms sediments: monografia, Lviv: SPOLOM. (in ukr.)
9. Pohrebennyk, V.D., Romanyuk, A.V. (2013). Computer measurement and information
systems for operational ecological monitoring of the aquatic environment: monografia, Lviv:
SPOLOM. (in ukr.)
10. Pokhodylo, Ye.V., Stoliarchuk, P. H. (2003). Methods of immittance control of quality,
Methods and Devices of Quality Control, 11, 105-108.
11. The Impedance Measurement Handbook. (2006). A Guide to Measurement
Technology and Techniques, Agilent Technologies, Inc. Printed in USA,
http://cp.literature.agilent.com/litweb/pdf/5950-3000.pdf
12. Hnedenkov, S.V., Synebriukhov, S.L. (2006). Impedance spectroscopy in the study
of charge transfer processes, Bulletin. Far Eastern Branch of Russian Academy of Sciences,
5, 6-16.
13. Mikhalieva, M.S. (2012). Development of normative and technical ensuring of
operational determination of characteristics of liquids to control waste water: abstract of
dissertation of Candidate of Engineering Science: 05.01.02, Lviv. (in ukr.)
14. Mikhalieva, M.S., Stoliarchuk, P.H., Boiko, T.H., Bubela, T.Z. (2008). Ways of
rationing improving of quality indicators of water environments, Eastern-European Journal
of Advanced Technologies, 2, 34-37. (in ukr.)
15. Mikhalieva, M.S. (2008). Problems of rationing of quality of water environments,
waste water, hardware and metrological maintenance of hydro-monitoring system, Measuring
Technology and Metrology, 68, 199-203.
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drinking water as food product of the number one, Interdepartmental Scientific and Technical
Collection “Measuring technology and metrology”, 71, 148-152.
17. Stolyarcuk, P., Yatsuk, V., Pokhodylo, Ye., Mikhalieva, M., Boyko, T.,
Basalkevych, O. (2010). Electric Sensors for Express-Method Checking of Liquid Quality
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18. Mikhalieva, M.S. (2010). Results of experimental studies of model water solutions
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Water Security: Monograph 121

ENVIRONMENTAL STATUS OF SURFACE WATER RESOURCES


IN MYKOLAIV REGION

Prof., Dr.Sc. Olena Mitryasova


Andrii Mats
Petro Mohyla Black Sea National University, eco-terra@ukr.net, Ukraine

ABSTRACT
Environmental quality assessment of surface water is the foundation for
establishing environmental standards of the quality of water for individual water
bodies. Environmental assessment is also the basis for the definition and
management of ecological risks posed by anthropogenic pressure on the
environment.
Based on data from the Ministry of Ecology and Natural Resources of Ukraine,
who conducted an assessment of the environmental status of surface water Mykolaiv
region, this research sought:
- to conduct a qualitative and quantitative assessment of the ecological status,
and
- to determine the environmental risk to surface water resources of the Mykolaiv
region.
Environmental indices and categories of water quality are calculated using the
functions of the software package MS Excel.
The data indicates that the predominant class (see Table 1) of water quality is
class III with numerous sites of class IV and V, that is, water in most rivers and
reservoirs of the Mykolaiv region are "satisfactory" to "unsatisfactory" in quality.
In general, the assessment of the status of water in terms of ecological risk coincides
with the assessment of environmental quality. Individual points manage to achieve
class II quality ("good"). Quite often water is "unsatisfactory" (class IV) quality (r.
Southern Bug in the city of Pervomaisk, and within Mykolaiv itself).
Keywords: surface water pollution, maximum allowable concentration,
environmental risk.
122 Water Security: Monograph

INTRODUCTION
Environmental problems pose a risk to human existence at all scales – from local
to global. The majority of these problems are in areas that are experiencing
significant anthropogenic pressure. Water is a natural resource and an integral part
of the existence of all living creatures on the planet. The problem of providing
humanity with pure water is currently highly relevant because the availability of
water resources in many areas is insufficient to provide for everyone, not only for
the future but also for the present. The percentage of water used by population and
in the industry is very limited. Indicators of the quality of the water are the
determinants in the assessment of the environmental situation [2].
The most promising method for identifying zones of high ecological risk is to
assess their current ecological status and anthropogenic load. It allows you to
determine the permissible anthropogenic pressure in order to maintain the balance
of the natural environment.
Environmental assessment of surface water quality is the basis for the setting of
environmental standards of water quality for individual water bodies, groups of
water bodies and river basins. It is also the basis for the definition and management
of ecological risk of anthropogenic impact on the environment.
For the Mykolaiv region, it is the very important problem of water resources
pollution from wastewater discharge, which is greatly influenced by the lack of both
centralized sanitation and quality cleaning of domestic and industrial effluents [9].
What is important is the monitoring of the waters in the direction of the state
national policy for improving the quality and efficiency of water resources
management; the need for scientific substantiation of protection measures; and to
develop further strategies for using water resources for ecological rehabilitation of
the rivers of the Southern Bug river basin [9].

METHODOLOGY OF RESEARCH
Risk analysis is the process of solving complex tasks of a predictive and
probabilistic nature, and requires consideration of a wide range of issues and the
undertaking of a comprehensive study and evaluation of the technical, economic,
managerial and social factors.
Risk analysis should answer three basic questions:
1. What could go wrong? (Hazard identification)
2. How often could this happen? (Frequency)
3. What are the consequences? (Impact assessment)
The main element of risk analysis is to identify hazards that can lead to negative
consequences. Expressed in the most general form, the process of risk analysis can
be presented as a series of sequential events:
- planning and organization of work;
- identification of hazards;
Water Security: Monograph 123

- risk assessment;
- analysis of the frequency;
- analysis of consequences;
- uncertainty analysis;
- development of recommendations on risk management.
Closely related to the process of risk analysis is risk assessment. Risk assessment
is the analysis of frequency and consequences and their combinations. In this case,
the criteria of acceptable risk and risk assessment can be expressed both qualitatively
and quantitatively.
When assessing the environmental risk of degradation of water bodies, the
following was taken into account:
– organoleptic properties of water;
– sanitary-toxicological properties of water;
– hydrobiological data.
The risk for water bodies was determined by the formulas 1–3 [1] and shown in
fig. 3.
R = - ln(P), (1)

– where , (2)

– where , (3)

– where Ci is the concentration of the pollutant substances (PS),


MPC (PS that do not exceed the MPC in the formula (3) is substituted);
N – is the total number of analyzed PS.
The total environmental risk of deterioration in the status of water bodies is
determined by the rule of multiplication of probabilities, where the multipliers are
not the values of the risk, and values characterizing the probability of its absence
(1 – Rn):
ER = 1 – (1 – R1) x (1 – R2) x ... x (1 – Rn), (4)
where ER is the total environmental risk of deterioration of water objects;
R1, ...Rn – environmental risk of each pollutant.
In the interpretation of the obtained values to the environmental risk, it is
proposed to use the following ranking scale (tabl.1).
124 Water Security: Monograph

Table 1
Dependence of surface water quality from the ecological risk

RESULTS OF RESEARCH
Objective: to conduct qualitative and quantitative assessment of the ecological
status, and to determine the environmental risk, of surface water resources of the
Mykolaiv region on the basis of the selection of appropriate techniques.
The formulated goal is realized in work by the following tasks:
• analysis and characterization of water resources of the Mykolaiv region on the
basis of literary sources;
• identify and evaluate water quality based on the available hydrochemical
information on water quality in the water bodies of the Mykolaiv region;
• based on an environmental assessment of water resources, the rationale of
appropriate conclusions and proposals.
The total area occupied by surface water objects of the Mykolaiv region is 150,5
thousand hectares, which is 6,1 % of its territory. In the area, there are 121 rivers,
beams and 26 lakes, 45 reservoirs, 1153 ponds, 7 swamps and estuaries. Water
resources in the region are very limited and depend mainly on inflows from other
regions.
The government has registered 47 water users that discharge wastewater into surface
water bodies. In the course of 2015, the total wastewater discharge amounted to
105,2 million m3, of which 24,3% (25,55 million m3) was contaminated wastewater [6].
Water Security: Monograph 125

Since 2010, the Mykolaiv region has not recorded discharges of wastewater
without treatment (emergency wastewater discharges). Large wastewater discharges
without any treatment were observed from 1995 to 2003. Discharges of
insufficiently treated wastewater are annually decreasing in comparison with 1990
when discharge was equal to 70,5 million m3 [3].
The total discharge of regulatory clean water without wastewater treatment in
2015 was 57,34 million m3.
The discharge of industrial effluent into surface water bodies is carried out in
particular by the energy companies and the engineering industry. In these discharges
include heat exchangers waters that the composition is classified as normatively
clean without treatment. The discharge of normatively clean, which don’t need
treatment in 2015 amounted to 51,98 million m3, which in comparison with the
corresponding volume of water discharged in 2014, more to 9,02 million or 17,4 %
[3].
The greatest discharge of normatively clean without treatment of wastewater in
the Mykolaiv region is made by South Ukraine Nuclear Power Plant which includes
Alexandrivka hydroelectric power station and Tashlyk pumped storage power plant.
The volume of discharge is 47, 4 % of the total volume of wastewater discharges in
the region, and is 39,76 million m3. Exceeding the established norms of wastewater
discharges is undertaken by enterprises and public utilities.
In the area of Mykolaiv city, «Mykolaivvodokanal» has over the last eight years
been the main polluter of local water resources. For example, in the last year, they
discharged 26, 23 million m3 of wastewater, of which 23,83 million m3 (91%) was
insufficiently treated [6].
The principle of quality management of the environment is currently expected
to ensure that maximum permissible concentrations (MPCs) of polluting substances
in natural components (air, water, soil), and physical factors (noise, vibration and
the like) are not exceeded. Therefore, according to conservation methodology, the
assessment of pollution of the environment is performed by comparing the actual
concentration of the contaminant with the published MPC. However, to the hygienic
standards is inherent in the anthropocentric approach to the assessment of the
environmental state, i.e., under safe conditions of living are not taken into account
peculiarities of functioning of the actual ecosystems [8].
Relevant is the need to develop more comprehensive criteria for assessing the
quality of the environment.
According to the Water Code of Ukraine [10] assessment of water quality is based
on regulations of environmental safety of water use and environmental standards of
water quality of water bodies. At present time there are many of methods of
evaluation and classification of water quality, but none of them has wide applications
in water management practices because they do not account for the integral indexes
quality of water, i.e. the total influence of hydrochemical and other data.
126 Water Security: Monograph

On the basis of «Methods of environmental quality assessment of surface waters


by corresponding categories» (Romanenko, V. D., Ghkynky, V. M., Oksiyuk, O. P.
[7]), we developed a more complete and more accessible methodology that includes
the definition of environmental assessment of surface water quality and ecological
risk for the water bodies.
Ecological quality classification of surface waters and estuaries of Ukraine is
built on the ecosystem principle. The necessary completeness and objectivity of the
characteristics of surface water quality are achieved by a fairly wide set of indicators
that reflect the characteristics of abiotic and biotic components of aquatic
ecosystems [4]. A set of indicators of ecological quality classification of surface
waters includes both general and specific indicators. The overall performance, which
includes indices of the salt composition, trophy-saprobes waters (ecological and
health), which characterize usual water ecosystems, the ingredients, the
concentration of which can vary under the influence of economic activity. Specific
indicators characterize the level of polluting substances of toxic and radiation action.
Assessment of the water quality and ecological status of surface waters in the
Mykolaiv region (namely, Southern Bug, Ingul, Mertvovod) was performed in the
period from 1990 to 2015 for 13 sites for which data are available. Figure 1 shows the
13 sampling points. T.1 – Syniucha, above Pervomaysk; T.2 – Southern Bug,
Pervomaysk; T.3 – Southern Bug, Oleksyivka; T.4 – Tashlyk reservoir, the discharge
in Southern Bug; T.5 – Southern Bug, Оleksandrivka; T.6 – Southern Bug, Voznesensk;
T.7 – Southern Bug, Kovalivka; T.8. – Mertvovod, Voznesensk; T.9 – Ingul,
Rozanivka; T.10 – Ingul, Sofiyivka; T.11. – Ingul, Pryvilne; T.12. – Ingul, Mykolaiv,
pedestrian bridge; T.13 – Bug estuary, Mykolaiv, water intake of power plants.

Figure 1. Point sampling for assessment of ecological status of surface water resources in
Mykolaiv region
Water Security: Monograph 127

The study is based on selected organoleptic and sanitary-toxicological indices


of water quality, because they most fully reflect the ecological condition of the water
resources. Assessment of the ecological status, according to the organoleptic
properties of water, provides for evaluation of colour, hydrogen index and suspended
solids. Sanitary-toxicology data includes the assessment of COD, nitrates (NO3-),
total hardness, chlorides, sulphates, phosphates, ferrum and manganese [5].
Environmental assessment of water quality is performed according to systematic
observations on the basis of ecological quality classification of the surface waters
of Ukraine, covering a set of hydrophysical and hydrochemical indices which reflect
the characteristics of the components of aquatic ecosystems [9]. Source data
according to the «Methodology for environmental quality assessment of surface
waters by corresponding categories» were grouped into three blocks: the salt
composition of water (ІА); ecological sanitation indicators (ІВ); and specific
substances of toxic action (ІС). The calculations are performed within each of the
three blocks and defined by the integral (ІЕ) of environmental characteristics.

DISCUSSION
Environmental indices and categories of water quality are calculated using the
functions of the software package MS Excel and are the average values at each point
of the selection in fig. 2.

Figure 2. Environmental indices of water quality

Assessment of environmental water quality has a significant drawback – it does


not take into account the maximum of the maximum permissible concentration of
polluting substances.
128 Water Security: Monograph

The risk for a water facility is determined by the formula (1) [1] and shown in
fig. 3.
The data indicates that most water bodies fall into class III with significant areas
of class IV and V, that is, water in most rivers and reservoirs of the Mykolaiv region
are «satisfactory» and «unsatisfactory», implying minor to moderate contamination.
In general, the assessment of the status of water in terms of ecological risk
coincides with the assessment of environmental quality. Individual points achieve
class II quality («good») though most do not. Quite often water is «unsatisfactory»
(class IV) quality (r. Southern Bug in the city of Pervomaisk, and within Mykolaiv
city itself). Class V is «dangerous», separately found almost for each item of
observations, due to excessive concentrations as a result of the anthropogenic impact
on water objects.
This situation indicates that water bodies in the study area have somewhat
disturbed the ecological parameters of their ecological status is estimated as
«ecological regression».
The ecological status of the water resources of the region indicate deterioration
of the chemical trophic-aerobiological criteria of pollution, namely: pH, suspended
solids, color, COD, sulfates and chlorides. Indicators related to radionuclide
contamination are «average».

Figure 3. Ecological risk of deterioration of water objects

CONCLUSIONS
The main problem of the Mykolaiv area remains the problem of polluted water
resources in an unsatisfactory condition, namely, the deterioration of sewage
treatment facilities. This issue can be solved if wastewater treatment plants in
Water Security: Monograph 129

Mykolaiv, Pervomaisk and Voznesensk were expanded and reconstructed, along


with the sewage systems in these cities; a system of local sewage treatment plants
and disinfection stations were introduced to expand and reconstruct the rainwater
drains in the city of Mykolaiv; modern technologies were implemented for
alternative, treated high quality drinking water; and a system of forest vegetation
filter for wastewater treatment was created, from the territories of settlements,
industrial facilities, farms, landfills and fields of filtration.
The study showed that water bodies in the area are unsuitable for drinking water
supply, the ecological condition is characterized by ecological imbalance due to
excess concentrations of pH, suspended solids, color, COD, total hardness, sulfates,
chlorides, total iron and manganese.
All this requires nature conservation agencies and industrial organizations
involved in the field of drinking water, taking appropriate measures to improve the
situation. The main purpose of this research must be to contribute to a reduction of
concentrations of priority pollutants, particularly, suspended solids, total iron,
manganese, sulphates and chlorides. Of course, these measures will not completely
solve the problem of the lack of quality drinking water supply in the area, but it will
be a decisive step forward towards the improvement of the ecological situation in
the region.
To ensure the balanced use and protection of waters, it is appropriate to develop
integrated monitoring programs for the protection and use of potable water supply
sources and quality of drinking water in the region; to implement low-water and
water-saving technologies, modern means of treatment and disinfection of water;
and to strengthen management support of entrepreneurial efforts to create a domestic
water purification equipment.
Due to the limited reserves of fresh underground water and the impact on the
ecosystem of water bodies by the discharge of insufficiently treated waste water
from plants and utilities, high-quality drinking water supply is a priority for the
region.

ACKNOWLEDGEMENTS
We would thank Southern-Bug Basin Management of Water Resources and
Management of Environment and Natural Resources Mykolaiv Region State
Administration for time and space monitoring data.

REFERENCES

1. Alymov, V. T., & Tarasov, N. P. (2005). Technological risk: analysis and assessment.
М., Akademkniga, 118 p. (in rush.)
130 Water Security: Monograph

2. Cordoba, E. B., & Martinez, A. C., Ferrer E. V. (2010). Water quality indicators:
Comparison of a probabilistic index and a general quality index, The case of the
Confederacion Hidrogaafica del Jucar (Spain). Ecological Indicators, 10 (5), 1049-1054.
3. The dynamics of discharge of sewage in Mykolaiv region for 1990-2012. (2013).
Management of water resources in Mykolaiv region, Mykolaiv. The report. (in ukr.)
4. Klymenko, M. O., & Prishchepa, A. M., Voznyuk, N.M. (2006). Monitoring of the
environment: Tutorial, K. Alma Mater, 360 p. (in ukr.)
5. Reporting data on the state of the Southern Bug and its tributaries for the 1990-2014.
(2015) Management of water resources in Mykolaiv region. Mykolaiv. (in ukr.)
6. The regional report on the State of the environment in Mykolaiv region in 2014. (2015).
Department for environment and natural resources of the Mykolaiv regional State
administration, Mykolaiv, 204 p. (in ukr.)
7. Romanenko, V. D., & Ghkynky, V. M., Oksiyuk, O. P. (1998). The methodology of
ecological assessment of surface water quality according to the relevant category. By Ed.
Shevchuk, Y. K., Symbol-T, 28 p. (in ukr.)
8. Rybalova, О.V. (2011). A comprehensive approach to the determination of the small
rivers pools environmental state, The problems of environmental protection and technological
safety. Col. of science works, Ukraine, UkrSRI, Vol. XXXIII, Kharkiv, 88-97. (in ukr.)
9. Selivanova, A. M., & Mitryasova, O. P. (2013). Questions quality assessment of surface
water resources of Mykolaiv region. Regional environmental problems: scientific-
methodological and applied aspects of their solutions. Materials of the VI International
Scientific Conference of students, graduates and post-graduates. Odessa, OSEU, 252-255.
(in ukr.)
10. The water code of Ukraine: Law of Ukraine on June 6, 1995, № 213/95-UP [electronic
resource], The Verkhovna Rada of Ukraine. Last edited from 27.07.2013. Mode of access:
from http://zakon4.rada.gov.ua/laws/show/213/95-%D0%B2%D1%80
Water Security: Monograph 131

MULTISPECTRAL METHODS AND MEANS OF WATER POLLUTION


MONITORING BY USING MACROPHYTES FOR BIOINDICATION

Prof., Dr.Sc. Vasyl Petruk


Ass.Prof., PhD. Sergii Kvaternyuk
Ass. Olga Bondarchuk
Ass.Prof., PhD. Roman Petruk
Ass.Prof., PhD. Igor Vasilkovsky
Vinnytsia National Technical University, petrukvg@gmail.com, Ukraine

ABSTRACT
Bioindication of aquatic environment quality can be carried out using of
macrophytes, including duckweed (Lemna minor). The study recorded the following
morphological deviation from the norm duckweed plants under the influence of
pollutant: chlorosis, yellowing, wilting leaves, specific reaction. Vital staining
method was used for the cell damage studying. The multispectral television
monitoring method was used to automate the calculation of bioindicators
parameters, which task is to obtain a series of images using a CCD-camera at the
characteristic wavelengths of pigments. This method gives the possibility to
compute for each pixel of image the distance in multispectral space that allows to
divide the image into three areas: free of duckweed water surface (A), the surface
occupied by duckweed without damage (B), as well as the surface occupied by
duckweed damaged as a result of exposure to toxic compounds in water (C). To
evaluate the water quality in the river Snivoda following steps were performed: a
sample in a petri dish containing 150-200 plants were divided by species. After
sampling, it was estimated the number of plants of each species, the total number
of shields, the number of shields with damages. These damages include black and
white spots (necrosis), yellowing (chlorosis). After staining by safranin, we obtained
a number of digital images using a CCD camera at characteristic wavelengths.
Improved methods for multispectral measuring television monitoring of water
bodies’ ecological condition by macrophyte groups characteristics were developed
to assess the complex human impact on the environment. Integral assessment of
water pollution is based on research products of higher aquatic plants and their
communities by optical methods.
Keywords: multispectral, monitoring, bioindication, macrophytes
132 Water Security: Monograph

INTRODUCTION
Increased human influence on natural ecosystems leads to the needed
development of appropriate methods and means of water bodies’ ecological state
control and evaluation. Modern methods of environmental control should enable
the possibility to take quick decisions in case of ecological disbalance as a result of
certain enterprises-pollutants activity.
Relevance of the research work is determined by necessity of integrated
operational control parameters that characterize ecosystems natural water bodies.
For the evaluation of natural aquatic ecosystems it is need to collect information
about its chemical, biological, hydrological and physical parameters simultaneously
over a large area of water bodies (rivers or lakes). Control of water pollution by
industrial enterprises requires periodic measurement of all parameters, resulting in
significant costs for the laboratory studies, and the transportation of samples
determined the site. As a result, the subjects of water bodies’ state monitoring have
limited financial resources; control of natural ecological state of water bodies is
performed infrequently. During the measurement interval the real state of water
pollution is not controlled, it leads to increasing of water pollution and significant
deterioration of the ecological state. Excessive human influence leads to an
imbalance of ecosystems of water bodies, causing the critical state of many of them
and the loss of the ability of self-healing.
Significant deterioration of natural water bodies’ quality is an extremely serious
problem for the world in general and Ukraine particularly. As a result of human
activity, industrial, municipal or agricultural runoff enters the water body and
accumulates large variety of pollutants: heavy metals, nutrients, compounds of
organic origin (pesticides, herbicides, surfactants, oil products, etc.).
Theoretical and practical aspects of remote control integrated optical parameters
characterizing the ecosystems of natural water bodies are enough developed. This
already known methods and means of water pollution parameters integrated optical
control do not provide high probability of control, making it difficult to assess the
extent of water pollution. Therefore, to increase the probability of control is
necessary to improve methods, development of special water quality control
methods that would more accurately determine the integral parameters
characterizing the state of water ecosystems, and, accordingly, that allows to assess
human impact on aquatic ecosystems and predict the quality of surface water.
Water quality – is a characteristic which determines the suitability of water for
a specific method of its use in human life and economic activity. Water quality
assessment is the primary goal of any measures in the field of water management,
environmental management and implementation of environmental action in bodies
of water (The Directive 2000). Biological methods for assessment of water quality
have a large number of advantages over chemical and physical as well as the
grouping of living organisms show all changes to the aquatic environment, while
responding to a variety of complex natural and anthropogenic factors, including
Water Security: Monograph 133

pollutants. Assessment of water pollution degree on its population goal is to quickly


determine its sanitary condition, trophic status, the degree of contamination.
Bioindication – is a method of evaluating water quality and ecological status of the
water body composition indicator species or groups of structural indicators. In other
words, bioindication – is a way to assess the anthropogenic load on the reaction to
it of living organisms and their communities.
The use of certain types of macrophytes, as well as groups like the ecological
status of water bodies’ indicators, looks very attractive because they are convenient
for the object of observation. Even a brief investigation of the vegetation of the
reservoir allows you to make a rapid assessment of its environmental condition.
Bioindication by using macrophytes has certain limitations. First of all, it is only
possible when the sum certain set of external conditions are favorable for the
development of aquatic plants, namely in the pond: a moderate flow rate, the
availability of sheltered and shallow water waves suitable sediments, water clarity
and others. Good results for bioindication macrophytes can be obtained in the case
of study of the lakes or ponds vegetation with good shallow area, or small and
medium size rivers characterized by slow flow and shallow depths. Bioindication
for macrophytes is limited in time and is only possible in the vegetation period (Arsan
et al. 2006). Selecting a group of organisms for which bioindication will be held, it
should be remembered that water macrophytes characterized by a certain permanency
by the reaction to short-term changes in environmental conditions. The most rapidly
in aquatic ecosystems respond to changes in the environment of phytoplankton
groups, which are subject to a short life cycle. The grouping of macrophytes consist
mainly of perennial plants, it is stable, more adaptable to changes in the environment,
so they are less responsive to short-term transformation of the state of the water body.

METHODOLOGY OF RESEARCH
Integral control of contamination can be realized by means of bioindication
for the various water organisms. In particular, the "One in interdepartmental
leadership of the organization and implementation of state monitoring of waters"
bioassay is listed as a compulsory method of analysis of surface water toxicity.
The use of macrophytes as indicators of ecological state of water bodies is
extremely attractive, because they – visible and convenient facility for observation
(Heine et al. 1993). The Directive 2000/60 / EC (The Directive 2000) macrophytes
considered as an important "element of quality for classification of ecological status"
natural and "ecological potential" heavily modified and artificial water bodies. Thus,
for rivers and lakes as "biological quality element" recommended higher aquatic
plants. In the study of heavily modified and artificial water bodies recommended
"biological quality elements" for these types of characteristics of natural surface
water, which like most studied reservoirs.
Water macrophytes – is a collective group that combines large plants (visible to
the naked eye) belonging to different taxonomic groups and whose existence is closely
134 Water Security: Monograph

linked to water. These include some algae, mosses, ferns, club mosses, horsetails and
flowering plants that can grow in conditions of water environment or excess moisture
(live directly in the water and in the coastal zone) (Arsan et al. 2006).
Macrophytes susceptible to change many parameters and characteristics of the
water body, the hydrological regime trophic status, stage of development, specific
water chemistry and so on. Even preliminary examination vegetation reservoir
allows you to make rapid assessment of ecological condition (Heine et al. 1993).
In the papers (Bishop et al. 1989, Dunbabin et al. 1992, Healy et al. 2002,
Blankenberg et al. 2003, Lloyd et al. 2001) described ecological and biological
methods of wastewater treatment by using higher aquatic vegetation.
Higher aquatic plants as part of the food chain hydra biocenosis act as one of the
main components autotrophic unit, providing energy flow and transformation of
mineral components in the original organic matter. Macrophytes affect the
physicochemical parameters of hydro, determine the dynamics of overgrowing waters
enriched qualitative and quantitative composition of heterotrophic block, create
favorable conditions for the reproduction of fish fauna. A special role is played by
higher aquatic plants in the self-cleaning hydro, ensuring implementation of a number
of functions (filtration, absorption, storage, sanitary, oxidation, detoxification) which
made extracting a significant amount of nutrients and accumulation of pollutants
contributing to the formation of water quality indicators. Thickets of higher aquatic
vegetation can serve as a barrier to entering aquatic ecosystems from surface runoff
trace contaminants. Regarding surface waters Ukraine of different types, the team of
experts of the Institute of hydrobiology of NASU quantitative nine bit classification
of development of macrophytes was worked out on three indexes (biomass, the
percentage of overgrowth of water bodies in general, projective cover in the bush).
It can be used as a basis by criteria for evaluating the extent and nature of
macrophytes (Arsan et al. 2006). In the study of the nature and distribution of
vegetation overgrowth necessary cartographic materials or plans water body
(preferably with deep marks), based on which you can hold it and make a
preliminary zoning scheme overgrowth, taking into account, above all,
morphometric characteristics. A detailed study of vegetation carried out in separate
areas directly to water bodies. You can use of aerial photographs in the growing
season. With aero methods can also determine the nature of the placement of air-
water vegetation and vegetation with floating leaves in the water area of water
bodies, to determine the shape and structure of the undergrowth, calculate the area
of overgrowth. Species composition, nature of the distribution structure of plant
communities, indicators of biomass and area overgrown waters are markers that
visually show the ecological state of water bodies. Observation of the dynamics of
qualitative and quantitative indicators of aquatic vegetation can determine the
direction of succession aquatic ecosystems (Heine et al. 1993).
As one of the methods that can quickly get information about the disruption of the
functioning of aquatic ecosystems, using analysis of optical parameters in the visible
Water Security: Monograph 135

and near infrared spectrum using remote control devices. This method of monitoring
of water bodies that are directly associated with aerospace means, to date, not found
wide application in the monitoring system of groundwater freshwater ecosystems of
rivers and lakes. Benefits aerospace method is to obtain information relative simplicity,
efficiency of collection simultaneously over large areas. The disadvantage is that the
information obtained by this method in general is difficult to interpret as the traditional
parameters of hydrobiology and hydrochemistry. This is due to the low resolution and
low accuracy of these parameters using optical methods aerospace remote control as
obtained with the optical signal slightly change with changes of water present in the
compounds. The main focus of research of groundwater by remote optical sensing is
studying the process of eutrophication of water bodies.
This is due to the low resolution and low accuracy of these parameters using
optical methods aerospace remote control as obtained with the optical signal slightly
change with changes of water present in the compounds. In optical remote sensing
upward flux of water environment may not directly investigated in the water and
close to the object, so maybe not ignore signal distortion atmosphere between the
object and the radiation detector. Direct optical task is to calculate coefficients of
brightness spectra for water bodies, knowing primary hydro optical characteristics
and concentrations of pollutants. The inverse problem is to move from the spectral
characteristics of radiation to rising concentrations of pollutants, as there is a
relationship between the measured spectral characteristics and integrated hydro
biological and hydro chemical parameters of the object. In the first phase of the rising
emission spectra obtained and compare them with the concentrations of pollutants
received traditional chemical and biological methods (reference information). In the
second phase determine the concentration of pollutants on spectral characteristics
(Petruk et al. 2012, Petruk et al. 2015, Martsenyuk et al. 2016). Scheme of the
processing results of remote optical monitoring of water bodies shown in fig. 1.

Figure 1. Block diagram of the processing results of remote optical monitoring


of water bodies
Get spectral image large natural water bodies and assess the state of its ecosystem
might, for example, satellite data, but spend the interpretation of these data is possible
only with the involvement of the supporting information. Certainly one of the most
subjective factors in studies using remote spectrometry are the way you present
results. This concerns, first of all, the method of decoding multispectral satellite
images since the final deciphered data may carry a significant inaccuracies due to
geometric and atmospheric correction. A more accurate picture is a spectrometer,
136 Water Security: Monograph

made from the aircraft, which flies at low altitude. Research carried out at
characteristic wavelengths algal pigments, especially chlorophyll a. In this case, the
most informative in the visible spectrum are violet-blue region 420..460 nm and red
region 660..700 nm. With distance range the polarimetric control water pollution
compared to the brightness of radiation emanating from the water environment in
these regions of the spectrum. This significant contribution to the visible and near
infrared wavelengths in the measuring signal allows atmospheric aerosols and signal
mirror reflection from a surface water body that generally reaches 90% of the
luminance signal. Contribution, which allows atmospheric aerosols can be removed
as systematic error. The residue will make 1..2% determined by methodological error
associated with inaccurate mathematical model of atmospheric aerosol. The
component of the luminance signal formed by reflection from a surface water body,
carries information about contamination of its surface. First of all, pollution fuel and
lubricants that are appropriate to investigate in the range of about 400 nm. As
powerful sources of radiation for this range using pulsed ruby lasers with doubled
frequency (350 nm) or yttrium-aluminum garnet with neodymium working on the
third harmonic (355 nm). The depth at which the remote control range the
polarimetric water pollution is limited attenuation of optical radiation in layer
thickness , where - damping, k - the imaginary part of the
complex index of refraction. Such a surface layer of the water environment generates
95 % of the radiation. Thus, in pure water, which belongs to the same class as at a
wavelength of 700 nm can study layer thickness to 8,7 m. Changing the wavelength
in the visible and near infrared allows you to control pollution at near-surface layer
required thickness.
Due to the need for consistent correction spectrometric at multiple levels
necessary to use a three-tier control system where information is obtained on the
upper level (spacecraft), specifies the information obtained similar equipment from
a plane or helicopter, which flies at low altitude. The latter, in this experiment is
going to sync with traditional hydro chemical and hydro biological data (fig. 2).
Further investigation of water pollution range the colorimetric methods associated
with the use of television controls and the formation of the most informative images
by selecting optimal spectral and polarization filters. This matrix compares water
body images obtained from multiple spectral bands at different positions of rotation
angle polarizing filter. Correlation sets range the polarimetric image processing
allows high accuracy to locate the place of water pollution and assess its value.
Analysis of the viability of the species and their resistance to stress factors can be
carried out at different levels: cellular, organismal, population. These morphological
responses of organisms on technological factors are included in the practice of
environmental quality assessment. In studies of are recorded morphological deviations
from the norm macrophytes under the influence of the pollutant:
1. Chlorosis;
2. Yellowing;
3. Withering of leaves;
Water Security: Monograph 137

4. Specific reactions.
The biological parameters are change of leaf color (Heine et al. 1993):
1. Yellowing;
2. Browning;
3. The loss of color intensity.
For the diagnosis of cell damage are using vital staining method. It is based on
staining with safranin stain of dead cells. Living cells severely limit penetration into
organic substances, and placed in a dye solution almost not colored. The dye
penetrates dead cells freely, so they can be immediately detected and taken into
account. Safranin used as a dye, as it has the ability to paint well cell walls.
Phytotoxicity – the ability of toxic substances present in soil, water, air, etc. have
poisonous (toxic) effects on the plant. The number of filled cells as a percentage of
the total leaf area index of phytotoxicity was adopted.

Figure 2. Block diagram of the optical monitoring of the ecological state of water bodies
on the characteristics macrophytes
RESULTS OF RESEARCH
To automate the calculation of parameters used bioindicators method
multispectral television monitoring, which is to obtain a series of images using a
CCD-camera at the characteristic wavelengths of pigments [4]. For each pixel in
the image is computed distance in the multi spectral space that allows to divide the
138 Water Security: Monograph

image into three areas: free of duckweed water surface (A), the surface occupied
by duckweed without damage (B), as well as the surface occupied by duckweed
damaged as a result of exposure to toxic compounds in water (C). Further
calculation C / B ratio allows us to estimate toxicity index and water quality (fig.3.).

Figure 3. Application of the method of vital staining to study the degree of phytotoxicity
environment by the example of duckweed (Lemna minor): a) "a mesh" staining associated
with the penetration of the dye apoplastichnym way; b) "a mesh" staining, combined with
damage at the edges of the sheet, as well as partial damage to young leaf; c) the
combination of "mesh" with the local coloring dye penetration
To evaluate the water quality in the river Snivoda (sample selection was carried
out on the river of the Zhigalovka village) following steps were performed: a sample
in a petri dish containing 150-200 plants were divided by type. After sampling, it
was estimated the number of plants of each species, the total number of shields
(parent and child), the number of shields with damages. To damage include black
and white spots (necrosis), and yellowing (chlorosis). The next step was to prepare
the slide preparation leaves little duckweed (Lemna minor). According to the results
it can be concluded that the water quality correspondence estimation "3" by 5-point
scale in accordance to the characteristics of duckweed. Also determined toxicity
index was equal to 17% according to the percent of plants stained. Images duckweed
(Lemna minor) at different wavelengths is shown in fig. 4.

660 nm 520 nm 450 nm

870 nm 590 nm
Figure 4. Images of duckweed (Lemna minor) at different wavelengths
Water Security: Monograph 139

DISCUSSION
It is noteworthy that at the wavelengths corresponding to the absorption of
chlorophyll a, intact plant duckweed appear dark (450 nm, 660 nm). In contrast to
other wavelengths (520 nm, 870 nm) intact plants and duckweed plants with
chlorosis did not differ.
Duckweed was first used for testing water contamination by pesticides. The
correct assessment use indicators’ parameters: growth rate, length and number of
roots, leaf area, the reaction of photosynthesis and other physiological and
morphological characteristics. Currently, by using species of the family Lemna
minor bioassays conducted on the toxicity of heavy metals, petroleum products,
radionuclides and other pollutants (Arsan et al. 2006).
During the 3-day experiment was determined Lemna minor response to various
types of contaminants (Petruk et al. 2016). For the experiment were prepared 0,5M
solution NaI, NaCl, Na2SO4, NH4NO3, NaH2PO4, NaNO2. Biological testing
results after the first 24 hours, 48 hours and 72 hours of the experiment are presented
in table 1.
Table 1
Biological testing results by using duckweed (Lemna minor)

CONCLUSION
Macrophytes are the sensitive indicators of the hydrological and thermal regimes
of reservoirs, characterizing their trophic status, especially the chemistry and other
140 Water Security: Monograph

properties. Certain types of macrophytes appear effective bioindicators of changes


in the environment.
According to the results it can be concluded that the water quality
correspondence estimation "3" by 5-point scale in accordance to the characteristics
of duckweed. Also determined toxicity index was equal to 17% according to the
percent of plants stained.
Based on these results, we can conclude that the most profound effect on
duckweed (Lemna minor) include the following materials: NaI (some individuals
are reduced in size, darkening all the plants has increased), NH4NO3 (All the leaves
are separated and become a little lighter), NaH2PO4 (duckweed greatly reduced in
size and became lighter) and Na2SO4 (some individuals are reduced in size,
darkening all the plants has increased). The smallest impact on the duckweed had
the following substances: NaCl, NaNO2. Also suggests that duckweed (Lemna
minor) can comfortably compared with low contamination exist chlorides and
nitrites, but strongly react to the presence of water iodides, nitrates, sulfates,
orthophosphates. Also, it can be concluded that the duckweed (Lemna minor)
bioindicators sufficiently sensitive, since changes were noticeable after 24 hours of
the experiment.
Improved multi multispectral optical systems allow continuous control
monitoring of the ecological state of water bodies that can reduce the cost of
monitoring environmental studies with an increase in their environmental
performance. Multi optical inspection system can increase accuracy by adjusting
several stages of measurement results on the test sites, which received reference
hydro biological and hydro chemical information.

REFERENCES
1. The Directive 2000/60/EP of the European Parliament and of the Council establishing
a framework for community action in the fi eld of water policy. OJL, 327.
2. Arsan, O.M., Davydov, O.A., Dyachenko, T.M. et al. (2006). Methods of
hydroecological studies of surface water. National Academy of Sciences of Ukraine. Institute
of Hydrobiology. – Kiev: Logos.
3. Heine, S., Sytnik, K. (1993). Macrophytes - indicators of environmental changes. Kiev:
Naukova Dumka.
4. Dunbabin, J. S., Bowner, K. H. (1992) Potential use of constructen wetlands for
treatment of industrial wasterwaters containing mettals. Sci. Total. Environ., 2, 56–60.
5. Healy, M., Cawley, A.M. (2002) Nutrient Processing Capacity of a Constructed
Wetland in Western Ireland. Journal of Environmental Quality, 31, 1739–1747.
6. Bishop, P. L., Eighmy, T. T. (1989) Aguatic wastewater treatment using Elodea nuttallii.
Water Pollut. Contr. Fed., 61(5). 641–663.
Water Security: Monograph 141

7. Blankenberg, A. B., Braskerud, B. C. (2003) “LIERDAMMEN” – a wetland testfield


in Norway. Retention of nutrients, pesticides and sediments from a agriculture runoff. Diffuse
Pollution Conference, 114–125.
8. Lloyd, S. D, Fletcher, T. D, Wong, T. H. F., Wootton, R. M. (2001) Assessment of
Pollutant Removal Performance in a Biofiltration System. Preliminary Results, 2nd South
Pacific Stormwater Conference; Rain the Forgotten Resource. 20–30.
9. Petruk, R. V., Pohrebennyk, V. D., Kvaternyuk, S. М. et al. (2016). Multispectral
television monitoring of contamination of water objects by using macrophyte-based
bioindication. In: 16th International Multidisciplinary Scientific GeoConference, Book 5,
Vol. 2, 597-602.
10. Petruk, V., Kvaternyuk, S., Kozachuk, A. et al. (2015). Multispectral televisional
measuring control of the ecological state of waterbodies on the characteristics macrophytes.
Proc. SPIE 9816, doi:10.1117/12.2229343.
11. Petruk, V., Kvaternyuk, S., Yasynska, V. et al. (2015).The method of multispectral
image processing of phytoplankton processing for environmental control of water pollution.
Proc. SPIE 9816, doi:10.1117/12.2229202.
12. Petruk, V. G., Kvanternyuk, S. M., Denysiuk, Y. M. et al. (2012).The spectral
polarimetric control of phytoplankton in photobioreactor of the wastewater treatment . Proc.
SPIE 8698, doi:10.1117/12.2019736.
13. Martsenyuk, V., Petruk, V. G., Kvaternyuk, S. M. et al. (2016).Multispectral control
of water bodies for biological diversity with the index of phytoplankton. In: 16th International
Conference on Control, Automation and Systems (ICCAS 2016), 988-993.
142 Water Security: Monograph

IMPROVING THE ACCURACY OF OPERATIVE CONTROL


PARAMETERS OF WATER ENVIRONMENT

Prof., Dr.Sc. Volodymyr Pohrebennyk 1, 2


1Lviv Polytechnic National University Lviv, e-mail: vpohreb@gmail.com,
Ukraine
2 State Higher Technical School in Nowy Sacz, Poland

ABSTRACT
Operational environmental monitoring of water environment provides real-time
monitoring parameters for the individual objects in the area of the accident and the
areas of environmental emergencies.
Known today controls allow you to measure these integral parameters such as
conductivity, salinity, pH, Eh of, temperature, dissolved oxygen, turbidity, biological
oxygen demand, chemical oxygen demand. However, they have low efficiency, the
temporal and spatial resolution, accuracy, sensitivity and reliability. The aim is to
develop new methods and means of improving the accuracy of the computer systems
of ecological monitoring the aquatic environment.
Mathematical model of the control system and acoustic method for measuring
the total concentration of impurities in the water it is proposed.
New methods and means to improve the accuracy of the computer system to
сontrol the ecological status of water environment are reported. These are based on
interference-free measurement of the time parameters of multiple reflected
ultrasonic signals in the two reference and study environments.
A computer system that made it possible to improve the accuracy and reduce
measurement time, quickly send text information and conduct dialogue with
technology CDMA.
Keywords: computer systems; operational environmental control; integral
parameters; water environment.
Water Security: Monograph 143

INTRODUCTION
Knowledge of the ecological state of the seas, rivers and lakes need to develop
national and international programs of environmental restoration and economic
cooperation. Hence – the need for environmental monitoring environment.
Environmental monitoring and control pollution of surface waters occupy an
important place in the overall health and nature are important components of the
solution to the problem of sustainable development. Operational (crisis) monitoring
the aquatic environment provides monitoring in real time the parameters of
individual objects in the areas of accidents and environmental emergency zones,
and making decisions on their elimination.
Examples of emergencies are floods and the destruction of dams. Significant
increase in water level. On rivers this happens due to the increased flow of water,
melting snow, rain, etc. In lakes or reservoirs – as a result of excess water intake
source.
Causes of flood:
– Wind, which "catches up" water;
– Shortness of leakage due to technical faults in artificial reservoirs or natural
dams formed on the mountain rivers due to landslides (after the earthquake);
– Breakthrough in plain water rate, which is below the water level. Such floods
usually occur because of a rush of dams or river bed changes;
– Cutting Carpathian forests.
Classification of flooding depending on the scale and repeatability:
– low (small) – flooding observed on lowland rivers. Flooded less than 10% of
agricultural land. Almost do not break the rhythm of life. The frequency of 5-10
years;
– high – cause appreciable losses sustained cover relatively large plots of river
valleys, flood approximately 10-15% of agricultural land. Significantly violate
economic and household structure of the population. Leads to a partial evacuation.
The frequency of 20-25 years;
– outstanding – causing extensive damage, including targets for river basins.
Floods approximately 50-70% of agricultural land, some localities. Paralyzing
economic activity and dramatically violate household structure of the population.
Leads to the need for a mass evacuation of the population and wealth of the flood
zone and protection of important objects. The frequency of 50-100 years;
– catastrophic – causing huge material damage and lead to loss of life, covering
vast areas within one or several river systems. Flooded more than 70% of
agricultural land, many ettlements, industrial plants and utilities. Completely
paralyzed economic and industrial activity, temporarily changing lifestyles of
people. Frequency of 100 to 200 years.
144 Water Security: Monograph

Risk undermining the dam:


– in the world – 35,000 large dams;
– intermediate risk the destruction of dams – 2,10-4;
– in Ukraine - limit regulatory risk – 5,10-4;
– in the Carpathians flood runoff coefficient – 0,9–0,95;
– air – 20 mm/h, the density of the river network – 1 km/km2, significant
deviations – 0,02-0,008;
– low absorptive capacity of rocks;
– major damage – floods rapid formation of supply of 10%.
Flooding in Central Europe in 2010 and flood in Ukraine. Over the past 15 years
in Ukraine significant flooding that led to emergency situations, observed in 1995,
1997, 1998, 2001, 2008 and the flood of 2010. Thus, the average losses from floods
in 1995-1998 amounted to 899.3 million USD, 1999-2007 – over 1500 million in
2008 - about 6000 million. Every third year characterized by high water levels show
a low-flow period.
The main characteristics of flooding is a sharp increase in water level and an
abrupt change in its concentration. Therefore, timely detection of floods essential
rapid automatic analyzers that must have high speed and probability. However, at
present the theoretical and practical aspects of automated operational control of
aquatic ecosystems developed enough.
A feature-scale process systems, the minimum spatial and temporal parameters
of which are limited to 0,1 m and 1. This puts very high demands on the measurement
of time (less than 0,05), and the minimum size sensors (less than 0,1 m).
Now is increasing the accuracy of surgical integral method for determining the
total content of impurities in the water.
The purpose – to develop new methods of environmental control integrated
operational parameters of water pollution.
Modern methods of evaluating the concentration of impurities can be divided
into indirect, where the desired value are based on its dependence on the measured
values and direct when it obtained directly from experimental data. According to
different classification methods of measuring the concentration of contaminants in
water can be divided into chemical, conductometric, acoustic, optical and
comprehensive [1–3].
Chemical methods require sampling is sufficiently accurate, but unsuitable for
rapid control.
Conductometric method is to measure the electrical conductivity of solutions.
They are highly sensitive, easy to implement, but mixed conductivity depends on
Water Security: Monograph 145

the concentration and also strongly influenced by temperature (conductivity


increases by about 2% with an increase in temperature 1 ºC).
The principle of the method is the optical absorption, scattering, refraction and
polarization of light and infrared rays, use luminescence phenomena and spectral
analysis. Their total lack – high sensitivity optical parameters to environmental
changes.
Complex methods involve measuring pressure, temperature and velocity of
sound in the solution. Then, using one of approximate formulas calculate the
concentration of contaminants in the water.
Consider existing ultrasonic methods and tools to measure water pollution. Their
advantages are: no distortion researched field, a significant amount and variety of
received information. The express, as the possibility of probing and distance
measurements. With these methods can determine the flow rate and its components,
the speed of sound, swirl component of flow rate, level, depth, concentration of
salts, alkalis, acids, alcohols, molten metals, pH, organic matter, cost, density,
coefficient of sound absorption, kinematic, shear and bulk viscosity, compressibility
and thermal expansion, temperature, explore the internal waves, turbulence
phenomena on the surface. But the accuracy affects temperature.
Presently known systems can measure such integral parameters – conductivity,
salinity, pH, Eh, temperature, dissolved oxygen, turbidity, biological oxygen
demand, chemical oxygen demand [4–7].
However, they have low efficiency, the temporal and spatial resolution, accuracy,
sensitivity and reliability. All this necessitates the development of automated
systems with improved metrological characteristics.
The purpose – to develop new methods of environmental control integrated
operational parameters of water pollution.
The object of study – the process control parameters of integrated water
pollution.
Description of the problem to be solved – the development of new methods and
efficiency of integrated environmental monitoring parameters contamination of
aquatic ecosystems.
The tasks that need to be addressed to achieve the goal:
– development of mathematical models of aquatic environments and
experimental methods for integrated environmental control parameters of pollution;
– development and improvement of tools and automated test systems for
integrated environmental control parameters of water pollution;
– development of specialized software for the implementation of specific control
methods integral parameters of water pollution.
146 Water Security: Monograph

There is a system of environmental monitoring of water with low efficiency,


temporal and spatial resolution, accuracy, sensitivity and reliability. This necessitates
the development of automated systems with improved metrological characteristics
to determine the operational parameters of the aquatic environment.

METHODOLOGY OF RESEARCH
Mathematical model of the control system
Based information model ultrasound emission sensing placed signal C(t)
channels in many medium and obtaining the sum of many reflected signals MRS
S(t). Among active internal noise N(t) and external disturbance F(t). Adopted MRS
converted into digital code Ni, then work out, resulting code Ni ascertain belonging
to a given class Oi aquatic environment.
MRS equation presented in the form
, (1)

where A – the operator that describes the acoustic emission signal; W – operator
that describes the influence of propagation conditions in the environment; T –
operator diagnostic facility; Cj (f; x, y, z, t) – the operator of the electrical signal
sensing; f – frequency signal; x, y, z – spatial coordinates; t – time; j – number of
channel radiation; і – the reflected signal; Sij, Nij, Fij – respectively, the echo-
operators, internal and external noise.
Operators A, W, T described expressions
; (2)
; (3)
T = F3(RS), (4)
where F1, F2, F3 – pursuant operators that convert electrical signals into acoustic
describe propagation in the medium and characterize reflection signal; S – salinity;
T – temperature; P – pressure; R – statement describing the radiation pattern of the
sensor; v, rot v – respectively, the density, speed and rotational component of
flow rate; – damping factor of the acoustic signal in the medium and nonlinear
acoustic parameter; RS – reflection coefficient of sound.
Introduce the characteristics of the echo signal and through and
denote the characteristic parameters of the aquatic environment and
reflectors:
, (5)
where WS – operator that describes the influence of propagation conditions in
the environment and is the operator of solving direct problems.
Water Security: Monograph 147

Define the parameters of the water environment , given the characteristics


of the echo signals in the presence of internal and external
noise:
; (6)
where operators WSW–1 and WST–1 is inversely relative to carrier WS.
Inverse problems in acoustic remote sensing allow you to determine various
characteristics of objects of study: water pollution, reflectors and diffusers.

RESULTS OF RESEARCH
An acoustic method for measuring the total concentration of impurities in the water
As a result, a systematic review of operational environmental monitoring of
integrated water environment parameters methods found that the most promising
and at the same time the least developed is the ultrasonic method. Its advantages
are: the practical absence of inertia, lack of distortion of the test field, a significant
amount and variety of information received, rapidity, the possibility of a probe, and
remote measurements [8-12]. However, the result and the accuracy of measurements
influenced by temperature.
In [13] introduced a new integrated informative parameter – the total
concentration of the impurities СΣ in water, which makes it possible to quickly
identify pollution and their level. It consists of concentrations of inorganic the
impurities СNOR and the concentration of organic the impurities СORG:
СΣ = СNOR + СORG. (7)
The connection of the total concentration of the impurities СΣ in water with
ultrasonic vibration parameters with the influence of the basic thermodynamic
parameters: temperature, pressure, speed of sound. On this basis, we developed a
new invariant ultrasound parameter measurement method СΣ in water, which is
based on measurement of the time parameters of multiply reflected ultrasonic
signals in the two reference and study environments, which reduced an order of
magnitude concentration measurement error.
The peculiarity of the measurement parameter СΣ is the use of multiple reflected
signals, which allows to determine the total concentration of the impurities in water,
in real time, irrespective of the water temperature and pressure, as well as an analysis
of organic and inorganic liquids.
The total concentration of impurities in the water is determined by the formula

, (8)

where a – the slope of the calibration curve – the relationship between the values
148 Water Security: Monograph

of the quantities at the exit and during the measuring instruments, drawn up in a
table, graph or formula; Тv, Т1 and Т2 – the time intervals of the signals, respectively,
in the sample liquid in the first and second reference channels; С1, С2 –
concentration reference liquids.
In (3) the concentration СΣ It is a function only of time slots Тv, Т1 and Т2 and
concentration С1 and С2, known with high accuracy.
Analysis of errors
The dependence of the methodical error δС determining the total concentration
of impurities in an aqueous medium СΣ by the standard deviation σTv:

(9)

where ΔT1, ΔT2, ΔTv – absolute error of measurement of time intervals,


respectively, Т1, Т2, Тv.
Constructed (fig. 1) according to δС from σTv at different values α at С1 = 0,1
and С2 = 0,9. At α < - 3 and ΔT1 = ΔT2 = ΔTv = ΔT =10-4 сoncentration measuring
error does not exceed 1% in the range σTv from 0,2 to 1. With the reduction of the
measurement error of time intervals ΔT =10-5 сoncentration measuring error does
not exceed (fig. 2) does not exceed 0,12 % in the range σTv from 0,2 to 1. In the
calculation of these dependences it is assumed that the measurement error of С1and
С2 have concentrations of the order of 10-5 and therefore can be neglected.
Consequently, the errors of the assay (the expression (9), fig. 1 and fig. 2) that the
use of an additional measurement channel and reference fluids can reduce the
measurement error on the order of the total concentration of the impurities in the water.

Figure 1. Dependence of the methodical error of measurement of the total concentration


of impurities in the water environment δС by the standard deviation of the time interval
σTv with an absolute error of measurement of time intervals ΔТ = 1∙10-4
Water Security: Monograph 149

Figure 2. Dependence of the methodical error of measurement of the total concentration


of impurities in the water environment δС by the standard deviation of the time interval
σTv with an absolute error of measurement of time intervals ΔТ = 1∙10-5
A [14] a new method of error-correcting timing measurements of ultrasonic
pulse signals on the basis of a two-channel integrating the scanning conversion,
which can improve the noise immunity of an order and accuracy. Based on this
method of measurement device antinoise synthesized timing of ultrasonic signals,
which has high speed and accuracy.
Features of this method is the ability to measure time shifts between signals or
triangular shapes with the top Keystone short duration and sequencing of incoming
signals. The proposed method, data processing algorithm in terms of sensing
disturbances and device are characterized by high noise immunity, high speed by
providing opportunities to work with single signals, in addition, the measured time
shift is independent of amplitude signals. These algorithms are the basis for the
synthesis processor.
Evaluation time offset by the expression:

(10)

(11)

(12)

(13)
(14)
respectively, H1, H2, H3 – the phase space integral state signal; mx – the average
value of the parameter.
Based on the proposed algorithms synthesized processor evaluation time offset.
150 Water Security: Monograph

A device for converting time offset between the two signals (fig. 3) includes
channels 1 and 2 conversion, power control 3 and logic element "inequivalent" 4.
Channels 1 and 2 have peak detectors 5 and 6, switches 7 and 8, large-scale inverters
9 and 10, switches 11 and 12, integrators 13 and 14, electronic keys 15 and 16,
comparators 17 and 18, the device 19 determining the sequence of incoming signals,
indicator 20, block 21 delays, n-channel conversion unit 22, n-channel conversion
unit 23 in the code. The peak detector inputs 5 and 6 is the input device.
Time shift between the two signals given by

, (15)

where:
tx – time shift between signals; tiv – output time interval after each cycle delay;
K – coefficient scale transformation; tz – the length of time one cycle delay; m –
number of cycles delay.

Figure 3. Functional diagram of the device measuring the timing of ultrasonic signals
Water Security: Monograph 151

The computer system of environmental control


A system of ecological control of water environment in which the use of
ultrasound, conductometric and potentiometric methods. As an algorithmic method
of increasing the accuracy of determination of the total concentration of the
impurities in the water provided a method of exemplary signals that are distributed
in an aqueous medium, to reduce bias.
Heuristically synthesis of the block diagram of the system of ecological
monitoring of water environment, which contains measurement modules integrated,
selective and hydro-physical parameters. Each of the modules comprises measuring
channels, which consist of sensors and measuring secondary ADC.
Ultrasonic channel system is implemented as a three-channel device, in which
two channels are exemplary solutions of water corresponding to the beginning and
end of the measurement range, for example, 0,1 C and 0,9S, and the third – liquid
analyzed.
Block diagram of the ultrasonic channel is shown in fig. 4.

Figure 4. Block diagram of the acoustic channel: 1, 1′, 1′′ – reflectors; 2, 2′, 2′′ – acoustic
sensors; 3, 3′, 3′′– switches; 4 – unit of time measurement intervals; 5′ и 5′′ – blocks of
time measurement sound propagation in the reference media; 6 – sensing generator; 7 –
crystal oscillator; 8, 8′, 8′′ – counters; 9 – microcontroller

It can be divided into three parts: I - primary converters (sensors); II - time meter
intervals; III - the microcontroller. It works as follows. The pulses from the sampling
frequency f0 trigger generator 6. Sensing electric pulse through switches 3, 3', 3'' is
supplied to the inverse acoustic transducers 2, 2' and 2'', which convert it into
acoustic pulses. These pulses are distributed in the test media and the two on the
152 Water Security: Monograph

basis of the reference L, repeatedly reflected from the reflector 1, 1', 1'' and the
inverse of acoustic transducers 2, 2' and 2 '', gradually fading amplitude.
Equation (8) is realized by the built-in micro-computer, which come timeslots
Тv, Т1 and Т2, and the parameters , С1 and С2 administered manually. The
microcontroller calculates the total concentration СΣ and it takes a value in digital
form on a personal computer.
On the basis of theoretical and experimental studies designed computer system
of environmental control that will automate the process parameter measurements
aquatic environment, improve the measurement accuracy, quickly transmit
information and to conduct a dialogue with the text remote participants via
telecommunication CDMA technology (fig. 5).

Figure 5. Block diagram of a computer system environmental control: R1 - R3 –


reflectors; AT1 - AT3 – acoustic transducers; SU1 - SU3 – switching units; ATS1 - ATS3 –
analyzers time shifts; PPN – polarity voltage converter
Water Security: Monograph 153

The basis of the computer system is a single-chip 8-bit microcontroller PIC16F876


firm Microchip Technology Incorporated. He has programmed program memory
protection, energy saving mode, the clock frequency – 200 MHz high-speed
architecture, all commands are executed in one cycle, the low voltage programming
mode, the supply voltage of 9-12 V, a power saving mode, the consumption of 1 mA.
The microcontroller operates at a given program. To coordinate the work of
microcontroller with computer use FT232BM chip, which is a USB to serial converter.
To create a data radio channel used by 3G modem PCMCIA EVDO Air Card
SIERRA 580. This portable device allows you to organize a mobile high-speed
Internet, transfer rates up to 3,1 Mbit / c.
The main advantages of the environmental control system: rapid control of on-
site investigations; Simultaneous analysis of the temperature, conductivity, pH, the
total concentration of impurities, concentration of chlorine, nitrates, and other
ingredients; a microcontroller, a PC, a developed measuring periphery which
receives and uses the a priori information. The computer system can process, if
necessary, the sensor signals of tens, while in turn one bus will handle data signals
of several sensors.
The main characteristics of the system: the water temperature measuring range
– 0 ... 50 °C with an accuracy of 0,5 °C; conductivity measuring range - 0,03 ...
19,9 mS / cm (error – 5%); measuring the total concentration range the impurities
in water – 0,1 to 40 g / kg (accuracy 0,1 g / kg), the automatic temperature
compensation of the measurement, the software update control frequency; Power
Rechargeable Battery voltage of 9-12 V and AC 220 V; consumption of I / O ports
of the current – 25 mA, power consumption of 1,5-2 Watts.
Developed methods and software tools pilot study an aqueous environment
parameters based on the C ++ language, which are advantages of high performance
and memory usage, for ease of access to the HTTP protocol data, real-time operation,
the simultaneous processing of measurement results and data transmission on a given
address, which is important in detecting and preventing man-made disasters.

CONCLUSIONS
Operative environmental monitoring of water parameters provides live control
for individual objects in the areas of accidents and zones of ecological emergency.
The aim is to develop methods and means to improve the accuracy of computer
information-measuring systems for operational environmental control of the water.
The new integrated information parameter is introduced such as the total impurities’
concentration in the water that makes it possible to quickly detect the presence and
level of contamination. A new methodology of the operational monitoring of water is
elaborate. The methodology is the use of linear and nonlinear effects of acoustic waves
interaction with the environment. Options of acoustic method operative determine the
total impurities’ concentration in the water is offered. The advantage of the method is
154 Water Security: Monograph

a possibility of determining regardless of water temperature in real time. It is shown


that the sensitivity of the method for determining water salinity using nonlinear acoustic
parameter is almost 20 times higher than that for the method, which is based on the
phenomenon of linear acoustics.
A computer system that made it possible to improve the accuracy and reduce
measurement time, quickly send text information and conduct dialogue with
technology CDMA.

REFERENCES
1. Zori, А.А., Korneev, V.D. and Khlamov, N.G. (2000). Methods, tools, measurement and
control system parameters aquatic environments. Donetsk: DonTU. (in ukr.)
2. Lomnitska, Ja.F., Vasylechko, V.O. and Chykhriy, S.I. (2011). Structure and chemical
control of environmental objects, Lviv: New Svit. (in ukr.)
3. Mokin, V.B., Mokin, B.І., Kostrov, М.М., Volokhova, А.І. et all. (2009). Automated
system of eco inspection Ukraine state pollution and emissions, discharges and waste
"EcoInspector." Part I. Subsystem "Emissions", Vinnitsa: UNIVERSYM–VINNITSA. (in ukr.)
4. Grimes, C.A., Dickey, E.C., and Pishko, M.V. (2006). Encyclopedia of Sensors /
American Scientific Publishers, Stevenson Ranch, Calif.
5. Gründler, P. (2007). Chemical Sensors: An Introduction for Scientists and Engineers.
Berlin: Springer-Verlag.
6. Lieberzeit, P.A. and Dickert, F.L. (2007). Sensor technology and its application in
environmental analysis / Anal. Bioanal. Chem., 387, 237–247.
7. Wanekaya, A.K., Chen, W., and Mulchandani, A. Recent biosensing developments in
environmental security. J. Environ. Monit., 2008. 10, 703–712.
8. Krylovich, V.I. (1985). Ultrasonic frequency-phase research methods and non-destructive
testing. Pod. red. A.G. Shashkova.[Ulrazvykovye chastotno-fazovye metody issledovaniya i
nerazrychayuschego kontrolya], Minsk: Science and Technology.
9. Jakovlev, V.F., Kushlyk, R.V., Mykytenko, O.V., Kushlyk, R.R. (2009). Ultrasound rapid
method to control the presence of water and fuel in the oil fractions [Uktrazvukovyy ekspres-
metod kontrolyu nayavnosti vodu i palyvnykh frakcii v motornykh olyvakh. Metody ta prylady
kontrolyu jakosti, 22, 33–36. (in ukr.)
10. Barwiez, A. (1989). Electronic measurement structure for ultrasonic analysis of solution.
IEEE Instrum. and Meas. Technol., Washington, 25–27 Apr., , New-York, 139–140.
11. Patent Japan no. 62-35063. (1988). The ultrasonic method and apparatus for measuring
the concentrations of the solutions, Tarymo, K.K.
12. Patent Ukraine no. 33870A. (2001). Method of ultrasonic testing the chemical
composition of the environment and device for its implementation, Sochenko, P.S.,
Zelenkov, O.A. and Zubchenko, О.М. (in ukr.)
13. Pohrebennyk, V.D. (2011). Operative measure of integrated parameters of water
environment and bottoms sediments: monografia, Lviv: SPOLOM. (in ukr.)
14. Patent Ukraine no 112031. (2016). Method of transformation time offset between the
two signals and device for its implementation, Pohrebennyk, V.D., Politylo, R.V. (in ukr.)
Water Security: Monograph 155

EVALUATION OF IMPACT OF MINING AND CHEMICAL


ENTERPRISE ON ECOLOGICAL STATE OF THE WATER
ENVIRONMENT

Prof., Dr.Sc. Volodymyr Pohrebennyk1


Mas. Elvira Dzhumelia2
1
Lviv Polytechnic National University, e-mail: vpohreb@gmail.com, Ukraine
2
Lviv Polytechnic National University, e-mail: elviradzhumelia@gmail.com,
Ukraine

ABSTRACT
As a result long-term production of sulfur in the territory of Rozdil State Mining
and Chemical Enterprise «Sirka» emerged the unpredictable technological
phenomena associated with changes in the hydrological situation that threaten with
ecological disaster.
The purpose of this work is to evaluate the ecological state of water bodies and
the impact technogenic wastes on the water quality in the territory Rozdil State
Mining and Chemical Enterprise (SMCE) «Sirka».
The Enterprise is included in a list of the top 100 companies for causing
environmental pollution. In the Rozdil State Mining and Chemical Enterprise
«Sirka» are water objects – lakes, formed from of sulfuric pits: Hlyboke, Seredne,
Kysle; channels. It was established that in the water present heavy metals (zinc,
cadmium, manganese, lead, copper, chromium, iron). There are exceeding norms
of maximum permissible concentrations of biological oxygen demand, chemical
oxygen demand, hardness, mineralization phosphate, ammonium and etc.
Pollution of water occurs because of reasons:
– reservoirs were formed in place of sulfuric pits where are some wastes of the
former activity;
– modifier such as «MG», which is made from neutralized tars and maleic acid
anhydride;
– large wastes of phosphogypsum, which are located near the lake Kysle.
All water bodies flowing into the river Dniester and their negative state can
threaten international importance.
156 Water Security: Monograph

The paper analyzes the hydrochemical parameters of water bodies territory of


Rozdil State Mining and Chemical Enterprise «Sirka».
Exceeding of MPC was discovered by many hydrochemical parameters: COD,
pH, sulphates, mineralization, dry residue, iron, cadmium, manganese, chromium,
hardness, etc.
Keywords: water pollution, mining and chemical enterprise, tars,
phosphogypsum, limestone quarry.

INTRODUCTION
Every production of is a sequence of three basic operations: preparation of raw
materials, production (chemical transformations) and the selection of target
products. This sequence is a common technological system. Not always existing
technologies allow full use of valuable raw ingredients, this leading to the
transformation of a part of waste production and emissions that cause pollution of
the atmosphere, hydrosphere and lithosphere (fig. 1) [1].
The main consumer of water and the biggest source of wasted water in
industrialized countries is industry. Industrial effluents in the rivers by volume are
in 3 times higher than municipal. Water performs various functions, such as the raw
material, heater and cooling in technological processes, in addition, it transports,
sorts and washes various materials. Water also removes wastes at all stages of
production. As much cheaper to throw away different wastes production cycles than
to remake them and recycle, with the industrial effluents are discharged the huge
variety of organic and inorganic substances. Due to the growing amount of industrial
wastes is disturbed ecological balance of many lakes and rivers [2].

Figure 1. The scheme of pollutions


Water Security: Monograph 157

Formation of the water environment in the sulfurous water bodies is occurred


under the mixing of atmospheric precipitation, surface, soil and groundwater, under
chemical interaction of water from the flooded quarry sediments and various
biochemical processes. In the formation of the water environment in the sulfurous
water bodies are distinguished three periods:
1) Flooding quarry excavation. At this time are the intensive mixing of
atmospheric water, surface and groundwater. Flooding is finished at conditions of
achieving project mark and the water masses begin to flow in watercourses. In 2012
completely were filled lakes Chyste, Seredne and Hlyboke. Creation of lakes helps
to restore independent flow into river Dniester.
2) Transformation of water masses. Tributaries of groundwater are decreased
and gradually stabilized. Ponds become poorly flowing and there is adaptation of
aquatic organisms to water environment. The shore line, shallow water areas and
vertical thermal, hydrochemical and biochemical stratification of water are formed.
The period of transformation is from 5 to 20 years;
3) Stabilization of water environment. This period is completed with adaptation
hydrocoles to the environment. Finally are formed shallow and deep part of the
reservoirs. At the depth of 10 m into the water sunlight penetrates and macrophytes
develop that enriches water environment by oxygen and assimilates by dissolved
nutrients, cleans water from phosphorus, potassium, nitrogen and sulfur. In its turn,
in the deep parts of water bodies are decomposed dead organic parts and is released
hydrogen sulfide, ammonia and carbon acid. The intensity of the hydrogen sulfide
formation depends on the amount of organic matter and eventually will grow.
Sulfurous reservoirs currently have not reached stable hydroecological indicators.
Most of the sulfur water bodies are at the stage of the transformation of water
masses, when their stratification occurs. With this is highlighted the upper oxygen-
rich and intensely repositionable layer (epilimnion), transition layer with sharp
changes in basic hydroecological indicators (metalimnion) and deep layer of poorly
repositionable constant hydroecological indicators (hipolimnion) [3; 4].
After long-term mining of sulfur in the territory Rozdil State Mining and
Chemical Enterprise «Sirka» was emerged unpredictable technological phenomena
associated with changes in the hydrological situation that threatens ecological
disaster in the region. Sulphurous quarry conditionally is divided into: south, central
and north. The first two are filled by internal dumps and on the territory was built
factory of the complex fertilizers and phosphogypsum storage. On the figure 2 there
is map of Rozdil State Mining and Chemical Enterprise «Sirka», where:
1. The factory of the production of ammonia.
2. Place dump of hundreds tons of tars in the building of chemical water
treatment in 2002.
3. The factory of the complex fertilizer. Departments of sulfuric, nitric,
phosphoric acids. Department of NPK fertilizer.
158 Water Security: Monograph

4. The factory of the complex fertilizers. Current department (former department


high-modulus cryolite).
5. The territories of sulphate departments.
6. Industrial Park (is projected).
7. The territory of direct sulfur production.
8. The liquid sulfurous storage.
9. The lumpy sulphurous storage.
10. The territory, which was washed away the dispersed ground sulfur.
11. «Energia – Novyi Rozdil» Ltd, CHP, wastewater treatment of the plant and
the city.
12. The territories of auxiliary stations and storage premises for service of Rozdil
state mining and chemical enterprise «Sirka».
13. The territory of the plant of building materials and the old auto base.
14. The territory of mine equipment repair stations, motor transport department,
the former small construction companies.
Only in the central was remained excavation with volume of 1,2 mln m3, which
is filled with acidic water that flow from the dump phosphogypsum.
North Quarry is divided into three parts. In the west lies the lake Chyste, this
was formed in a secluded part of quarry. Absolute mark water in the lake is 270 m;
the depth of the lake is 17 m. It is powered by atmospheric precipitation and sources
which flow at high west coast. In periods of rain water from the lake flows into the
river Kolodnytsya.
The lake Seredne is the largest area. Here contains 10.6 mln m3 of thin fractions
of sulfuric ore tailings. The thickness of the layer of wastes is 33 m. Then the recess
was filled out of recycled water and precipitation, the lake was formed by depth to
16 m. The volume of water is 9,9 mln m3, the absolute mark water is approximately
270,5 m, and the area is 93,5 hectares. To improve the situation on the lake, it is
necessary to lower the water level to 265 m to reduce the depth of the lake to
7-10 m. With such depth sunlight reaches the bottom of the reservoirs and at the
bottom actively develops algae that serve as food for fish.
Eastern part of the quarry was flooded to the 253 m mark, it was formed the
lake Hlyboke. The catchment area of lake is 280 hectares, area is 82 hectares. Its
name suggests a greater depth that reaches 40 meters. The banks of lake are steep
and precipitous, so it dangerous for swimming. Only on the small areas can
artificially create shallow water.
Water Security: Monograph 159

Figure 2. The territory of Rozdil State Mining and Chemical Enterprise «Sirka»

The inflow of atmospheric precipitation in the area of water intake is an average


of 1 mln m3/year. From the upper lakes in the lake will come another 1 mln m3/year
of water. The average annual leakage of lake is 2 mln m3/year. Flooding of the lake
Hlyboke was completed in 2010.
The purpose of this work is to evaluate the ecological state of water bodies and
the impact technogenic wastes on the water quality in the territory Rozdil State
Mining and Chemical Enterprise (SMCE) «Sirka».

METHODOLOGY OF RESEARCH
All water bodies belonging to the area of industrial fishing and flowing into the
river Dniester. In the territory of Rozdil SMCE «Sirka» in 2013 were selected
samples of water in five places in the bodies of water that flowing into the river
Dniester (Fig. 3) and were analyzed by different parameters:
160 Water Security: Monograph

1 – channel (lake Hlyboke – r. Dniester, near tars);


2 – channel (lake Hlyboke – r. Dniester), 30 m after the merger r. Sirchanka and
canal, discharge in the r. Dniester;
3 – channel drainage rainwater (Eastern Channel), the discharge in the r. Dniester;
4 – r. Dniester, 200 m below the two discharge of channels from Rozdil SMCE
«Sirka»;
5 – r. Dniester, village Berezyna, higher discharges of Rozdil SMCE «Sirka» [5].

Figure 3. Satellite image territory of sampling

RESULTS OF RESEARCH
Maximum permissible concentration of pH in water for fishery use should be
within 6,5–8,5. Fig. 4 shows the pH in the sampling points. In the channel drainage
rainwater pH is 4,07, which is below normal MPC and indicates the acidic
environment [6].
Water Security: Monograph 161

Figure 4. The pH of water in sampling points


Biochemical oxygen demand (BOD) is a measure of pollution, characterized by
the amount of oxygen (mg), which is in a period of time when it spend at oxidation
reservoirs pollutants as contained in a unit volume (usually 1 liter) at 20°C. In
practice often is determined BOD for 5 days (BOD5), but can be determined BOD2,
BOD3, BOD10 and others. As a rule, during 5 days under normal conditions occurs
oxidation ~ 70% easy oxidation organic substances; almost complete oxidation
(BODcompl or BOD20) is reached within 20 days. Was established that the more
water contains organic substances, the more they need oxygen for oxidation, i.e.
the higher BOD. The presence of substances that inhibit biochemical processes
reduces it. Natural waters have not high rates of BOD (usually BOD5 not exceed
0,5-2 mg/l). Higher rates of BOD indicate pollution of natural waters. For
centralized sources of drinking water and water bodies that are used in fishery BSK5
should not exceed 3 mg/l (National Standards of Ukraine 17.1.3.03-77). As shown
in fig. 5.there is a significant excess of BOD.

Figure 5. Biological oxygen demand


162 Water Security: Monograph

The concentration of sulphate in natural water varies widely. In river waters and
the waters of freshwater lakes sulfate content often varies from 5-10 to 60 mg/dm3,
the rain waters – from 1 to 10 mg/dm3. In groundwater sulphate content often
reaches much higher values. MPC sulfate is 100 mg/dm3 [7].
Increase of sulphate impairs the organoleptic properties of water and provides
physiological effects on the human body.
So, let`s do comparative description of the content of sulfate in samples (fig. 6),
with the maximum permissible concentrations of substances in water. Indicators of
tests №1, №3 and №5 meet the standards water bodies of fisheries and categories
of domestic water use. Significant excess was found in samples №2 and №4, they
do not meet the limits.

Figure 6. The content of sulfates in the water

Under alkalinity of natural or treated water is understood capacity to some of


their components bind equivalent amount of strong acids. The alkalinity in the water
was caused by presence anions of weak acids. Their sum is called the total alkalinity.
Alkalinity is determined the number of strong acid, which necessary to neutralize
1 dm3 of water. Alkalinity of most natural waters only determined calcium and
magnesium hydrocarbonate, the pH of the water does not exceed 8,3. Determination
of alkalinity useful during dosing chemicals needed for processing of water for the
purpose of water supply and the reagent processing of some sewage [8].
So, compare the data (fig. 7) of the total alkalinity in all samples.
Alkalinity is not among limited in value to water quality, but the State Sanitary
Rules and Norms of Ukraine recommends so-called indicators of physiological
usefulness of water, which includes the total alkalinity 0,5-6,5 mEq/dm3. The alkalinity
of water is an important indicator of many processes during water treatment, especially
for the treatment of coagulants and mitigate. Results of samples not exceed MPC.
Water Security: Monograph 163

Figure 7. Parameter of alkalinity in the sampling points


Distribution of nutrients (ammonium, nitrite ions) is shown in fig. 8-9. The
content of nitrate ions (table. 1) in water does not exceed the MCL.
Ammonium ion ( NH4+) appears in water due to the dissolution of ammonia in
it - this is a product of decomposition of organic nitrogen compounds. Concentration
in unpolluted surface waters is usually hundredths of mhN/dm³ and increased to
0,5 mhN/dm³. Ion is unstable, it rapidly is oxidized to nitrite and nitrate. Elevated
levels of ammonia indicates the anaerobic conditions of the chemical composition
of water and its poor quality [9].
MPC of ammonium in water for fishery use is 0,5 mg/dm³.
Number of ammonium channel drainage rain water exceeds the MPC in 49,2
times.MPC nitrite ions in the water for fishery use is 0,08 mg/dm³.Number of nitrite
ions exceeds MPC in r. Dniester higher discharges Rozdil SMCE «Sirka» and below
discharges of Rozdil SMCE «Sirka».

Figure 8. The content of ammonium in the water


164 Water Security: Monograph

Table 1
The measurement results hydrochemical parameters
at different points in sampling

Figure 9. The content of nitrite ions in water bodies


Water Security: Monograph 165

DISCUSSION
In Rozdil State Mining and Chemical Enterprise «Sirka» is:
– about 60 million tons of sulfur ore tailings;
– 3 045 400 tons of phosphogypsum;
– 1,5 million m3 acid water;
– 17,195 thousand tons modifier such as «MG», made from neutralized tar
residues and residues boiler anhydrite maleic acid;
– thousands of tons of sulfur sub-standard residues and other chemicals;
– thousands of hectares of land disturbed by mining works which are not used;
– ruins of buildings that will never be used for new productions and others.
Enterprise has not been working since 2001, since 2006 has been subordinating
the State Property Fund, it has been passed readjustment.
Pollution of water is due to many reasons.
The first reason is that at the industrial place of enterprise near the lake Hlyboke
(fig. 10) is stored modifier such as "MG", made of tar residues. It is known that
acidic tars (goudrons) are hazardous wastes which generated during petroleum
purification of concentrated sulfuric acid. State Enterprise «Spetsservis» rented to
the 2005 land in Rozdil State Mining and Chemical Enterprise «Sirka» where and
shipped more than 17 thousands tones of tars. However, there are only managed to
burn a few tons. Therefore rest in modifier allegedly was processed. The process
was a mixture of clay, earth, lime or charcoal.
Tars are not under cover and remain without appropriate conditions. Do not
conducted pumping of sewage from the area in accumulative storage capacity and
sewage contaminated with tars get deep into the lake, which is part of the recreation
area Dniester River Basin (fig. 11). Cars that temporary garbage dumps go on the
road, where sewages are spill of tar, polluting the city, which adversely affects the
ecological status and health. It is also established in the soil near tars are contained
heavy metals that exceed the MPC level and negatively impact on the environment.

Figure 10.
The Hlyboke lake
166 Water Security: Monograph

Figure 11.
Leakage of tars

Water pollution happens because at the lake Kysle is dump of phosphogypsum


(fig. 12). In soils are contained heavy metals and exceed MPC level. The lake
Kysle was formed in the residual excavation of central quarry. It is filled with
acid water due to leaching sulfuric, phosphoric, hidrofluorits acid from
phosphogypsum dump. In the rainy season the lake is full of water and it flows in
the surrounding area and the river Dniester. As a result, the water gradually diluted
rainfall [10; 11].

Figure 12.
The Kysle lake.
In the background
there is dump of
phosphogypsum

Also cause contamination of ponds is that reservoirs were formed in sulfur pits
sites, where are remained of some former activities. The most negative impact on
the geological environment is mining. Over the irrational use of geological
environment is is destroyed not only the environment but also related other
Water Security: Monograph 167

components of the biosphere, soil and plant cover, surface water, groundwater and
more. Thus, there are not only processes of destruction and contamination of the
environment, but it geochemical pollution. So, the chemical elements in the
thickness of the planet unevenly distributed. Living organisms have adapted to those
elements that are most common in the surface layers of the crust. However, human
activity picks up from the depths of the Earth's huge mass of endogenous minerals
that enriched rare for surface chemical elements – heavy metals, radionuclides, etc.,
even small concentrations which are hazardous to living organisms. Because the
extraction, enrichment and processing of mineral resources, the accumulation of
empty and waste production rocks is the concentration of these harmful elements
over large areas, leading to serious illness and even mass mortality of plants, animals
and people.
The main activity Rozdil SMCE «Sirka» is performance the of environmental
works according to the project «Liquidation of sulfuric pits and restore the
ecological balance and landscape in the area of Rozdil SMCE «Sirka» developed
by OJSC «Hirhimprom», which in 2003 passed a complex examination
Ukrinvestexpertise.
During 2014–2015 was carried out recultivation (reconstruction) affected mining
operations lands on area of 46.40 hectares in the zone of Rozdil State Mining and
Chemical Enterprise «Sirka». The area of enterprise is 1816,24 hectares. The total
estimated cost accordance with project is 6 758 384 UAH, the actual expenditure
of public fund are 500 thousands UAH. Due to lack of funding in the enterprise
there was done: cutting and uprooting of dense undergrowth and shrubs, raking his,
transportation bushes and stumps, burning with shaking shafts with dense bushes,
undergrowth and roots. There were done works of development, transport and soil
compaction.
To 2021 disturbed lands of Rozdil SMCE «Sirka» will be conservated, that are
occupied by quarry field, outside overburden dumps and tailings, ponds, settling tanks
with total area of 1640,1 hectares. During the period of conservation lands (2011–2021)
tasked to perform a full range of project support ecological balance, recultivation of
land and transfer them to local councils for their intended use [12–15].

CONCLUSIONS
It was established that Rozdil State Mining and Chemical Enterprise «Sirka» is
object of increased environmental hazard and environmental instability of territory.
On its territory are dumps of industrial wastes, which lead to disruption of the
ecological balance of the region.
In the Rozdil State Mining and Chemical Enterprise «Sirka» are water objects
– lakes, formed from of sulfuric pits: Hlyboke, Seredne, Kysle; channels. They all
fall into the river Dniester. Was discovered exceeding of MPC by many
hydrochemical parameters: COD, pH, sulphates, mineralization, dry residue, iron,
168 Water Security: Monograph

cadmium, manganese, chromium, hardness, etc. This pollution is due to the former
activities of Rozdil State Mining and Chemical Enterprise «Sirka».
It is necessary to carry out land reclamation in the territory of spent open pit
mining. It covers the whole complex of works aimed at restoring fertility and
national economic value of disturbed land. The main and common drawback of
existing research is inadequate funding and insufficient implementation of
systematic approach to scientific solving mining and environmental problems.

REFERENCES
1. Rybachok, V.M. (1997). Basic technologies and industrial ecology, Tutorial,K.: IZMN,
160. (in ukr.)
2. Lomnytska, Ya.F., Vasylechko, V.O., Chykhrii, S.I. (2011). Composition and chemical
control of environmental objects, Lviv: «Novyi Svit-2000», 589. (in ukr.)
3. Pliatsuk, L.D., Burla, О.А. (2008). The impact of of the technogenic objects in the
hydrosphere as a factor in environmental risk, Environmental safety,2, 40-43. (in ukr.)
4. Ivanov, Ye.А. (2000). Ecological landscape analysis of mining areas.Geographical
research in Ukraine at the turn of the millennium: Proceedings of the All-Ukrainian scientific
conference of students and graduate students, К.: VTS «Kyivskyjuniversytet», 17-18. (in
ukr.)
5. Pohrebennyk, V.D., Dzhumelia, E.A., Cygnar, М., Kohanek, А., Korostynska, О.
(2016). Environmental problems of technogenic reservoirs of Rozdil State Mining and
Chemical Enterprise «Sirka», The 15 International Scientific Conference "Natural Water
Resources of the Carpathian region”, Lviv, the 26-27of May, 2016, 6-10. (in ukr.)
6. Maximum permissible values of water quality for fisheries waters.The total list of
MPC and ESLE of harmful substances for fishery ponds water: [№ 12-04-11 current from
09-08-1990].(1990), К: Ministry of Fisheries of the USSR, 45. (in ukr.)
7. Water Quality Indicators, Germany, Access mode: http://www.gewaesser-
monitoring.de/en/?Water-Quality-Indicators.
8. Cordoba, E. B., Martinez, A. C., Ferrer, E. V. Water quality indicators: Comparison of
a probabilis¬tic index and a general quality index, The case of the Confederacion
Hidrogaafica del Jucar (Spain). Ecological Indicators, Spain, 2010, 10 (5), 1049-1054.
9. Shumov, S.М., Terlyk, Т.А., Vyshar, І.S. (2011). Hydrochemical information and
condition of surface water, Hydrology, hydrochemistry and hydroecology, 3 (24),106-125.
10. Rudko, G., Shkitsa, L. (2002). Ecological consequences of the activity of Western
Ukraine mining complexes. Rocznik AGH, Wiertnictwo Nafta Gaz”, Poland, T. 19/2, 415-
418.
11. Sun, J., Geng, C.L., Zhang, Z.T., Wang, X.T., (2012). Present situation of
comprehensive utilization technology of industrial solid waste. Materials Review, China,
2012, 11(2), 105-109.
Water Security: Monograph 169

12. Decree of the Head of Mykolaiv District Administration of January 25, 2012 № 44
city of Mykolaiv About the conservation lands of Rozdil SMCE "Sirka". Access mode:
http://mykolaiv-rda.lviv.ua/dokumenti-rda/rozporjadzhennja/item/2693-№-44-pro-
konservatsiyu-zemel-rozdilskogo-dghp-sirka.html
13. Pohrebennyk, V.D., Dzhumelia, E.A. Environmental Problems of Water Bodies in
Mining and Chemical Industries. Annual International Scientific and Technical Conference
"Environmental and technological safety. Protection of water and air basins. Waste
management ", Kharkiv, Ukraine, April 27-28, 2016, 145-147. (in ukr.)
14. Pohrebennyk, V.D., Dzhumelia, E.A. The Current State of Technogenic Water
Reservoirs in Lviv Region. The International Conference for Young Scientists "The current
status and environmental quality of individual regions," Odessa, Ukraine, the 1-3 of June.
2016, 88-92. (in ukr.)
15. Pohrebennyk, V.D., Dzhumelia, E.A. The Impact of Mining and Chemical Industries
on Water Resources. The III International Scientific and Practical Conference "State of natural
resources the prospects for their preservation and restoration", Drohobych, Ukraine, the 12-
14 of October, 2016, 42-44. (in ukr.)
170 Water Security: Monograph

IMPACT OF LVIV MUNICIPAL SOLID WASTE LANDFILL ON WATER


BODIES

Prof., Dr.Sc. Volodymyr Pohrebennyk1,2


Postgraduate Iryna Podolchak1
1
Lviv Polytechnic National University, e-mail: vpohreb@gmail.com,
Lviv, Ukraine
2
State Higher Technical School in Nowy Sacz, Poland

ABSTRACT
Solid waste landfills are intended for isolation and neutralization of the solid
waste and they should ensure sanitary and epidemiological safeties of the
population. However, the most of solid waste landfills in Ukraine do not meet
sanitary standards. As a result, there are a large number of ecological problems such
as pollution of groundwater by the filtrate of these landfills and the migration of
polluting components together with an underground stream. The most vulnerable
components of the environment are groundwater and surface water. Processes,
which occur in landfills and dumps in different periods of existence, are poorly
understood and are great interest for research.
The aim of the work is the assessment of Lviv municipal solid waste landfill
impact on water bodies in the region.
The purification technology of infiltration water on a station of physical and
chemical purification has 5 main parts of treatment. The quality of wastewater
treatment was evaluated by such parameters as color, clarity, odor, suspended solids,
salt content, BOD5, COD, chlorides, ammonia nitrogen, pH. For the analysis of
water were used chemical, physicochemical and physical methods.
The value of indicators of water quality was decreased significantly after. The
suspended matter was decreased in 3 times, dry residue in 1,2 times, ammonium
nitrogen in 15,4 times, nitrates in 1,7 times, nitrites in 1,4 times, sulphates in 2 times,
chlorides in 6,7 times, phosphates in 1,2 times, total iron in 1,1 times, COD in 15
times and BOD5 in 11,9 times.
In groundwater, average exceeding of MPC was established for total iron 17,3
times, for cadmium 11,5 times, for manganese 5,7 times.
In surface waters of the Маlеkhіvkа river, upstream, downstream and at the point
of soil-reclamation canal confluence exceeding of MPC was established for
mineralization 1,2 times, total iron – 1,4 times, cadmium – 5,2 times, manganese –
4,0 times.
Water Security: Monograph 171

In surface waters – soil-reclamation canal К–30 (1 km from MSW landfill foot,


nearby highway Lviv – Zhovkva), exceeding of MPC was established for:
mineralization – 1,9 times, total iron – 1,6 times, cadmium – 6,8 times, manganese
–1,9 times, plumb – 1,1 times.
Keywords: surface water, groundwater, wastewater, pollution, purification.

INTRODUCTION
The problem of municipal solid waste is one of the most topical environmental
issues of the beginning of the third millennium, in this connection essential
contribution into unfavourable environmental situation is brought by city dumps of
municipal solid wastes, by poisoning with its existence of soil and air, surface and
underground waters, killing both flora and fauna, being the source of heavy
contagious diseases [1; 2].
The most hazardous impact factor of MSW landfills on components of the
environment is leachate – liquid phase of waste [3]. Peculiarity of hazard concerned
with filtrate is that these liquid decay products, which are organic constituents of
municipal waste, enriched with heavy metals, mineral salts, colourants, surfactants,
petrochemicals, which in case of absence of proper engineering facilities get into
surface water and groundwater [4; 5]
Groundwater contamination occurs as a result of leachate percolation into
aquifers [6]. As a rule, protection from soil and groundwater contamination is
executed by inserting special contra-filtration screen throughout all bottom and
banks of landfill, system of interceptors, drainage and purification of filtrate, as well
as system of monitoring wells for control over the quality of groundwater [7; 8].
Surface waters can be contaminated either by direct flow of leachate into water
bodies, in this case, peak negative effect is observed, or during intrusion of
groundwater contaminated by leachate into them, which is especially dangerous in
mean (low) water period [9; 10].
Protection of surface water bodies from pollution caused by storm waters and
meltwaters, which outflow from landfill territory, limited by a woodland belt, is
executed by treatment of surface runoff and drainage of transit surface waters [11; 12].
The objective of the research is the assessment of Lviv municipal solid waste
landfill impact on water bodies in the region.

METHODS AND EXPERIMENTAL PROCEDURES


Lviv utility enterprise “Zbyranka” carries out the collection of leachate into
storage basins, from which later on leachate is injected into landfill body. To avoid
self-ignition of wastes and moisturizing of the MSW landfill works for re-circulation
of leachate water into the landfill body are held by the enterprise. Recirculation
172 Water Security: Monograph

(pumping) is operated with the help of pumping station ПСГ-160 and collection
pipework system. Provided pumping at distance 900 m, with a height difference
100 m, the station output makes 80 m3/per hour. On average, 208 m3 per night-and-
day (24 hours) of leachates is pumped.
During the period from 06.07.2012 to 19.09.2013, 14680 m3 of leachates were
pumped for a moisturizing waste of MSW landfill from leachate storage basins.
The purification technology of infiltration water on a station of physical and
chemical purification has 5 main parts of treatment.
Unit 1 is for removal of indissoluble compounds, high-molecular compounds
and soluble low-molecular components in the insoluble form (salts, hydroxides), as
well as for oxidation of organic substances to harmless products (SO42-, NO3-, N2).
It includes two sister modules for conversion and sorting out contaminants.
Unit 2 includes equipment for deamination by means of air desorption,
clarifying air from ammonia, chemisorption. In desorber, optimal conditions for a
concentration of ammonia in the gas phase are provided. Parameters of
chemisorption meet standards of effective air clarifying and obtaining the saturated
solution of ammonia (air and ammonia solution), which is re-used in purification
processes.
Unit 3 is intended for extra purification from ammonia and soluble compounds,
which indicate toxicity and extent of water mineralization.
Unit 4 is designed for treatment of sediment, which is created on installations
complex of unit 1.
Unit 5 – is reagent facilities (storage room).
The quality of wastewater treatment was evaluated by such parameters as color,
clarity, odor, suspended solids, salt content, BOD5, COD, chlorides, ammonia
nitrogen, pH. For the analysis of water chemical, physical-chemical and physical
methods were used.
During assessment of MSW landfill impact on eco-condition of landscape
components, samples of surface water were taken from the river Malekhivka
upstream, downstream and at location point of soil-reclamation canal
confluence, as well as from surface waters – soil-reclamation canal К–30 (1 km
from foot of MSW landfill, nearby highway Lviv –Zhovkvа (N49 0 53'47,4";
E 024003'25,6").
Groundwater samples were taken from monitoring well № 26а, located in the
area of MSW landfill (N 49°54'05.3" EO 24°02'46,2"). Equipment to have been
used in pumping water out of the well (vibration pump, portable generator, plastic
hose, cables of a power supply). Studying of the samples collected was carried out
according to current techniques for water – ДсанПіН (state sanitary regulations and
norms) 2.2.4-171-10. For water analysis, chemical, physical-chemical and physical
methods were applied.
Water Security: Monograph 173

The quality of surface waters was evaluated by parameters as follows: sulphates,


chlorides, calcium, magnesium, ammonium nitrogen, nitrites, nitrates, phosphates,
BOD5, TBOD, COD, total iron, petrochemicals, anionic synthetic surfactants,
mineralization, suspended solids, hardness, zinc, cadmium, nickel, manganese,
plumb, copper, total chrome. Groundwater was estimated by parameters as follows:
sulphates, chlorides, calcium, magnesium, ammonium nitrogen, nitrites, nitrates,
phosphates, total iron, petrochemicals, anionic synthetic surfactants, mineralization,
suspended solids, ammonium, hardness, zinc, cadmium, nickel, manganese, plumb,
copper, total chrome.

RESULTS OF RESEARCH AND DISCUSSIONS


Sewage
Station of physical and chemical purification is intended for purification of
leachates (drainage water) from municipal solid waste landfill, that is, concentrated
multi-compound solutions. The volume of ferroconcrete storage tank of the station
for physical and chemical purification of leachate is 50 m³. Leachate purification
is executed with the aid of reagents: lime, hydrogen superoxide, ferric(ІІІ) sulphate,
coagulants «Magnofloc» and «Polvak». At the stage of start-up and commissioning
works, wastewater after undergoing purification meets standards of discharge into
surface basins. Discharge of treated wastes effluent is carried out into a ditch, the
tributary of the river Маlekhivka, located at 100 m from the station.
The facilities mentioned, with volume 4,5 m³, purifies 18m³ per 12 hours of
drainage water from pollutants (96%), in particular, from heavy metals, the
remaining volume of reactor tanks is sediment, which is generated in the process
of purification, to be transported to the landfill in hermetically sealed barrels.
Purified water should have parameters as follows: colorless, clear, odorless,
suspended solids 5 mg/dm³; salt content up to 1000 mg/dm³; BOD5 3–5mg О2/dm³;
COD 10–15 mg О2/dm³; chlorides up to 300 mg/dm³; ammonium nitrogen
0,5 mg/dm³; рН 7-9.
Water both before and after treatment operations was sampled. The results of
the research are given in Figures 1 and 2. It was also found out that in polluted
water рН was 9,2; alkalinity – 76,6 mg-еq/dm³; colour – brown; odor – 5 points;
clarity – invisible (opaque); manganese – 0,27 mg/dm ³; cuprum – 0,06 mg/dm³;
chrome - 0,06 mg/dm³; petrochemicals – 1,2 mg/dm³; phenol, formaldehyde,
nickel, plumb, zinc – under method’s sensitivity. Water after treatment operations
had temperature 10,6 ºС; рН made 7,68; alkalinity – 8 mg-eq/dm³; colour – light-
yellow; odor – 2 points; clarity – 22 cm; manganese, cuprum, chrome,
petrochemicals, phenol, formaldehyde, nickel, plumb, zinc – under method’s
sensitivity.
Also control over analysis of wastewater composition both before and after
purification, as well as in control wells, is carried out (including in the case of
174 Water Security: Monograph

absence of 25 local treatment plants), as well as evaluation of effluent amount to be


discharged.

Figure 1. Hydro-chemical parameters of polluted water

Figure 2. Hydro-chemical parameters of water after treatment operations

Thus, from the data obtained and according to the provided diagrams as to
hydro-chemical parameters of water before and after purification, it was found out
that the values of water parameters after purification significantly decreased:
Water Security: Monograph 175

suspended solids – from 56,4 mg/dm³ to 18,6 mg/dm³; dry residue – from
1784,0 mg/dm³ to 1466 mg/dm³; ammonium nitrogen – from 192,0 mg/dm³ to
12,5 mg/dm³; nitrates – from 14,6 mg/dm³ to 8,4 mg/dm³; nitrites – from
2,2 mg/dm³ to 1,6 mg/dm³; sulphates – from 156,0 mg/dm³ to 78,4 mg/dm³;
chlorides – from 3220,0 mg/dm³ to 482,3 mg/dm³; phosphates – from 37,2 mg/dm³
to 29,8 mg/dm³; total iron – from 3,2 mg/dm³ to 2,8 mg/dm³; COD – from
1920,0 mg/dm³ to 128,0 mg/dm³; BOD5 – from 760,0 to 64,0 mg/dm³.
There is the fact that exploitation of treatment plants sometimes is operated with
violation of technological regime. Thus, a unit of reverse osmosis is not applied,
hence, complete cycle of a purification is not implemented. Partly purified filtrate
waters are discharged into hermetic sealed storage tank and transported for
purification.
With design capacity (16 m³/per 24 hours) of the station for physical and
chemical purification (in case it would work round-the-clock) with the average
amount of filtrate (42-58 m³/per 24 hours), treatment plants do not provide
purification of required filtrate amount. In treatment plants on average 11-12 m3/per
24 hours of filtrates are purified daily.

Surface waters
A sampling and measuring of water composition and properties parameters were
carried out in checkpoints:
- location point №3 (1 km from the foot of MSW landfill, nearby highway Lviv
–Zhovkvа (N49°53'47,4"; E 024°03'25,6" );
- the Маlеkhivkа river, 50 m upstream soil-reclamation canal confluence,
v. Маlеkhiv (N49°53'10,9"; E 024°03'33.3" );
- The Маlеkhivkа river, 100 m downstream soil-reclamation canal confluence,
v. Маlеkhiv (N49°53'11,8"; E 024°04'07.4" );
A sampling of water in above-mentioned location points was implemented
during the period as follows: 25.09.2012, 14.05.2013; 12.09.2013.
The results of instrumental and laboratory measurements for surface water
quality of the Маlеkhivkа river upstream, downstream and at location point of soil-
reclamation canal confluence are provided in table 1.
According to the data represented in Table 1, slight and occasionally average
exceeding MPC was established for mineralization 1,2 times (1000,0 MPC) –
22.05.2013, for total iron 1,4 times (0,3 MPC) –18.09.2013, for cadmium 5,2 times
(0,001 MPC) –22.05.2013, for manganese 4,0 times (0,1 MPC) – 22.05.2013, for
plumb 0,92 times (0,03 MPC) – 22.05.2013, in compliance with the standards
CаНПіН (sanitary regulations and norms) № 4630-88.
176 Water Security: Monograph

Table 1
Results of laboratory measuring of the Маlеkhivka river surface
water quality

The results of measurements for surface water quality – soil-reclamation canal


К–30 (1 km from a foot of MSW landfill, nearby highway Lviv-Zhovkvа
(N49°53'47,4"; E 024°03'/25,6") – Т3, given in table 2.
According to the data represented in Table 2 for results of laboratory
measurements, also both slight and occasionally average exceeding MPC was
established: mineralization – 1,9 times (1000,0 MPC) – 01.10.2012, total iron 1,6
times (0,3 MPC) – 22.05.2013, cadmium - 6,8 times (0,001 MPC) –01.10.2012,
manganese 1,9 times (0,1 MPC) – 01.10.2012, plumb 1,1 times (0,03 MPC) –
Water Security: Monograph 177

22.05.2013 , in compliance with the standards CаНПіН (sanitary regulations and


norms) № 4630-88 [13].
Тable 2
Results of laboratory measuring for surface water quality near highway

Groundwater
A sampling of groundwater was carried out from monitoring well № 26а, and
in compliance with measuring done its diameter d=100 mm; depth h=30 m; the
timing of pumping out to the moment of sampling t=40 min were estimated [14].
178 Water Security: Monograph

Analysis of groundwater from monitoring well № 26а was accomplished, its


data are given in table 3.
In compliance with the results given for the study of groundwater quality,
average exceeding of MPC was established in total iron 17,3 times, cadmium 11,5
times, manganese 5,7 times according to the standards CаНПіН (sanitary
regulations and norms) № 4630-88.
Table 3
Results of measurements for groundwater from monitoring well № 26а
Water Security: Monograph 179

CONCLUSIONS
Thus, based on the abovementioned results as to estimation of hydro-chemical
parameters for samples of leachate (drainage waters) from Lviv MSW landfill, both
before and after treatment, it can be stated that the values of the mentioned
parameters after treatment operations considerably decreased. In particular, рН was
– 9,2 but reduced to 7,68; alkalinity – 76,6 to 8 mg-еq./dm³; suspended solids –
from 56,4 mg/dm³ to 18,6 mg/dm³; dry residue – from 1784,0 mg/dm³ to
1466 mg/dm³; ammonium nitrogen – from 192,0 mg/dm³ to 12,5 mg/dm³; nitrates
– from 14,6 mg/dm³ to 8,4 mg/dm³; nitrites – from 2,2 mg/dm³ to 1,6 mg/dm³;
sulphates – from 156,0 mg/dm³ to 78,4 mg/dm³; chlorides – from 3220,0 mg/dm³
to 482,3 mg/dm³; phosphates – from 37,2 mg/dm³ to 29,8 mg/dm³; total iron – from
3,2 mg/dm³ to 2,8 mg/dm ³; COD – from 1920,0 mg/dm ³ to 128,0 mg/dm ³; BOD5
– from 760,0 to 64.0 mg/dm ³; manganese – 0,27 mg/dm ³ to a parameter under
method’s sensitivity; cuprum – 0,06 mg/dm³ to a parameter under method’s
sensitivity; chrome – 0,06 mg/dm³ to a parameter under method’s sensitivity;
petrochemicals – 1,2 mg/dm³ to a parameter under method’s sensitivity.
Nonetheless, purification of leachates of municipal solid wastes landfill in
municipal treatment plants is not efficient enough way to solving the problem since
drainage waters (leachate) are not applied, as it occurs in the world practice. The
issue of wastewater needs developing of specialized technologies and equipment.
In this connection, it is expedient to use the experience of Switzerland, USA,
Germany in the field of treatment of leachates from MSW landfills.
Under the effect of leachate in groundwater average exceeding of MPC was
established for total iron 17,3 times, cadmium 11,5 times, manganese 5,7 times
according to the standards of CаНПіН (sanitary regulations and norms) № 4630-
88. The fact detected is the evidence that steps taken are not enough to prevent and
stop pollution of groundwater by leachates.
In surface water of the Маlеkhivka river upstream, downstream and at location
point of soil-reclamation canal confluence, slight and occasionally average
exceeding of MPC was established for mineralization 1,2 times, total iron –1,4
times, cadmium – 5,2 times, manganese – 4,0 times according to the standards
CаНПіН № 4630-88.
In surface water – soil-reclamation canal К–30 (1 km from foot of MSW landfill,
nearby highway Lviv-Zhovkvа), exceeding of MPC was established: mineralization
– 1,9 times, total iron 1,6 times, cadmium 6,8 times, manganese 1,9 times, plumb
1,1 times.
Thus, functioning of Lviv landfill keeps having immediate impact on the
environment pollution, in particular on surface water and groundwater, main source
of which is leachates, generated as a result of both atmospheric precipitations and
the processes, occurring in «body» of the landfill [15]. Beneath trash hill 80 m high
180 Water Security: Monograph

there is the whole lake of leachate. Five million tons of waste press on it, hence
outflows to pollute soil and surface water with heavy metals (ions of plumb,
manganese, cadmium, copper, iron), yet water in wells, located within landfill
impact zone, is contaminated with chrome.

REFERENCES
1. Baccini, P., Henseler, G., Figi, R., Belevi, H. (1987). Water and element balances
of municipal solid waste landfills, Waste Management and Research, 5, 4, 483-499.
2. Beketov, A.Y., Bekrenevm B.A., Viktorovskii, I.V. and all. (1988). On the leachate
treatment problem polygons for the disposal of municipal solid waste, Environmental
chemistry, 7, 4, 217-228.
3. Slack, R.J., Gronow, J.R., Hall, D.H., Voulvoulis, N. (2007). Household hazardous
waste disposal to landfill: Using LandSim to model leachate migration. Sci. Total
Environ., 501-509.
4. Kashkovskyy, V.I., Kuchar, V.P. (2005). Methods of disposal of highly toxic waste
dumps of solid waste, Science and Innovation, 1, 6, 107-116. (in ukr.)
5. Kashkovsky, V.I., Voynovskiy, V.V. (2006). Sewage municipal solid waste landfills:
problems and solutions, III International Conference "Cooperation for Waste Issues",
Kharkiv, 151-153. (in ukr.)
6. Turkadze, Ts.D., Kamkamidze, N.R., Bogveradze, M.Z. (2006). The study of the
intensity of the processes of self-purification of groundwater in the area of the city dump
for household waste, Ecological systems and devices, 5, 13-14.
7. Zalzberg, E. (2009). Monitoring the quality of groundwater in order to prevent
accidents in the dumps areas (for example, Canada), Water, 24, 5, 630-633.
8. Yakovenko, M.B., Hvozdevych, O.V., Kulchyska-Zhygaylo, L.Z. Butin, O.Z.,
Voytsykhovska, A.S. (2007). Lviv sanitary waste landfill filtrates: impact and
neutralization, Natural Water Resources of the Carpathian region (problems of protection
and rational use), May 29-30, 2007, Lviv, 169-174. (in ukr.)
9. Shevchenko, O.A., Derkachov, E.A. (2002). Ecological and hygienic assessment
of the danger area municipal landfills and measures for their rehabilitation. Problems of
gathering, processing and recycling: Coll. Science. Art. IV Intern. nauk. and practical.
Conf., Odessa, 224-227. (in ukr.)
10. Buchynska, A., Gvozdevych, O., Podolskyy, M., Stefanyk, Y. (2008). Activities
of polish-ukrainian centre "CENCON" for realization of environmental problems of lviv
s sanitary landfill, Natural Water Resources of the Carpathian region (problems of
protection and rational use), May 29-30, 2008, Lviv,199-203. (in ukr.)
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11. Rybak, S., Tomaszewski, O. (2011). State and the degree of degradation of natural
systems being influenced by Lviv city landfill and environmental and economic
assessment of the impact of its operations for the future. Problems and prospects of
Ukrainian science in the beginning of the third millennium: Coll. Science. works III All-
Ukrainian scientific Internet - conference. Pereyaslav - Khmelnytsky, 14-16 December
2011, 9-12. (in ukr.)
12. Pohrebennyk, V., Podolchak, I. (2015) The efficiency of wastewater treatment
L'landfill, International scientific conference «New Trends in Ecological and Biological
Research», September 09-11, 2015, Prešov, Slovak Republic, 103.
13. Podolchak, I.I., Pohrebennyk, V.D. (2015). Effect of Lviv landfill on ground
surface water region, Natural Water Resources of the Carpathian region (problems of
protection and rational use), Lviv, 177-181. (in ukr.)
14. Podolchak, I.I., Pohrebennyk, V.D. (2015). The impact of the Lviv city dump on
the state of groundwater quality. V All-Ukrainian congress of ecologists with international
participation, September 23-26, 2015, Vinnitsa, 25. (in ukr.)
15. Voloshin, P. K. (2005). Assessing the impact of the Lviv landfill on the ecological
state of the hydrosphere. Natural Water Resources of the Carpathian region (problems of
protection and rational use), Lviv, 30-33. (in ukr.)
182 Water Security: Monograph

EFFICIENCY OF WASTEWATER TREATMENT IN A MOUNTAINOUS


AREA OF POLAND

Dr. Grzegorz Przydatek1


Dr. Anna Kochanek2
Prof., Dr.Sc. Volodymyr Pohrebennyk 1,3
1
State Higher Technical School in Nowy Sacz, e-mail: g.przydatek@gmail.com,
Poland
2
State Higher Technical School in Nowy Sacz, e-mail: annakochanek@op.pl,
Poland
3
Lviv Polytechnic National University, e-mail: vpohreb@gmail.com, Ukraine

ABSTRACT
Wastewater treatment is an essential component of the protection of the
environment, which has a significant impact on the state of groundwater, rivers and
seas. A lack of wastewater treatment can lead to the destruction and extinction of
many species of animals and plants. Wastewater can be purified, re-used and
reprocessed for life.
The subject of the study is to evaluate the efficiency of wastewater treatment
plants in Limanowa (Poland).
Wastewater treatment here is based on mechanical and biological removal of
pollution with activated sludge methods. The analysis of test results from the period
2012-2013 showed no fully effective removal of contaminants. The hydraulic load
of sewage treatment plants in the period stood at 1,384.0 ÷ 3148.0 m3 ∙ d-1. Raw
sewage flowing into the treatment plant in Limanowej in the analyzed period was
characterized by a very uneven quality and composition.
The quality of wastewater effluent corresponded fully with the requirements
specified in the water permit. The average efficiency of removal of contaminants
from wastewater, specific indicators was: BOD5 – 97,72 %, COD – 95,58 %, a
suspension total of 95,25 %, Ntotal – 97,72 %, Ptotal – 96,37 %. Wastewater
treatment here has limited efficiency, which explains the increased nitrogen content.
Keywords: municipal wastewater, pollution, sewage treatment plant

INTRODUCTION
The chemical composition of urban wastewater depends on the quantity of
wastewater produced per person and the city's infrastructure. There is a theory that
Water Security: Monograph 183

the more modern urban development is, the greater the amount of sewage per day
per person[1].
Wastewater treatment is an essential component of the protection of the
environment, which has a significant impact on the state of groundwater, rivers and
seas. A lack of wastewater treatment can lead to the destruction and extinction of
many species of animals and plants. Wastewater can be purified, re-used and
reprocessed for life.
Wastewater passes through several purification steps to meet all sanitary-
hygienic requirements of its quality. The reliability of a wastewater treatment plant's
ability to dispose of the expected amount of wastewater to the extent required due
to the receiver sewage under certain conditions, depends on the existence and
operation of wastewater treatment, within an established time of operation, and the
random changes in the characteristics of the functional elements of treatment [2].
Depending on the type of polluted substances or their degree of dispersion and
the desired degree of removal, the purification of wastewater requires the use of
various kinds of methods for separating solutions. The greater the dispersion, the
more difficult it becomes to achieve a desired degree of purification and the
separation of ionic solutions requires the use of an entirely different method in
comparison to the separation of the dispersion that is at least two-component system
consisting of a disperse phase (diffusion) and the dispersed phase (dispersoid) [3].
Wastewater treatment is also one of the basic methods for improving the purity
of the water environment. Therefore, it is necessary to discharge effluent of adequate
quality, including in terms of its nutrient content. Designed and operated wastewater
treatment plants are expected to have high performance, and be efficient and reliable
at removing impurities from the full range of loads [4]. It is necessary to verify the
operation of sewage treatment plants through analysis which would allow for
potential correction of technological parameters and various hydraulic stages of the
treatment process [5].
The aim of this study is to analyze the efficiency of the purification system based
on pollution physico-chemical treatment plants in 2012-2013 in a water treatment
plant located in the city Limanowa.

METHODOLOGY AND MATERIALS


The basis of the analysis was the size of the flow and physicochemical
composition of wastewater (BOD5, COD, total suspended solids, total nitrogen,
total phosphorus) with reference to relevant Polish norms. Qualitative research of
wastewater before and after treatment was conducted once a month during the years
2012 – 2013, while the size of the inflow of wastewater was measured daily.
Laboratory assays included the determination of 5 indicators which characterize
chemical properties (total suspended solids), oxygen (BOD5, COD) and the presence
184 Water Security: Monograph

of nutrients (total nitrogen, total phosphorus). The basis for assessing the quality of
wastewater discharged into the receiver was the Regulation of the Minister of
Environment of 24 July 2006 on the conditions to be met when placing waste in water
or the ground and on substances particularly harmful to the aquatic environment [6].
General characteristics of the wastewater treatment plant
The present treatment plant is located in the north-western part of the city of
Limanowa. This is an area located outside the city limits. It uses mechanical
wastewater treatment and biological SBR wastewater treatment with activated
sludge. It is located on the right bank of the river Łososina, in the flow stream of
Sowliniankaand contains the treated wastewater. The diameter of the channel, into
which treated effluent is discharged is 500 mm. The projected daily average flow of
wastewater is Qd = 4224 m3 . d-1, while the maximum flow is Qmaxd = 6700 m3 . d-1.
The population equivalent has been defined at the level of 17600 pe, which classifies
it among the medium-sized treatment plants. Urban wastewater from residential
buildings and from food production facilities runs into the main sewage collector,
and is delivered by barrel carts due to not being fully served by sewerage reticulation.
The degree of mechanical wastewater treatment, is to rough them clean.
Wastewater is treated with elements with physical characteristics that allow
elimination through mechanical processes. This process consists of:
• integrated sieve-grit;
• settler Imhoff, who is also part of the processing of excess sludge.
The second purification stage of biological treatment uses a sequential batch
reactor (SBR), where in the phase sequentially; filling of the reaction (aeration /
stirring), sedimentation and decantation rest. In this way, biologically treated
wastewater flows into the measuring chamber, where an inductive flow meter is
installed. The next stage of effluent flow is to bring them to the receiving
wastewater. Sedimentary sludge drying beds have the task of sludge dewatering.
The precipitate enters the beds with a fermentation trap zone Imhoff. The SBR
bioreactor wastewater treatment plant is divided into three rectangular chambers.
The SBR uses six technological systems that allow the execution of its functions,
and these are [7]:
– an installation which brings raw sewage, mechanically pretreated;
– an installation used to discharge treated sewage;
– an installation with an air mission, which is to bring the air blower to the
individual aeration grids placed at the bottom chambers of the SBR;
– an installation for excess sludge, which is designed to discharge sludge into
the settling tank Imhoff;
– an installation of the PIX, which has the function of dosing iron sulphate into
the chambers of the SBR;
– an installation with the task of removing scum.
Water Security: Monograph 185

According to the water permit, sewage legally discharged into the receiver does
not exceed the following parameters: BOD5 – 15,0 mg O2 . dm-3,
COD – 125,0 mg O2 . dm-3, total suspended solids – 35,0 mg . dm-3, total nitrogen
– 15 mg . N dm-3 and total phosphorus – 2 mg P . dm-3.

RESULTS AND DISCUSSION


The hydraulic load of wastewater ranged from 2,644 m3 . d-1 to 4001 m3 . d-1,
which accounted for 95% of the plant’s designed capacity. In the analyzed years
there has been a reduction in the amount of wastewater flowing into the treatment
plant with a decrease in the daily quantity of treated wastewater of approx. 3%.
The analysis determined the value of BOD5 and COD, total suspended solids,
and the content of phosphorus and total nitrogen of treated wastewater in the years
2012 – 2013. Selected descriptive characteristics are shown in table 2.
Table 1
Characteristics of quantitative wastewater flowing into the treatment
plant in Limanowa in 2012-2013

Table 2
Selected descriptive statistics indicators of pollution
in the raw sewage inlet in 2012-2013
186 Water Security: Monograph

The degree of reduction is shown in the value of the analyzed indicators of


pollution. The effectiveness of wastewater treatment, expressed as the quality of
effluent and reducing the percentage of pollution, are presented in table 3 and
illustrated in the graphs (fig. 1 – fig. 5). A small variation of the analyzed quality
parameters mainly provide low standard deviation.

Figure 1. Variation of Total suspended solids in raw sewage treated each month
Quantitative and qualitative changes were observed in the wastewater as it went
through the treatment process. The highest differences are noticeable in the case of
nutrient content. The quality of wastewater flowing into the treatment plant showed
high volatility. The quality of raw sewage was typical of the general-treatment plants
reported in the literature. Raw sewage inflow to the wastewater characterized was
by highly uneven composition quality.
Average concentrations of nitrogen and phosphorus have exceeded while the
remaining designations fall within the limit values.

Figure 2. Variation of BOD5 in raw sewage atreated each month


Water Security: Monograph 187

This is certainly due to the considerable share of industrial waste from a local
dairy plant. The quality of wastewater flowing into the treatment plant was
characterized by considerable diversity.

Figure 3. Variation of СOD in raw sewage treated each month

Figure 4. Variation of total phosphorus in raw sewage treated each month

Figure 5. Variation of total nitrogen in raw sewage treated each month


188 Water Security: Monograph

Concentrations of the analyzed indicators of pollution in the flow of the sewage


treatment plant in Limanowej were not all the same as in the water permit. The
calculated mean a is very intuitive measure of concentrationss, but this measure is
susceptible to outliers, especially in the case of large numbers.
A better estimator of the expected value is the median, which is the middle value
and means the same number of observations are above and below this figure.
In the case of the concentration of nitrogen and total suspended median gives a
more accurate measure of the value of the center against the arithmetic mean. The
large variability of the analyzed concentrations of pollution indicators provide both
the standard deviation and variance (especially for the BOD5 and COD).
Table 3
Selected descriptive statistics indicators pollutants in treated wastewater
outlet in 2012–2013

The effectiveness of removing contaminants identified on the basis of test


results, and raw sewage purified determined on the basis of the analyzed indicators
of pollution, amounted to:
• BOD5 - average removal rates of 97,72 %;
• COD average removal rates of 95,58 %;
• total suspension - average removal rates of of 95,25 %;
• total nitrogen - average removal rates of 97,72 %;
• total phosphorus - average removal rates of 96,37 %.
Quoted values are significantly higher than the minimum reduction of pollution
to be cleaned in wastewater treatment, which are: BOD5 0%, COD, 24,08 %, 0%
Water Security: Monograph 189

of total suspended solids, total nitrogen – 211,2 % and total phosphorus – 2% [6].
This confirms that the levels achieved in the outflow in the treated wastewater in
the latter two were at a level above 15 and 2 mg O2 dm-3, respectively. Also in the
case of total nitrogen, the data shows some instances of high variability in
nitrification/denitrification outcome.
The statistics indicate on the basis of specific indicators for removal efficiency
that treatment did not function entirely correctly, and two of the requirements
specified in the current water permit are not met. Diverse load substrates and
hydraulic treatment often cause considerable disturbances in functioning, thereby
leading to abnormal amounts of pollutants [8]. The effectiveness of removing all
contaminants from wastewater during the relevant period remained stable. In
addition, the analysis results show that the performance of this plant is comparable
to the effectiveness of other plants, similar in terms of capacity and the technology
employed (multiphase sludge) [1; 4; 10; 13].
For qualitative analysis of raw and treated wastewater, correlations between
were determined for the COD and BOD5 indicators of pollution. For raw sewage,
we consider two cases: COD / BOD5 < 2 (sewage readily biodegradable) and COD
/ BOD5 > 2 (biodegradable waste is difficult) [9]. The effluent COD / BOD5 = 5–6.
In the proposed treatment, these conditions are as follows: raw sewage COD / BOD5
= 1,97 – hardly biodegradable, untreated effluent COD / BOD5 = 4,60.
In addition to assessing the effectiveness of wastewater treatment plants, it is
useful to determine the reliability of the technology in relation to obtaining the
assumed requirements of the effluent. The basis for calculating reliability is the
reliability factor (WN) [10; 11]. The average value of HV during the relevant period
amounted to: BOD5 – 0,739; COD – 0,408; total suspension – 0,573. Nitrogen and
phosphorus’s ratio’s reliability needs to be specific to the requirements of Regulation
of the Minister of Environment of 24 July 2006 on the conditions to be met during
placing waste in water or ground and on substances particularly harmful to the
aquatic environment. These reached the level of 1,689 (Ntotal) and 0,710 (Ptotal). If
you need to remove biogenic compounds it is desirable to optimize the biological
treatment of wastewater in order to obtain the required quality of effluent and WN.
The biggest problem is the reduction of nitrogen treatment. According to [12],
temperature is one of the most important factors affecting the ability of sewage
treatment, because bacteria thrive in a certain temperatire range, taking an active
part in the process of disposal of pollutants. The drop in temperature reduces the
effectiveness of nitrification and denitrification [12]. Because it is unlikely that the
temperature is below 12° all year round, it can be concluded that the reason for the
drop lies in the biological treatment process. The temperature of wastewater does
not significantly affect the temperature of the air temperature, only influent [12].
The concentration of nitrogen at the outlet is reduced, and still are exceeded, which
is due to a mismatched or inefficient aeration system that causes aeration to be too
weak or too strong, low temperature wastewater in the chamber of the bioreactor
during the winter or the high concentration of suspensions in the drain and rare
190 Water Security: Monograph

removal of sludge, which causes enrichment in biogenic compounds, favoring


eutrophication [12–14]. The reason for this state of affairs may be local food
factories, including those that produce dairy, meat and ice cream.

CONCLUSIONS
The chemical composition of wastewater varies widely. The composition of
wastewater also depends on a city's infrastructure and, above all, of the quantity
and quality of wastewater discharged to the sewer network by ordinary citizens and
small and large factories manufacturing industrial and food products.
The performance indicators BOD5, COD and suspended solids in this study were
within acceptable standards, while total nitrogen and total phosphorus did not meet
the standards laid down in the Regulation of the Minister of Environment of 24 July
2006 on the conditions to be met by placing waste in water or ground or on
substances particularly harmful to the aquatic environment. (Dz. U. No. 168, item.
1763). Wastewater inflow to the plant had high levels of pollution indicators, which
were caused by a considerable share of industrial waste from a local dairy plant. In
addition, the wastewater also had a highly uneven qualitative composition.
The contents of all indicators has no relation to the amount of wastewater flow,
but in the case of nitrogen and phosphorus analysis showed that the level of the
limit value was exceeded by more than acceptable level. Other attained
concentrations of sewage on the examined plant were significantly below an
acceptable level. Other research supports the thesis that the process of biological
treatment is insufficient.

REFERENCES
1. Krzywy, E., Izhevska, A. (2004). Sewage and sludge, Agricultural University in
Szczecin, Poland. (in pol.)
2. Lowe, D.F., Oubre, C.L., Ward, C.H. (1999). Surfactants and Cosolvents for NAPL
Remediation, A Technology Practices Manual, Boca Raton, Lewis Publishers, USA.
3. Gawronski, R. (1999). The processes of purification of the liquid, Warsaw University
of Technology, 2nd Ed., Poland. (in pol.)
4. Dymaczewski, Z. (2011). Guide exploiter sewage treatment plant, PZITS, Poland.
(in pol.)
5. Brzezicka, S. (2008). Analytical control of sewage sludge, Overview National
Laboratory, Poland, 11-46. (in pol.)
6. Regulation of the Minister of Environment of 24 July 2006. (2006). On the conditions
to be met during placing waste in water or ground and on substances particularly harmful to
the aquatic environment, Poland. (in pol.)
Water Security: Monograph 191

7. Operating Instructions bioreactor wastewater treatment plant in Limanowej. (2007),


Poland. (in pol.)
8. Masłoń, A., (2014). Evaluation of the effectiveness of wastewater treatment plant in
Jaslo under different hydraulic loading. Archives of Waste Management and Environmental
Protection, Poland, 16, 2, 57-66.
9. Sadecka, Z. (2010). Fundamentals of biological wastewater treatment, Ed. first.
Józefosław, Poland, 24-25. (in pol.)
10. Andraka, D. Modeling work wastewater treatment plant using the Monte Carlo
simulation. (2011), Environmental Engineering, Poland, 24, 7-16. (in pol.)
11. Wałęga, A. (2009). Assessment of the wastewater treatment plant static methods,
Forum exploiter, Poland, 5, 30-34. (in pol.)
12. Bugajski, P., Kaczor, G. (2012), Influence of selected factors on the temperature of
the wastewater in the bioreactor flow, Infrastructure and Environment Rural, Poland, 02.
(in pol.)
13. Bugajski, P. (2011). The effect of temperature treatment plant the size of the selected
indicators of pollution from sewage running in a sequential SBR, Infrastructure and
Environment Rural, Poland, № 2. (in pol.)
14. Bugajski, P., Gregory, K. (2006). Removal of nutrients in domestic sewage treatment
plant type Turbojet and Biocompact. Infrastructure and Environment Rural, Poland, № 2.
(in pol.)
192 Water Security: Monograph

BALANCED MINERAL COMPOSITION OF DRINKING WATER


AS AN INFLUENCE ON THE PUBLIC HEALTH AT THE URBAN
AGGLOMERATIONS OF THE NORTHWESTERN
BLACK SEA REGION

Prof., Dr.Sc. Tamerlan Safranov1


Kateryna Husieva2
1 Odessa State Environmental University, e-mail: safranov@ukr.net, Ukraine
2 Odessa State Environmental University, kate.gusyeva@gmail.com, Ukraine

ABSTRACT
The hygienic aspect of drinking water safety and quality can be defined by the
indices of epidemic safety, sanitary, chemical and radiation indices, as well as the
optimal content of mineral substances, i.e. a mineral composition adequate to the
physiological need of a human body: total hardness, total alkalinity, the content of
iodine, potassium, calcium, magnesium, sodium, solid residual and fluorine. The
paper studies the possible impact of the mineral composition of drinking water on
the public health at urban agglomerations in the Northwestern Black Sea Region.
The indices of balanced mineral composition of drinking water, obtained after
treatment of the river water, mainly meet the normative requirements, but the
sodium content is higher and the fluorine content is substantially lower than the
optimal value. The values of almost all indices show that the mineral composition
deviates from optimal value range in the ground water. The concentrations of
calcium, magnesium and sodium ions in the ground water decrease after purification
in pump-rooms, which further leads to the development of diseases due to deficiency
of the essential cations. Fluorine deficiency in drinking water, both from surface
and ground sources of water-supply, is also observed. Long-term consumption of
drinking water with an imbalance of essential mineral components can be one of
the negative impacts on public health.
Keywords: mineral substances, optimal content, balance of water composition,
public health.

INTRODUCTION
Provision of the drinking water of high quality is among the socially important
issues, because water has a direct impact on the public health and determines the
Water Security: Monograph 193

degree of environmental and epidemiological safety in particular cities and regions


of Ukraine. The balanced mineral composition of drinking water is not only an
indicator of drinking water quality, but also an important factor for the public health,
therefore research into regional characteristics of drinking water supply in the
conditions of a coastal zone at the Northwestern Black Sea Region (NWBSR) and
clarification of the role of water factor in sickness rate, determination of the role of
various combinations of the mineral components of of drinking water in the health
of the drinking water consumers is a topical task.
The paper is aimed at assessment of the balanced mineral composition of
drinking water for the urban agglomerations within the NWBSR as a possible
influence on the public health.
To achieve this goal the following tasks have been formulated and solved: to
analyze existent approaches to assessment of the quality of drinking water from
surface and underground sources; to give a general description of household and
drinking water supply sources; to analyze the spatial and temporal patterns for
distribution of the indices of balanced mineral composition of drinking water, to
assess the possible impact of the imbalance in the mineral composition of drinking
water on the public health.
The object of research is the drinking water from surface and underground
sources for the urban agglomerations in the NWBSR, and the subject of research is
the balance of their mineral composition.
Public health is an integral indicator of environmental welfare and one of the
main criteria for environmental quality, while the environmental processes are major
determinants of human health and well-being. The diseases associated with the
environmental impact are conventionally divided into two groups: 1) the diseases
of nonspecific nature arising against a background of the altered environment; thus
the environmental factors provoke pathogenic mechanisms and complicate the
course of a disease (increase in the overall incidence of cardiovascular, oncological,
endocrine, pediatric diseases, pregnancy pathology etc.); 2) the diseases of specific
nature when the environmental conditions are a causative agent of a disease
(endemic diseases, natural nidal infections, diseases caused by chemicals, radiation
or biological allergens) [1].
Stability of the chemical composition of the human body is one of the most
important and indispensable conditions for its proper functioning. Deviation in the
content of macro- and microelements in the body from the norm, caused by physical,
geographical, anthropogenic and other factors, leads to disturbance of a human
health. The diseases of specific nature include ‘biogeochemical endemics’ or
microelementoses, i.e. diseases (symptoms) caused by deficiency, excess or
imbalance of trace elements in the body. Trace elements for humans can be: essential
(Fe, Cu, Zn, Mn, Cr, Se, Mo, I, Co), conditionally essential (As, B, Br, F, Li, Ni, Si,
V), and toxic (Al, Cd, Pb, Hg, Be, Ba, Bi, Tl) [2]. Most of these microcomponents
enter the human body with foodstuff and drinking water.
194 Water Security: Monograph

Review of the published data confirms that the balanced mineral composition
of drinking water is a factor having significant influence on the population health
[3; 4; 5; 6; 7, etc.]. Research into the balanced mineral composition of drinking
water will make it possible to substantiate the role of this factor in public health
formation for particular areas of Ukraine.
Assessment of the balanced mineral composition of drinking water at the coastal
zone of NWBSR has not yet been made, except for Odessa urban agglomeration
[7; 8; 9, etc.]. Therefore, the authors have made an attempt to give a brief description
of the indicators of a balanced mineral composition of drinking water from surface
and underground sources as an influence on public health within the urban
agglomerations at the coastal zone of NWBSR, inhabited by a major part of the
population of Odessa, Mykolaiv and Kherson provinces.

METHODOLOGY OF RESEARCH
The research object is the drinking water at Odessa, Mykolaiv and Kherson
urban agglomerations. Hygienic assessment of drinking water safety and quality
is made not only in terms of epidemiological safety (microbiological,
parasitological), sanitary-and-chemical (organoleptic, physical, chemical, sanitary
and toxicological) and radiation indices, but also in terms of balanced mineral
composition indices [10], the standard values of which comprise: total hardness
– 1,5-7,0 mmol/dm3; total alkalinity – 0,5-6,5 mmol/dm3; the content of iodine –
20-30 mg/dm3; potassium – 2-20 mg/dm3; calcium – 25-75 mg/dm3; magnesium
– 10-50 mg/dm3; sodium – 2-20 mg/dm3; solid residual – 200-500 mg/dm3;
fluorine – 0,7-1,2 mg/dm3. Indices of the balanced mineral composition of
drinking water determine adequacy of its mineral composition to the biological
needs of the human body. They are based on advisability to consider, for a number
of nutrients, not only the maximum permissible, but also the minimum required
content in the water.
Description of the indices of balanced mineral composition of the drinking water
from surface and underground sources is provided as a result of the research carried
out by: the Branch of ‘Infoxvodokanal’ for 2006-2007 and 2010-2015, and State
Enterprise ‘Ukrainian Scientific Research Institute of Transport Medicine attached
to the Ministry of Health of Ukraine’ for 2001-2011 (Odessa); Municipal Utility
Enterprise (MUE) ‘Mykolayivvodokanal’ for 2005-2014 (Mykolaiv); MUE ‘The
Industrial Direction of Water and Sewage Utilities of Kherson’ for 2015 (Kherson).
In addition, the data on particular indices of balanced mineral composition of
drinking water were obtained from the published sources. The research outcomes
were generalized and represented in the tables and graphs being built by means of
the Excel program. Furthermore, the methods of statistical, comparative geographic
and cartographic data analysis were used.
Water Security: Monograph 195

RESULTS OF RESEARCH
The drinking water supply of Odessa agglomeration is based primarily on
surface waters (the Dniester River). At the ‘Dniester’ wastewater treatment plant
(WWTP) there is a traditional classical purification pattern, consisting of settling
tanks and rapid filters. After fish-protecting constructions the river water enters a
sedimentation canal intended for initial settling and deposition of suspended
particles. Then, through a transversal canal, the partially clarified water is withdrawn
by pumping stations for the first lifting and goes to rapid filters at the units 1-4.
Water treatment at the rapid filters is performed according to a single-stage scheme
on contact coagulation of water impurities (with aluminium sulfate taken as a
coagulant) in the layer of filtering media. Unit 5, built in 1983-1986, includes
settling tanks and rapid filters in order to provide high-quality water purification,
regardless of initial condition of the river water. After filters the water goes into
clean water reservoirs, where it is disinfected with a liquid chlorine (transformed
into a gaseous state in the special vaporizers prior to contacting the water), in doses
which provide its bacterial purity and the residual chlorine concentration at an outlet
from a clean water reservoir of 0,8-1,2 mg/dm3. At the subsequent step, the water
is delivered to the city area through five flow passages to be distributed among the
consumers. Since the water inflow from the ‘Dniester’ WWTP to the city takes from
3 to 6 hours, then prior to entering the municipal water-supply pipeline network the
water is additionally disinfected with sodium hypochlorite at 8 chlorination stations
in order to provide epidemiological safety of the drinking water for end-users. The
‘Dniester’ WWTP has been constructed according to development of the municipal
water-supply system since 1873, with step-by-step expansion and increase in the
purified water volumes. The major reconstruction fell on 1960-1980, when building
of new rapid filter units started and a new lifting electric pump station on the Dnister
River opened. The facilities are continually reconstructed, and an outdated
equipment is replaced by the modern one [11]
Deviations from the standard values in river water (the Dniester river) is
registered only for specific parameters (total microbial count, coliform index,
turbidity, total iron, manganese, indices of biochemical and chemical oxygen
demand), but after the water treatment their values meet normative requirements
for drinking water quality. Extremely high concentrations among the identified toxic
metals and organic compounds have not been found, but the data obtained do not
provide a complete picture on a wide range of pollutants, especially those of organic
origin. Both the river water and the water flowing into the supply conduit meet
normative requirements by most of the indices defined. The drinking water quality
deteriorates primarily in water-supply pipeline and in-house networks, which
technical condition in many spots does not meet sanitary and hygienic safety
regulations [11].
As regards the balanced mineral composition indices, according to the data for
2010-2011, the value of these indices for source water from the Dniester River and
tap water mainly met standard requirements. Only in one case K+ content in river
196 Water Security: Monograph

water was observed below the minimum standard value. However, Na+
concentrations were higher (↑) than the maximum norm (maxN), and F- – lower (↓)
than minimum standards (minN). If we consider Na+ and F- as sanitary and chemical
indices of drinking water safety and quality [10], then Na+ concentrations satisfy
the normative requirements (≤ 200 mg/dm3), as well as F- concentration
(≤ 1,2 mg/dm3). Na+ content was below the maximum norm (maxN) only in May
through September 2010, while in the remaining months of 2010-2011 it exceeded
the maximum standard value (maxN). Concerning F-, during all the months of 2010-
2011 its content usually does not exceed 0,2 mg/dm3, which is far below the required
range (0,7-1,2 mg/dm3). Average annual concentrations of F- (0,16-0,39 mg/dm3)
in the river water, regardless of a seasonal water content, and in the water supplied
to the conduit after treatment do not reach the standard value [8; 9].
According to the data for 2014-2015, the indices of balanced mineral
composition of water from the Dniester River and the tap water also meet normative
requirements, except for some deviations from the standard values for K+ and Na+
(table 1).
Table 1
Some indices of physiological adequacy of the mineral water from the
Dniester River and the tap water in Odessa agglomeration (2014-2015)

Mykolaiv region ranks last in Ukraine for provision of the useful ground water
resources (0,06 m3/d per 1 inhabitant, with an average value of 0,33 m3/d per 1
inhabitant in Ukraine), therefore, it is natural that the main source of water supply
in Mykolaiv is surface water from the Dnipro River which is supplied through the
conduit of 280 thousand m3/d capacity. The length of water-supply networks in the
city makes up more than 1050 km, and about 10% of them are in emergency
condition. The technological scheme for water treatment consists of the following
Water Security: Monograph 197

stages: filtering, coagulation, disinfection, desilting. The water, purified on rapid


filters, inflows into the tank of clean water. The total depreciation of equipment at
the treatment facilities is about 50% [12]. Average daily water consumption of the
city is about 170 m3/d, 80% of which is consumed by the population. The indices
of balanced mineral composition of river and tap water are shown in table 2.
Thus, according to the data for 2010-2014, the indices of balanced mineral
composition for water from the Dniester River and tap water in Odessa meet the
normative requirements, except for certain deviations from the standard values for
K+ and Na+. Average annual concentrations of F- (0,16-0,42 mg/dm3) in river water,
regardless of seasonal water content, and in the water, supplied to the conduit after
treatment (0,11-0,32 mg/dm3), do not reach the norm. The value of the studied
parameters of balanced composition for water from the Dnipro river (total hardness,
total alkalinity, solid residual) and tap water in Mykolaiv (total hardness, total
alkalinity, calcium, magnesium, solid residual) conform to standard requirements,
except for F- deficit.
Table 2
Indices of balanced mineral composition of water from the Dnipro River

Note: * the range of values; ** the average value of indices

An alternative source of drinking water supply for Odessa agglomeration is the


stratal (artesian) groundwater related to Upper Sarmatia Miocene aquifer, which
lies on about 120-130 m depth. The consumers are supplied with the groundwater
through 15 pump-room complexes located in various parts of Odessa: #1 – Gagarin
Ave.; #2 – Peremohy Park; #3 – the 6th Station of the Large Fountain; #4 – 1
Academician Glushko Str.; #5 – 14 Marshal Zhukov Str.; #6 – the 25th Chapaivska
Division Str., build. 1; #7 - 1 Rabin Str.; #8 – 25 Dalnytska Str.; #9 - Starobazarnyi
Square; #10 - Mechnykov Square; #11 – 71 Krymska Str.; #12 – Mykhailovskyi
198 Water Security: Monograph

Square; #13 – ‘Vympel’ Cinema; #14 – Gorkyi Park; #15 – Prokhorovskyi Square.
Every day about 50 thousand inhabitants of Odessa consume more than 20 m3 of
water from pump-room complexes.
The technology for water treatment which is used in pump rooms consists of
the following purification stages: 1) mechanic and catalytic filtering (Fe2+, Mn2+
and H2S oxidation, removal of fine-dispersed suspended particles); 2) reverse
osmotic desalination of the part of water volume (removal of Ca2+, Mg2+, Na+, SO42-,
Cl-, HCO3-, and microorganisms); 3) mixing of the water, purified by reverse osmosis,
with the water after mechanical filtration in a certain ratio, aimed at bringing the
values of total hardness, mineralization, Na+, SO42- and Cl- content to the hygienic
standards; 4) ozonation of the water, balanced in mineral composition, to ensure its
microbiological quality, deodorization, degasation, saturation with O2, and oxidation
of organic and inorganic substances; 5) adsorption treatment of ozonated water at
the filters with activated carbon, resulting in removal of O3, oxidated organic and
some inorganic compounds; 6) secondary ozonation of the water prior to delivering
it to the end-users [13].
The graphs for the average monthly values of the indices for balanced mineral
composition of the drinking groundwater in Odessa, which have been drawn
according to the research for the period of 2006-2007, show a more complex
distribution pattern compared to similar graphs for the tap water [7; 8]. The
distribution pattern for these parameters may largely depend on the data array
components, i.e. the data on a specific indicator for various pump rooms. Herewith,
the natural hydrodynamic and hydrogeochemical zonality of the groundwater, the
operating conditions and other factors need to be considered.
In this regard, the data on the average yearly values of some indices for balanced
mineral composition of the groundwater before and after treatment in particular
pump-room complexes within Odessa are of interest (table 3).
Table 3
Average annual (2001-2010) values of certain indices of balanced mineral
composition of the groundwater from pump rooms in Odessa before
Water Security: Monograph 199

Note: ↓ - below the minimum norm / standard (minN), ↑ - above the maximum
norm (maxN)

The values of certain parameters (hardness, alkalinity) for 2015 in particular


pump rooms (# 2, 4, 13 and 14) did not differ significantly from the average values
given in the tab. 2. Seasonal fluctuations are typical for the values of such
groundwater indices as total hardness, Ca2+ concentration (the confidence
probability α is 70-50% or less), and the most constant values were observed for
alkalinity and Na+ content (the confidence probability α is 90% or higher). The
groundwater purification efficiency usually ranges 19,5 - 76,2% (depending on the
initial water quality), except for the water from the pump room #11, where the
purification efficiency comprises 96,8 - 99,2%, i.e. the saltish water is fully
desalinated [13].
71 artesian well, the water of which is used for household and drinking purposes
by a small part of the population, is operated on the territory of Mykolaiv. For solid
residual, total hardness and other indices of balanced mineral composition, the
groundwater parameters are usually higher than the maximum rate (table 4) [14].
200 Water Security: Monograph

Table 4
Certain indices of balanced mineral composition of the water from
particular wells in Mykolaiv, according to [14]

Water supply of the city of Kherson is provided by groundwater. The main source
of water supply is an Upper Sarmatia aquifer. The total number of artesian wells is
151 (with the depth ranging from 80 to 100 m), about half of which are in operation.
The drinking groundwater quality meets the requirements [10] in 47 wells, where the
water volume is 12,9 mln. m3 per year. The groundwater quality meets the
requirements [10] for certain parameters in 44 wells, which are running with
permission of the sanitary and epidemiological station (the volume is 9,1 mln. m3
per year). The groundwater inflows into the water supply network over 820 km long.
It should be noticed that Pontian Upper Miocene aquifer, which had been used for
dumping household sewage until the late 1960s, is a source of pollution, since the
polluted water overflows into the Upper Sarmatia aquifer through the annular space
of unserviceable wells. The groundwater of the Upper Sarmatia aquifer is polluted
with nitrates (250 mg/dm3, while the standard is 45 mg/dm3).
Beginning of intensive development of the Upper Miocene aquifer complex in
the Dnipro Basin area within the Kherson Oblast fell on 1965-1975, when a large
number of water intake wells was drilled. As a result of a survey for operating wells
performed under the works on prospecting of drinking groundwater in 2002-2010,
it was found that by course of the average values of indices in time there was a
change in the hydrogeochemical type of aquifers from freshwater (SO42- – HCO3-
– Cl- , Ca2+– Mg2+– Na+) to saltish water (SO42- – Cl- – Na+ – Mg2+) [15]. During
the specified time the changes in some indices of balanced mineral composition of
the groundwater are also defined (table 5).
Table 5
Some indices of balanced mineral composition of the groundwater in the Upper Miocene
aquifer complex of the Dnipro Basin within the Kherson Oblast, according to [15]
Water Security: Monograph 201

DISCUSSION
Heightened concentrations of iron, boron and bromine, which are not included
into the list of balanced composition indices for drinking water [10] but belong to
essential (iron) and conditionally essential (boron and bromine) microelements,
were registered in the groundwater of Upper Sarmatia aquifer in Odessa [2]. The
excessive iron (Fe2+) can be removed by mechanical catalytic filtration. The average
boron content in the groundwater before treatment ranges from 0,64 ± 0,05 mg/dm3
to 5,22 ± 0,18 mg/dm3. The content of bromine (bromide anion) ranges from
0,10 mg / dm3 to 2,0 mg/dm3. After treatment boron and bromine concentration in
the groundwater is below the required value (≤ 0,5 mg/dm3 and ≤ 2,5 mg/dm3
respectively), but the above-standard values are periodically observed at all pump
rooms, since the efficiency of boron removal by means of existing technology is
20 - 65,42 % and bromine anion removal – 21,74 - 90,16 %. Therefore, it is
reasonable to remove boron and bromine by reverse osmosis in two stages or by
electrodialysis and reverse osmosis consecutively [13]. This is important because
excessive boron in the environment causes an endemic disease of human and animal
alimentary canal, accompanied by enteritis, diarrhea, weight loss, general weakness,
disturbance of carbohydrate and protein assimilation [2, 16], and the excessive
bromine contributes to the circulatory system diseases, suppression of the thyroid
gland and blocking of iodine flux into it.
While the groundwater from most of wells in Mykolaiv and Kherson is
characterized by abnormal values of total hardness, the average values of total
hardness of the groundwater before treatment at all pump rooms in Odessa are
within the standard range, except for the pump rooms # 9, 11 and 15, where the
value of this indicator was slightly higher than the standard maximum (see tab. 3).
After the groundwater treatment the average values of hardness at 8 pump-room
complexes were within the normal limits, and at the rest of them – below the
minimum standard (minN). These data indirectly indicate calcium and magnesium
surplus (but not their correlation) in groundwater used for drinking purposes in most
of the pump rooms. Magnesium and possibly calcium come into the human body
mainly as constituents of drinking water. Internal use of hard drinking water leads
to the disturbed process of intestinal fat absorption owing to formation of insoluble
calcium and magnesium soaps during the saponification of fats.
In some authors’ opinion [17], the heightened hardness of drinking water
contributes to the increase in circulatory system diseases. According to the World
Health Organization materials, the epidemiological studies conducted in various
countries over the past 50 years have shown a link between the growing number of
circulatory system diseases, followed by a fatal outcome, and soft water
consumption [14], but there are quite a few papers in which the point is that such
indices of drinking water, as hardness, calcium and magnesium content do not affect
the incidence of the circulatory system diseases [5]. Soft drinking waters sometimes
have a high natural content of sodium, but its excess is an additional factor in the
development of some forms of hypertension.
202 Water Security: Monograph

Average values of total alkalinity in the groundwater from pump-room


complexes in Odessa do not go beyond the standard range both before and after
treatment (see tab. 3), which is a positive factor for the public health. A slight excess
of the standard value of total alkalinity was registered only for groundwater from
the pump room #11 before purification. The use of alkaline drinking water is known
to contribute to higher life expectancy by 20-30%.
Calcium content in the groundwater of Odessa in 2006-2007 was within the
range of its standard values, i.e. it did not reach the minimum standard level (minN)
[7; 8]. The same pattern is observed for the average annual values for 2001-2010,
except for the pump rooms #7 and #14 (see tab. 3), however, Ca2+ concentration in
the water from all the pump rooms after treatment is below the minimum standards
(minN) [10]. According to the data for 1965-1975, Ca2+ content in the groundwater
from the Upper Miocene aquifer complex of the Dnipro Basin (within the Kherson
Oblast) was within the standard, but according to the data for 2002-2010 the content
almost 2 times exceeded the maximum standard (75 mg/dm3) [10]. A wide body of
opinion that the occurence of Ca2+ in drinking water contributes to induration of
the arteries, formation of kidney stones and liver diseases, is not confirmed by the
factual evidence. Having high physiological activity, Calcium performs various
functions in the organism, such as bone formation, mineralization of teeth,
regulation of intracellular processes, regulation of nerve conduction and muscular
contractions, and maintenance of stable cardiac activity. High calcium in the body
may be the reason for arthritis, osteodystrophy, osteofibrosis, muscle weakness et
al. Calcium deficiency is the cause of 147 diseases (osteoporosis, tachycardia,
arrhythmia, albication of hands and feet, renal and hepatic colics, hyperexcitability,
etc.). For instance, osteoporosis, a disease that ranks 10th on mortality among adults,
is caused by calcium deficiency in the body [14].
Magnesium content, similarly to the value of total hardness, in the waters from
the pump-room complexes within Odessa in November and December 2006 and
January-March 2007 was slightly lower than the minimum standard value (minN)
[7; 8]. Magnesium is the most constitutive intracellular element. The normal level
of magnesium in the body is necessary for many vital processes; magnesium
reinforces the immune system. Excessive amounts of magnesium cause a laxative
effect. As magnesium concentration in the blood decreases, the symptoms of neural
excitation and even seizures are observed. Reduction of magnesium content in the
body results in the increased calcium content while a surplus of magnesium leads
to calcium and phosphorus deficiency. Since the major part of magnesium is
ingested with food, the question on significance of magnesium concentration in
drinking water is debatable. However, such form of magnesium has a higher
bioaccumulation factor than magnesium received from food. Magnesium content
in drinking water is assumed to be a decisive factor for those people who consume
it in small amounts with food, but drink the magnesium-rich water. A connection
between magnesium content in water and Mg in a cardiac muscle, a skeletal muscle
and coronary arteries is revealed [14].
Water Security: Monograph 203

As for sodium concentration, an apparent excess of the maximum normal value


(maxN) both before and after treatment of the groundwater is traced throughout the
observation period in all urban agglomerations under the study (see Tab. 2, 3, 4). If
we consider the content of Na+ as a physicochemical indicator of drinking water
safety and quality, the groundwater meets the requirements (≤ 200 mg/dm3) [10].
Sodium is known to be of importance in intracellular and intercellular exchange.
Sodium and potassium correlation is in charge of two important interconnected
processes: maintenance of a constant osmotic pressure and a constant volume of
fluid. Sodium consumption in large quantities leads to the loss of potassium.
Therefore, a balanced intake of these substances (Na+ and K+ ) is of particular
significance. The main purpose of Na+ is maintenance of water-salt balance in the
cells of a human body, normalization of neuromuscular activity and renal function.
In addition, sodium keeps mineral substances soluble in the blood. Excess sodium
can cause hyperexcitability, hypersensitivity and hyperactivity. In some cases,
excessive thirst, hyperhidrosis and frequent urination unusual for this particular
person are likely to appear. Most of sodium is included in chlorides, and therefore
the high sodium content correlates with the heightened mineralization of drinking
water.
Solid residual is the amount of dissolved substances, mainly minerals, in 1
dm3 of water. The fraction of organic matter in the solid residual makes up no
more than 10%, so we can assume that this indicator defines a total mineralization
of water. The waters from Upper Sarmatia aquifer on the predominant part of
Odessa agglomeration are fresh and light saltish. The most mineralized water
relates to the areas, located to the north of Peresyp district, as evidenced by the
highest content of solid residual (almost 4 g/dm3) in the water from pump room
#11. In addition to high mineralization, the heightened values of hardness,
alkalinity, potassium and sodium content are typical of such ground water, that is
why they can be used for drinking purposes only after further treatment. The
treated ground water is characterized by the average content of solid residual
within the standard optimal range. The groundwater from the studied wells in
Mykolaiv usually exceeds the maximum standard for the value of solid residual
(see tab. 3). A significant excess of the maximum norm (maxN) is also typical for
the groundwater from Upper Miocene aquifer in Kherson [10]. The drinking water
with heightened mineralization affects gastric secretion and disturbs a water-salt
balance that leads to various adverse physiological abnormalities in the body (heat
exhaustion under hot weather, disturbed sense of quenching the thirst, increased
hydrophily of tissues, change in gastric secretion, reinforced motor functions of
the stomach and intestinal peristalsis etc.). On the other hand, a long-term
consumption of low-mineral water may bring to some adverse physiological
disturbances in the human organism, particularly, to the decreased chloride content
in tissues etc. [17].
The fluoride content both in river and tap water as well as in groundwater
within industrial-and-urban agglomerations of the Northwestern Black Sea
Region usually does not reach the minimum standards (minN) [10]. The
204 Water Security: Monograph

physiological role of fluoride consists in its plastic function, participation in


blood formation and regulation of immunogenesis, functioning of the endocrine
glands, development of collagen, bone and cartilaginous tissue. Fluoride
deficiency is thought to be the primary cause of caries and hypofluorosis
occurrence (late teething, a fluoride-dependent osteoporosis, etc.). F-
concentration in water of less than 0,5 mg/dm3 is one of the major causes of tooth
decay. It is believed that F- concentration in the drinking water of more than
1,5 – 2 mg/dm3 is also detrimental to the public health. Under the use of water
with F- concentration ≥ 5 mg/dm3 fluorosis occurs in almost all of the population.
If in the temperate climate the use of drinking water with F-concentration of
4 – 8 mg/dm3 does not provoke the symptoms of bone fluorosis, in the
subtropical and tropical climate fluoride concentration of above 5 mg/dm3 calls
forth osteoporosis and skeletal deformation. The major part of fluoride gets into
the human organism with water and food (bread, fish, meat, tea, etc.).
Additionally, fluoride can also be ingested with toothpaste [1]. Since fluoride is
a microelement with a relatively abrupt transition from the physiologically
beneficial concentrations to the concentrations provoking a toxicosis, then
convincing arguments both from supporters and opponents of drinking-water
fluorination as well as on the use of fluorinated toothpastes are offered in
Ukrainian and foreign publications.
For tentative assessment of the mineral composition of drinking water, the use
of biologically significant concentration value [18] is suggested. This makes it
possible to distinguish the components, which content can exert influence on the
human trace element balance. Tab. 6 shows the data on compliance of the content
of particular chemical elements from the Dniester River and tap water in Odessa
agglomeration with the minimum biologically significant concentration of drinking
water components.
As follows from the data provided, the content of all identified chemical
elements are usually below the minimum biologically significant concentration
of drinking water components. Some biologically important chemical elements
are available in insufficient concentration for the full functioning of the human
body. Exceptions are copper and strontium, which average annual concentrations
slightly exceed minimum biologically significant concentration of drinking water
components, but are below the norms of sanitary and toxicological indicators of
drinking water safety and quality (copper ≤ 1,0 mg/dm3, strontium ≤ 7,0 mg/dm3)
[10]. Perhaps, the values of biologically significant concentrations of the mineral
components of drinking water and their lower limit are not sufficiently
substantiated, but they extend the range of assessment criteria for the rate of
balanced mineral composition of drinking water.
Water Security: Monograph 205

Table 6
Compliance of the content of particular chemical elements from the Dniester
River and tap water in Odessa agglomeration with the minimum biologically
significant concentration of drinking water components

CONCLUSIONS
As a result of the conducted research the following conclusions can be made:
- It is advisable to make assessment of the drinking water safety and quality not
only by the epidemic safety, sanitary-and-chemical, sanitary-and-toxicological and
radiological indices, but also by the criteria of balanced mineral composition;
- Normative values of the indices for physiological adequacy of mineral
composition (total hardness, total alkalinity, iodine, potassium, calcium, magnesium,
sodium, solid residual, fluorides), recommended in the State Sanitary Regulations
and Standards 2.2.4-171-10, are important criteria for assessment of the drinking
water quality, but they do not reflect the whole variety of chemical elements and
mineral compounds in drinking water;
- The values of balanced mineral composition of the tap water in Odessa
prepared from the Dniester river water mainly satisfy the normative requirements,
except for minor deviations from the standard values for fluorides, potassium and
sodium;
- The studied indices of balanced mineral composition of the water from the
Dnipro River and tap water in Mykolaiv do not always meet the standard
requirements, except for the fluoride deficiency;
- Deviation from optimal value range is typical for almost all the identifiable
parameters of balanced mineral composition of groundwater in the studied urban
206 Water Security: Monograph

agglomerations, yet after the groundwater treatment the concentrations of calcium,


magnesium and sodium in groundwater decrease significantly, that further provokes
the development of diseases associated with deficiency of these elements;
- Additional treatment of groundwater only partially solves the problem of
balancing the mineral components of drinking water, and in some cases may even
aggravate the problem;
- Fluoride concentration in drinking water from surface and ground sources of
water-supply does not reach the minimum standards, that requires substantiation of
appropriateness to perform the water fluorination, use fluorinated toothpastes and
other means of prevention of caries and other diseases among public at large;
- Long-term consumption of drinking water with an imbalance of the mineral
composition can be one of the negative impact factors for the public health, so there
is a need for further special studies.

REFERENCES
1. Bardov, V.G., Fedorenko, V.І., Bіletska, E.M. (Eds.). Fundamentals of Ecology.
Vinnitsa: Nova Kniga Publ., 2013, 424 p. (in ukr.)
2. Avcyn, A.P., Zhavoronkov, A.A. Human Microelementoses. Moscow: Medicine Publ.,
1991, 496 p. (in rush.)
3. Vorohta, Y.M. Hygienic estimation of mineral composition of drinking water on human
health]. Kyiv, 2007, 22 p. (in ukr.)
4. Introduction into Medical Geology. In 2 volumes]. Kyiv: Akadempres Publ., 2010
(Eds: G.I. Rudko, O.M. Adamenko).
5. Ivanov, A.V., Tafeeva, E.A., Davletova, N.H., Vavashkin, K.V. Current views on the
impact of drinking water on human health. Water: chemistry and ecology, 2012, no. 3, pp.
48-53.
6. Prokopov, V.O., Lipovetska, O.B. The influence of the mineral composition of drinking
water on public health (literature review). Hygiene of populated revenge, 2012, no. 59, pp.
63-73.
7. Ed. prof. Rudka, H.I. Medical-hydrogeochemical factors of geological environment
in Ukraine.- Kyjiv-Černivci: Bukrek Publ., 2015,724 p. (in rush.)
8. Safranov, T.A., Polіshchuk, A.A., Volkov, A.І. Physiological full-value of the mineral
composition of drinking water Odessa agglomeration]. Bulletin оf Odessa State
Environmental University, 2013, no. 15, pp. 5-16. (in rush.)
9. Safranov, T.A. Physiological adequacy of the mineral composition of underground
drinking water as a formation factor of population health (with Odessa agglomeration as an
example). The use of mineral resources in Ukraine. Kyiv, 2014, рр. 284-291. (in ukr.)
10. SanPiN 2.2.4-171-10. Hygienic requirements for drinking water intended for human
consumption. Kyiv, 2010.12 p. (in ukr.)
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11. Safranov, T.A., Gusyeva, K.D., Polіshchuk, A.A., et al. Quality of the source of
centralized water supply of the Odesa industrial-and-urban agglomeration. Bulletin оf Odessa
State Environmental University, 2011, no. 11, pp. 3-16. (in ukr.)
12. Lebid, S.H., Holodniuk, N.A., Onyshchenko, O.O. The problem of purification of
drinking water of the Mykolaiv city. Proceedings of The Petro Mohyla Mykolaiv
Humanitarian University. Ser. Ecology, 2008, vol. 7, pp. 89-96. (in ukr.)
13. Petrenko, N.F., Sozinova, O.K., Vlasjuk, G.V., Opanasenko,V.M. Hygienic evaluation
of the combined use of ozone and membrane-sorption methods of purification and
disinfection of water used for pump-room complex in the Odessa city. Black Sea ecological
bulletin, 2012, no. 4(46), pp. 160-170. (in ukr.)
14. Smyrnova, S.M., Smyrnov, V.M., Bahatiuk, D.V. Assessment of the Capacity to Use
Underground Water Sources as Drinking Water, with the Ternovka Microdistrict of
Mykolayiv taken as an Example. Scientific Bulletin of V. Sukhomlynsky Mykolayiv State
University. Biological sciences, 2014, vol. 6.2 (107), pp. 57-63. (in ukr.)
15. Shcherbak, O.V., Lobasov, O.P., Kalіnіchenko, L.O. Evolution of Macrocomposition
of the Drinking Groundwater under Technogenesis in the Kherson Oblast. Bulletin оf Odessa
National University. Geographic and geological sciences, 2014, vol. 19, no.3, pp. 289-298.
(in ukr.)
16. Practical Toxicology and Medical Ecology]. Kyiv: Avіcena Publ., 2010, 248 p. (Ed.:
Mem. NAMSU І.M. Trahtenberg). (in ukr.)
17. Akulov, K.I., Bushtueva, K.A., Goncharuk, E.I. (Eds). Сommunal Hygiene. Moscow:
Medicina Publ., 1986. 608 p. (in rush.)
18. Goncharuk, E.I. Сommunal Hygiene. Kyiv: “Zdorovya” Publ., 2006. 792 p. (in ukr.)
208 Water Security: Monograph

SAFETY STUDY OF WASTEWATERS FROM BAKERY ENTERPRISES


USING BIOTEST ORGANISMS OF DIFFERENT TROPHIC LEVELS

Mas. Katherine Savvova


Senior Lecturer Irina Kondratenko
PhD. Lyudmila Lobotskaya
PhD. Bondar Sergey
PhD. Elena Sevastyanova
Odessa National Academy of Food Technologies,
e-mail: mark6109@rambler.ru, Ukraine

ABSTRACT
A safety study of wastewaters samples frombakeries was undertaken. The
enterprise wastewaters safety was determined using biotest methods with test-
organisms of different systematic groups. Investigation of waster waters safety by
phytotesting was conducted basing on the study of morphological changes during
the small radish seeds germination. Anaqueous extract or the wastewater sample
was filtered and reacted with small radish seeds for 96 hours at a water duty of 1:5
and a temperature of 20 °С. Dynamics of change in root length wasinvestigated. In
the second stage of the study, protozoa ciliates (Colpoda steinii) were used as a
bioassay system. The method used was based on the extraction of the studied
products of different fractions of toxic substances, of a polar and nonpolar nature,
followed by exposure to cultured of C. steinii. For the third phase of the experiment,
animal cells as bioassay-organisms were used. The method usedwasbased on the
ability of methylene blue to bind the hydrogen that is detached from oxidizing
substrate (animal cell) in the respiration process and reduces into a colorless
leucoform.
The obtained result confirms the appropriateness oftoxicity determination of
studiedsamples using the biotest-systems of different classes, thus, the possibility
of the later usage as biotest-organisms during determination ofindustrial wastewaters
safety.
Keywords: safety, bioassay, toxicity, phytotesting, ciliates, sewage.
INTRODUCTION
In the modern world, significantly increased requirements to foods safety, for
which arewidely used the biological methods, including the biosensor and bioassay
Water Security: Monograph 209

techniques [1; 2]. The most intensive development of bioassay obtainedat the
boundary of the twentieth and twenty-first centuries. At present, an expanding range
of test-organisms is usedincludinga variety of aquatic organisms (green algae),
macrophytes, protozoa (ciliates, flagellates), coelenterates (hydras), worms
(planarians, leeches), mollusks (elasmobranch, gastropods), crustaceans (daphnia,
gammarus), fish, etc.
Statement of a problem. Classification in bioassay methods includes such
criteria as the type of the test-object, the test-reaction, toxicity, and the usage of
instrumentation (fig.1).
Literary review. The severity of toxins contained in foods, raw materials and
foods can only be established through direct methods, which evaluate their impact
on living organisms [3; 5]. Chemico-analytical methods cannot fully evaluate the
real danger of toxic substances present in food, as the simultaneous presence of
several substances even at concentrations that do not exceed their MACs. can
manifest biological effects that cannot be predicted based on their chemical
composition [6; 8].

Figure 1. Classification of bioassay techniques

Toxicity is abiological characteristics andcannot be determined without the usage


of biological object. Only direct biological methods can make an integral assessment
of the level of danger, caused by cumulative exposure to toxicants, taking into
accounts on their synergism and antagonism, mutual influence, as well as the
formation of biodegradation and biotransformation of toxic substances and relevant
products [6]. Bioassay methods provide actual and predictive safetycontrol,
thatenable prediction of behavioral responses to food toxicants. The benefits of
bioassays as the main method of foods safety testing arepresented in fig. 2.
210 Water Security: Monograph

Figure 2. Benefits of bioassays


The main part. Although they possess specific advantages, no one of bioassays
can serve as a universal test-object, which is equally sensitive to all substances.
Differences in sensitivity of organisms to individual chemical ingredients calls the
necessity of usage, for safety control, at least 3 − 4 biotests on animal, algal and
bacterial organisms ofdifferent trophic level. The choiceof used type of tests
depends, first of all, on the aim of investigation, as well as the properties of the test
sample and the available resources [9−12].
Biotesting of wastewater is conducted to determine theirtoxicity, possibility and
supply conditions on the facilities of biological treatment, to assess the effectiveness
of the treatment plants and toestablish the potential impactsof discharging treated
wastewaters into water bodies. Bioassay methods allow us to solve many practical
problems associated with treatment, recycling and discharging of industrial waste
waters.
Biotesting of industrial waste waterswhich is due to undergothe treatment
method of fermentation should provide the ability to predict theircompatibility with
functioning of the biota in treatment facilities. Among the methods bioassay
ofsewage for this purpose, the most appropriate ones are based on the use oftest
objects as typical representatives of the microfauna of active biofilms and sludge
in treatment facilities, since just this part of their biocenosis is most sensitive to
toxicants. These microorganisms are primarily eliminated in toxic stress, while the
destructors of chemical pollution of wastewaters (bacteria, actinomycetes, fungi)
are significantly more resistant to fluctuations in toxicity. Integral estimates of
damage to the aquatic environment as a result of the discharge of waste waters
containing hazardous ingredients can only be produced by considering the extent
of their toxicity to aquatic organisms. Thedefinition of "toxicity" isthe degree of
manifestation of toxic action byvarious compounds and mixtures thereof which
cause morphological changes, behavioral, functional, genetic indices and eventually
the death of organisms. Waste waters must be treated and checked for content of a
range of chemical components, as well as toxicity, before being discharged.
Water Security: Monograph 211

The ecotoxicological monitoring of aqueous media is expected to use at least


two methods of test-organisms from different taxonomic groups, and for the final
result, the test sample toxicity from tests, that have shown the highest
sensitivity,should be used in accordance with the principle of damage to the weakest
link in the ecosystem. In practice, it is impossible to assess the impact of wastes on
the state of all living organisms in the biocenosis, so it is necessary to select those
that, on the one hand, characterize the ecosystem most reliably, and on the other
hand, are highly sensitive to pollutants.
This principle, and based on the task, solves the problem of the choice of the
test object. There areplenty of bioassay methods using more than 145 different test
objects, but for operational monitoring of water quality in water supply systems
andsewage treatment plants, industrial laboratories prefer short-term (express)
automated methods using sensitive living organisms or systems that are not
expensive and which are convenient for laboratory cultivation. When choosing
methods, suitable for practical use in industrial laboratories, many factorsmust be
taken into account, such as their cost-effectiveness, the requirements for the
premises, qualification of personnel, compliance with sterile conditions, the need
to have cultivators, boxes, luminostates, etc.
The aimof this study was to investigate thesafety of bakery wastewaters before
and after anaerobic treatment.

METHODOLOGY OF RESEARCH
Safety was determined by means of wastewaters bioassay test- organisms of
different taxonomic groups:
- higher plants;
- microorganisms;
- unicellulars.
The phytotesting safety studies of
wastewaterswere conducted on the
basis of morphological changes
during radish seeds germination
according to SanPiN 2.1.7.573-96.
Anaqueous extract taken fromthe
samples of waste waters was filtered
and reacted with red radish seeds for
96 hours at a water duty of 1:5 and
temperature of 20°°С (fig. 3). Acontrol
sample contained the distilled water.
The dynamics of change in the length
of the roots wasstudied. Figure 3.Biotesting by germination of red radish
212 Water Security: Monograph

Inthe second stage of the


investigation,a simple bioassay
system wasused – the ciliates
Colpoda steinii (fig.4.). The method
is based on the extraction of the
studied products of different
fractions of toxic substances of a
polar and nonpolar nature with
subsequent exposure to cultured of
C. steiniia according to GOST
13496.7-97.
The criterion of toxicity
Figure 4.Сiliates Colpoda steinii determination is the time from the
beginning of the test’s impact on the
extract to the death of the majority (over 90%) of C. steinii, which is determined on
the basis of a complete cessation of their movement.
Ciliates’survival was calculated using the formula 1:

N= –
N2 .
N1
100% , (1)

where N2 - the total number of ciliates in the test sample, 4-5 replicates after
the test exposure time;
and N1 - the total number of ciliates in the test sample for 4-5 replicates at the
beginning of the experiment.
For the third phase of the experiment animal cells were used as bioassay-
organisms (fig. 5).
The method used is based on the
ability of methylene blue to attach to
the hydrogen that is detached from
oxidation substrate (in the animal
cell) during respiration and is
reduced in a colorless leucoform in
accordance with MR 2.1.7.2279-07
1.1.037-95 MU. The experiment
included the exposure of a solution
of methylene blue and sodium
chloridewith animal cells at 37 °С.
We determined the time it took Figure 5. Ram’s sperm
for the suspension to become
bleached. The toxicity of wastewater samples is directly proportional to the time of
bleaching, taking into account the toxicity scale shown in table 1.
Water Security: Monograph 213

For all experiments, themeanstandard deviation was calculated. Statistical results


of the study treatment were carried out at a significance level of 0,05.
Table 1
Toxicity scale according the duration of methylene blue discoloration

RESULTS OF INVESTIGATION
In the first step of the study, sensory evaluation of complex data samples was
performed. The results are shown in table. 2.
Table 2
Sensory evaluation study of wastewatersfrom a bakery enterprise before
treatment by anaerobic fermentation

The results of the sensory evaluation of bakery wastewaters before treatment by


anaerobic fermentation indicates, that all the wastewaters complies with regulatory
parameters [10; 11; 12].
The results of the wastewater
samples safety testsperformed
withbioassays using red radish
seeds are shown in figure 6.
Changes in the length of the
roots of red radish when exposed
to sewage from a baking
enterprise after purification by
anaerobic fermentation match
those of the control sample
Figure 6. Dynamics of red round radish root length number 3. Dynamics of change
during its exposure to sewage from a baking in the length of roots in a
enterprise:1 - waste water before treatmentby medium before wastewater
anaerobicfermentation, 2- waste water after treatment
by anaerobicfermentation, 3- control sample. treatment (sample number 1) is
214 Water Security: Monograph

significantly different from the control sample, indicating the presence of root
growth inhibitors in respectivesample of wastewaters.
These findings indicatethat sewage from a baking enterprise after treatment by
anaerobicfermentationaresubstantially free of pollutants and theirdegree of toxicity
varies in the range of 1−5% (table 3).Thus the studied waste waters can be ascribed
as nontoxic [13].
Table 3
Degree of toxicity of wastewater samplesfrom bakeries during bioassay by
phytotesting

The wastewater samplesfrom abakery enterprisebefore purification by anaerobic


fermentation was characterized by a maximum degree of toxicity, indicating the
presence of toxic substances that inhibit the growth of the test organism.
The survival rate of C. steinii during biotesting of the wastewater is presented
in table 4.
The survival rate in wastewater № 2 is in the range of 90–95% after 24 hours of
exposure, suggesting a high degree of safety of the baking enterprise’s wastewaters
after treatment by anaerobicfermentation. The survival rate in wastewater № 1 is
35% lower thanin the control sample, which confirms the presence of substances
that exhibit toxic effects.
Table 4
Survival rate of ciliates Colpoda steinii in bioassay samples of wastewater
from bakeries
Water Security: Monograph 215

The results of experimental studies using animal cells as the test-organisms are
shown in table 5.
Table 5
Degree of toxicity of wastewater samples from bakeries in bioassays on
animal cells

The results of theseexperimentsconfirmed the presence of toxins in waste


watersfrom the baking enterprise which were oppressive to animal cells. However,
the wastewatershada high degree of safety after treatment.

CONCLUSIONS
At the end of the experiment, we can conclude that the degree of toxicity of
wastewaters samples frombakeriesafter treatment by anaerobic fermentation varies
by 2 - 10%, which indicates their safety. The most toxic wastewater samples were
thosebefore treatment.
The comparative study of the toxicity of wastewaters samples from bakeries
before and aftertreatmentby anaerobicfermentationbioassay systems, belonging to
different taxonomic groups was conducted. These results confirm the pattern of
toxicity inthe samples usingdifferent classes of bioassay system, and, consequently,
the possibility to use themas bioassay-organisms in determining the safety of
bakerywastewaters.

REFERENCES
1. The Law of Ukraine «About the quality and safety of foods and food raw materials»
[Electron resource]: the camp of 17 piles. 2009 p. / Verkhovna Rada of Ukraine-mode access:
http: //searh/ligazakon.ua/l_doc2/ (in ukr.)
2. Zaitseva, O. (1994).The modern biotesting of waters, requirements to test organism
and test-functions from positions of comparative physiology and physiological adaptational
processes. JL Evolutionary, 30, number 4, 575-592.
216 Water Security: Monograph

3. Filenko, O. (2007). Biological methodsin quality control of the environment.


Ecological systems and devices, 6, 18-20.
4. Vosyliene, M. (2007). Review of the methods for acute and chronic toxicity assessment
of single substances, effluents and industrial waters. ActaZoologicaLituanica, 1, 3-15.
5. Joshi, V.K. & Satish Sharma (2011).Food Processing Waste Management. Treatment
and Utilization Technology -285-288
6. Flerov, B., Volgograd, (1983). Bioassay: terminology, objectives, perspectives. Institute
of Biology of Inland Waters, 13-20.
7. Wadhia, K. (2009). Ecotoxicological characterization of waste. Springer Science
Business Media, 145-152.
8. Terekhova, V. (2009). Bioassay techniques in the evaluation of ecotoxicity of wastes.
Ecology of production, 1, 48-51.
9. Yung-Tse Hung, Lawrence K. Wang, Nazih K. Shammas (2012). Advanced Waste
Treatment in the Food Processing Industry. CRC Press, 223-243
10. Sokolova, S., Volgograd, (1983). On the question of unification of methods for
toxicological experimentsaimed in bioassay Theoretical questionsofbioassay: Sat. scientific.
tr. Institute of Biology, inland waters, 79-81.
11. Rubin, A. (2000). Biophysical methods in environmental monitoring. Soros
Educational Journal, V.6, №4, 7-13.
12. Barna, Sz., Szabo Z., Fleky , G., Dobolyi, Cs. (2006). Eco-toxicological evaluation
of soils polluted with copper. Trace Elements in the Food Chain, 186-190.
13. Sanitary rules and norms of surface waters protection from pollution. SanPіN 4630-
88; pravila, normy od 04.07.1988 № 4630-88(in ukr.)
Water Security: Monograph 217

ENVIRONMENTAL ASSESSMENT OF WASTEWATER TREATMENT


TECHNOLOGIES FOR THE DAIRY INDUSTRY

Ass.Prof., PhD. Roman Shevchenko


Ass.Prof., PhD. Anna Kiriyak
Mas. Mariya Korotkevich
Prof., Dr.Sc. Ivan Krestinkov
Ass.Prof., PhD. Tatyana Shpirko
Odessa National Academy of Food Technologies, e-mail: onaft-eko@yandex.ua,
Ukraine

ABSTRACT
The analysis of modern wastewater treatment methods for the dairy industry is
carried out. The eco-efficiency was calculated for most representative technologies.
It justifies the choice of the best technology and prepares recommendations for its
optimization in terms of eco-efficiency. On the basis of the analysis, it is established
most environmentally friendly on the emission of greenhouse gases is anaerobic-
aerobic treatment technology. This technology involves the following main stages
of wastewater treatment: flotation with flotation sludge separation, cleaning of pre-
treated wastewater in the anaerobic reactor, aerobic post-treatment in a membrane
reactor, anaerobic digestion of flotation sludge and excess sludge from anaerobic
and aerobic reactors in the digester. From an environmental point of view, this
optimal technology also leads to the formation of additional resources in the form
of bio-fertilizer and biogas energy, which increase the economic benefit of
technology. It was revealed that methane fermentation of sewage is the most
important step of investigated technology, which significantly affects the ecological
effect of the cleaning process. The balanced on optimum parameters methanogenesis
determines the course of the entire further treatment process, provides efficiency
and pollutant removal rate of the wastewater and the overall economic effect of the
technology implementation.
Keywords: dairy wastewater, environmental assessment, a carbon trace,
wastewater treatment technology, local treatment facilities, methane fermentation.

INTRODUCTION
For today level of impurity of environment products of ability to live of the
person reaches a critical point. Special influence is necessary on sources of waters.
One of the greatest consumers of water are the food-processing industry enterprises,
218 Water Security: Monograph

where 95 % of the sewage formed in the course of manufacture, polluting substances


containing high concentration. For finished goods reception it is spent several times
more waters, than it is processed raw materials.
Now the food-processing industry enterprises are provided by own complex of
constructions for sewage treatment. At the best the enterprises dump the drains in a
city sewer network but because in the specified waste specific pollution can contain,
their dump in the water drain is limited by a number of requirements.
Working out effective resource conservation technologies scheme of processing
of sewage of this category will allow creating system of clearing of the drains which
quality will meet standard requirements at dump of sewage in the city water drain
or local waterways, a reuse.
Sewage of food manufactures represents difficult dispersed systems and contains
various pollution by the nature: fat, milk, scales, wool, blood, salts, sand, fibers,
mineral insoluble impurity, washing-up liquids, etc. It complicates work of sewer
networks, pump stations and treatment facilities. Sewage of food manufactures is
various both on componential structure, and on concentration of polluting
substances and is difficult physical and chemical system.

METHODOLOGY OF RESEARCH
In aerobic conditions dominant gas causing the greenhouse effect is carbon
dioxide. In anaerobic be analyzed along with emissions of carbon dioxide and
methane emissions. Treatment of surplus sludge and raw sludge is usually
performed as wastewater treatment plant and includes compaction, stabilization,
dewatering and disinfection.
The calculation of greenhouse gas (GHG) emissions of local sewage treatment
plants (LSTP) during work to clean highly concentrated wastewater dairy
enterprises will implement the methodology of the Intergovernmental Panel on
Climate Change (IPCC) [1−2]. This methodology offers incremental calculation
using the methodology of the second and third level calculation.
Carbon footprint (CF) – a set of greenhouse gas emissions made directly and
indirectly, a person, an organization, a region associated with the implementation
of some activities, services, manufacture products or even its life cycle as a whole.
Sun can assess calculating greenhouse gas emissions and especially carbon dioxide,
methane, nitrous oxide and substances containing chlorine. IPCC methodology
applied to biological treatment plants intended for the treatment of domestic and
industrial waste water, or mixtures thereof.
Consider the following scenarios sewage and sludge treatment sludge:
˗ biological wastewater treatment processes include nitrification and
denitrification, accompanied by the release of nitrogen oxide;
Water Security: Monograph 219

˗ treatment plant work correctly (failure to discharge sludge from primary


settling tanks, overload bioreactor) that causes the formation of methane;
˗ dehydration sediment sludge in areas with subsequent placement at the site or
used to dehydration and improvement of soil;
˗ sludge processed in anaerobic reactor (digesters) from burning biogas or biogas
to produce electricity and heat. The residue from the anaerobic reactor dehydration
stored at the site or introduced into the soil;
˗ residue is burned to produce a thermal or electrical energy.
Definition sun any company, as it was first proposed in the World Resources
Institute [3] can be carried out in several approximations, different scope of coverage
processes.
Approaching 1. Calculation of greenhouse gas emissions is limited only
production site of the company. This may be the direct emissions from pipes
(organized emission sources) as a result of fossil fuel combustion and fugitive
emissions, which is also the result of the processes at the site (e.g. refrigerant leakage
from refrigerators or air conditioners).
Approaching 2. In this case, take into account all the electrical and thermal
energy consumed on-site. As is usually supplied with electricity networks centrally,
in denim approaching greenhouse gas emissions are determined by multiplying the
amount of energy consumed for a national factor that determines GHG emissions
in CO2-eq per unit of electricity consumed.
Approaching 3. The approach taken into account greenhouse gas emissions
outside the production site, not associated with the generation of energy consumed
discussed now. For example, it used GHG emissions from transport enterprises,
including public and private transport, transport of workers. There may also be taken
into account emissions caused by the production of materials used now analyzed.
Thus, for the construction company, for example, can be considered the emissions
that accompany the production of cement and bricks used in the construction of
buildings and structures. However, a number of techniques considered that such
records for the excess inventory of emissions, because it can lead to double counting
the same reductions in the overall balance of the country.
Traditional local treatment facilities of the enterprises of the food-processing
industry work a stably because of non-uniform water delivery on clearing, both by
quantity, and on quality of drains with considerable fluctuations of chemical
consumption of oxygen. Often it is connected with one-shift work of the enterprise
and features of technological process.
Therefore the substantiation of a choice of the most effective technology and
working out of actions for increase of efficiency and ecological safety of recycling
of sewage advances to the forefront.
As an example, consider the features of volatile organic dairy company.
Wastewater dairy industry is classified as highly unstable and has the quality and
220 Water Security: Monograph

quantity indicators. The greatest prospect for treating highly wastewater is biological
treatment methods. In the dairy industry sewage problem is not completely solved.
Conventional wastewater treatment technology is highly imperfect and, in some
cases, do not provide the required degree of purification and recycling of by-
products generated in the process.

RESULTS OF RESEARCH
Wastewater number of dairy plants are generally relatively small – a few hundred
m3 per day. Depending on the number of scale wastewater may range from 20 to
2000 m3 per day. Wastewater formed mainly from washing equipment, motor
vehicles, and rail tank facilities. The dairy industry can be divided in cheese-making
plants and urban dairies other than the level of contamination of waste water [4–6].
In the dairy industry generated two types of production wastewater
contaminated and uncontaminated. Wastewater processing enterprises milk contains
significant amounts of organic substances, including many protein compounds,
which quickly rot and cause pollution. Wastewater is also characterized by a high
content of nutrients (nitrogen, potassium).
Sewage purification using complex, which includes mechanical, chemical,
physic-chemical and biological methods [6-9]. General classification methods of
sewage treatment is shown in fig. 1 and almost all methods are used in practice.
Typically, mechanical and chemical methods of handling wastewater are ancillary.
Because they are used as the first stage to send wastewater to the main purification
or as the final stages of treatment before being discharged into natural water bodies.

Figure 1. Classification methods for sewage treatment


Water Security: Monograph 221

Clearing of industrial sewage of polluting substances at the enterprises of the


dairy industry it should be carried out on local treatment facilities. There are various
methods of their clearing. It is expedient to apply methane fermentation at which
concentration of pollution essentially decreases and in addition allows receiving
from 1 m3 sewage more than 15 m3 biogas. The further application of aerobic
clearing becomes effective and does not demand considerable expenses. In this
connection research of process of methane fermentation and aerobic clearing of a
waste of food manufactures and working out on this basis complex conservation of
resources technologies is actual, can be in demand in the industry
Therefore following technologies of clearing СВ will be considered further:
1. Т1 – traditional aerobic with use aeration tank (fig. 2);
2. Т2 – traditional anaerobic-aerobic with trickling filter use (fig. 3);
3. Т3 – anaerobic-aerobic with use aero tanks and methane tank with biogas
manufacture (fig. 4);
4. Т4 − anaerobic-aerobic with use anaerobic the reactor, methane tank and
membrane the reactor as aerobic additional cleaning with biogas manufacture (fig. 5).
Т1 – traditional aerobic with use aerationtank.
On fig. 2 it is shown the traditional scheme full biological aerobic clearing of
sewage with use aerations to the basic treatment facilities. Such scheme can be used
as in the conditions of the enterprise – sources highly sewage, and at the centralized
clearing stations.

Figure 2. Scheme of a traditional wastewater treatment


222 Water Security: Monograph

After mechanical clearing on lattices, sand trap and primary sediment bowls the
wastewater moves on aero tanks in aerobic conditions polluting substances are
oxidized under the influence of organisms of active silt. For maintenance of normal
ability to live of these organisms, for silt maintenance in a suspension and for silt
and sewage hashing in aerotanks constantly moves. Sludge remover the mix is
divided on a secondary sediment bowl after aero tanks. The part of the detained silt
– superfluous active silt (SAS). Other part of activity restoration in a regenerator,
comes back in aero tanks for maintenance in it constant concentration.
For disinfecting the cleared water is disinfected, and then it can be dumped in
natural reservoirs. A lack of this and of some similar schemes for use as local system
of clearing necessity of recycling of considerable volumes of a deposit and active
silt, and also necessity of the organization of a sanitary-protective zone.
Т2 - Traditional anaerobiont-aerobic with biofilter use under the scheme,
wastewater the ambassador of constructions of mechanical clearing (a lattice, sand
trap and primary sediment bowls) water arrives on biofilters, and then in secondary
sediment bowls in which the biological film (biofilm) which is taken out by water
from the biofilter is late, further water arrives in the contact tank, is disinfected and
dumped in a reservoir. Passing through filtering loading of the biofilter, the polluted
water leaves in it weighed colloidal organic substances which have not settled in
primary sediment bowls. They form a film densely occupied by microorganisms.
Biofilm microorganisms oxidase organic substances and receive energy necessary
for their ability to live. Thus, from sewage organic substances leave, and in a
biofilter body the weight of a biological film increases. Fulfilled the film also has
become lifeless is washed off by proceeding water and taken out from the biofilter.

Figure 3. Scheme of biological


wastewater treatment on bio filters
Water Security: Monograph 223

T3 - anaerobic-aerobic aeration tank and using biogas digesters.


First on the grid and sand trap removed from wastewater coarser suspended
particles. Then the liquid is fed into digesters where withdrawn the bulk of polluting
substances in anaerobic (without oxygen) conditions under the influence of activated
sludge microorganisms. It formed biogas collected in gas container, and then enters
the combustion in the boiler room of the company. The resulting heat provides the
necessary temperature conditions in digesters, and sometimes can be given to the
energy needs of primary production or sold to other consumers.
Anaerobic activated sludge separated from the waste water in the secondary
settling tank. This activated sludge containing valuable biologically active
substances widely used as a fertilizer or supplement to the feed of farm animals.
For the final disposal of pollutants from the waste liquid used aerotanks I and II
degrees, are continuously fed air to create aerobic conditions.

Figure 4. Scheme of sewage


treatment with anaerobic digestion

After aerotanks an aqueous compositions divided into components in the


secondary clarifier. Part of the sludge –after a regenerator where it recovers
biological activity, comes back in the aeration tanks to ensure constant concentration
of sludge in the building. SAS fed into digesters on origin to obtain additional
biogas.
Before being discharged into natural water bodies clean liquid must be
disinfected.
T4 - anaerobic-aerobic using anaerobic reactor and membrane reactor
methane tank as aerobic purification of biogas production.
224 Water Security: Monograph

Fig. 5 presents an improved scheme anaerobic-aerobic treatment of highly


concentrated wastewater [6], which is different from the previous use of flotation
to remove suspended particles, two digesters for separate cleaning sludge in
mesophilic regime and sewage – in thermophilic and membrane bioreactor as more
modern aerobic purification method wastewater.

Figure 5. Diagram of anaerobic-


aerobic wastewater treatment

According to the scheme of wastewater enterprises entering the mechanical


treatment unit for removal of coarse impurities by gravity and enter the buffer
capacity, where the averaging volume of waste water of neutralization and pH
control. Then the average runoff sent to floaters, which, through the use of physical
and chemical methods of cleaning, removes suspended particles (SP) and fats.
Purified bulk of water SP served in the anaerobic reactor, where as a result of life
methanogenic bacteria decomposes organic pollution in wastewater component gas
(biogas) and water. Next purification of waste water is carried out on the membrane
modules (MBR). The precipitate that formed during cleaning, served in a methane
fermentation reactor, during which also stands biogas and sludge stabilization is
that it provides security in sanitary terms. After the methane reactor, the digested
sludge is fed to the filter press for dewatering to reduce its volume. Dehydrated
sludge suitable for disposal as fertilizer or landfill to landfill. Biogas formed in
digesters with methane content of 70-85% under constant pressure enters the CHP
unit where the combustion process produces heat and electricity or burned on its
own boiler for the needs of the enterprise.
Source establishment of sewage – the dairy industry. Number of educated
concentrated wastewater – 295 m3 / day of wastewater (including 35 m3 whey) [6].
Water Security: Monograph 225

The results of calculations of GHG emissions from all sources of emission of


each of the investigated technologies built in shown in fig. 6-7.

T1 – traditional T2 – traditional T3 – aerotank T4 – anaerobic reactor+


(aerotank) (biofilter) + methane tank methane tank+ methane
Figure 6. Total GHG emissions in tons of CO2-eq.. When cleared wastewater studied
techniques without the use of biogas formed

T1 – traditional T2 – traditional T3 – aerotank+ T4 – anaerobic reactor+


(aerotank) (biofiltr) methane tank methane tank+ methane
Figure 7. Total GHG emissions in tons of CO2-eq.. When cleared wastewater technologies
studied with regard to the use of biogas formed

CONCLUSIONS
Analyzed 12 selected technologies and concluded that most of them have
significant drawbacks. Options technologies that do not include biological treatment
stage cannot be applied to wastewater concentrated, they can only serve to pre-
treatment for LSTP.
Further studies were selected 4 main technologies that are fundamentally
different in one or more stages of purification. Investigated anaerobic treatment
using aeration tanks and biofilters. And anaerobic-aerobic treatment of aeration
tanks and digesters for processing formed in the aeration tanks sediment sludge and
anaerobic digesters as a pre-treatment before aerobic cleaning, sludge digesters for
processing sludge and membrane reactor for purification. In the last two cases
envisaged formation of biogas, the latter also been arising as a result of fertilizer
processing sediment sludge.
226 Water Security: Monograph

The criterion for the environmental assessment was to determine studied


technology the carbon footprint of each technology for the purification step,
utilization of sediment sludge, and the use of energy and fluids, transportation,
reagents and materials, biogas in the latter two cases. Assessment of the carbon
footprint of treatment facilities included a calculation of GHG emissions, especially
CO2, CH4, N2O.
The results of the calculations for the IPCC methodology [10] concluded that
the most environmentally safe largest full GHG emissions generated in the process
of implementing the technology, is the second version of the technology anaerobic-
aerobic treatment. The size of the issue was on T4 – -12.86 t CO2-eq. / Year (T1 –
2067.98, T2 – 1946.09, T3 – 472.68). Negative emissions for this version of the
technology is the result of the formation of biogas in the anaerobic treatment of
wastewater and sediment sludge, as a consequence of overlapping considerable size
energy costs during operation technology for LSTP.

REFERENCES
1. IPCC Guidelines for National Greenhouse Gas Inventories (2006). Volume 5, chapter
6 “Wastewater Treatment and Dis-charge”, from http://www.ipcc-
nggip.iges.or.jp/public/2006gl/index.html.
2. Product life cycle accounting and reporting standard. World Resourses Institute. – 146
p., from http://pdf.wri.org/ghgp_produkt_life_cycle_stendart.pdf
3. World Resources Institute (2001) The greenhouse gas protocol: A Corporate
Accounting and Reporting Standard. World Business Council for Sustainable Development.
The Hague p. 27.
4. Krusir, G.V., Shevchenko R.I., etc. (2014) Waste management food production. –
Odessa: “Astroprint”. – 257 p. (in ukr.)
5. Levandovsky, L.V. (2013) Prirodoohoronnі tehnologії that obladnannya. – K.: NUFT.
– 223 p. (in ukr.)
6. Wastewater treatment of the food industry with production of biogas, from
http://www.ekoton.com/o-nas/publikacii/ochistka-stochnyh-vod-predpriyatij-piwevoj-
promyshlennosti-s-vyrabotkoj-biogaza1. (in rush.)
7. Technical reference for water treatment (2007): 2t. T1: New magazine. – P. 1-775.
ISBN 5-901336-05-4 (in rush.)
8. Technical reference for water treatment (2007): 2t. T2: New magazine. – P. 776-1696.
ISBN 5-901336-05-4 (in rush.)
9. Qin Yuje, Wu Jiandong1, Ouyang Hai1 (2013) The Application of Organica Ecological
Technology in Residential Sewage Treatment, from http://www.SciRP.org/joumal/jep
10. Begak T., etc. (2013) Monitoring and reducing carbon footprint of Russian water end
wastwater companies. Methodology for assessing carbon footprint of wastewater treatment
plants. Begak T., M. Guseva, Ya. Molchanova, E. Averochkin VL Sagayduk. - M.: D.
Mendeleev University of Chemical Technology of Russia. – 54 p.
Water Security: Monograph 227

WASTEWATER TREATMENT OF COMPANY


«TERNOPIL MILK PLANT»

Ass.Prof., PhD. Alla Shybanova1


Prof., Dr.Sc. Volodymyr Pohrebennyk1
Prof., Dr.Sc. Olena Mitryasova2
PhD. Roman Politylo1
1 Lviv Polytechnic National University, e-mail: vpohreb@gmail.com, Ukraine
2 Petro Mohyla Black Sea National University, e-mail: eco-terra@ukr.net,
Ukraine

ABSTRACT
The dairy industry is one of the major consumers of fresh water and it is a source
of formation of significant amounts of wastewater. Taking into account that at many
milk plants treatment facilities are either absent or are ineffective, the question of
effective local wastewater treatment is very important.
The lack of free space on the territory of milk plant suitable for the installation
of wastewater treatment, heavy fines for sewage and the constant threat of stopping
of the company, up to closing, is stimulated by the development of efficient and
compact systems for a partial solution of problem.
The aim of the work is developing of technological solution to the problem of
quality wastewater of «Ternopil milk plant».
The basic technological schemes of wastewater treatment were analyzed. The
technological scheme of treatment facilities for wastewater treatment was suggested.
To reduce the anthropogenic impact on the hydrosphere by enterprise is
efficiently to use the system of mechanical and physical-chemical methods for
wastewater treatment.
Using this technology we can reduce the economic losses caused by discharge
into urban sewage treatment facilities pollutants in concentrations greater than the
maximum allowable concentrations.
Keywords: milk plant, wastewater, purification, flowsheet, mechanical, physical
and chemical methods.
228 Water Security: Monograph

INTRODUCTION
The food industry is one of the largest consumers of fresh water. Wastewater of
its companies is by far the most polluted. The dairy industry is one of the major
consumers of fresh water and it is a source of formation of significant amounts of
wastewater. Specific consumption wastewater of milk plants averages 5-7 m3 per
1 ton of milk, which is processed, but often, especially in plants with outdated
technology, this value is much higher.
Wastewater generated during milk processing is divided into contaminated and
uncontaminated. The source of uncontaminated wastewater is condensates of
refrigeration systems that use for cooling milk and dairy products. They immediately
often use in systems of water recycling or re-use for washing equipment and
containers, as well as for other industrial purposes. Contaminated wastewater is
approximately 20 to 50 percent of total waste. Polluted industrial wastewaters of
the dairy industry include losses of milk and dairy products, waste products,
reagents, which are used for washing containers and impurities, which are washed
away from the surface of containers, equipment, floors and panels facilities. These
wastewaters have mostly neutral reaction, but it may be changed to slightly acidic
or slightly alkaline side during the relevant emission pollution, serum or residue of
detergent alkaline solutions.
Wastewater of milk plants contains high concentrations of organic contaminants
(fat, protein, lactose), inorganic compounds and synthetic surfactants (detergents).
The composition and concentration of wastewaters contaminants depend on the
profile and performance of enterprises.
For the treatment of wastewater milk plants is used different methods. The
choice of method depends on the number and characteristic of the wastewater
pollution and condition of their discharge, which are established by environmental
authorities and municipal institutions of water supply and sewerage. According to
the current requirements, wastewater of milk plants before its discharge to the city
sewer or own biological treatment facilities, should be purified locally.
Local treatment facilities of milk plants must be compact, simple and reliable
in operation, providing the necessary degree of wastewater treatment. For this
purpose, a widespread coagulation followed by settling or flotation, but its use in
milk plants has several shortcomings: high doses of traditional types of coagulants,
the need for adjusting pH, no coagulation process stability and as a result,
insufficient degree of reduction in the concentration of organic contaminants. This
is due to the heterogeneity of wastewater composition of milk plants that combine
usually wastewater from various dairy products. Taking into account that at many
milk plants treatment facilities are either absent or are ineffective, the question of
effective local wastewater treatment is very important.
Private joint-stock company «Ternopil milk plant» is located in the densely
populated area of the city. It does not has much free space for the introduction of
modern systems of local sewage treatment followed by discharge in municipal
Water Security: Monograph 229

wastewater system. Historically, all industrial wastewater is discharged into the


municipal sewage system in urban treatment plants. This leads to the fact that the last
two years was observed cases of discharging unreasonably large amount of wastewater
which was reason of further accidents on urban wastewater treatment plants. One of
them was the death of fish into the river Seret. The lack of free space on the territory
of milk plant suitable for the installation of wastewater treatment, heavy fines for
sewage and the constant threat of stopping of the company, up to closing, is stimulated
by the development of efficient and compact systems for a partial solution of problem.
The aim of the work is developing of technological solution to the problem of
quality wastewater of «Ternopil milk plant».

METHODOLOGY OF RESEARCH
The qualitative and quantitative characteristics of wastewater depend on the
capacity of milk plant and product range, while water consumption is on average
3-12 m3/t of milk [4].
First of all, the problem of wastewater treatment, which is generated in the
technological process of milk production, is the problem of decontamination.
Wastewater of milk plants contains fat (100 mg/l) and many different bacteria.
An integral indicator of biochemical oxygen demand (BOD) traditionally
characterizes the number of bacteria in wastewater. In wastewater of milk plants
BOD reaches values of 1800-2000 mg/l. Traditional biochemical purification
methods allow purification water, starting from 600 mg/l.
In the sanitary norms SN 245-71 for dairy enterprises (milk plants) is established
sanitary protection zone of 150 meters from the purification complex to the main
building of dairy production, where the technological process of milk processing
and dairy production is made. The chemical composition of wastewater of milk
plant is shown in table 1.
Table 1
The chemical composition of wastewater of milk plant
230 Water Security: Monograph

Using presented data in Table 1 we can see, that the highest values of BOD have
characterized significant biological charged of wastewater of milk plant [5].
Estimating of wastewater treatment as the complex problem, we should consider
existing methods, objective analysis of which will assess the advantages and
disadvantages, and determine the prospects for further research in this area [7].
The analysis of the literature showed that in Ukraine and modern European
countries is conducted an intensive search for rational and efficient methods and
technologies for treating highly concentrated wastewater of food industry (including
dairy industry). The most common solution in this area is a combination of classical
purification methods with new methods [8].
For wastewater treatment of industrial enterprises are used the following
methods:
– Mechanical (sedimentation, lattice, settling tank, precipitate treatment,
filtration);
– Physic and chemical (flotation, sorption, extraction, ion exchange,
electrochemical);
– Chemical (oxidation, neutralization, recovery, coagulation, flocculation);
– Biological (biofilters, biological ponds, aerotanks);
– Electrochemical;
– Combined.
Using these methods in each case depends on the nature of contamination and
degree of hazard impurities [9].
At the company during the milk processing and washing of equipment, piping,
containers and production facilities, highly concentrated wastewater is formed. This
wastewater contains insoluble flakes of proteins, particles of fat, soluble milk sugar,
solutions of proteins, detergents and disinfectants. The wastewater is the most polluted
by milk whey. The COD of milk whey, depending on the quality of milk, can reach
60,000 mgO2/dm3, which greatly complicates the wastewater treatment. The
qualitative and quantitative characteristics of wastewater depend on the capacity and
variety of products, which are produced by enterprise. The pH of wastewater is
determined by production technology and variety of products. For industries which
are not related to the process of lactic fermentation, pH is close to neutral value (6,8-
7,4 for milk plants). At the cheese-making plants, local dairy factories and other
enterprises that produce cheese and dairy products, a certain amount of milk whey is
discharged into the sewer network that causes the reduction of wastewater pH to 6,2.
The pH fluctuations often are caused by discharge into the sewer network
containing acid and alkaline reagents, which are used for washing equipment. The
sharp increase in short-term pH to 10-10,5 in total runoff can be explained by
discharging of large amounts of alkaline washing solutions, which are mainly used
at milk plants.
Prolonged presence of wastewater under anaerobic conditions (in the sewer
network, settling tanks) causes to souring fluid as a result of lactic acid fermentation
Water Security: Monograph 231

and leads to lower pH. Suspended substances in wastewater of milk plants are
presented by solid particles of dairy products (cheese slices, milk films) and other
impurities (soil, sand) that get into the sewers during washing equipment, containers
and facilities.
The main part of suspensions (90%) are organic substances usually protein
origin. The concentration of suspended substances varies widely depending on the
technological cycle of production. Fluctuations in the concentration of suspended
substances in wastewater of milk plants are observed throughout the day. The largest
number of suspensions comes in the initial period during washing equipment.
The content of fat in the wastewater of the dairy industry is mainly determined
by the variety of products and production technology. Depending on these factors
varies not only fat concentration in wastewater, but also kind of pollution. Wastewater
of whole milk production contains fats in the same form as the natural milk because
loss of milk is major sewage pollution. Fats of milk are the small balls, surrounded
hydrated protein shell, which very slowly float upon standing wastewater.
During the production of products with large content of fat (cream, sour cream,
butter), from milk are extracted large balls, then they adhesion and consolidation
together, as well as the protein shell is destructed. Then fat impurities contained in
wastewater of such production differ significantly by the type and concentration of
contaminants from such wastewater of other milk plants. Excretion of fat impurities
from wastewater during the production of products with large content of fat, such
as settling fluid, is much faster and more efficiently than from wastewater of other
productions.
Quality indicators of wastewater at the plant are summarized and presented in
table 2, taking into account the daily and seasonal irregularity. Thus, exceeding of
standard values for all parameters of the quality of wastewater of milk plant is
observed. The maximum allowable concentrations of substances in wastewater during
their discharge into the basin of river Seret, in mg / dm3, is given in the table 3.
Table 2
Quality indicators of wastewater of milk plant
232 Water Security: Monograph

Table 3
The maximum allowable concentrations of substances in wastewater during
their discharge into the basin of river Seret

Analyzing of existing projects of treatment facilities of milk plants, local and


international developments in this field, we can suggest two main technological
schemes of water purification.
Typical scheme of treatment facilities of milk plant with discharge into
water pond.
In this scheme, wastewater of milk production follow next stages of treatment:
– A biofilter aerobic filtration;
– Cleaning in aeration tanks;
– Filtering refining;
– Ultraviolet disinfection.
Biological processes occur in the aeration tanks with intensive mixing and cyclic
aeration. This allows to actively oxidize organic compounds. Inputting of reagent
in the aeration tanks additionally runs process nitrification and denitrification. The
final stages of purification are filtration after purification of and UV disinfection. It
will help to clean the water that is discharged to indicators that meet the standards
for industrial fishing ponds.
Water Security: Monograph 233

Typical scheme of treatment facilities of milk plant with discharge into


municipal drainage system.
In the case of discharge water into municipal drainage systems, wastewater
treatment follow next stages:
– Straining;
– Homogenization and neutralization;
– Degreasing;
– Flotation purification;
– Two-stage anaerobic treatment;
– Aerobic purification using biofilters;
– Dehydration of received precipitate.
In case, if such scheme of treatment, is based on modern technological
equipment, the residual concentration of dissolved organic matter does not exceed
140-200 mg/l for BOD and 40-45 mg/l for fats. These values include the possibility
of emergency discharges from the main dairy production.

RESULTS OF RESEARCH AND DISCUSSION


Developing of typical scheme of treatment facilities of private company
«Ternopil Milk Plant» with discharge into municipal drainage system.
The product range of private company «Ternopil milk plant» includes: milk,
yogurt, sour cream, kefir, butter and cheese short shelf life.
Wastewater of milk plant is highly contaminated by waste materials and products
and they should be cleaned. Wastewater of milk plant contains large amounts of
suspended organic substances. Particular attention is paid to the full using of milk
whey. It is not allowed to discharge milk whey into the sewerage.
Wastewater from the company without any pre-treatment in full size is
discharged into the sewer, which can cause a reaction of municipal institutions of
water supply and sewerage. A significant increase of fines and number of inspections
by environmental and public authorities in recent years has forced the company to
seek an alternative way of reducing wastewater from milk production.
The development of technological scheme of wastewater treatment of milk
production, that contains high concentration of fat and protein, with next discharging
into urban sewage, is a technical task. The wastewater treatment on milk plant
occurs with using technologies of locally purification before discharge into urban
sewerage. The analysis shows that the local sewage treatment reduces primarily the
content of fat particles. From fat, wastewater purified by sedimentation. During this
process, large particles of fat and other suspended particles are released. The
concentration of fat in these waters may exceed 100 mg/l. Sedimentation is
performed in fat collectors, which is set on production of wastewater of milk plant.
234 Water Security: Monograph

Another effective device that can easily be put into exploitation is averager with
aeration. It has next advantages:
– averager with aeration works without adding microorganisms and only a few
hours a day;
– averager with aeration resistants sudden discharges of wastewater and
increases the concentration of pollutants;
– one block averager with aeration reduces pollution from sewage by 60-70%
(for COD)
– amount of sludge formation is less than 1%;
– maintenance is not required specialist staff, special monitoring and analysis
of waste water every day.
Using special permitting, the amount of wastewater of private company
"Ternopil milk plant" is less than 500 m3 per day. According to the agreement, in
the sewer network of Ternopil municipal institution of water supply and sewerage
is provided wastewater discharge of 200 thousand m3 per year.
The choosing methods of purification and their combination depends on the
specifics of production and composition of the wastewater. To reduce the
anthropogenic impact on hydrosphere by private company «Ternopil milk plant» at
this stage it needs to use the system of mechanical and physical-chemical methods
of treatment for industrial wastewater.
The block diagram of mechanical and physical-chemical methods of wastewater
treatment is shown in fig. 1. The recommended scheme of mechanical and physical-
chemical methods of wastewater treatment of company «Ternopil milk plant» is
shown on fig. 2.

Figure 1. Block diagram of the mechanical, physical-chemical methods of wastewater


treatment

The technological scheme of the combination of mechanical and physical-


chemical methods for wastewater treatment of company «Ternopil milk plant» was
suggested. It is shown in fig. 3.
Water Security: Monograph 235

Figure 2. Recommended scheme of mechanical and physical-chemical methods


wastewater treatment of company «Ternopil milk plant»: 1 – milk processing shop;
2 – grate; 3 – averager; 4 – vertical settling tank; 5 – reagent section; 6 – recycling of
precipitate; 7 – two-step flow flotator; 8 – drainage

Figure 3. Technological scheme of wastewater treatment of company «Ternopil milk


plant»: 1 – grate; 2 – horizontal settling tank; 3 – vertical settling tank, fat collector;
4 – averager; 5 – flotator; 6,7 – tanks
According to the suggested scheme of mechanical and physical-chemical
methods of wastewater treatment of company «Ternopil milk plant», wastewater
from milk processing shop (1) fall into receiving tank by gravity. At the entrance to
the tank is installed mechanical grate (2). Trapped rubbish is unloaded to the
container for the next waste disposal in due course.
From the receiving tank, waste effluents are pumped to the projected averager
(3) where they are bubbled by air supplied to the aeration blower elements. Then
wastewater fall into a vertical tank, where is the initial settling. Then waste effluents
are entered into fat collector (4). The fat mass that accumulates in the receiving tank
can utilize by different ways (mechanically, using special equipment or a scraper
mechanism).
236 Water Security: Monograph

Then wastewater treatment is carried out by using flotation (7). The effectiveness
of wastewater treatment using the two-stage flotator of pressure with reagents (5)
is up to 95%. After wastewater treatment, they are discharged into the urban sewer
(6) if the requirements of local environmental authorities are satisfied.
The technology treatment of industrial wastewater involves falling wastewater
through a grid to the average for aligning sewage by concentration, acidity and costs.
The averager is an adjusting capacity, which provides the evenly filing
wastewater with averaged concentrations to the treatment facilities. Alignment in
average of quantitative indicators of wastewater (concentration of substances, pH)
is the result of intense mixing. Fullest mixing is achieved by using average of
bubbling type (fig. 4).
Bubbling is a mixing of wastewater by compressed air. It is carried out through
perforated pipes with the holes, which are located below. Pipes are placed exactly
by horizontally along the reservoir. Using air for mixing is particularly efficiently
in treatment facilities with total air system.

Figure 4.
Scheme of average
by bubbling type
1 – tank of average;
2 – bubbler;
3 – final device;
4 – exhaust chamber;
5 – intake openings;
6 – trays

After averaging wastewater enter to the fat collector. Fats contained in large
quantities in dairy wastewater are not allowed to discharge into the pond. Because,
they can cover large areas with a thin film of water surface and prevent the access
of oxygen, which causes deceleration of self-purification processes of the pond.
Beside this, fats that are contained in industrial wastewater also are a raw
material, which can be re-used to secondary processing for technical purposes.
Because wastewater are passed through the fat collector.
Fat collectors typically have form of rectangular tanks depth up to 2 meters.
Wastewater enters to the distribution tray and then to settling part of fat collector. For
detention of substances is used semiflooded wall at the end of fat collector and for
collect are rotary slotted pipes, which are installed at the end of each section. Pipes
can be rotated around its axis and adjust the height of the layer of fat that is removed.
Water Security: Monograph 237

The collected mass comes into receiving tank by pipeline where periodically is
pumped into another settling tank, where is a further separation of oil and water.
Water that obtained is returned to the fat collector and fat goes for further processing.
The precipitate formed in fat collector enters to dibholes where periodically is
pumped into tankers. To avoid clogging mud pipelines periodically are flushed with
a sharp pair. For washing of fat collector is provided supply of hot water.
For the complete separation of the fat particles in the settling tank temperature
is maintained above 60 °C. To increase the efficiency of fat collecting process is
applied fat collector with aeration (fig. 5).

Figure 5.
Fat collector that aerates:
1 – water-jet device;
2 – drainage collector;
3 – settling zone; 4 – flotation
zone; 5 – case; 6 – tray for
collecting fat mass; 7 – drive
and scraper; 8 – ring's unit;
9 – purified water;
10 – sewage; 11 – air-water
emulsion; 12 – precipitate

The scheme of designed fat collector is shown in fig. 6.

Figure 6.
Projected fat collector:
1 – supply of wastewater to
the unit; 2 – settling zone;
3 – the zone of precipitate
accumulation; 4 – pump;
5 – partition; 6 – tray under
precipitate and fat, 7 – scraper
mechanism; 8 – sensor of
level; 9 – production of
purified water
238 Water Security: Monograph

The fat collector is dedicated for primary treatment of wastewater from fat. The
main task of fat collector is preparation of wastewater for a deeper cleaning at local
wastewater treatment facilities and for avoiding contamination of sewer pipes by
fat deposits.
This sewage treatment facility is easy to use and widely used in sewage
treatment of milk plant.
The design of fat collector provides as manual and automated way to remove
precipitate and sludge. During the automatic removal of precipitate in a separate
tank, is allowed to submit a heavily polluted wastewater. The concentration of
pollutants can exceed 5000 mg/l.
During the automatic accumulation of sludge is recommended to use a separate
vessel. Its design can allow the distribution of the extracted contaminants into
separate fractions (eg. oil, precipitate, solid phase). This solution will allow
efficiently recycle waste from treatment facilities.
The flotator is a coagulator (fig. 7), which has two sections separated by
partitions inside the common case. The surplus of water through a rotary valve
enters to the transfusion pipe and it is diverted back into the intermediate tank. The
main part of water enters to upper part of the coagulator through the mixer, where
simultaneously from both tanks for preparation of reagent through rotameter and
ejector water enters with coagulant. Then during the movement of water from the
top and from bottom to top, which is changed during the passage through the lateral
septum, the process of coagulation is performed. Thus it is made formation of large
(2-3 mm) flakes.
From the coagulation section, wastewater with flakes is poured into the flotator
where is the separation of polluted flakes from water and rise them to the surface in
the form of foam.
Inside of flotator are located barrier, which directs the jet, and the screening
wall. Wastewater enters from the coagulation section to the bottom of the flotation
section. Also, coagulants are come to this section.
Contaminants that accumulated as a foam (sludge) are removed via the valve,
which is located in the receiving compartment. When valve is closed, sludge from
flotation section together with a small amount of water, moves into the slurry
section. Illuminated water downstream moves down along the screening wall and
then to the flotators collector. During commissioning flotator must fill with clean
(tap) water to the upper of working level, then polluted flake will separate of treated
water.
Sludge section is used to discharge sludge. The section is equipped by sensor of
relay upper level. Sludge section of flotator-coagulator and flotation tank of complex
are capacities, where sludge from section moves by pipelines into sludge tank of
station.
Water Security: Monograph 239

Removing the foam from flotator to trays is carried out by short-term raising of
the water level or using scraper mechanisms that are established in flotator. Water
losses during discharge of foam is 1,5% of the total of treated water. When removing
foam is performed by scraper mechanisms, speed of scrapers in rectangular sections
is up to 0,02 m/s. Bottoms of trays are carried out with a slope 0,025 towards the
withdrawal of foam. The upper edge of the tray is placed on the mark at
0,1–0,15 m above the water level in flotator.
The recommendations of speed of moving sewage and other parameters at
different stages of processing were given:
– The speed of water supply in flotator should not exceed its speed at the exit
from the tank where is the formation of flakes;
– The speed of illuminated water should be uniform; its values must be within
0,9-1,2 m/s;
– The volume of fluid that is lost when it is moving with flotation water to the
foam is 1,5%.
According to [6], the main parameters of pressure flotation unit have the
following meanings: pressure in the pressure tank is 0,2-0,5 MPa; stay of wastewater
in the pressure tank is 1-3 min., in flotator is 15-30 min.; the amount of liquid that
is recirculated is 30-50%; the volume of air to the saturation of water is 3,1%;
coagulants concentration of ammonium sulfate, ferric chloride is 25 mg / dm3 and
more; fat content in wastewater after the first treatment is 20-25 mg / dm3, after the
second treatment is 20-40 mg / dm3; solids content is 15-20 and 25-40 mg / dm3;
cleaning efficiency from mechanical solids is 80-95%.

Figure 7. Flotator: 1 – initial water; 2 – supply of coagulant; 3 – mixer of


hydrocyclone type; 4 – scraper; 5 – the first stage of flotation; 6 – second stage
flotation; 7 – settling chamber; 8 – intake tray; 9 – purified water; 10 – pump;
11 – ejector; 12 – saturator; 13 – diaphragm; 14 – pipeline distribution of water-air
mixture; 15 – drainage of precipitate; 16 – collector of foam
240 Water Security: Monograph

Power consumption is 0,47 kWh per 1 m3 of waste water [6]. Known pressure
unit designed for flotation have performance from 5 to 2000 m3 / h. The usual stay
of water in pressure capacity is 1-2 minutes. The volume of air is from 1,5 to 5% of
volume suspension parts, or emulsions (depending on the concentration and
properties of impurities).

CONCLUSIONS
Wastewater of «Ternopil milk plant» is characterized by exceeding of normative
values of quality indicators. All industrial effluents are discharged into the municipal
sewage system of urban treatment facilities. Incidents of discharging unreasonably
large amounts of wastewater are causes of accidents on urban wastewater treatment
facilities.
The basic technological schemes of wastewater treatment was analyzed. The
necessary of establish of efficient and compact sewage treatment systems was
determined.
The technological scheme of treatment facilities for wastewater treatment of
«Ternopil milk plant» was suggested. Using of technology of mechanical and
physical-chemical methods of sewage treatment can reduce amount harmful
contaminants in wastewater before its discharged into the sewer network of the city.
Using this technology at private company «Ternopil milk plant», we can reduce
anthropogenic impact on the hydrosphere and economic losses caused by discharge
into urban sewage treatment facilities pollutants in concentrations greater than the
maximum allowable concentrations.

REFERENCES
1.Varnam, Alan H. (2012) Milk and Milk Products – Technology, Сhemistry and
Microbiology Handbook, Volume 1.
2. Qasim, Syed R. (1999). Wastewater Treatment Plants, Planning, Design and Operation.
3. Yazaki, M. (2002). Milk and Dairy Products, The Best Treatment of Food Processing
Wastewater Handbook, Science Forum, 298.
4. DWA Manual. (2007). Industrial wastewater treatment – Legal bases, Process
technology, Wastewater treatment for selected industrial sectors, Production-integrated
environmental protection.
5. Wastewater Treatment in Food Processing Factories. (1970). Shinko Pfaudler Technical
Report, 13, 4.
6. Payer, David C. (2000). Treating and Disposing of Milking Center Wastewater.
7. Dennis, A., Burke, P.E. Dairy. (2001). Waste Anaerobic Digestion Handbook.
Environmental Energy Company.
Water Security: Monograph 241

8. Fox, P. F. and Mc Sweeney, P.L.H. (1998). Dairy Chemistry and Biochemistry. Ireland.
9. Graz, C.J.M.; McComb, D.G. Dairy. (1999). CIP-A South African review. Dairy, Food
Environ. Sanit.
10. Hui, Y.H. (1993). Dairy Science and Technology Handbook, Volumes 1-3.
11. METCALF and EDDY INC. (1991). Wastewater engineering treatment disposal, Mc
Graw-Hill Inc., New York, 178-195
12. Zhuravleva, L. L., Artemenko, S. E. and Ustinova, T. P. (2004). Selection of methods
of industrial wastewater treatment, Fibre Chemistry, 36(2), 156-159.
242 Water Security: Monograph

THE ENVIRONMENTAL QUALITY EVALUATION OF THE SURFACE


WATER RESOURCES OF THE INHUL RIVER WITHIN MYKOLAIV
REGION

PhD. Victor Smyrnov1


PhD. Sviitlana Smyrnova2
1 Petro Mohyla Black Sea National University, vsmirnov@e-mail.ua, Ukraine
2 Mykolaiv National University Named after V.O. Sukhomlynsky, Ukraine

ABSTRACT
The environmental quality evaluation of the surface water resources of the Inhul
River within Mykolaiv Region was carried out by hydro chemical indicators based
on observational data 2010-2015.It was established that excess of concentration of
chemicals was recorded at the level to 1-3 MPC according to the most water tests
in the Ingulets’ River. The level of pollution of surface waters should be attributed
to the second category as “moderately hazardous” Elements of 2-3 hazard class
(iron, sulfates, phosphates, surfactants, petroleum products, nitrites, biological
oxygen demand (BOD), salinity take predominantly place in some pollutants.
Keywords: the maximum permissible concentration, the quality of drinking
water, surface water resources, hydro chemical indicator.

INTRODUCTION
The quality evaluation of the surface water resources which are used for
householding and drinking purposes is a priority direction of the research and it is
carried out from 01.01.2000 in Ukraine, according to the document State sanitary
rules and norms №383 (186/1940) “Drinking water, hygienic requirements for
water quality of the centralized householding drinking water supply" [1]. The
document regulates 54 controlled indicators of quality of drinking water. Sanitary
rules presented in this document are stricter compared to the previous document
and they are approaching to European standards.
More than 80% human diseases as the WHO affirms are related to water quality
which people consume. Therefore, compliance with regulations and analysis of the
quality of drinking water is essential to maintaining health, improving work
conditions and living standards of the population. Namely, the problem of providing
the population with quality drinking water is highly relevant for Mykolaiv Region.
Water Security: Monograph 243

Monitoring of hydro chemical indices of water resources of Mykolaiv and


Mykolaiv Region is conducted by Mykolaiv Regional Management of water
resources [2], State Environmental Inspectorate in Mykolaiv Region [3], which are
highlighted within the Regional report about the state of environment in Mykolaiv
Region for the period of 2010-2015 years [4]. The results of these researches and
general data show a rapid deterioration of the situation to ensure the population with
drinking water.
In order to implement of the State strategy of achievement environmental
standards safe for human and sustainable using of natural resources in the Mykolaiv
Region the Program “Drinking Water of Mykolaiv Region)” was worked out
according to the decision of Regional Council of 28 March 2008 №5 [5] for the
period to 2020 under the Law of Ukraine On State Target Program “Drinking Water
of Ukraine” for 2011-2020 [6].
The Inhul River is one of the sources of householding and drinking water in
accordance with Chapter II Section. 2.1. of the mentioned Program [5] for
Bashtanka and certain villages.
In the framework of the Regional Program “Drinking Water of Mykolaiv
Region)” for the period to 2020 the main problems which realize the approach to
sustainable using of water and protection of water resources [5] were identified:
- implementation of scientifically based system of water using and water
consumption, which would provide maximum with water all sectors of the economy
on the one hand, and on the other hand, did not allow such changes in aquatic
ecosystems, which could lead to their degradation and depletion in the future;
- development and implementation of the most perfect methods of protection
water recourses from eutrophication;
- the creation of water protection systems in places of excessive concentration
of pollutants of water bodies and introduction of the automated control systems of
water protection complexes;
- development and implementation of integrated water supply and sewerage and
of water protection measures on the scale of the industrial regions and entire river
basins;
- development and implementation of wasteless and waterless technology,
transfer the industrial enterprises to water recycling, construction of water treatment
facilities;
- rational distribution of productive forces on the basis of water factor,
scientifically justified placing of slurry sectors of the economy, avoiding excessive
concentration of industrial companies that consume large amounts of water in
shallow and arid areas.
All these measures show the relevance and indicate the urgent need for
summarizing data. Accordingly the purpose of the work is the optimization of
244 Water Security: Monograph

monitoring data of hydro chemical parameters of surface water resources of the


river Inhul and analysis of tendencies of changes, the water quality in the Inhul
River within the limits of Mykolaiv region for the period 2010-2015.

METHODOLOGY OF RESEARCH
Experimental data of hydro chemical monitoring of surface water within the
river Inhul in Mykolaiv region serves as materials research which are provided by
Mykolaiv regional management of water resources [2], and the State Environmental
Inspectorate in the Mykolaiv region [3].
The following indicators: total iron, zinc, copper, chromium, nickel, petroleum,
chlorides, sulfates, phosphates, nitrites, nitrates, ammonium ions, salinity, BOD,
COD, surfactants were used for analytical research of qualitative and quantitative
composition of water.
The maximum permissible concentration (hereinafter - MPC) is the basic
criterion of hygienic assessment of danger of pollution of drinking water with
harmful chemicals, which characterizes the concentration of substances in the water,
in the case of excess of it, water is considered unsuitable for the needs of
householding and drinking purpose [7].
The hazard coefficient controlled substance is also used in the work Kn
calculated as the ratio of the actual content of controlled substances in the water
(C) to the maximum permissible concentration (MPC):

(1)

It is offered to use a formalized summary indicator of chemical pollution (ICP)


[8] for a cumulative evaluation of dangerous levels of water pollution in the
determination of zones of ecological emergency and ecological disaster. This
indicator is particularly important for of water bodies where contamination by
several chemicals is observed (n- substances) each of them greatly exceeds the
permissible level MPC and it is calculated as follows:

(2)
Where Cn – is the concentration (n- pollutant substance) in the water, MPCn -
maximum permissible concentration of index in water values of drinking purposes.
For an estimation of danger of pollution of drinking water for the sanitary
criteria, MPC, ) the following gradation is applied: allowable, moderately hazardous,
hazardous and extremely hazardous (table 1)
Water Security: Monograph 245

Table 1
Criteria for evaluating chemical contamination of drinking water [8]

Hydro chemical index of water pollution (hereinafter – WPI) which were


established by USSR State Committee for Hydrometeorology and belongs to the
category of indicators most commonly used to evaluate the quality of water bodies
[9; 10]. This index is a common additive coefficient is the average percentage of
MPC according to a strictly limited number of individual components:

(3)

where n – is the number of indicators used to calculate the index.


Depending on the size of WPI water objects are divided into classes (table 2).
Table 2
Class of water quality according to the water pollution index [9; 10]
246 Water Security: Monograph

A requirement is set: index of water pollution should be compared to water


bodies of one biogeochemical province and a similar type.

RESULTS OF RESEARCH
Hydro chemical observations of surface water resources of the Inhul River (left
tributary of the river Southern Bug) were carried out by the State Environmental
Inspectorate in Mykolaiv region in three points (5 places of sampling) from the
border of Kirovograd Region (village Rozanivka) to Mykolaiv. Data from
monitoring of surface water resources of the Inhul River were used in the research
for16 indicators, which were observed for 6 years from 2010 to 2015 [1]. During
the study it was conducted the optimization of monitoring data of hydro chemical
parameters of surface water resources of the Inhul River (fig. 1-3). For a specified
period tendency of increasing sulfates is defined from 420 mg/l (2010) to 460 mg/l
(2015) (fig. 1). The authors [11] indicate that the consumption of water containing
sulfates, exceeding MPC (100 mg/l) can cause diseases of the cardiovascular
system.Inhul River: surfactants, chlorides, sulfates, mineralization.

Figure 1. Dynamics of changes in of hydro chemical parameters in surface waters of the


Inhul River: surfactants, chlorides, sulfates, mineralization.

The dynamics of reduction in river water is typical for chlorides from 340 to
260 mg/l. Mineralization remains in a range of values from an average indicator
1600 mg/l. There is a varying of content of surface active agents (surfactants) in
surface waters of the Inhul River from 200 to 240 mg/l with average index of
230 mg/l. The concentration of surfactant exceeds MPC (100 mg/l) more than
doubled, which be explained by using of these chemicals in human life.
One of the main problems is water oil pollution. In the Inhul River the negative
tendency of increasing of concentration of oil in surface waters from 0,65 to
0,8 mg/l (fig. 2). Analysis of literary sources [11; 12] shows that water polluted
with oil products can cause gastrointestinal bleeding, kidney failure, liver toxicity,
violations of blood pressure.
Water Security: Monograph 247

Analysis of varying of heavy metals indicates a decrease zinc from 0,8 to


0,7 mg/l; copper from 0,09 to 0,07 mg/l; nickel from 0,6 to 0,5 mg/l. There was a
significant increase in the water content of chromium from 0,05 to 0,07 mg/l. The
increasing tendency of content of general iron in surface water resources of the
Inhul River especially attracts attention, so in 2010 concentration was defined at a
level of 1,5 mg/l, and in 2015 it reached 1,8 mg/l, which is almost five times higher
than the maximum permissible concentration (MPC) (0,3 mg / l). The authors point
out [11; 12] that iron compounds are able to accumulate in organs and tissues, which
in turn can cause dysfunction of the gastric mucosa.

Figure 2. Dynamics of changes in of hydro chemical parameters in surface waters the


Inhul River: heavy metals, petroleum products
Positive dynamics as for reducing the concentration of chemicals is observed
according to BOD from 4 to 3,6 mg/l and COD from 3 to 2,4 mg/l and for
phosphates from 10,3 to 9,0 mg/l. The concentration of ammonium ions in surface
waters of is defined in the range from 2,0 to 3,0 mg/l. (fig. 3).

Figure 3. Dynamics of changes in of hydro chemical parameters in surface waters of the


Inhul River: nitrates, phosphates, nitrites, BOD, COD, ammonium ions
248 Water Security: Monograph

Comparing the data of long-term observations of The Inhul River (during the
years 1970-1973 and 1991-1993) made by the Institute of Zoology named after I.I.
Shmalgauzen [4] and the current state of the river (monitoring data 2010-2015), it
can be noted tendency towards reducing the content of the aforementioned
indicators explained mainly by a significant reduction of irrigation. For comparison,
in 2013, of surface water for the needs of irrigation of agricultural land 46,56 million
m3 were withdrawn, those were 8 times less than in 1993. But there is increasing
nitrate concentrations in surface waters from 12.3 to 18.2 mg/l, which may indicates
the presence filtration of sewage into the water and can affect the biodiversity of
species hidrobiocenose. Analysis of literary sources [11] also indicates that water
polluted with nitrates can cause disease aqueous nitric methemoglobinemia, which
is manifested with cyanosis and increasing of blood content of methemoglobin,
lower blood pressure.
Ecological evaluation of surface water for the sanitary criteria involves
determining levels of exceeding the maximum allowable concentrations of
chemicals (fig. 4). Most cases of exceeded MPC for the phosphate content in surface
waters were registered to 78%. Second place is occupied by iron (69% exceeded
MPC) and petroleum products (48%). There is a relatively a high surge of
concentration in cross-sections of copper (40% inflated figures), salinity (34%),
ammonium ions (31%). Negligible amount of exceeding MPC determined by nickel
(2%) and chromium (3%) form the "unit pollution".

Figure 4. The number of cases of exceeding the MPC in the district of the Inhul River,%

The main criterion for evaluating the danger of pollution of drinking water with
harmful chemicals is the danger factor, calculated based on the MPC (fig. 5).
Analysis of the levels of exceeded MPC for the coefficient of hazard Kn of
chemicals allows to construct the number of reducing (data 2015): iron (5,9 MPC)>
sulfates (4,6 MPC)> phosphates (2,6 MPC)> petroleum products (2,5 MPC)>
Water Security: Monograph 249

surfactants (2,4 MPC)> nitrites (2,2 MPC)> BOD (1,8 MPC)> mineralization
(1,6 MPC)> ammonium ions (1,4 MPC)> COD (1,3 MPC) (fig. 5).

Figure 5. Coefficient of hazardous chemicals of the Inhul River

Notes: The trend line at Kn = 1.0 demonstrates a clear excess of the MPC.
Within the sample on the average values for hazard coefficient of surface waters
of the Inhul River belong to the second category of «moderately hazardous»:
- Kn value in the surface water amount to 5,7 and 4,6 for iron and sulfates,
respectively;
- Kn of pollution with elements of 2-3 class of danger within 2 to 3 for oil
products, phosphates, nitrites, surfactants.
For the averaged values coefficient the danger level of pollution elements below
the MPC (zinc, copper, chromium, chloride, nitrate, nickel).
For total indicator of chemical pollution ICP10 (26,1), the Inhul River refers to
«moderately hazardous» level of pollution, a slight excess of MPC of separate
chemical elements. According to the hydro chemical index of water pollution, the
surface water of the Inhul River (WIP = 2,5) belongs to Class IV of water quality,
which corresponds to "contaminated water".

CONCLUSIONS
Application of unified methodical approach of using of sanitary and hygienic
criteria allows estimating the level of contamination of surface water resources of
the Inhul River and their suitability to use it as drinking water.
It is established that the surface water resources of the river Ingul at a rate of
dangers belong to the second category of "moderately hazardous" by hydrochemical
250 Water Security: Monograph

pollution index - the level of «contaminated water». The priority pollutants should
be considered as elements of hazard class 2-3 (iron, sulfates, phosphates, surfactants,
petroleum products, nitrites, BOD, salinity).
The carried out research of priority tendencies of levels of pollution of surface
water resources the Inhul River within the Mykolaiv region is the basis for further
developing a set of recommendations to optimize anthropogenic activity.

REFERENCES
1. State sanitary rules and norms №383 (186/1940) «Drinking water, hygienic requirements
for water quality of the centralized house holding drinking water supply» (in ukr.)
2. Mykolaiv Regional management of water resources [Еlectronic resource]. - Access:
http://www.vodhoz.com.ua/. (ukr.)
3. State Environmental Inspection in Mykolaiv region [Еlectronic resource]. - Access:
http://dei.gov.ua/. (in ukr.)
4. A regional report on the state of the environment in the Mykolayiv region for the period
2010-2015. [Electronic resource] // Department of Ecology and Natural Resources of Mykolayiv
Regional Administration [site] / environment. National Report. - Access:
http://www.duecomk.gov.ua/. (in ukr.)
5. Decision number 20/7 On approval of the program «Drinking water of Mykolaiv in 2007-
2020 years» [Electronic resource]. - 2007. - Access: http://mkrada.gov.ua/documents/1045.html
6. The Law of Ukraine «On the National Target Program» Drinking Water of Ukraine for
2011-2020. As amended and supplemented by the Law of Ukraine on October 20, 2011 N 3933-
VI (the Law of Ukraine on October 20, 2011 N 3933-VI described this law as amended). (in
ukr.)
7. State sanitary rules and norms 2.2.4-171-10 "Hygienic requirements for drinking water
intended for human consumption" (Ministry of Health of Ukraine vid12.05.2010, №400). (in
ukr.)
8. Criteria for assessing the ecological environment areas to identify areas of ecological
emergency and zones of ecological disaster [Electron resource] / Ministry of Natural Resources.
(Methods of 30.11. 1992). - Access mode:
[http://www.businesspravo.ru/Docum/DocumShow_DocumI] (in ukr.)
9. Standards and criteria for evaluating the pollution of water bodies of St. Petersburg
Regional standard - [approved by the Chief State Sanitary Doctor of St. Petersburg 17.06.1996
and the Chairman of the Committee for Environmental Protection and Natural Resources of St.
Petersburg and Leningrad region 07.22.1996]. - Saint-Petersburg, 1996. - 11 p.(in rush.)
10. Snizhko, S.I. Evaluation and forecasting of natural water quality / S.I. Snizhko - K.:
Nicka center, 2010. – 262 p. (ukr.)
11. Datsenko, I. Preventive Medicine. General hygiene basics of ecology; Textbook / II
Datsenko, RD Habovych - K .: Health, 1999. - 694 p. (ukr.)
12. Health and basics of human ecology: Textbook for students. Executive. Honey. Proc.
Institutions / Y. Pivovarov, V. Korolik, L.Zinevych; Ed. Pivovarova. - 2-end ed. - M .: Publishing
Center «Academy», 2006. - 528 p. (in rush.)
Water Security: Monograph 251

WATER RESOURCES LANDSCAPE ECOSYSTEMS OF RIVER


VALLEYS OF THE CENTRAL BUG REGION

Prof., Dr.Sc. Svitlana Sovgira


Pavlo Tychyna Uman State Pedagogical University,
e-mail: SovgiraSV@yandex.ua, Ukraine

Abstract
The article deals with water resources landscape ecosystems of river valleys of
the Central Bug region. It has been established that water resources landscape
ecosystems according to their classification are the part of the main anthropogenic
landscape ecosystems. The classification is based on an integral environmental
functional and genetic principle that reflects the relationships between the natural
landscape with its functional use and environmental impacts and consequences. It
has been proved that they include water reservoirs, ponds, canals, environmentally
transformed water resources landscapes. It has been found out that the impact on
water resources ecosystems results in the alienation of valuable lands, their flooding
and flooding of forests, water pollution with untreated sewage and toxic substances,
radioactive and chemical contamination of an excessive concentration. The effects
are as follows: changes of hydrological, hydrochemical and hydrobiological regimes
of water bodies, increase of ground waters in the surrounding areas, activation of
abrasive and security processes, algal bloom, siltation of ponds, small rivers
disappearance.
Keywords: water resources landscape ecosystems, anthropogenic influence.

INTRODUCTION
The environmental situation of the central Bug region is determined by a large
saturated basic material assets of the national economy, intensive agriculture,
industries aggressive towards the environment (mining, food, energy industries and
others), uneven spread of forests, a well-developed transport system with the
network of railways, roads and pipelines, as well as a significant recreational
activity. This has led to the formation of anthropogenically transformed landscapes.

METHODOLOGY OF RESEARCH
The methodological basis of the research is current understanding of geography
about optimization of the interaction between man and nature that has been
252 Water Security: Monograph

developed by such scholars as A. Isachenko, F. Milkov, A. Marynych, P.


Shyshchenko, G. Denysyk. The research methodology includes theoretical methods
(analysis, synthesis, comparison, modelling and forecasting) and practices
(expeditions, experiments, sampling and testing).

RESULTS OF RESEARCH
The structure of anthropogenically transformed landscapes can be properly
presented by three groups: the actual man-made landscapes, landscape engineering,
man-made and environmentally transformed systems. G. Denysyk believes that
man-made landscapes are the systems of different organizations. Their knowledge
is a far more complex process than the study of natural landscapes and, therefore,
it should take place at different levels [2, p. 6].
The structure of man-made landscapes of Ukraine involves an increasing role
and importance of man-made landscape systems [3]. With anthropogenic origin,
they are different from actual man-made landscapes and landscape-engineering by
their internal organization, the degree and nature of contemporary human influence
on it.
Man-made landscapes as well as landscape engineering systems are not
component, but block systems. They are formed by a natural and technical unit
(subsystems), the development of which is subordinate to the two laws - the natural
and socio-economic ones. A key role is played by a man-made unit, periodically
monitored by man. As a result, man-made landscape systems, opposed to the actual
man-made landscapes, are not capable of natural development.
The same attention should be paid to environmentally transformed landscapes.
The existence of such landscapes was pointed out by an outstanding Ukrainian
geographer A. Syniavskyi who noted that special attention should be paid to
ecological landscapes (anthropogenic, man-made ones) that have the social structure
that has the most impact on nature and the emergence of certain cultural relations
and economic order. The scientist also emphasized the complexity of the structure
of ecological landscapes in comparison with natural, ones which depends on “...the
level of technical culture, the degree of social and economic development…”
[10, p. 241]. Undoubtedly, the transition of natural landscape in cultural and
ecological or environmentally transformed is the result of historical development.
According to A. Syniavskyi, natural landscape is influenced by other cultural, social
and environmental landscapes [10, p. 251].
Examples of landscape and man-made systems are as follows: dams, roads, the
majority of the urban settler landscapes and others. Examples of environmentally
transformed ones are as follows: cut forest areas in large areas, weediness of
abandoned agricultural fields etc.
Based on the above classifications it is evident that there are two concepts to
the understanding of anthropogenic landscapes. The first one (S.Zhekulin,
Water Security: Monograph 253

A. Isachenko, S.Kalesnyk, K. Raman et al.) is that there are no anthropogenic


landscapes, only natural ones, changed by human to some extent and after the
termination of the impact they can return to the natural state . These provisions are
unlawful concepts as they are not implemented on a local level. The first concept
provides a positive statement that the human impact on nature is of a different
character depth which enables the formation according to the transformation degree
of anthropogenic landscapes, though this group is called by the authors as
“completely artificial” one.
The second concept (G. Denysyk, N. Johansen, F. Milkov et al.) shows that if
at least one of the components of the geosystem has been influenced by human, it
becomes anthropogenic and this type of landscape is predominant on the Earth,
although there are such areas with little impact on nature due to adverse climatic
conditions. These landscapes are advisable to be called quazinatural ones. In
addition, according to the second concept, most man-made landscapes are not able
to return to their original state.
Today there is the third concept which is associated with the formation of the
modern outlook of the humanity and linked to the impact of human activity on the
nature. This landscape the authors call “a technical landscape”, i.e. the landscape
includes people and technology. The technology is represented by different technical
components: according to material composition (bricks), iron and concrete, clay,
metal and iron, wood, concrete, glass, asphalt); the degree of mobility: stationary
(houses, garages, fences, industrial buildings, etc.); semi-stationary (mobile rides,
drilling rigs), mobile (cars, trains, airplanes, ships, etc.). Under this concept there
is no need for different classifications, only the notion “landscape” remains. This is
the opinion of V. Kazakov [8], Yu. Tiutiunnyk [12; 13].
Most of these classifications are rather generic, abstract. It is necessary to
implement the systematization of anthropogenic impacts on the landscape in relation
to a particular region, directly from its advanced environmental usage and ecological
effects.
We appreciate the classification of anthropogenic landscapes developed by G.
Denysyk as it most fully reveals the landscape diversity on the example of Podillia.
The classification is based on the principle of the territory dependence on the
characteristics of economic activity. Accordingly, the author distinguishes such
landscapes:
- agricultural: І − field, ІІ – meadow pasture, ІІІ − garden;
- forest anthropogenic: І − silvicultural, ІІ − derivatives, ІІІ – conditioned
natural;
- water anthropogenic: І – water reservoirs, ІІ − ponds, ІІІ − channels;
- industrial: І – career dumping, ІІ – peat and bog, ІІІ − actual industrial;
- residential: І − rural, ІІ − urban;
- road;
254 Water Security: Monograph

- recreational;
- beligerative.
To establish functional characteristics of the landscape the following should be
considered: 1) the degree of compliance of natural properties of the landscape with
technology of nature usage; 2) natural resource potential of the landscape; 3) social
and economic needs of this type of nature; 4) environmental situation and the
possibility of deterioration in the performance of its landscape features.
The following main factors are the bases for the functional assessment of
landscapes of the researched region are:
- for industrial and domestic construction – slopes and surface dissection degree,
the rocks character of creating it, hydrogeological and climatic conditions;
- for agriculture – the degree of erosion division of the territory and the surface
slopes, climatic conditions, availability of fertile soil, water resources and forage
land, the need of irrigation;
- for the development of the recreational function of the landscape – landscape
diversity, climatic conditions, traffic access, availability if open water areas;
- for forest landscapes – climatic and soil and plant conditions;
- for the development of the ecological network in semi-transformed,
quazinatural and natural landscapes – the unique character on the general
background of the region landscape structure and the degree of their anthropogenic
transformation.
The basis of our classification is comprised by integrated environmental
functional and genetic principle that reflects the relationships between the natural
landscape and its functional use as well as environmental impacts and consequences.
We distinguish 9 classes of fixed anthropogenic landscape ecosystems and 20
subclasses. In the classification the matrix for each landscape unit meets its
ecological class or their combination. We identified the following landscape
ecosystems:
- residential (urban and urban villages; rural; ecologically transformed
residential);
- industrial (actual industrial; mining industrial; ecologically transformed
industrial);
- agricultural (field; meadow pasture; ecologically transformed agricultural);
- water resources (water reservoirs and ponds; rivers; ecologically transformed
water resources);
- forestry (forests of group І; forests of group ІІ; forests of group ІІІ; ecologically
transformed forestry);
- road (railroad; highway; pipeline; ecologically transformed road);
Water Security: Monograph 255

- recreational (organized tourism; unorganized tourism; ecologically transformed


recreational);
- beligerative (tafal fortification ecosystems; landfills; ecologically transformed
beligerative);
- reserve and environmental (natural; man-made; environmental anthropogenic
reserves).
The researchers have paid attention to water resources landscapes, the studying
of which was conducted in the basin of the river valleys of the Central Bug region
which is characterized by: 1) a high level of component diversity of lithological,
morphological, climate and biotoresource landscape, 2) a high value of performance
assessment of landscape diversity of recreational and environmental protection
purposes, 3) landscape diversity of a large number of attractive components. But
this territory has been subjected to intensive economic impact since human
settlement, resulting in a substantial transformation.
According to the causes of transformation of landscape ecosystems, the Central
Bug region is considered to be a part of the basin of the river Pivdennnyi Bug from
the confluence of the river Vovk in the river Pivdennyi Bug (town of Letychiv,
Khmelnitskyi region) to the confluence of the river Mertvovid into the river
Pivdennyi Bug (town of Voznesensk, Mykolaiv region).
A catchment basin as an ecosystem is an extremely complex subject. The
concept of a catchment basin detects lots of problems that may arise in the future in
case of illogical defining of the limits of the ecosystem. For example, the causes of
water pollution and measures to combat this phenomenon cannot be solved with
only the water study.
Soil erosion and loss of nutrients in damaged forest or on improperly treated
fields not only pollute these ecosystems, but often cause eutrophication (organic
pollution caused by human activities) or other adverse effects in ecosystems that
are downstream or on the slopes. Thus, the minimum unit of ecosystem is not only
a piece of land covered with vegetation but the whole catchment area. The
comparison of the water surface with the catchment area varies widely, depending
on rainfalls, the structure and type of geological massives and terrain. Therefore,
forests, fields, lakes and cities linked by the river or the river system, and perhaps
by a network of underground sources, interacting form an ecosystem level unit,
which is also isolated from the practical management, use and study. Thus, there is
a close link between land and aquatic ecosystems and in many cases it is necessary
to allocate subecosystems to explore the entire ecosystem together and organize its
effective protection.
The Central Bug region is comprised by the following subclasses of landscape
water ecosystems: rivers, reservoirs, ponds and canals.
It is believed that the water reservoirs contain water bodies with the volume of
useful water exceeding 1 mln. m3. However, in this case the water reservoir includes,
256 Water Security: Monograph

for example, Mygiyske (Mykolaiv region) and Tyvrivske (Vinnytsia region), although
the volume of the first one is less than 0.1 mln. m3, and the second − 0,3 mln. m3.
The Central Bug basin includes 47 water bodies with the volume of 276 mln.m3
[47, p.8], particularly the river itself comprises 16 water bodies with the total volume
of about 242 mln. m3. Among them there are the ones with the volumes from 0,1 to
10 mln. m3 − 12, from 10 to 50 mln. m3 − 3 (Schedrivske, Hlybochivske and
Gavoronske), more than 50 mln. m3 − 1.
The largest is Ladyzhynske water reservoir which was established in 1964. It
covers an area of 2080 hectares with the length of 45 km, the average width of
460 m, maximum depth of 16 m, the total water volume of 150,8 m3. Right banks
of the water reservoir Ladyzhynske are mostly low, left ones are high, sometimes
abrupt. The coastline in the upper and middle parts of the water reservoir is winding.
Mineralization of the water varies within 460-470 mg/l. The content of dissolved
oxygen in the water near the surface is 5-14 mg/l. In summer the temperature of the
water surface is + 28оС, in winter +5 ... + 6оС. Fluctuations of the water levels
during the year are 1,5 m [112, p. 200].
The site of Ladyzynska Heat Power Station (HPS) is located on I and II water
right bank terraces on the banks of Ladyzhynske water reservoir. The industrial site
and the building yard are situated in the forest. The total relief slope is toward the
reservoir. The relief is gentle, with small plains and depressions. The highest point
of the industrial site is 205 meters, the lowest − 177 m. The ashes wastes site is
located in the river hollow with the river flowing into the river valley of Silnytsia
(Byche tract) on the pastures. The intermediate cooling pond is situated in the hollow
adjacent to the water reservoir in the north-west of the industrial site. The site relief
is plain-wavy with a slope toward the river. The geological structure of the area is
comprised by alluvial sand and clay deposits that lie directly on the Ukrainian Shield
rocks.
Within the above-mentioned terrace in upper quaternary sediments there have
been defined sands and sand-clay, seldom - loam. Sands of particle size contents
are mostly shallow, seldom dusty, medium-sized and large. To the depth of 2 m from
the ground, sands are characterized by loose sand layers with the density below the
average. Below the level of the ground water sand-clay is hard and plastic, lower it
is flow. Loam is characterized mainly by solid and soft, elastic state.
The capacity of upper quaternary eluvial deposits is rather unstable and varies
from 3 to 23 m. Modern quaternary eluvial deposits are interbedded sands (from
shallow to large), sand-clay and loam. The capacity of these sediments is
4,9 – 7,3 m. Crystalline rocks of the underlying surface of the river valley are mostly
pink granites, seldom gneisses. The upper part of crystalline rocks is intensely
weathered and presented by kaolin and gneisses, and the lower one by sod-
podzolized soils. The total capacity of weathering is 5 m. Granites that lie below,
are heavily eroded on the top and heavily weathered. The capacity of these zones
ranges from a few tens of centimetres to 19 m.
Water Security: Monograph 257

The cover of monolithic granite is quite unequal and settles to 135,4−172,4 m.


The construction of the left bank of the river near the hydraulic project in
geomorphological and engineering-geological terms is significantly different from
the structure of the right bank. Crystalline rocks occur at shallow depths (from 2 to
3 m) and blocked by aeolian deluvial sand loam from ancient to modern-quaternary
one. The ground water is characterized by a high content of sulphates and free
carbon dioxide.
In the depth of the hollow there are developed upper quaternary and modern
quaternary (from the river side) eluvial deposits. On the slopes of the hollow there
are neogene sediments, covered from top by eluvial and deluvial sandy loams. These
deposits cover crystalline rocks and their weathering products.
The ground waters during flooding meet on absolute marks 175,37 – 191,24 m,
corresponding to a depth of 0,5 – 27,5 m. The direction of the ground water flows
from the sides to the middle of the valley of the river Pivdennyi Bug. The
hydroelectric facility is on the site, and the part of the territory up to 177 m mark is
flooded by the water reservoir. The bed of the reservoir has the geological structure:
- the crystalline rocks bed ranges from 157 to 182 m. The rocks have big inside
cracks;
- crystalline rocks are weathered in their upper part to the kaolin condition. The
capacity ranges from 0,2 to 12 m;
- on the top of the hollow boards along the weathering crust there are overlying
Neogene Baltic formation represented by kaolin capacity clays of plastic
consistency. The capacity of clays in their fields is 10,3−14,1 m. The Baltic clay is
with sand with the capacity of 5,1−5,6 m;
- Baltic and red and brown clay covered with a layer of eluvial and deluvial
loams with layers of fine sand and sandy loam. Carbonate loams are of yellow and
brown colour, macroporous with subsidence properties from 4,1 to 10,7 m;
- In the valley hollow on the weathering crust of crystalline rocks there are
upper-quaternary eluvial sands (shallow and medium size), sand clay, loam and
seldom clay. The capacity of upper-quartnary eluvial deposits from 6 to 20 m.
The geological structure of the start of the front of the hollow is slightly different
from the structure of the middle part of the hollow.
Strong crystalline rocks and cracked rocks lie at a depth of 5−17 m,
corresponding to absolute marks of 156−183 m. The weathered zone is situated
above of strongly fractured granite with cracks. The capacity of the zone is 2−4 m.
The cover of those granites is located at marks 157,2−189,5 m. The weathered crust
of granites in this area is represented by sod-podzolic soils with capacity of
0,1− 6,1 m, seldom podzolized kaolin rocks with capacity of 1,2−3,1 m.
Sedimentary deposits are represented by modern alluvial sands from 0 to 13 m.
Above the hollow slope the sands vary for upper quaternary eluvial loam, sandy
258 Water Security: Monograph

loam and shallow sand as well as aeolian and deluvial loam. The total capacity of
sedimentary rocks on the slopes of the hollow is 3,5−2,7 m. The ground waters
reach marks of 185−186 m. Given the fact that the upper area of granite up to a
depth of 2−4 m has cracks and is covered with sand and gravel of various sizes, we
should expect significant filtration losses on the basis of the projected dam, and to
a lesser extent, bypassing its sides.
The bed of a projected cooling pond is covered with sand, lying in unmediated
places in crystalline rocks that are cracked, that’s why despite the presence of
powerful cover of clay soil in the pond banks, it does not exclude the filtration of
water towards the industrial site, leading to flooding. As noted above, hollow
borders, marked for the construction of the cooling pond, are lined with clay. The
steepness of the banks in some areas reaches 10-15 °C. Irrigation of such slopes
and a wave action on the banks negatively influence the stability of slopes.
The terrace of the drain channel in the northern platform extends along the
Ladyzhynske water reservoir. The total length of the terrace is about 5 km. The
terrace of the channel is geomorphologically dedicated to the basis of the first
terraces of the river Pivdennyi Bug, and in some areas it crosses useful composition
of the river valley.
The terraces relief is quite complex - large fluctuations of absolute marks. The
terrace crosses many shallow ponds. Almost the entire length is characterized by a
significant mountainousness. Due to the heterogeneous geological structure of the
terrace, its description takes place by areas (beginning from the end of the channel
and to its main part).
The first site (from well №650 to №672) is located at the top of the terrace,
along with a primary slope. The axis of the terrace channel contains upper
quaternary eluvial deposits with a capacity exceeding 18 m. Alluvial deposits are
comprised mostly of loam, which are impurities of clay, sand and sandy loam. Sandy
loam is characterized by hard- and soft layer state. In the area of holes 642, 641,
646 sandy loam is changed by sandy clay. Sandy clay above the ground water is
plate-like, and higher – marsh-like. In places where the terrace crosses a primary
slope, aeolian deluvial deposits are represented mainly by sandy clay with sandy
loam and sand intervals (well 652).
The area is covered not evenly with primary deposits with major settlings at
marks from 164,7 to 176,4 m.
The second site (from well №622 to №630) is characterized by a kind of rugged
terrain, complicated with shallow water bodies, and wells 631-638 are crossed by
the water reservoir. Fluctuations of absolute surface markers on this site is from
166,7 m to 196,5 m.
Geomorphologically timed, this area is similar to the aforementioned
description. A characteristic feature of the geological structure of the area is a close
bedding of crystalline rocks from the surface with the crust of weathering capacity
Water Security: Monograph 259

of about 2,0−5,0 m. The crystalline basement is covered with quaternary eluvial


and aeolian-deluvial sand and clay sediments.
The third site (from well №630 to №615) is partially within the above-mentioned
terrace and partially within the watershed. The relief of the area is originally
dissected with great introduction to the side of the water reservoir. It is characterized
by high mark of the surface (from 19 m and in the area of well №620).
The geological structure of the area involves upper quaternary eluvial and
inseparable eolian and deluvial deposits, and those and others are mainly sandy
loam and sandy soil with a layer of fine sand. Crystalline rocks lie at depths from 6
to 20 m, with common occurrence of more than a meter.
The fourth site (from well №615 for a HES industrial site) is dedicated to the
first terrace of the river. It is characterized by a calm relief and absolute marks of
the surface vary from 175 to 182 m.
The geological structure of the area is different from the above described by
presence of layers of quaternary deposits of a rather powerful layer of sandy loam,
lying below the ground water characterized mainly by fluid state. The layer capacity
of sandy loam is from 2,7 to 13 m. There are layers of impurities and fine sands
and clays there. Indigenous deposits occur at depths of 6,2-18,9 m from the surface.
Within the channel terrace there is an embedded eluvial aquifer traced, which lies
at marks close to marking the water level of the water reservoir.
The water reservoirs of the Central Bug region have two stages in their
development – an early and a mature one. An early stage lasted from the 30th to
60th years of the XX century at this time the water reservoirs were ruthlessly
exploited in the national economy of the USSR. This stage is “characterized by
activation of geomorphological processes in the coastal zone and in shallow water,
siltation of water reservoirs, as well as the formation of the bottom profile of stable
equilibrium. This was also contributed by the annual high river (up to 4,6 m) and
seasonal (2-5 m) amplitude levels of water reservoirs. The difference in the volume
of water at the highest and lowest supported levels accounted for 151 and 24,4 in
Ladyzynske water reservoir, 10,7 and 1,3 in Glybochivske, and 13,6 and 2,3 м3 in
Dmytrenkivske, and the water surface area decreased respectively 2, 3 and 6,5
times” [11, p. 145]. That is why, in the coastal parts of the water reservoir there
were lines of temporary flooding and drying, the structure of which is dominated
by low-lying marsh complexes. Such systems have become a commonplace for
water reservoirs of the Pivdennyi Bug.
It is important to note that at the early stage the composition and diversity of
flora and fauna are significantly changing in a negative way.
The mature stage of the development has begun since the 70s and is continuing
to our days. At this stage, seasonal and annual fluctuations of water do not exceed
0,5-1 m, geomorphological processes have stopped, a permanent composition of
the flora and fauna has been formed. Because of planting forest strips, the rate of
siltation decreased.
260 Water Security: Monograph

Such water reservoirs of Pivdennyi Bug as Gaivoronske in Kirovograd, Sutyske,


Sabarivske, Sandrakske in Vinnytsia and Shchedrivske in Khmelnytskyi regions
today have been characterized by lake-wetland attributes [3, p.196].
In the landscape structure, most water reservoirs of the Central Bug region
belong to a shallow (depth of 5 m) landscapes type. It was at a depth of 5 meters
which allows the water reservoir to be heated best, enabling chemical and physical
processes to go on more actively, with biota evolving. The characteristics of the
shallow water landscape allow using the water reservoir with recreational purposes.
A deep type of landscape (over 5 m deep) is a characteristic of Ladyzhynske
water reservoir. It is characterized by intense accumulation of silt at the early stage
of development, increasing concentration of organic matter, with a lot of dead
organisms concentrated at the bottom.
Sandrakske water reservoir is located in the region of villages Shyroka Greblia
and Sandraky. It flooded meadows for 3,5 km (188 ha) downstream of Pivdennyi
Bug. In the area of influence of the water reservoir in the upper pond of the dam
there are flooded areas, with watery and wet meadows. The examples of plant
communities of the meadows is a description of key areas of vegetation of the left
bank of Sandrakske water reservoir (2,2 km above the dam) [9, p. 203].
Watery meadows are dominated by black-ear and coast sedge, broadleaf cattail,
marsh marigold. In wet meadows are dominated by black-ear sedge, goose
cinquefoil and marsh marigold and cereals: Poa pratensis, Dactylis glomerata,
Trifolium repent [9, p. 204].
Above the profile there are widespread meadows of grasses and forb groups
dominated by bluegrass meadow, dactylis team, cinquefoil goose, plantain medium
and lance-leafed, white clover, yarrow and couch. These groups are exposed to
grazing.
In a lower pool of Sandrakske water reservoir the flood regime is violated and
meadows of low floodplain are not flooded any more. In this regard, there is no
division on the marsh, watery and wet meadows.
The banks of Pivdennyi Bug in a lower pool of Sandrakske hydroelectric
complex are steep, 2−2,2 m high as near the dam, so 3 km downstream. As a result
of earlier drains of the water, the channel has been deepened. With further reducing
of the drain some conditions for drying floodplains occurred. Accordingly, some
groups of meadows have appeared which are characterized by dense growth of
oddity flower, yarrow, beardless rump [9, p. 204]. Rather widely the following plants
are involved in communities: sorrel horse, red clover, dandelion, plantain large and
angustifolia, yarrow and various types of weeds - burdock real, creeping thistle,
nettle deaf, oxeye daisy, chamomile not fragrant, shepherd's purse and nettle. In the
driest places in small quantities verbascum densiflorum and wormwood can be met.
In depressions with the depth of 40−50 cm, elongated parallelly to the river flow
for 150−200 m with a width of 30−35 m depleted sedge-motley-cereal plant groups
Water Security: Monograph 261

are formed, which are dominated by reed and black-eared sedge. Also the meadow
buttercup and sorrel horse can be met [9, p.205].
Thus, the impact of the overregulated flow of Pivdennyi Bug by Sandrakskyi
hydroelectric complex led to the flooding of large areas of low floodplain in the
upper pool of the dam and formed the group of watery and wet meadows in
waterlogged areas where ground water rose to 10-50 cm. In contrast, in the low
pool of the dam, where the floods stopped that flooded the floodplain, there low
floodplain drainage conditions appeared, and therefore the level of groundwater has
fallen to 1,5 m and below; the group fresh floodplain meadows with dry elements
have been formed [9, p. 205].
Along with the impact of hydroelectric complexes of water reservoirs that
changed the flow regime of the river, the floodplain of Pivdennyi Bug influenced
agricultural development as well – it is transformed in fields and gardens, which
often approach directly the river.
The content of dissolved oxygen in the Sandrakske water reservoir is
2,8 mgО2/dm3, which is below the maximum limit allowed. The highest
concentrations of organic compounds are observed in April, May, July, August,
October 2006 (5,6−15,4 mgО2/dm3). Exceeding maximum limit allowed rate of
BOD indicates water contamination with organic compounds (3,09−6,0 mgО2/dm3).
Total water hardness ranged from 4,85−5,09 mg. ekv./dm3 [11, p. 65].
Total iron concentration is less than maximum limit allowed and it is
0,2 mg/dm3. The highest numbers of color were recorded in January-March and
August. The content of nitrates, nitrites, sulphates, chlorides, calcium, magnesium,
copper in the Pivdemmyi Bug river is below the MPC. There was no hexavalent
chromium content detected in the water.
Hydrochemical analysis results indicate contamination of the surface water of
the Riv river basin (which contains Sandrakske water reservoir) with organic
compounds.
The ponds are outstanding representatives of aquatic landscape ecosystems of
the Central Bug region; they are characterized by a small size and a low volume.
The study area contains ponds of flood and slope type of terrain, as well as gorge
and hollow ponds of watershed areas.
The Pivdennyi Bug river basin has 7,000 ponds totalling to 610 million m3, with
water surface area of 47,5 thousand ha [1]. There ponds are built on medium and
small rivers with their tributaries to meet the needs of different industries. Today of
the part of ponds is abandoned, muddy, with no owners [6, p.8-9].
Ponds of a flood type of terrain are quite common in the Central Bug region.
Typically, these water bodies are under the territory of the villages. The duration of
their existence is short-lived, as the water reservoir becomes silt and overgrown
within 10−15 years, and then it requires urgent clearing. Ponds fully regulate rivers
and floodplain in this type of terrain turns into a pond-floodplain one.
262 Water Security: Monograph

Ponds of a slope type of terrain belong to the slopes of river valleys; they are
built in hollows and ravines. They are not widely spread in the Central Bug region.
They are characterized by the following features: a small area (0,2−12 ha),
sometimes reaching 50 hectares, near the dam they may have a depth of 6,12 m.
Dams of such ponds are built mostly of clay, reinforced concrete and granite with
height from 3 to 10 m. Examples of such ponds can be seen in village. Voronovytsia
(Vinnytsia region) and Balta city (Odessa region). Here, in large hollows the whole
cascades of ponds of a slope type are created.
Gorge and hollow ponds of watershed areas are the most common type in the
south of the region under study. These are small ponds with marshes in the top rate
(0,2-3 hectares), with the depth of 0,5 to 2 m. They have rain and snow supply. In
their early years the water bodies are used in fisheries. If for some reason a pond
loses water, it is destroyed and used for planting crops.
The creation of canals in the Central Bug region was actively conducted
throughout the twentieth century. However, for example, we will consider the
drainage canal that was built in Sokilets village of Podolsk province during 1894-
1898. It was specially dug to divert water from the main canal of Pivdennyi Bug
and its supply to the turbine of the roller mill. The construction of the canal in the
left-bank floodplain of Bug led to the creation of the island. The modern island is a
part of the former left-bank floodplain of Pivdennyi Bug. The granite dam effected
the raise of the water level by 3 m. The canal water almost completely flooded the
left-bank floodplain. Today the canal is 114 years old, but as previously it
conscientiously performs its function. This is because the canal bottom and its banks
are lined with granite stones with the aim of strengthening. At the entrance of the
water into the canal nowadays there is a gateway to a bridge. This place is called
Opust by the old local inhabitants. At a time when the mill was working, the canal
was regularly cleaned. For this purpose the gateway was blocked by oak logs that
were put one on another. The modern canal is of length of over 1,200 m, width
12.11 m, depth 1-1,5 m, when filling the canal with water its volume is 44,523 m3.
The rate of flow is low - 0,3−0,4 m/s. The canal is almost straight and parallel to
the main rivers in the south-east. Aquatic vegetation is virtually absent, very rarely
in the coastal part of the channel yellow water-lily (Nuphar lutea (L.) Smith) can
be seen. The right bank of the canal and the bottom nowadays are set with stones,
though in many places its fortifications are destroyed. In the middle of the canal
there is a small bridge that connects the island with the left-bank floodplain. The
modern left bank canal doesn’t have a stone building. It is steep with the height
above the water level of 0,5−0,7.
Environmentally transformed water resources landscape ecosystems result from
radioactive and chemical contamination of excessive concentration, restoring them
requires a long period. Deep transformation of water resources landscape
ecosystems results from algal blooms, siltation ponds, and small rivers
disappearance. Most ponds of flooding type areas are built directly on the river (a
channel subtype). They flood the floodplain and completely transform it [4].
Water Security: Monograph 263

Affected landscape ecosystems are caused by long-term unsustainable economic


use of natural ecosystems (secondary depleted forests, shrubs, overly exploited
pastures and meadows, river valleys, etc.). They result from uncontrolled conduct
of such business activities as logging, over-grazing by cattle and poultry. The
disturbed landscape ecosystems show simplifying of environmental conditions,
species diversity and abundance of flora and fauna.
The transformed landscape ecosystem involves natural components and
connections between them are purposefully changed, those changes are scientifically
proved by the system of engineering, land reclamation, environmental and
organizational measures.
Thus, the change and transformation of natural processes and natural
components of economic activity include:
- changing of units of the cycle of matter and energy,
- degradation of natural ingredients,
- formation of anthropogenic landscape modifications [11, p.38].
The appearance of a man-made elements or environmental factors of any type
and complexity in landscape ecosystems leads to the fact that they are beginning to
be processes that transform (rebuild) the structure of the landscape complex. The
human impact has not changed the action of physiographic process, but rather made
it even more difficult. Physical and geographical process interacts with economic
and geographical one. Thus, they together take part in the transformation of the
environment [7, p. 43].
A similar effect is experienced by water resources landscape ecosystems.
Nowadays transformed river valleys of the Central Bug region require
improvement of the ecological state by joint efforts of the youth and the public, as
well as creation of reserves in the field of detection of the slightest transformation
of landscapes.

DISCUSSION
Water resources landscape ecosystems are classified as the main anthropogenic
landscape ecosystems. The classification is assigned by integrated environmental
functional and genetic principle that reflects the relationship of the natural landscape
with its functional use, environmental impacts and consequences.
We identified the following landscape ecosystems: residential (urban and urban
villages; rural; ecologically transformed residential); industrial (actual industrial;
mining industrial; ecologically transformed industrial); agricultural (field; meadow
pasture; ecologically transformed agricultural); water resources (water reservoirs
and ponds; rivers; ecologically transformed water resources); forestry (forests of
group І; forests of group ІІ; forests of group ІІІ; ecologically transformed forestry);
road (railroad; highway; pipeline; ecologically transformed road); recreational
264 Water Security: Monograph

(organized tourism; unorganized tourism; ecologically transformed recreational);


beligerative (tafal fortification ecosystems; landfills; ecologically transformed
beligerative); reserve and environmental (natural; man-made; environmental
anthropogenic reserves).
In our work we offer the systematization of effects on different types of
landscapes of the Central Bug region, with a possible further detail on the impact
of water reservoirs, ponds, canals, environmentally transformed water resources
landscapes. In the Central Bug region there were the following subclasses of
landscape water ecosystems identified: rivers, water reservoirs, ponds, canals,
environmentally-transformed water resources landscape ecosystems.
The Pivdennyi Bug basin involves 47 water reservoirs with the volume of
276 mln. m3, in particular the river contains 16 water reservoirs with the total
volume of about 242 mln. m3. They are with the volume from 0,1 to 10 mln. m3 −
12, from 10 to 50 mln. m3 − 3 (Shchedrivske, Glybochivske and Gaivoronske),
more than 50 mln. m3 − 1. The biggest is Ladyzynske water reservoir created in
1964. It covers an area of 2080 ha, with the length of 45 km, the average width of
460 m, maximum depth of 16 m, the total water volume is 150,8 m3.
Ponds are outstanding representatives of aquatic landscape ecosystems of the
Central Bug region; they are characterized by a small size and a low volume. In the
study area there are ponds of a flood and slope type of terrain as well as gorge and
hollow ponds of watershed areas. In The Pivdennyi Bug river basin there are 7,000
ponds with total water volume of 610 mln. m3, and water surface area of 47,5
thousand ha. Ponds are built on medium and small rivers and they are attributed to
the needs of different industries. Nowadays some ponds are abandoned, muddy,
without owners.
Water resources landscape ecosystems include canals. We studied canals of the
Central Bug region on the example of a drainage canal in Sokilets village. The canal
length is more than 1200 m, with width of 11−12 m, depth of 1−1,5 m, while filling
in the channel, the water volume is 44523 m3.
Environmentally transformed water resources landscape ecosystems are studied
while giving characteristics to rivers Zgar, Riv, Silnytsia, Sob, Kodyma, Syniuha,
Velyka Vys, Gnylyi Tikach, Girskyi Tikach, Yatran, Chornyi Tashlyk, Mertvovid.
Transformation of landscapes is due to human activity and influences it causes,
from natural causes of internal (spontaneous) and external various forces, even
disastrous, including, indirectly caused ones by human.
Among the changed landscape ecosystems as potentially dangerous ones from
the position of the emergence of complex ecological environments and even
emergencies we can define transformed landscape complexes that should be subject
to monitoring research in the early stages of their formation and in the development
process. Right now some steps must be taken to preserve the unique landscapes,
rare and endangered species of plants and animals, the whole gene pool of flora and
Water Security: Monograph 265

fauna. This will help to reveal certain regular changes in the dynamics of
anthropogenic and natural systems of the environment and control these processes
in order to prevent environmental disasters and emergencies of technogenic and
natural character that can be triggered by disturbances of natural balance in any
component of the environment through uncontrolled growth of transformed
landscape ecosystems.

CONCLUSIONS
Thus, water resources landscape ecosystem is one of the categories of
anthropogenic landscape complexes. They include water reservoirs, ponds, canals,
environmentally transformed water resources landscapes. Impact on landscape
water reservoir ecosystems and ponds leads to the alienation of land to flooding and
forest areas; canals - to untreated sewage pollution and toxic substances, getting
man-made elements in aquatic landscapes; environmentally transformed water
resources – to radioactive and chemical contamination of excessive concentration.
To restore them the desired long term is necessary. The impact effects on the
landscape ecosystems of water reservoirs and ponds are changing hydrological,
hydrochemical and hydrobiological regimes of water bodies, improvement of
ground waters in the surrounding areas, activation of abrasive and security
processes, migration of animals; for canals – to change the water balance and
hydrochemical regime of water, depletion of the species composition of aquatic
fauna, barrier effect; environmentally transformed water resources - algal blooms,
siltation ponds, small rivers disappearance.

REFERENCES
1. Water resources // Basin management of water resources of the river Pivdennyi Bug
[Electronic resource]. – Access: http://www.vcvodxoz.vinnitsa.com/vresurs.htm. – Headline
from the screen. (in ukr.)
2. Denysyk, G.І. (2005) Anthropogenic geography and landscape study in Ukraine /
G. І. Denysyk // Theoretical, regional, applied trends of anthropogenic geography and
landscape study development: mat. of ІІ International scientific conference (Kryvyi Rig,
October, 5–8 2005) / Ministry of education and science of Ukraine, Kryvyi Rig State
Teachers’ Training University [et al.]. – Kryvyi Rig : Vydavnychyi dim, 2005. – P.6. (in ukr.)
3. Denysyk, G.І. (1998) Anthropogenous landscapes of the Right-bank Ukraine. –
Vinnytsia: Arbat, 1998. – 289 p. (in ukr.)
4. Denysyk, G.І. (2001) Forest field of Ukraine. – Vinnytsia: PE «Vydavnytstvo «Teza»,
2001. – 284 p. (in ukr.)
5. Pogorelska, V. (2006) Environment of Vinnytsia region for 2005: Statistical collection
of works / Under editing of V. Pogorelska. – Vinnytsia: Main Department of Statistics in
Vinnytsia region, 2006. – 27 p. (in ukr.)
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6. Pryimak, V.P. (2006) Environment of Cherkashchyna for 2005: Statistical collection


of works / Under editing of V.P. Pryimak. – Cherkasy: Main Department of Statistics in
Cherkasy region, 2006. – 144 p. (in ukr.)
7. Zadorozhnia, G.М. (2006) Derivative processes and phenomena in landscape zones
of technogenesis // Scientific notes of Vinnytsia State Pedagogical University named after
Mykhailo Kotsiubynskyi. – Vinnytsia, 2006. – Ed.11. – P. 43–47. – (Series: Geography)
(in ukr.)
8. Kazakov, V.L. (2005) Main methodological problems of anthropogenic landscape study
/ Theoretical, regional, applied trends of anthropogenic geography and landscape study:
materials of ІІ International scientific conference, (Kryvyi Rig, October, 5–8, 2005) / Ministry
of education and science of Ukraine, Kryviy Rig State Pedagogical University [et al.]. –
Kryvyi Rig : Vydavnychyi dim 2005. – P.34–42. (in ukr.)
9. Denysyk, G.І. (2002) Middle Bug region / Under edition of Denysyk G.І. – Vinnytsia:
Gipanis, 2002. – 280 p. (in ukr.)
10. Syniavskyi, А.S. (1993) Selected works. – К.: Naukova dumka, 1993. – 384 p.
(in ukr.)
11. Goncharenko, G. Ye., Sovgira, S. V. (2009) Transformation of landscape ecosystems
of river valleys of the Central Bug region: monograph / [Goncharenko G. Ye., Sovgira S. V.,
Lavryk О. D., Goncharenko V. G.]. − К. : Scient. world, 2009. − 329 p. (in ukr.)
12. Tiutiunnyk, Yu.G. (1991) Identification, structure and classification of urbanized
territories landscapes // Geography and natural resources. – 1991. – №3. – P.22–28. (in ukr.)
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Water Security: Monograph 267

SOCIO-CULTURAL DRIVERS OF WATER DEMAND IN STUDENT


RESIDENTIAL ACCOMMODATION1

Prof., Dr. Chad Staddon


Dr. Deirdre Toher
Mas. Karen Simpson
Dr. Fabia Jeddere-Fisher
University of the West of England, Bristol, e-mail: chad.staddon@uwe.ac.uk,
United Kingdom

ABSTRACT
In 2012 UWE, Bristol entered into partnership with Bristol Water Plc (the local
water services company that serves the city of Bristol, UK) to initiate a longitudinal,
multimethod study of water consumption by students in first year accommodations
on the main UWE campus at Frenchay, Bristol. Now in its fourth cycle (each runs
from September to June, following the academic year) we are in a position to report
on patterns of water consumption, underlying socio-economic drivers and the
impacts (or not) of both ‘hard’ (new fixtures such as low flow showerheads) and
«soft» (conservation messaging) attempts at achieving greater water savings. So
far, one of the ‘surprise’ findings has been that behavioural adaptation to hard
interventions can easily offset any initial water savings. We have also found that
our growing dataset has considerable application in facilities management as well
as water conservation programming.
Keywords: water, demand, behaviour, universities

INTRODUCTION
In late 2012 UWE, Bristol (henceforth UWE) and Bristol Water Plc (the local
water services company, henceforth BW) agreed to jointly launch a long-term
programme of research into water use at an on-campus student accommodation
facility known as the ‘UWE Student Village’ (Figure 1). Occupancy for the Student
Village as at 01/02/2015 was 1878 students (against a total capacity of 1932) making
for a useful study population. In effect, the Student Village became a ‘laboratory’
for studying different aspects of water consumption, including basic patterns,

1 This paper was originally presented at the Watef Network Water Efficiency conference,
held September 5-7. 2016 at Coventry University, UK.
268 Water Security: Monograph

underlying drivers and the efficacy of conservation measures. Both UWE and BW
expected that this work could improve the information base for such measures
elsewhere and help both institutions to achieve business objectives (e.g. UWE’s
KPI around water demand and, indirectly, energy consumption and BW’s company
targets around demand management).
Scientifically the Student Village is very useful because it is well-understood in
terms of both physical infrastructure and also demographics, and experiences 100%
student turn-over each summer. This means that, almost uniquely, it is possible to run
and re-run ‘experiments’ in water efficiency through ‘hard’ (e.g. new fittings) and ‘soft’
(behaviour change) measures for water efficiency. It was also felt, especially after BW
completed a site investigation in July 2012 and UWE completed audits in 2015 and
2016, that there were also changes to physical infrastructure (e.g. water tanks, pumps,
etc.) that could realise significant additional water efficiencies and cost savings.
In this paper we focus on what has been learned to date about the patterns of
water use within the Student Village and the relative impact of certain hard versus
soft water conservation measures. We end with a brief discussion of planned
activities for the 2016-2017 project cycle.
According to peer-reviewed and grey literature, water efficiency can be achieved
essentially through either hard or soft measures. Hard water efficiency measures
include devices and fixtures installation resulting in reduction of water uses; actually
altering physical infrastructure to use less water. Soft water efficiency measures refer
to behaviour-based interventions, usually involving user education towards more
sustainable use. These measures are important in influencing consumer behaviour
and in ensuring the take-up and use of water efficiency devices and products. Soft
measures are generally underpinned by theoretical assumptions about the links
between attitudes and behaviours. Such assumptions fall into three broad classes:
- Those who view resource use choices as largely determined by the associated
material incentive (e.g. price or other zero-sum incentive). Such models tend to
depend heavily on the idea of ‘price elasticity of demand’, something for which
there is only weak evidence in domestic water systems around the world.
- Behavioural models which, whilst acknowledging the importance of price
elasticity, also insist that non-materially derived attitudes, perceptions and beliefs
also play a part in constraining resource use choices, for example cultural attitudes
about bodily cleanliness.
- Practice based models which proceed from a rejection of (imputed)
hypostatization of the individual decision maker as the unit of analysis and instead
focus attention on resource-using practices such as showering or car-washing or
gardening as ‘social practices’.
A number of studies have found the association between positive attitudes
toward water conservation and actual water conservation behaviour to be weak
(Bagozzi. 1979; Miller and Buys, 2008). This means some individuals may have
Water Security: Monograph 269

positive attitudes in relation to water conservation but may not put them into practice
– we say one thing, but do something else. Nevertheless, most attention to soft
measures has tended to focus on measuring attitudes and then attempting to change
them. Our approach is broadly behavioural, but eschews crude message-based
didacticism in favour of more sophisticated ways of engaging study participants.
These are currently under development for implementation in the 2016-2017 cycle
and will be discussed briefly in the final section of this paper.
In recent decades, university and educational institutions have become
increasingly interested in measures, such as those noted in Table 2, to reduce water
consumption and therefore, costs. In 2013, Yale University’s Office of
Sustainability released a Sustainability Strategic Plan for 2013–2016. Yale identified
four technologies that could contribute to improved water efficiency:
• Sub-Metering: Yale relies on water meters capturing the total extent of campus
water use. The university installed additional building-level sub-meters in 2012 to
obtain more detailed water-use data. The intent of this effort was to permit building-
level water consumption benchmarking.
• High-efficiency plumbing fixtures: The university installed high-efficiency
plumbing fixtures within all buildings. Installations generally included low-flow
appliances and the sorts of measures noted in table 2.
• Reclaimed water systems: System that retains non potable water to be used for
non-potable demand. Yale has installed seven reclaimed water systems in six
buildings since 2005, with various design and operational approaches and a range
of performance outcomes.
• Water-Use Monitoring: Real-time monitoring enabled quick response in the
case of leaks or system anomalies.
Smith College, a small private college in Massachusetts, has also conducted a
study of soft measures for water conservation (Mailloux, 2011). The purpose of the
study was to test the hypothesis that increased signage, installation of shower timers,
and educational events would change behavioural patterns and encourage students
to reduce water consumption. Campus accommodation at Smith consists of seven
houses, each with a water meter. Three houses were chosen for the study with two
receiving educational materials and one acting as a control. The results of the study
provided support for the idea that educational materials and increased awareness of
water could alter behavioural patterns and encourage students to conserve more
water. In addition, students across the Smith campus were encouraged to participate
in an online survey to measure water-use patterns. Findings from the online surveys
also supported the need for increased education and transparency.
Our approach to both hard and soft interventions draws on recent developments
within the behavioural approach, and in particular those approaches that emphasise
the “choice architecture” around water use decisions. Choice architecture refers to
the conscious, and science-based, design of different ways in which choices can be
270 Water Security: Monograph

presented to water users, For example, the number of choices presented, the manner
in which attributes are described, and the presence of a ‘default’ (or habitual)
choice/pattern can all influence consumer choice (Thayler et al 2013).

METHODOLOGY
The UWE Student Village was opened and occupied for the first time in 2005.
As figure 1 shows, the Student Village is made up for four ‘Courts’ (Brecon,
Cotswold, Mendip and Quantock), each constituted of five, six or seven story
‘Blocks’ arranged into ‘Courts’. The courtyards between pairs of buildings contain
a few communal buildings, including reception, post and laundry facilities, which
are water metered separately and do not form part of this study.
Each Block is physically self-contained and is comprised of five, six or seven
levels, with two flats on each level, either side of a small landing/common space.
Flats typically have 6 rooms, though some flats may have only five where larger
rooms have been designed to accommodate disabled students (usually on lower
levels). Each room is provided with a single toilet/shower room, which includes a
hand basin, a shower with a thermostatic control (TRV) valve and a dual flush
lavatory. The five or six occupants of a single flat share a dedicated communal
kitchen/lounge area equipped with a wash basin, two hobs, two refrigerators and
sofas and chairs.
In our study each Block is separately metered, with the supply meter located in
the nearby externally accessed services room, implying a meter coverage of one
meter per 66 to 84 students depending on the exact configuration of the Block. These
meters report every 30 minutes directly into the university building management
system (BMS).
In line with the aims of the project, it was decided to analyse water consumption
using an experimental approach, by means of different degrees of planned
intervention and the implementation of specific water efficiency measures in each
of the Courts. Specifically, Mendip (400 rooms) has been selected as a representative
Court, with no intervention (the control). For the other Courts, both hard and soft
measures were implemented, as shown in Table 1. Simple aerating tap inserts were
installed in all hand basins in Brecon Courtyard (564 rooms). Tap inserts and low
flow showerheads were installed in Cotswold Courtyard (500 rooms). In Quantock
Courtyard (468 rooms) soft measures including shower timers and paper posters
promoting water conservation were installed. Using the reported water consumption
data we hoped to test the following commonly-held ideas:
- Hard measures such as flow restrictors and low flow showerheads should
reduce water consumption by forcing users to use less water per activity (e.g. teeth
brushing or showering)
- Additional soft measures, such as shower timers and passive messaging may
further reduce water consumption, though the additionality may be transitory.
Water Security: Monograph 271

We were also able to explore the relationships, such as they may exist, between
water consumption and certain demographic and lifestyle characteristics of the
studied population, including:
- Is there a measurable difference between male and female water use?
- Are there differences in water use by national/regional origin?
- Does involvement in sporting activities increase/decrease showering at home?
Exploration of these questions has thus far involved use of anonymised
occupancy data provided by UWE Accommodation Services but in future could
involve direct surveys of the student-occupants themselves.
Each month, consumption figures are examined to ensure that obvious anomalies
(e.g. leaks) can be quickly observed and discussed with the Facilities team. Boxplots
are produced to visualise the distribution of the consumption values, usually reported
as ‘per capita consumption’ on a half-hourly or daily basis, by Block and Courtyard.
Statistical comparison with available demographic data highlighted that some
observed differences could be due, in part at least, to the quite different demographic
make-up of the different blocks in the study. As students are not randomly allocated
to rooms, but are often grouped together (e.g. by national origin) for their own
comfort, or needs, this has made the analysis much more complex.
General linear models were then used to model the per occupant consumption
based on occupancy figures in February 2015, including ‘day number’ [number of
days since October 1st]; the day of the week; whether the date was during the
academic teaching block; the proportion of UK students; proportion of gym
members; proportion of females and the proportion of African/Asian students as
explanatory variables. Consumption was modelled for each courtyard separately,
with the socio-demographic factors used to help explain the differences in
consumption within each courtyard.

RESULTS & DISCUSSION


Figure 2 shows the median water consumption per capita per Courtyard across
an average day during February 2015. Extreme outliers (see below) have not been
removed from this calculation. The diurnal water consumption pattern revealed is
similar to what one sees in other studies of residential water consumption. From a
late evening/early morning low, water consumption quickly rises during the waking
up period towards a peak before falling off again as occupants attend to their daily
affairs. Because these students live on campus and because they often prefer to
study in their flats, water use does not fall off as much as might be expected in more
conventional residential settings with higher daytime vacancy rates. There is a
second early evening peak in water use which falls off after about 11 pm as
occupants either retire for the evening or go out.
Intriguingly figure 2 also suggests that, visually at least, the control Court,
Mendip, did not actually consume less water than the others. In fact Mendip seems
272 Water Security: Monograph

to have recorded, if anything, the lowest water use. This obviously runs counter to
original expectation, and the finding caused us to very carefully explore and re-
validate the meter data system and to re-engage with Student Accommodation
Services regarding occupancy rates and the rules/procedures for allocating students
to rooms and flats. Data systems were found to be valid and reliable and, as we
discuss below, demographic variables do seem to make a measurable difference in
water consumption, but there are other issues at work too.
First among these is intra-Court variability. Figure 3 shows box and whisker
plots for all the constituent Blocks within the four Courts. As is readily apparent,
intra-Block variability is quite considerable, particularly within Cotswold and
Quantock. Block median consumption ranges from about 120 litres/day to well over
300, a phenomenal range given average domestic consumption across the UK ranges
from 140–160 litres per person per day (Staddon, 2010). Also, the spread of values
around the medians (the thicker black lines within the boxplots) challenges our
initial assumptions about homogeneity within Blocks and perhaps even within Flats.
Holding that issue to one side for a moment, if we remove the more extreme outliers
(M1, B4, B7, C4-6) from consideration then we obtain average water consumption
figures more in line with expectation: Mendip=135 lpd, Brecon=160 lpd,
Cotswold=125 lpd and Quantock about 150 lpd. As we will see below (from the
regression model presented later on in this paper) part of this variability can be
explained by different habitation styles linked to different student national origins.
Another portion of this variability is, however, due to inefficiency in fittings
themselves, including leaky WC cisterns and user tampering with fittings, something
that we discuss in the conclusion to this paper.
The original design of this study was predicated on an assumption, confirmed
in 2013 with Accommodation Services, that students were allocated non-
systematically to rooms and Flats. The results reported above caused us to go back
to Accommodation Services to probe this issue further and we then discovered that
there are in fact allocation rules, though they are somewhat ad hoc and non-
systematic. For example, whilst there is no general policy to create majority male
or female Blocks, this has been done for some non-EU nationals where it has been
deemed culturally sensitive. So, for example, during academic year 2014-2015,
Brecon 6 was 100% female and Cotswold 6 was 75% male (all other Blocks were
at least 60:40 or better). The gender composition of Brecon 6 is not easily explained
as a function of the cultural needs of non-EU nationals, since 50% of its population
were actually UK nationals – it seems that having allocated a group of female non-
EU nationals to B6, Accommodation Services then topped up the population with
UK/EU females to create an all-female Block. Cotswold 6 was 85% non-EU.
Comparing with the 2013–2014 and 2015–2016 study cycles we discovered similar
non-randomness, with the added complication that different Blocks are implicated
each year – e.g. whilst Cotswold 6 was 85% male in 2014–15, it was only 53% male
in 2013–2014. This had implications for our research in the 2015–2016 academic
cycle (still under review) and caused us to create a different strategy for defining
our control Blocks in future.
Water Security: Monograph 273

Further complicating the interpretation of data is the mounting evidence, from


maintenance records and periodic audits, that there is considerable water
consumption as a function of leaky and poorly maintained fittings and fixtures.

CONCLUSIONS
Generally, 2014–2015 results have marked a leap forward toward a better
understanding of water consumption dynamics within the Student Village. Water
meters have consistently reported ‘cleaner’ data during the academic year, which
has given the opportunity to work with over 99% of the half-hourly readings
(383,162 out of a possible maximum of 384,792 half-hourly readings). In addition,
2013–2014 results have been analysed more in depth and used as a temporal
baseline for subsequent years. Finally, with the new academic year student arrivals,
we were able to analyse the effects of demographic changes for the first time.
Overall, the following key findings were identified:
• Demographics seem to play a big role in water consumption.
The discrepancy between the Mendip actual data and the expected values has
been an important matter for the whole year. After confirming that appliance issues
could explain all the variation, demographic analysis was undertaken. The models
produced attempt to explain the inconsistency looking at the important demographic
differences found between the two years as well as day of week and time within the
academic term. The models confirm that demographics seem to play a big role in
water consumption. In 2016–2017 we hope to intervene in the allocation of students
such as a large enough group of Blocks is essentially randomly assigned.
• Maintenance is still a big factor
Many extreme readings were reported throughout the whole year. While part of
the explanation could be explained by the periodical flushing done for maintenance
purposes (esp. Legionella control), poor water systems maintenance is also clearly
a culprit (confirmed also during ‘Water Audits’ conducted in summer 2015).
Consequently we have engaged with Accommodation Services to help them design
a more robust water systems maintenance programme, which may actually save the
University thousands of pounds per year in unnecessary water charges. Switching
over to a fully automatic telemetry system (e.g. Elcomponent) will also enable the
creation of an ‘alarms’ system that could notify Accommodation Services whenever
there are water use anomalies. This will benefit maintenance schedules and costs.
• Intra-Court variability is so high that a Block-level control (reference) group
is required
The ‘Mendip baseline issues’ showed the importance of a much more
sophisticated approach to defining the control group. The models proposed for the
project have the benefit of being extremely flexible, permitting to work on different
levels. However, it has showed that Courtyard-level analysis are not fine enough.
274 Water Security: Monograph

Specifically, within the same Courtyards the results and the demographics have been
different year on year. This pushes the project towards the identification of Court-
level representative groups for the no-intervention and water-efficiency measures.
• Analysis of soft measures and student behaviour is likely to become an
important requirement for the project in future.
The significance of demographics in explaining this year’s results confirms that
user attributes and behaviour is an important factor in water consumption. While
hard measures effects have been easier to calculate, behavioural compensation is a
much more powerful confounding factor than originally anticipated. Soft measures
require more work. The results of both academic years imply that hard measures
simply reinforce lower water consumption without really affecting behaviour – those
who want or need to consume more water usually find ways to do so.
The work programme for 2016–2017 calls for the testing of a particular hard
measure, pressure-reducing flow restrictors, in the UWE Student Village. Research
to date suggests that pressure management is as important as flow control because
users often value pressure highly and often intervened when it was found
unsatisfactory. The devices selected for study are less visible and therefore less
likely to be tampered with than low flow shower heads (which were often removed
and replaced) and work to regulate both pressure and flow.
In another area of recently completed student accommodation we are proposing
a focus on soft measures, in particular the roll-out of in-unit messaging (standard
didactic model) alongside a phone based game which draws on near real time data
to enable users to actually ‘game the data’. Such ‘gamification’ processes are
gaining traction in environmental thinking and may offer an exciting way forward.
ACKNOWLEDGEMENTS
The authors wish to thank Bristol Water Plc and the Lloyd’s Register Foundation
for their financial and logistical support. Lloyd’s Register Foundation is a charitable
foundation helping to protect life and property by supporting engineering-related
education, public engagement and the application of research. We are also grateful
to the Estates and Accommodations departments at UWE, Bristol for their
continuing support for this interdepartmental research programme.
REFERENCES
1. Bagozzi, R.P (1979). Attitude Measurement and Behaviour Change: a Reconsideration
of Attitude Organization and Its Relationship to Behaviour. Association for Consumer
Research. 6, Pages 295-302. [Accessed 2015]
2. DEFRA, (2008). Future Water: The Government’s water strategy for England.
Available: http://archive.defra.gov.uk/environment/quality/water/strategy/pdf/future-
water.pdf. Accessed: 07/04/2014.
3. Fuente, D. & Robinson, M. (2007) Excellence in Metering: A Step Towards
Sustainability. Available from: http://sustain.indiana.edu/programs/internship-program-in-
sustainability/docs/final-reports/SU07/David-Fuente_SU07.pdf [Accessed 2015].
Water Security: Monograph 275

4. Indiana University - Bloomington (2013) Integrated Energy Master Plan Indiana


University - Bloomington. Available from: http://masterplan.indiana.edu/iub/IEMP%20
Report.pdf [Accessed 2015].
5. Mailloux, E. (2011) Improving Water Conservation in Smith College Housing through
Environmental Education. Available from: http://www.smith.edu/env/documents/Mailloux_
Water_11.pdf [Accessed 2015].
6. Miller, E and Buys, L. (2008). The Impact of Social Capital on Residential Water-
Affecting Behaviors in a Drought-Prone Australian Community. Society & Natural
Resources: An International Journal, 21(3), Pages 244-257. [Accessed 2015].
7. Staddon, C. (2010) Managing Europe’s Water: 21st century challenges, Ashgate Press.
8. Thaler, Richard H.; Sunstein, Cass R.; Balz, John P. (2013). Shafir, Eldar, ed. The
Behavioral Foundations of Public Policy. Princeton, New Jersey: Princeton University Press.
9. Yale Office of Facilities, Utilities & Engineering (2013) Yale University Water
Management Plan 2013–2016. Available from: http://sustainability.yale.edu/sites/default/
files/files/Water%20Management%20Plan.pdf [Accessed 2015].

FIGURES & TABLES

Figure 1: Plan view of the UWE Student Village


276 Water Security: Monograph

Table 1
Water efficiency measures implemented in Spring/Summer 2013

Table2
Hard Measures. SOURCE: DEFRA, 2003
Water Security: Monograph 277

Figure 2. Median Hourly Water Consumption Per Capita, February 2015

Figure 3. Median Per Capita Daily Water Consumption (in litres) by Block,
February 2015
278 Water Security: Monograph

ESTABLISHING THE OPTIMAL FREQUENCY OF THE SEWAGE


WATER PROCESSING BY MEANS OF DIFFERENT KINDS OF
CAVITATION GENERATORS

Prof., Dr.Sc. Volodymyr Starchevsky1


Prof., Dr.Sc. Volodymyr Pohrebennyk2
Mas. Nataliya Bernatska1
1 Lviv Polytechnic National University, e-mail: maksymiv.natali@gmail.com,
Ukraine
2 Lviv Polytechnic National University, e-mail: vpohreb@gmail.com, Ukraine

ABSTRACT
Industrial wastewater is one of the important pollution sources in the pollution
of water environment. In many parts of the world health problems have often been
caused by discharging untreated or inadequately treated wastewater. Compared to
other industrial sectors the food industry consume large quantities of water. Almost
50% of water utilized in food processing it for washing and rising purposes. This
water has been reported to be treated by aerobic and anaerobic biological techniques.
But the biological system due to fluctuating load and characteristics of wastewater
wich fluctuates widely. Conventional wastewater treatment methods like adsorption
on activated carbon, extraction, and chemical oxidation have limitations such as
limited applicability and lower efficiency
The treatment of wastewater is an increasingly important issue for food
producers.
Basic wastewater treatment facilities reduce organic and suspended solids to
limit pollution to the environment. Advancement in needs and technology have
necessitated the evolving of treatment processes that remove dissolved matter and
toxic substances. High organic matter content is a basic problem in food industry
wastewater.
Relatively simple wastewater treatment technologies can be designed to provide
low cost sanitation and environmental protection while providing additional benefits
from the reuse of water.
For a new technology to be considered it must have advantages over traditional
treatment processes. These can include lower capital and operations and
maintenance costs, higher efficiency, easier operation, better effluent water quality,
and lower waste production.
Water Security: Monograph 279

A technology which utilises the cavitating liquid environment can be considered


as a non-waste technology and environmentally friendly due to the possibility of
degradation of low biodegradable, hazardous.
The aim of this paper was establishing the optimal frequency of the sewage
water processing by means of cavitation generators.
There has been investigated in the paper the efficiency of water cleaning from
biological contamination by means of ultrasonic and vibration response cavitation.
There has been established that the decrease of the microbial amount of the sewage
water of brewery, yeast production, yeast lysates is positively outlined by the first
order reaction levels and differ only by decay constants. In as little as 1 hour of
processing with the frequency of 50Hz the level of living yeast cells destruction
reaches 99,8%, the maximum effect was reached with the frequency of 37 Hz. This
frequency is resonance, with which there is reached the maximum result with
minimum power input required for the perturbing of cavitation, in other words, the
oscillation frequency of deck is divisible by or equals to the oscillation frequency
of cavitation nuclei. It has been demonstrated that the application of the vibration
and cavitation equipment produces the same effects as in case of ultrasonic
cavitation. If to analyze the electrical power expenditures for the creation of
cavitation process then there may be drawn a conclusion that it is economically
reasonable for the perturbing of cavitation to use vibration response low-frequency
cavitators. The obtained results allow choosing optimal conditions for carrying out
the sewage water purification process at food industry enterprises and apply
vibration and cavitation equipment for the solution of the existing environmental
problems of the hydrospace.
Keywords: cavitation, cavitators, intensification of water purification, ultrasonic
radiation, biological contamination.

INTRODUCTION
The intensification of the production processes, as well as the solution of the
problems connected with power and resources preservation in recent times, has
become more important. One of the most effective ways to reach high technological
results in processing of liquid heterogeneous systems is an impulse action over the
media under processing [1–3]. According to the analysis of the typical technological
schemes and corresponding equipment, most of the processes in the food industry
are energy consuming and require an application of the intensification methods of
modern technological processes. To such methods belong the phenomena that
accompany cavitation [4; 5]. Cavitation may be created by means of different
methods, which include spark discharge, impulse passage of high-voltage current
(electro-hydraulic shock), ultrasonic radiation, hydrodynamic pressure loss in a
current to critical point (hydro dynamic cavitation) [6]. Spark discharge and electro
hydraulic shock effect are used to process the limited amount of liquid. In the case
of spark discharge and electro hydraulic shock an integral current rip in the liquid
280 Water Security: Monograph

followed by shock wave propagation is observed on the area between the electrodes.
Because of electric leakage in the liquid in the flow volume surrounding the
discharge channel, there are developed the high-pulse pressures, which generate the
local cavitation that in this particular case serves as a complementary factor in the
processing of the medium [7; 8]. The energy of the spherical shock wave, which is
distributed from the center of the liquid volume to its periphery is inversely
proportional to the squared distance from the area of electrical discharge [9; 10]. It
leads to uneven force action over the liquid and in case of increase in volume of the
liquid under the treatment, requires the power improvement and amount of electrical
discharges, which leads to increase of energy consumption for the processing
operation. Besides, the creation of the powerful shock waves throughout the liquid
volume requires the strengthening of the working chamber of the unit [11; 12].
The above-indicated defects exclude ultrasonic method, which consists in the
application of vibrations of the ultrasonic frequency for the creation of conditions
for the development of cavitation nuclei, which are the gas inclusions located in the
fluid. The shock waves are generated on the small territory around each cavitation
cavern [12]. It provides the uniformity of the force influence over the liquid and
absence of load impact on the wall of the working chamber of the unit. The energy
of ultrasonic radiation is located in a big amount of small volume of liquid and
allows decreasing energy consumption for the performance of processing in
comparison with the spark discharge and electro hydraulic shock. However, in the
course of ultrasonic processing, the cavitation arises on a working surface of the
acoustic radiator, excluding its destruction due to erosion. Besides, the passing of
ultrasound through the liquid is related to the great losses of energy of the acoustic
waves. Some of the indicated problems are solved in the conventional ultrasonic
apparatuses [11], where not all the liquid is being processed at once, but only its
part that flows through the working area of the apparatus, which allows avoiding
great consumption for the ultrasound radiation [12].
The transition to the perspective current processing scheme stipulates the
possibility to use the hydrodynamic method generating cavitation. In this case, the
appearance of cavitation is determined by the decrease of pressure in a flow to the
values that corresponds to the pressure of the saturated steam of the liquid under
the treatment. Hereby there are occupied the cavitation nuclei of different sizes,
which intensifies the development of hydrodynamic cavitation and the process of
the liquid treatment in comparison with ultrasonic method. In order to intensify the
industrial technologies, the most applicable are all kinds of hydrodynamic
cavitation, which allows processing of the big amount of liquid in a flow [11; 12].
Hydrodynamic cavitation may be carried out in the apparatuses of different kinds
of construction and by means of different methods. There are distinguished the
following kinds of hydrodynamic cavitation: static, dynamic, intermittent,
centrifugal, nozzle, fricative, current, mandatory, thermal, steam, gas. Apparatuses
that are based on the use of the effect of hydrodynamic cavitation are meant for the
processing of the liquid heterogeneous systems. The effect of cavitation is
significantly influenced by construction and principles of operation of the apparatus.
Water Security: Monograph 281

The equipment that the cavitation effects are used in, has the following advantages:
increased productiveness of the processes due to high carrying capacity, increased
level of the products quality due to high dispersibility of the particles, increased
resistance and uniformity of the system, decrease of the unit costs of energy for the
processing due to the local concentration of efforts, provision of the universality of
application. In this particular case, a gas cavern serves as the energy transformer,
which is being introduced and the object of influence [11; 12]. In case of intense
broadening, compression or pulsation of caverns under the influence of the external
pressure which is periodically changed, there are activated the carrying processes
both on the micro-level, throughout a separate cavern and on the macro-level, for
the whole volume, in consequence of a turbulence transition of the interphase
surface. The combined activity of these factors increases the total coefficient of the
mass-transfer in a system [11].
According to the classification of the cavitation equipment for the processing
of the technological media, there exist four groups of constructions.
To the first group, there is referred the equipment where cavitation appears due
to a sharp variation of the flow geometry. Because of local pressure release in the
current of a medium, there is developed a hydrodynamic cavitation. A change of
the flow geometry is reached by selection of a form of the flow chamber of
equipment or by placing of the bluff bodies in a flow – cavitators. Stimulation of
cavitation is made by means of a cavitator, which is turning round. These devices
are structurally simple, reliable, convenient and highly productive (up to
100 cu.m/hour),with broad technological properties [12].
In the industry, there are effectively used cavitation devices, the most perspective
of which is the dynamic type flowing device. A simplicity of the design provides it
with significant advantages over others. The processed medium comes to flow
cylindrical chamber and enters the placed there cone-shaped cavitator turned
towards the flow with the smaller foot. Entering the special spots of the cavitator,
the current of the liquid is spinning round and by means of speed increase there is
created a cavitation mode of the flow, making the cavitator spin round. Behind the
cavitator there are created the cavitation caverns that move along the circular helix
and generate and field of cavitation bubbles, which saturate a stream of a medium
throughout the whole volume of the flow chamber of a mixer or homogenizer. In a
flow chamber at the output behind the cavitator there is placed a conical nozzle,
which narrows a liquid flow, there increases a flow speed and decreases a
hydrostatical pressure. Under such conditions at the outlet of the chamber, there is
a flow with significantly big bubbles. Splashing inside, the cavitation bubbles create
the pulsating shock waves, which intensify the mixing process. Moving the cavitator
along the flow chamber, they change the length of the cavitation zone [12].
To the second group belong the devices (rotor and flowing type hydrodynamic
radiators), where the cavitation is generated periodically changing the pressure of
the liquid hydro dynamically. These devices are structurally simple, though their
productivity does not exceed 30 cu.m/hour [12].
282 Water Security: Monograph

Cavitation devices of the third group operate with acoustic radiator in the
ultrasonic frequency spectrum, those having low productivity (up to 30cu.m/hour)
and contain an expensive ultrasonic generator [12].
The fourth group includes the devices, which use high voltage discharge in the
liquid (electrohydraulic effect), in consequence of the electric breakdown of which
in the environment zone of discharge channel there appear high impulsive pressures
that generate cavitation [11; 12].
The aim of this paper was establishing the optimal frequency of the sewage
water processing by means of cavitation generators.

METHODOLOGY OF RESEARCH
There have been undertaken the studies of the influence of cavitation over
sewage water of the brewery, yeast production (private company limited by shares
«Enzime»), yeast lysates with different initial values of microbial number (MPN)
and different types of organic and biological contamination (COD). There was used
an ultrasonic generator UZDN-2Т with the capacity of 40 W (fig. 1) and low-
frequency vibration and resonance cavitator (fig. 2). The microbial number was
defined before and after the processing by means of surface plating at beef-extract
agar. The investigations connected with combustion of admixtures in water of the
natural reservoirs was carried out at the temperature 298 К and the pressure
1∙105 Pа, selecting the same experiment conditions for running the processes both
in the ultrasonic field and with application of the vibrocavitation.
Ultrasonic vibrations the frequency of which is 22 kHz from UZDN-2Т
generator were transferred by means of magnetostrictive radiator, dipped into the
volume of the liquid under the investigation (100 cb.cm) with known microbial
number.
For cavitation processing of water solutions and solutions with toxic and
chemically aggressive matters, there have been developed special constructions of
low-frequency vibration cavitators able to provide the processing at the increased
up to 3,5–4,0 kg/sq.cm liquid pressures and the temperature of up to 220 ˚С. They
are produced of stainless steel and the peculiar feature that differs them from the
traditional vibrocavitators is the absence of elastic corrugated tubes and resonance
elasticity of a pendant of the oscillating decks-cavitation stimulators.
In order to prevent from excessive overheating of the electric magnets of a drive
in these cavitators in the course of cavitation processing of the liquids in case of the
elevated temperatures there has been provided a cooling system for electrical drives.
In order to reduce vibrations that may be transmitted from oscillating parts of the
cavitator to the supporting pillars and the nearby-equipped devices, symmetrically
placed in cylindrical cases, anchors of the electromagnetic drive are provided with
synchronous antiphase oscillation. It is reached by a corresponding connection to
Water Security: Monograph 283

power supply of electromagnets stator


coils. Herewith the reaction force of
oscillation movements of the anchors,
being synchronous and directed in an
opposite way through the working space
and cylindrical case 3 mutually extinguish
and level each other reducing to a
minimum the vibratory transfer to the
base.
Having determined the optimum
performance of the cavitator, on its
remote control there is established the
necessary frequency range of the supply
variations of the electromagnet drive, by
means of socket pipes, through the
regulatory throttles the liquid and gas
under processing is delivered to the
operating chamber of the cavitator (in
case of process requirement) and carry
Figure. 1. The image of an ultrasonic out processing.This sample of research
generator UZDN-2T for combustion of
inclusions of organic matters and and industrial cavitator is demonstrated
disinfection of microorganisms in the in fig. 2.
ultrasonic field.

Figure 2. An image of the low-frequency vibration and resonance cavitator for cavitation
processing of water solutions with high content of MPN and COD under the pressure and
at the elevated temperature (with partially removed protective elements of a case) [11]
284 Water Security: Monograph

RESULTS OF RESEARCH
Investigation of the oxidation of microorganisms under ultrasound treatment
shows that the COD of dispersion is not changed in the absence of oxygen
(anaerobic conditions) (fig. 3, curve 1). At the same time the change of COD of
dispersion of microorganisms in air is high enough (Fig. 3, curve 2). Oxygen
bubbling by dispersion of yeast during sonication increases the rate of COD change
in comparison with the rate in air (curve 2, 3). Therefore main oxidizing agent is an
oxygen and .OH radicals formed from water during sonication play only secondary
role. Real energy of O-H bound breaking in water is close to 420 kJ/kal and it is
larger than energy of C-H or C-C bound breaking 360 or 260 kJ/kal correspondingly.

Figure 3. An image of the low-frequency vibration and resonance cavitator for cavitation
processing of water solutions with high content of MPN and COD under the pressure and
at the elevated temperature (with partially removed protective elements of a case) [11]

Our results shown the decrease of COD of sewage waters in time during
ultrasound and vibrocavitation treatment (fig. 4).

Figure 4. The change of COD of yeast dispersion in time during ultrasound and
vibrocavitation treatment
Water Security: Monograph 285

The decrease of MPN of sewage waters of the brewery, yeast production, yeast
lysates is satisfactory outlined by the first order reaction levels and are only
distinguished by the decay constant (fig. 5 а,b,c, table).

(а)

(b)

(c)
Figure 5. (а, b, c) Kinetic curve of MPN variation of yeast solutions, received from pure
culture а), sewage waters of the yeast plant b) and brewery c) with the use of
vibrocavitation (1) processed with the ultrasound (2), taken to 100W of electric power.
The temperature is 20˚С and the frequency is 37 Hz.
286 Water Security: Monograph

Table 1
Rate constants of destruction of yeast cells in water solution with the use
of ultrasound vibrocavitation, taken to 100W of electric power.
The temperature is 20 ˚С and the frequency is 37 Hz
MPN, kl/ml Vibrocavitation US cavitation
600 0,0342 0,0343
16000 0,0594 0,0563
2,6*1012 0,0878 0,0819

In as little as 1 hour while processing with the frequency of 50 Hz the level of


destruction of the living cells of yeast reaches 99,8%, which is a satisfactory index for
the technological implementation. However, the handling time depends very heavily
on the frequency. In Figure 6 there is shown the dependence of the level of dying away
of yeast cells from the oscillation frequency of decks-the stimulators of cavitation and
it may be seen that the best effect was reached with the frequency of 37 Hz.

Figure 6. Dependence of the level of dying away of the yeast cell on the oscillation
frequency of decks – the stimulators of cavitation and the initial concentration of the cells
of microorganisms
This frequency is a resonance frequency, where there is reached the maximal
result with the minimum energy consumption, required for the stimulation of the
Water Security: Monograph 287

cavitation, in other words the oscillation frequency of decks may be divisible by or


equals to the oscillation frequency of the cavitation nuclei. That is why the optimum
frequency is 37 Hz. In fig. 5 (а, b, c) it is shown that the use of vibrocavitation
devise gives the same effect as in case of US cavitation. Nevertheless if to analyze
the consumption of the electrical power to create the cavitation process, then it may
be drawn a conclusion that US generator consumes 1,4 kW and radiates only
100 W, which relates to the loss of energy in the course of transformation of electric
power to the magnetic field and it – into the mechanical oscillation of
magnetostrictor. Vibrocavitator consumes 800 W and also radiates 800 W (the
coefficient of efficiency is about 98%). The increase of the coefficient of efficiency
in these cavitators is reached by means of experimental selection of oscillation
frequency of deck-the stimulators of cavitation, close to divisible by resonance
oscillation frequencies of the cavitation nuclei. It is carried out by means of the
devise for investigation of oscillation frequencies in the cavitation nuclei liquids,
divisible by resonance. That is why it is economically reasonable for to use low
frequency vibration-resonance cavitators for stimulation of cavitation.

CONCLUSIONS
The efficiency of water purification from chemical and biological impurities in
ultrasonic and vibrocavitation conditions has been investigated.
It has been demonstrated that the decrease of microbial number of sewage waters
both with the use of ultrasonic cavitation, and with the use of vibrocavitator is
outlined by levels of the first order reactions and differs only by decay constants.
It has been investigated the efficiency of vibrocavitation processing in case of
cleaning the sewage waters with concentration of biological contamination with
different oscillation frequency of decks – the stimulators of cavitation. The best
effect has been reached with the frequency of 37 Hz.
It was demonstrated that the use of vibrocavitation device provides with the
same effect as with the use of US cavitation. However, the coefficient of efficiency
of the vibrocavitator makes about 98%, that is why it is economically reasonable to
use vibration-resonance low-frequency cavitators for stimulation of cavitation.
Establishing the optimal conditions of the sewage water processing by means
of vibrocavitation generators as a non-waste technology and environmentally
friendly technology.

ACKNOWLEDGMENTS
This work was supported by Lviv Polytechnic National University, Department
of general chemistry and Department of Ecological Safety and Nature Protection
Activity
288 Water Security: Monograph

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10. Madhu, G., Rajanandam, K., Thomas, A. (2010). Cavitation Techniques for
Wastewater Treatment: A Review, The IUP Journal of Chemical Engineering, 11 (3), 58-79.
11. Shevchuk, L., Aftanaziv, I., Strogan, O. (2012). Cavitation occurrence by the vibro-
rezonance method, 13th Meeting of the European Society of Sonochemistry, Lviv, 139.
(in ukr.)
12. Shevchuk, L., Strogan, O., Koval, I. (2012) Equipment for Magnetic-cavity Water
Disinfection, Chemistry and Chemical Technology, 6, (2), 219-223.
Water Security: Monograph 289

FORMATION OF NEW DELTAS IN LARGE WATER RESERVOIRS

Prof., Dr.Sc. Volodymyr Starodubtsev


National University of Life and Environmental Sciences of Ukraine,
e-mail: mailto:vmstarodubtsev@ukr.net, Ukraine

ABSTRACT
The formation of new deltaic landscape at the places where rivers flowing into
the large reservoir is considered as an important and major scientific and economic
problem. This process is estimated to be universal having a global character. New
landscapes, which are formed by delta type, are vary considerably depending on
climatic conditions. So here the processes of deltas formation in the temperate
climate of Ukraine are discussed in more detail. Problem analysis was carried out
using remote sensing data (Landsat satellite imagery) and ground-based
observations. Using satellite images made it possible to trace the process in time
and space over a long period. Deciphering of satellite images with the help of
specialized software gave a possibility to determine the area of the newly formed
landscapes and approximately to diagnose soil and vegetation objects that were
specified by ground monitoring in the reservoirs.
Keywords: delta, reservoir, satellite image, deciphering, landscape

INTRODUCTION
Creation of new large reservoirs for the development of hydropower, irrigation,
water supply, transport and other sectors of the economy is actively continued
worldwide. Most of the major rivers are regulated by reservoirs, in varying degrees
[1; 5; 10], despite the opposition of the environmentalists and the public to this
process. The impact of such large water bodies on the environment, including
vegetation and soil cover, on the coast flooding and destruction, and even on the
climate was studied comprehensively [1; 7]. However, one important aspect of the
interaction of water reservoirs and rivers on which they are made was completely
insufficiently researched and evaluated. This is - the formation of new deltas-like
landscapes at the confluence of the river into the reservoir. This process is especially
characteristic for rivers with large sediment load, which is often observed in arid,
subarid and in sub-humid regions [10]. Previously, researchers have considered this
process mainly from the standpoint of the silting of reservoirs and reduce of their
290 Water Security: Monograph

useful capacity. But in fact it turned out to be much more substantial and varied. In
many reservoirs of the world for many decades of their existence actually new deltas
with rich hydromorphic landscapes and unique vegetation and soil cover were
formed. This is the process we are witnessing in many reservoirs in Ukraine, Central
Asia, Kazakhstan, North and South America, southern Europe [2−11].
Initially, the formation of new deltas in large reservoirs we observed during field
hydrological and morphological, botanical, and soil studies. The essential
information is also provided by updated topographic maps and map service Google
Earth. But the real breakthrough in the study of this problem was made possible
with the advent of medium-sized and detailed satellite images that allow us to
evaluate this process in time and space. In particular, the huge role was played by
the opening of access to the NASA archives. It has made possible to use the Landsat
imagery for more than 40-year period for remote monitoring of this important
scientific, environmental and economic problems.

OBJECTS AND METHODOLOGY OF RESEARCH


Detailed field studies of deltas formed in large reservoirs, as well as the analysis
of remote sensing data held in Ukraine on a cascade of six reservoirs on the Dnieper
River (figure 1). To monitor the dynamics of
the hydromorphic landscapes area in these
water bodies space Landsat imagery obtained
from NASA's public archives, as well as
topographic and electronic Google Earth
maps were used. However, at the earliest
images of Landsat-2 outlines the boundaries
of the water surface and hydromorphic
landscapes are insufficiently clear. More
reliable results could be obtained from
satellite images Landsat 4-5 and 8.
The ISODATA algorithm, channel
combinations "true color", 7–5–3 (Landsat 4–
5) and 7–6–3 (Landsat 8) were used for the
decoding of satellite images. Field routes,
which since 2010 are held with accurate geo-
referenced GPS-receiver allows specifying
Figure1. Cascade of reservoirs on the the nature and characteristics of the delta
Dnieper River (Ukraine). landscape formation in reservoirs.
RESULTS OF RESEARCH AND DISCUSSION
The formation of new deltas in the cascade of reservoirs on the Dnieper River,
which are extending within a few natural zones, has, in our opinion, very essential
environmental, social and economic importance. For 50–60 years of the existence
Water Security: Monograph 291

of these reservoirs hydromorphic landscapes with delta features over an area of


40,000 hectares, and taking into account the water surface within these landscapes
– about 80,000 hectares, are formed in them. At the same time the growth rate of
deltaic landscapes has achieved in recent years in the whole cascade about 2,000
hectares per year.
This rapid development of new landscapes in the Dnieper reservoirs is related
not only to the accumulation of river sediment and activation of delta-litho-
morphogenesis, but also to the rapid spread of hygrophytic and hydrophytic
vegetation, including the "Red Book" species of vegetation - water chestnut (Trapa
natans). As a result, the unique natural-technogenic landscapes were formed that
promote enrichment of biodiversity in the region, as well as serving the recreational
base for many megacities. At the same time, the "blooming" of water and rotting of
the great mass of higher plants and algae leads to intense oxygen consumption and
deterioration of the living conditions of the entire biota of water bodies. Qquality
of river water for municipal and industrial water supply as well as for irrigation is
sharply deteriorating. Significant difficulties arose to water transport, energy
production, fisheries and other sectors of the economy as well.
The topmost reservoir (Kiev) in the cascade on the Dnieper River (fig.1) was
created in 1964-1965. It accumulates in its upper part a solid runoff (sediments) of
the Dnieper and Pripyat, as well as coastal erosion materials and nutrients. Therefore,
the processes of hydromorphic delta-like landscapes formation here are the fastest.
New riverine shafts and islands with a cellular topography (respectively - and new
land resources) the most actively form in the very upper part of the reservoir, that is,
in the «spurs» of the Dnieper and Pripyat. That is why we have called this area the
Pripyat-Dnieper Delta [2; 4]. Downstream the water area is heavily overgrown with
coastal-aquatic vegetation (Phragmites australis, Typha angustifolia, and Scirpus
lacustris). But in last years thickets of aquatic plants with floating leaves (Nymphaea
alba, Nuphar lutea, Trapa natans) spread rapidly here. On the already formed islands
tree-shrub vegetation, which is characteristic for floodplain forests, is developing.
The expansion of the new vegetation was so large that it exceeded our forecasts.
Therefore we had to significantly increase the area of the territory in which the
monitoring is carried out, with 16,547.8 to 25,842.2 hectares (tabl 1). The annual
increase in the area of hydromorphic landscapes in the Kiev reservoir for the period
up to 2005 was 100-200 ha. But in the last decade, this value in the hottest years
exceeded 1,000 hectares per year, creating significant problems even for navigation
[2; 4; 8; 9; 11]. At the same time, recreational use of the territory outside the
Chernobyl zone improved; the biodiversity of the region significantly enriched.
During the research we found that the materials of remote sensing make it
possible to quantify the formation of the Pripyat-Dnieper delta (table 1 and fig. 2),
and even to predict it in the near future. Nevertheless, the environmental and
economic value of the new landscape can be reliably assessed only after the
determination of their structure and the state based on detailed terrestrial surveys at
least in key areas.
292 Water Security: Monograph

Table 1
Dynamics of hydromorphic landscapes formation in the Pripyat-Dnieper
delta (upper part of Kiev reservoir)

Figure 2. Dynamics of the Pripyat-Dnieper Delta formation in the Kiev reservoir


With this purpose since 2010 we are holding ground (water) routes with the use
of the GPS-receiver to determine the exact geographical coordinates of the
investigated areas. Routes were carried out on newly formed islands, riverine shafts
and coastal areas outside the Chtrnobyl exclusion zone. First of all on the ground
we allocated terrestrial ecosystems with bog-meadow, meadow-bog and bog soils
under the sparse trees and shrubs with meadow grasses. Then we studied coastal-
aquatic ecosystems under continuous thickets of reeds (Phragmites australis) and
cattail (Typha angustifolia), thickets of aquatic vegetation with floating leaves
(Nymphaea alba, Nuphar lutea, Trapa natans). It was more difficult to explore areas
of submerged aquatic vegetation. In inaccessible to us the Chernobyl exclusion
Water Security: Monograph 293

zone, we allocated similar ecosystems on the detailed cartographic servise Google


Earth, drawn up on the basis of Spot and Quick Bird satellite images. This
experience has shown that the use of these cartographic materials is appropriate for
the approximate analysis of emerging hydromorphic landscape structure, in
particular, to determine the area of new land resources and wetlands. Only areas of
sparse aquatic vegetation, including more recently «Red Book» water chestnut, and
submerged aquatic vegetation are not clearly defined.
To objectively confirm the structure of the new deltaic landscape, we proposed
an analysis of their seasonal dynamics on satellite images. However, the launch in
2013 the Landsat 8 satellite with a new sensor OLI, which is slightly different
diagnoses landscape and water surface, created some difficulties for research as a
long-term and seasonal dynamics of the delta. However, the high quality of the
images still allows us to investigate the seasonal dynamics of landscapes and their
structure. It was possible to estimate the approximate structure of the delta
landscape, having isolated terrestrial ecosystems (mainly trees and shrubs), coastal-
aquatic ecosystems with a predominance of reeds and cattails as well as areals of
aquatic plants with floating leaves [4]. We can not yet diagnose areas of submerged
aquatic vegetation which occupy large areas here.
In the first half of the growing season hydro-morphological processes and
vegetation development depend on the power of the passage of spring floods and
ice drift. In the second half of the growing season landscapes change depends on
the temperature regime of water and air. Maximum development of coastal-aquatic
and aquatic vegetation reaches at the end of July – the first half of August (figure
3, image of the July 31, 2014). In September an extinction of aquatic vegetation
starts. In October - November, coastal aquatic vegetation dies, and than it is partly
destroyed by the spring ice drift. A study of the seasonal dynamics of the delta
landscapes (table 2) allows estimating approximately the structure of the landscape
and evaluating objectively enough in the future the long-term trend both the total
area of the new delta and its components.
Table 2
Seasonal changes in the landscape area of the Pripyat-Dnieper Delta in
the Kiev reservoir, ha
294 Water Security: Monograph

In general, the formation of the Pripyat-Dnieper Delta in the Kiev reservoir has
both positive and negative consequences. The positive effects include: 1) enrichment
of biodiversity in new terrestrial ecosystems and wetlands; 2) the possibility of
establishing new protected areas; 3) prospects for recreational development in the
region outside the Chernobyl exclusion zone; 4) burial dropped to the bottom of the
reservoir after the Chernobyl accident radioactive deposits with new mineral and
organic sediments; 5) expansion of fish spawning areas, etc.

Figure 3. Seasonal dynamics of the landscape of the Pripyat-Dnieper Delta in the Kiev
reservoir
The most important adverse effects include: 1) water quality deterioration due
to the decomposition of higher plants organic matter and algae"bloom"; 2) a
significant deterioration in conditions for water transport due to the overgrowth of
the reservoir water area; 3) reduction of the volume of water in the reservoir, which
is used for hydropower generation and water supply; 4) activation of erosion and
accumulation in the beds of the Dnieper and Pripyat above the reservoir, followed
by a horizontal and vertical changes in the channel that leads to the destruction of
beaches and flooding of lands; 5) deterioration of conditions for the passage of
powerful floods through the Kiev reservoir.
A limited size of this chapter does not allow us to give a detailed description of
the formation of the delta landscape in all the reservoirs created downstream of the
Dnieper River. We note only that close by the nature the processes of new deltaic
landscapes formation occur in large Kremenchug (third in the Dnieper cascade) and
Kakhovka (the sixth in the cascade) reservoirs (fig. 4 and 5).
Water Security: Monograph 295

Figure 4. The Kremenchug delta of the Dnieper on the satellite image Landsat-8

Kremenchug reservoir for many-year flow regulation was filled in 1960-1961. In


the upper part of this water body the hydromorphic landscape area fairly quickly
increases. By 2010 it was about 7 thousand hectares, an increase for 10 years
amounted more than 3 thousand hectares, while the growth rate reached 231 ha / year
[5; 9; 11]. In contrast to the Kiev reservoir, the area of aquatic and coastal-aquatic
vegetation increases here with the highest rates. However the formation of new islands
and shoals, which will soon become the land, there is also quite active.
In the largest Kakhovka reservoir (the sixth reservoir in the cascade, but the first
one according to the time of creation on the Dnieper River) ever since its filling in
50-ies of the last century almost all solid runoff (sediments) of the Dnieper River
have accumulated. In those years the coast with fertile chernozemic (black) soil
intensively destroyed there, the area of shallow water increased, new islands
appeared. In fact, these processes have been the beginning of the new (Kakhovka)
delta formation, that is, the formation of a unique landscape, which was not there
before. Later deposits of the Dnieper River began to accumulate since 1960 in
Kremenchug, and since 1964 - in the Kiev reservoir. However, an increase of new
deltaic area continued there due to overgrowth with coastal-aquatic, aquatic
vegetation and trees and shrubs, and due to the accumulation of organic sediments.
An accumulation of mineral deposits formed by coastal erosion and processes inside
the water body has continued with slower speed. According to preliminary data,
automorphic and hydromorphic soils in the Kakhovka delta occupy 15–20%, bog
and subaqueous soil under the reeds, cattails and other hygrophytes – 40–50%, and
the ranges of hydrophytes, including water chestnut with floating leaves – 30–40%.
296 Water Security: Monograph

Only in the years 2000-2010 the Kakhovka delta area has increased by 1,5 thousand
hectares, while the growth rate was about 150 ha/year [9; 10].

Figure 5. The Kakhovka delta of the Dnieper on the satellite image Landsat-8

Figure 6. Fragments of new deltas in the Kaniv (left) and Dniprodzerzhinsk (right)
reservoirs on the images Landsat-8

The formation of delta-like landscapes in two long and narrow reservoirs – the
Kanev (second in cascade) and the Dneprodzerzhinsk (fourth in the cascade) is less
clear (fig. 6). Here, the increase in the areas of hydromorphic landscapes occurs
Water Security: Monograph 297

mainly around the remaining islands and along the coast. New islands due to the
accumulation of mineral and organic sediments are formed as well. In the Kanev
reservoir natural processes of hydromorphic landscapes formation at the upper part
are complemented by a massive inwash of new lands by dredgers in the water area
and the subsequent a “dacha” construction there, as it can be seen even on satellite
images. Determination of areas on such images showed that in the period 1992–
2005 it was inwashed only within the territory that we studied more than 800
hectares of new land in the reservoir water area. Total area of hydromorphic
landscapes in upper part of reservoir exceeded 3 thousand hectares, and the rate of
their increase amounted 66 ha/year [3; 11]. The specific feature of this reservoir is
a strong "bloom" of water due to the high concentration of nutrients in it. In the
upper part of the Dneprodzerzhinsk reservoir (forth in the cascade) delta-like
landscapes are forming as islands as well. Total area of such lanscapes amounts
about 6 thousand hectares, the rate of its increase is about 100 ha/year [9; 10]. In
the most deep and narrow Dneprovskoye reservoir, which flow in rock bed, delta-
like landscapes were not formed.

CONCLUSIONS
Formation of new deltaic landscape in the upper part of large reservoirs is a
universal process, which manifests itself in different ways in different climatic
zones, depending on the amount of sediment in the river, flow regulation,
geomorphology of reservoir bed, soil and vegetation on coasts, and many other
factors. The new elements of relief are formed due to the accumulation of sediment
runoff, reshaping coasts, erosion, overgrown of shallow water, an accumulation of
organic matter, etc. Here the features of the deltas formation are shown in the
cascade reservoirs on the Dnieper River in Ukraine on the territory with temperate
climate and plain topography as an example.
Environmental and economic significance of new deltaic landscapes is enormous
and ambiguous. Positive consequences of these landscapes are: (1) enrichment of
unique biodiversity in such deltas; (2) capability of vast recreational development
of these territories, especially near large cities; (3) the possibility of establishing
new protected areas; (4) reclamation of new land resources; 5) expansion of fish
spawning areas, etc. Negative consequences of new deltas formation are as follows:
(1) decomposition of organic matter of higher vegetation and algae “bloom” cause
an essential deterioration of water quality that is used for industrial, communal and
agricultural use; (2) overgrowing of upper part of reservoirs creates hard problems
for a water transport; (3) conditions for fish farming become worse; (4) volume of
water in reservoirs for electricity generation gets lesser; (5) new deltas activate
regressive erosion in a river course upstream and increase a bank destruction and
land waterlogging; (6) threat of spring floods becomes stronger. That is why further
remote and terrestrial monitoring of such unique landscapes formation is a very
important scientific, economic and environmental task.
298 Water Security: Monograph

REFERENCE
1. Reservoirs and their impact on the environment. (1986). Edited by G.V. Voropaev and
A.B. Avakian. Moscow: Nauka. (in rush.)
2. Starodubtsev, V.M. (2011). Formation of Pripyat-Dnieper delta in Kiev reservoir. In:
Geography. Economy. Ecology. Tourism: Regional study. V.5, Nizhyn, 214-221. (in ukr.)
3. Starodubtsev, V.M. (2012). Kaniv reservoir: “Ukrainian Venice or environmental threat.
Kyiv: Agrar Media Group. (in ukr.)
4. Starodubtsev, V.M. (2012). Sesonal dynamics of landscapes in the Pripyat-Dnieper
delta of Kiev reservoir. In: Natural resources of Polessie: estimation, use, protection. Part 2.
Pinsk: Polessriy state university, 78-80. (in rush.)
5. Starodubtsev, V.M. (2013). Remote sensing of new deltas formation in a top of large
reservoirs. Problems of desert development,. № 1-2, 15-21. (in rush.)
6. Starodubtsev, V.M. (2017). Formation of new delta-like subject in the Kapchagay
reservoir on the Ili River. Water Resources, № 1. (in print)
7. Starodubtsev, V.M., Bogdanets V.A. (2010). Formation of new delta of the Ili River in
the Kapchagay reservoir. Arid Ecosystems. V. 16. № 4(44), 49-53. (in rush.)
8. Starodubtsev, V.M., Bogdanets V.A., Yatsenko S.V. et al. (2010). Formation of deltaic
landscapes in upper reservoirs of the Dnieper cascade. Scientific reports of NULES, №5(21).
http://www.nbuv.gov.ua/e-journals/Nd/2010_5/10svmdrc.pdf. (in ukr.)
9. Starodubtsev, V.M., Bogdanets V.A. (2010). Formation of new deltas in the Dnieper
reservoir. In: Nature management: ecology, economy, technology. Minsk, 279-282. (in rush.)
10. Starodubtsev, V.M., Bogdanets V.A. (2012). New deltas formation in large water
reservoirs. In: Fourth International Conference on Water Resources and Renewable Energy
Development in Asia. Chiang Mai, Thailand, Conference papers, CD.
11. Starodubtsev, V.M., Bogdanets V.A. (2012). Dynamics of hydromorphic landscapes
formation in upper part of Dnieper river reservoirs. Water Resources, v.39, #2, P. 165-168.
Water Security: Monograph 299

OIL POLLUTION MONITORING BY SATELLITE PHOTOGRAPHY


ANALYSIS

Ass. Prof., PhD. Andriy Volkov


Odessa State Environmental University, email: aandrew_v@rambler.ru, Ukraine

ABSTRACT
The problem of water pollution with oil is very important for northwestern coast
of Black Sea. That requires implementation of monitoring systems and approaches
to collecting appropriate data concerning water quality. These issues are even
sharper for water bodies around trade ports with hard traffic because it is expensive
to organize water quality monitoring which is based on water sampling. So, the one
of the best solutions is using methods of remote sensing.
The research contains detailed description of remote sensing methods which ate
directed to water quality assessment. The abilities of sensors are discussed. The
principals of spatial data arrangement utilizing geographical informational systems
are given. The complex approach to spatial analysis of water bodies polluted with
oil is offered and applied for pollution assessment of water bodies around trade port
of small town Chernomorsk which is in the South of Ukraine. The thematic digital
maps of water pollution with oil were designed.
Keywords: oil pollution, satellite sensing.

INTRODUCTION
Remote sensing (RS) is the measurement of object properties on the earth’s
surface using data acquired from aircraft and satellites [1].
There are two interrelated areas of remote sensing: scientific and engineering.
The subjects of remote sensing are spatial and temporal properties of natural and
socio-economic systems, which are represented as two dimensional pictures. RS is
based on utilizing of sensors which spacecrafts are equipped with. The sensors
record electromagnetic waves in format that is convenient for digital processing.
Devices, which are installed on satellites, usually trace visible, infrared and
microwave radiation [2-4] (fig. 1):
• visible 0,4 – 0,7 microns;
300 Water Security: Monograph

• infrared 0,7 – 1000 microns;


• microwave 1000 – 1,000,000 microns.
Nowadays remote sensing is a very powerful facility for studying the earth and
it is applied for solving local environmental problems as well as global ones. It is
necessary to admit remote sensing is part of a larger system of collecting,
processing, registration and using of data. Properly organized system of RS should
be focused on solving specific environmental problems that requires utilizing proper
equipment and data collecting systems [5–7]. The brief description of RS
fundamentals is given below.
The radiation from the subject reaches the sensor, which records the spatial
information. The ideal sensor must be simple, compact design and highly accurate.
Also, it mustn’t consume much energy. Recorded data are transmitted to the ground
station where they are saved in convenient format for future processing.
This research is dedicated to monitoring of water contamination with oil by RS
data analysis.

Figure 1. Spectral range of satellite equipment

METHODOLOGY OF RESEARCH
The most convenient tools for spatial analysis are geographical informational
systems (GIS). The research goal was to analyze oil pollution of water body around
port of Cherrnomorsk (small town in the South of Ukraine) in 2014. The initial
database was represented by set of satellite images in visual, infrared and microwave
range (fig. 2; 3). All these images show spatial distribution of albedo for water
surface which depends on water pollution with oil [8].
Water Security: Monograph 301

a b
Figure 2. Spatial image of water pollution by oil spill (а – visual, b – infrared)

Figure 3. Spatial image of water pollution


by oil spill (microwave)

We combined these three images into one so each cell of a new image was
represented with vector value (fig. 4) [9; 10]:
,
Xi - vector value which is appropriates to raster cell;
vi - visual map values;
iri - infrared map values;
mwi - microwave map value.

Figure 4. Map overlapping

Assigning vector values for every cell makes possible to implement cluster
analysis for zoning [11–13]. Brief description of cluster analysis formulated below
as four steps (fig. 5):
302 Water Security: Monograph

1. At the beginning ‘CLUSTER PLUS’ creates first cluster center c1 с1= х1 .


2. Next center is the vector c2 which has the biggest distance to c1 , с2=хj2, i.e.

3. When ‘CLUSTER PLUS’ creates k cluster centers the next


(k+1) center is хjk+1 which has the biggest distance to the closest cluster center
с1,...,сk, i.e.
4. Creating new clusters stops when the condition is ‘true’:

Figure 5. Cauterization scheme (e.g. for two dimensions)


To analyze these images we used QGIS [14-16] free software which contains
powerful spatial analysis tools [17, 18]. The procedure of zoning included manual
designing of vector polygon layer called ‘signature’. This layer contained attribute
‘type_num’, which described the type of water surface (fig. 6, 7):
0 – land surface;
1 – water surface which is not contaminated with oil;
2 – water surface which is contaminated with oil.

a b

Figure 6. Spatial image of water pollution with oil and signatures (а - visual, b - infrared)
Water Security: Monograph 303

Vector polygons were designed in the way that the cells within single polygon
were rather similar. So this vector layer described to GIS analytical engine how to
classify cells.

Figure 7. Spatial image of water pollution


with oil and signatures (microwave)

The next step was importing vector layer to module GRASS [14-16]. Then
GRASS calculated separate layers: raster.1 (v), raster.2 (ir), raster.3 (mw), and
combined them into multichannel raster that was implemented by running
command:
i.group group = raster subgroup = raster input = raster.1, raster.2, raster.3.
The next step was adjusting scale of area in question:
g.region rast = raster.1.
The next step was importing vector ‘signature’ by tool v.in.ogr.qgis and
converting it into raster format:
v.to.rast in = sig out = sig use = attr col = type_num
• in - name of initial vector layer;
• out - name of calculated raster layer;
• use - attributes initialization for initial vector layer;
• col - name of the column (in database) with class code (type_num).
Then using tool i.gensigset we calculated spectral statistics for all vector
polygons:
i.gensigset group = raster subgroup = raster sig = statistics training = sig
maxsig = 10
training ˗ name of register layer;
group - name of initial group of raster layers;
subgroup ˗ name of subgroup of raster layers;
sig ˗ group of signature file;
maxsig ˗ the maximum amount of signatures.
304 Water Security: Monograph

The final step is implementation of cluster analysis using module classification:


i.smap group = raster subgroup = raster sig = statistics blocksize = 128 out =
classification blocksize - size of raster block for neighboring cells. The increase of
blocksize makes raster matrix more homogeneous that is significant to maximize
accuracy of calculations.

RESULTS OF RESEARCH
The main result of research was zoning water body around Cherrnomorsk Port.
The cluster analysis allowed classifying all cells into two clusters (fig. 8):
I cluster – cells which relate to water polluted with oil;
II cluster – cells which relate to water without oil film on the surface.

Figure 8. Cluster analysis results

The polluted area was calculated on the grounds of I cluster cell amount. The
polluted area was 15.016 km2 that was about 19% of total area in question. This
results supposed to use a least two specialized vessels to eliminate consequences of
oil spills by collecting oil film from water surface.

DISCUSSION
Using of remote sensing techniques is vital for seawater quality monitoring. The
visible and infrared pictures provide the best differences between clean and covered
with oil film water surfaces. Thermal infrared sensors are able to work in the
daytime and at night, but their data is significantly distorted by clouds or
precipitation. Microwave sensors are better for bad weather conditions and
independent of the lighting, but its capabilities are limited to the state of the sea
surface so they aren’t used often.
Water Security: Monograph 305

On the RS radar images we determine the position, the shape and size of the oil
film. The above images demonstrate the ability of RS to detect and register the oil
in a wide range of environmental conditions on the surface of the sea.
Using RS with high resolution we are able to analyze water surface in question
for local and global water pollution with oil. We developed and successfully used
geographic information system for the monitoring of oil pollution of the
northwestern coast of Black Sea. However solving the problem of oil spots drifting
requires additional detailed information as high resolution time series of raster
images with relatively short time shift.

CONCLUSIONS
The satellite images contain useful information in various spectral ranges and
stored in digital form. Since satellite images cover different areas they are used for
thematic regional studies. Regular shooting allows monitoring water bodies which
vary under the influence of natural and anthropogenic factors as oil spills in
particular. Using RS it is rather simple to obtain data for inaccessible areas. Another
advantage is the possibility of obtaining RS images of high resolution. Researches
based on RS data require less field works that decreases monitoring expenses.
Updating of satellite images for medium- and small-scale maps is rather cost-
effective. RS images formed with three spectral channels contain more information
than a single ground or aerial photographs. Finally, the digital format of RS data
and implementation of GIS provide fast results.
The main advantages of RS are immediacy, detail, simultaneous coverage of
vast areas and chance for obtaining detailed information concerning areas which
are difficult of approach. That is important to mention that within this research the
best results were achieved because of using multichannel images.
Multichannel images are very widespread, when the area in question is
photographed or scanned in several relatively narrow ranges of the spectrum.
Multispectral sensors usually have 4-8 more lenses (sensors). Combining various
channels we get synthesized images which characterize pollutions in a best way.
Therefore, multispectral RS data is the most valuable material for environmental
monitoring and mapping of polluted areas.
This research provides the efficient and reliable approach to monitoring of oil
pollution. It is possible to use the approach for detection and determination of
polluted water bodies and estimate scales of pollution. The geographical
informational system has been developed on the basis of free software QGIS. The
system provides next options:
• integrated utilizing of digital images from satellites with various sensors.
• collect RS data concerning water pollution with oil;
• zoning polluted water bodies using cluster analysis;
• calculate areas of pollution.
306 Water Security: Monograph

The research results as digital pollution maps were sent to Cherrnomorsk Port
(Ukraine) in order to arrange activities directed to recovery water quality around
Cherrnomorsk Port.

ACKNOWLEDGEMENTS
I would like to express my sincere gratitude to Prof. Tamerlan Safranov for the
continuous support this research and scientific advices concerning methods of
spatial analysis.

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308 Water Security: Monograph

Scientific publication

Water Security: Monograph

Editors: prof. Olena Mitryasova & prof. Chad Staddon

Technical editors:
Michelle Kilfoyle, Science Writer, Science Communication Unit, UWE, Bristol
Wayne Powell, International Water Security Network, UWE, Bristol

Design and layout Yuriy Sevastyanov

ISBN 978-617-7421-13-8
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Свідоцтво суб’єкта видавничої справи серія ДК № 5078 від 01.04.2016 р.

The monograph was published with the support of British Council in the International
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