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Sea water distributed monitoring system

A proposal for architecture and data format

Lucrezia Cilenti1, Rita Dario2, Giuseppe Dentamaro3, Vincenzo Di Lecce3, Cataldo Guaragnella3, Angelo
Cardellicchio3, Giorgio Mancinelli4, Domenico Petruzzelli3, Alessandro Quarto5, Domenico Soldo5, Antonietta
Specchiulli1, Ierotheos Zacharias6
1
National Research Council, Institute of Marine Sciences, Unit of Lesina, Via Pola 4, Lesina (FG), Italy
2
Policlinico di Bari, Piazza Giulio Cesare 11, Bari, Italy
3
Dipartimento di Ingegneria Elettrica e dell’Informazione, Politecnico di Bari, Via Orabona 4, Bari, Italy
4
Department of Biological and Environmental Sciences and Tecnhnologies, University of Salento, Italy
5
myHermes Srl, Corso Italia 63, Taranto, Italy
6
Department of Civil Engineering, University of Patras, Patras, Greece

Abstract— Marine pollution is known and investigated. Moreover, sensors based on simple transducers and/or complex
In the case of economic exploitation of marine waters, i.e. analytical systems may be used as early warning systems.
aquaculture and recreational activities, continuous monitoring of
their quality is necessary. Commercial sensors may be used for In this latter context, two specific issues should be
speditive water monitoring but are usually used as stand-alone addressed in designing sensors-based protocols for early
systems with limited applications. In this article, after a brief warnings or EWSs [1] of anomalous conditions: a) real-time
review of commercial sensors as real time detectors of the monitoring and b) on-line monitoring. EWSs are integrated
relevant chemical/biological parameters, experimental data on systems based on a set of sensing technologies performing data
aquaculture plants are presented. The final objective is to analysis and acquisition aimed at a specific set of pollutants.
produce through techniques of data fusion from heterogeneous Data may be actively discerned, by determining low-
sources with a synthetic representation of the information that probability and high-impact contamination events and, at the
may be also used for early warning. Both data format and data same time, reliable methods to distinguish between normal data
architecture are covered fluctuations and variations due to accidental contamination
events, after, e.g., biochemical and physical interactions of
Keywords—sensor data fusion, aquaculture, marine pollutants different quality parameters. Several water facilities for
specific uses, e.g. aquaculture, are already adopting on-line
I. INTRODUCTION EWSs in all production steps including water intake,
Water bodies, e.g., coastal sea, natural lakes as well as protection, treatment and distribution operations. In the open
reservoirs are critical for human activities such as recreation, seawater many sensors are used as stand-alone systems thus
fishing and/or aquaculture. Monitoring relevant water quality loosing potentialities to model pollution events. In most cases
parameters for the assessment of their ecological state and are proprietary devices not allowing for immediate integration
environmental conditions are paramount important for proper and/or fusion of data. Moreover, real-time and on-line
management and planning protocols. Methods and techniques monitoring tools allow modifications of the sampling protocols
for assessing the status of water bodies are functional to the (e.g. the sampling rate), thus leading to more precise
nature of the body itself, the activities carried out therein and identification of time and location of a contamination event.
for the available control technologies. Conventional water Another important issue is the assessment of the parameters to
analysis protocols start from the sampling phase, albeit of monitor for the specific application. General indicators of the
simple collection by autosampler, sample storage, pretreatment seawater quality include pH, chlorine, temperature, total
and data validation based on the currently applied time- organic carbon (TOC), dissolved oxygen, conductivity and
consuming protocols. turbidity, whereas applications involving the assessment of the
sanitary impact include several other parameters [2].
__________________________________________________
The focus of the present paper is to assess the feasibility of
Partially supported by the grant of Lombardia Region - a monitoring system integrating heterogeneous parameters
Programma Operativo Regionale FESR 2014-2020 / acquired by a set of commercially available sensors, with two
Innovazione e Competitività Iniziativa realizzata nell’ambito main goals: a) to improve the selectivity of the system; b) to set
dell’Asse I - RAFFORZARE LA RICERCA, LO SVILUPPO E an alert recognition system based on the verification of an
L’INNOVAZIONE. Azione I.1.B.1.3 – Sostegno alle attività algorithm relying on data resulting from field sensors. The
collaborative di R&S per lo sviluppo di nuove tecnologie system must accomplish the mentioned requirements after: a)
sostenibili, di nuovi prodotti e servizi. Project MAUI real-time and on-line monitoring; b) assessment of the
(Monitoraggio continuo per le Acque reflue Urbane ed feasibility of the general approach.
Industriali per l’eco-industria).

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To the purpose, an applicative testbed was applied based on progress [7]. On the other hand, algae fluorescence is adopted
the assessment of the water quality in aquaculture plants, one by Algae Toximeter to monitor photosynthetic activity, which
of the main topics of interests in the framework of the is reduced by the presence of toxins in complex matrices. Fish
European Union Blue Growth Program [3]. Among other goals monitoring sensors, like ToxProtect, detect real time swimming
of the program, the fine-tuning of such systems, together with activity of about 20 fish species through an array of 80 LED; if
the assessment of the parameters of interest which are related an erratic swimming behavior is detected, the presence of water
to the human health. toxins can be assumed. However, this class of sensors requires
an accurate knowledge of the relationship between bacterial
The paper is organized as follows: section II reports an and algae activity and the amounts toxics detected.
overview of the related works. Section III discuss main aspects
of aquaculture monitoring, including the chemical aspects Recently new classes of sensors, i.e., e-noses (vapor and
(Section III-a), hydro-geological aspects (Section III-b) and gas phases) and e-tongue (liquid phase), have been introduced.
toxicological impact (Section III-c). Section IV shows the E-tongues envisage for direct contact between the sensing
proposed approach, Section V the conclusions. element matrix (complex) under analysis [8]. The main
drawback of this latter system is direct contact of the sensing
II. RELATED WORKS elements (e.g. electrodes, diodes, membranes, etc.) with the
liquid matrix and thus subject to the potential poisoning.
Many commercially available devices are on the market for Poisons may bind irreversibly to the sensing elements, thus
water monitoring and the most interesting and widespread impairing their performance. To overcome the problem, direct
systems are presented below. Many of these devices are contact must be avoided or minimized by transferring the
classified as multi-parametric probes, like J-Mar Biosentry, analyte from the liquid to the vapor phase. This is the working
UV-VIS, Censar, s:can Water Quality Monitoring Station and principle of VPeN [9], which employs a gas sensor array to
many more. The reference probes are used to assess real-time identify components related to, e.g., hydrocarbons, sulfur,
on-line quality of waters based on determination of the nitrogen and phosphorus derivatives present in the complex
following chemical parameters: turbidity, TOC, pH, BOD, matrix. Phase transfer from the liquid to the gas/vapour phase
nitrate, nitrite, phosphates and aromatic compounds, whereas may be accomplished by mild heating of the liquid phase.
biological parameters are essentially based on determination of
the water toxicity through bacterial bioluminescence, algae Table I shows a summary of some commercially available
fluorescence and fish activities. Bacterial bioluminescence sensors.
sensors like TOX are based on the ability of certain bacterial
strains, e.g. Vibrio fischeri, to produce light after cellular TABLE I. LIST OF COMMERCIALLY AVAILABLE SENSORS
respiration [4]. Many other indications may be obtained
through combination of the above parameters with chlorophyll Name Type
pigment (Chl a). Another relevant aspect of the aquatic J-Mar Biosentry Multi-parametric probe
ecosystems is obtained after quantification of the UV-VIS s:can spectroanalyser Multi-parametric probe
ToxProtect Fish activity monitor
phytoplankton because of its critical role in structuring and
TOXControl Bioluminescence monitor
functioning of the ecosystems. Indeed, phytoplankton biomass, VPeN e-nose for vapour
typically expressed as Chl a, plays an important role in Algae ToximeterII Toxicity monitor
photosynthetic processes and represents a functional ring Fish Activity Monitoring System Fish activity monitor
between food availability and the growth of filter-feeder SeaBird SBE19 Multi-parametric probe
bivalves and fish larval stages. In situ and real-time AquaTroll 400 Multi-parametric probe
measurements of the phytoplankton biomass allows for the
early warning of critical phenomena, such as toxic microalgae
blooms, which represent a risk for organisms and human
health. This latter aspect is important not only for an advanced III. PROBLEM OVERVIEW
and cost-effective control of aquaculture activities but also as Fish advisories warn consumers for possible toxicological
key step in any monitoring protocol focused on aquatic threats associated with consumption of certain families of fish
systems. Conventional dedicated sampling protocols and species. In this context, it is demonstrated that fetuses and
methods for the assessment of phytoplankton biomass are newborn are susceptible to toxicants while there are no doubts
liable, as a general limitation, to the low ability to detect short- that fishes are a source of valuable nutrients. Coastal
time variations after the interplay of e.g., climate, diurnal ecosystems are under increasing stress from a variety of human
phytoplankton movements, and small-scale water circulation. activities that induce pollution, flora and fauna changes,
The suitability of Chl as an indicator of water quality is related together physical alteration of the environmental microbioma
to technical factors such as the nutrients present and the ease of [10]. On seawaters, human activities face increasing sanitary
monitoring in situ [5]. The development of in-situ sensitive risks from growing shoreline urbanization. The authors live
sensors for chlorophyll is based on fluorescence, the ability to and work on the Adriatic and Ionian Sea coast (Bari and
absorb light at a specific wavelength and releasing it at lower Lesina, South-East, Italy and Patras, Greece). The Adriatic Sea
frequency [6]. is a closed basin with reduced waters interchange with the open
Mediterranean. The massive amounts of pollutants released
Works on many multiparametric probes are equipped with into the Mediterranean basin by rivers and sewage (controlled
fluorimeters for continuous monitoring of biological variables or not) remain therefore confined in a relatively narrow
at improved sensitivity and of robust construction are still in

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geographical area. The Marine Strategy Framework Directive nitrate may lead to excessive algal growth
[11] defines (Article 3) the good environmental status of water (eutrophication) together with preferential growth of
bodies through a template assessing interventions (Article 5), potentially toxic blue-green algae over less problematic
together with an extensive depiction of the monitoring algal species. Due to the solubility of nitrate
requirements for an ongoing assessment (Chapters III - V). compounds, relevant concentrations may be associated
Therefore, the need for a comprehensive evaluation with river waters flowing to the sea after heavy
framework for real-time and on-line monitoring raises directly rainfalls from agricultural origin.
from the EU Directive.
• Ortho-phosphate is another important nutrient for algal
growth in aquatic environments and likely to be the
A. Physical, chemical and Biological aspects
limiting nutrient in riverine waters. High
The integration of physical, chemical and biological data on concentrations of ortho-phosphate ions may induce
high frequency time scales represents a paramount important eutrophication phenomena as, in most, cases; it
tool in the legislative context of the water quality control, with represents the so–called limiting agent triggering
specific reference to aquaculture economic activities. Relevant eutrophication.
real-time information about the chemical status of a water body
are obtained by monitoring specific parameters allowing B. Hydro-geological aspects
identification of key processes related to the aquatic trophic
status. Several models for heterogeneous basins have been set-up
and adopted to evaluate pollutant fluxes in waters [14].
• Water temperature (T) and variations in water However, instruments assessing parameters needed to
temperature have an important impact on the aquatic characterize dispersion of pollutants in the basins must be
life. Biochemical reactions usually experience a assessed and measured while evaluating the environmental
doubling in reaction rate after 10°C rise of status of the water body. Aquaculture may be defined as the
temperature. Moreover, key constituents of water high-density production of fish, shellfish and vegetal species
either change their ionic form (ammonia) or alter their produced in a controlled environment. Stocking rates for high-
solubility (Dissolved Oxygen) after temperature rising. density aquaculture are typically thousand-fold greater than
wild environments.
• The salinity (S) is relevant to the aquatic ecosystem,
especially if it is characterized by species with low Modern aquaculture employs open and closed systems to
tolerance to salinity. Salinity affects the solubility of breed living species, with the former characterized by a rapid
oxygen in water. turnover of waters. Different forms of high density, intensive
aquaculture is similar as they all obey the same set of physical
Dissolved Oxygen (DO) concentrations in the water and chemical principles that are basic of the water chemistry
provide an indicator of the overall water quality of the and the net result is water quality. Poor chemical composition
system [12]. DO response is not specific to nutrient of the water leads to rapid degradation. Efficient feed
input; its depletion can indicate an excessive algal conversion, growth and marketability of the final product may
growth (eutrophication), with adverse effects on the not occur unless the pond is a well-balanced ecosystem. Hence,
organisms’ respiration, feeding and growth [13]. the overriding concern of the fish farmer is to maintain, balance
Oxygen measurements combined with temperature, or equilibrium conditions with respect to water chemistry and
salinity and chlorophyll a, allows for deeper insights its natural consequence is good water quality. High stocking
into the trophic status of water body. density of fish or crustaceans in ponds usually exacerbates
• BOD, a measure of the potential oxygen demand problems with water quality and sediment deterioration.
exercised within waters after decaying (oxidation) of Wastes generated (organic metabolites) from aquaculture
the organic matter. activities settle at the bottom of the ponds in the form of
• Ammonia containing nitrogen, an essential nutrient for biodegradable organic matter. When considering the protection
algal growth. It is present in all-natural waters in small of the marine life, conventional monitoring strategy provides
amounts. However, levels beyond 0.1mg N/L may be only space and time snapshots of the water quality.
indicative of sewage contamination. Total ammonia Measurements of the water quality may give an overview of
includes two chemical forms: ammonium ions (NH4+) the general status of the waters dependent on the intensity of
and non-ionised ammonia gas (NH3). Their relative the monitoring.
abundance varies with pH and temperature. High levels The snapshot strategy does not take hydrographical and
of un-ionised ammonia are toxic to invertebrates and weather conditions into account and does not provide forecasts
fish, causing respiratory stress, conditions such as gill of the water quality. To overcome these problems,
hyperplasia and reduced resistance to parasites and hydrodynamic and water quality modelling is needed to
disease. Nitrification, i.e., conversion of ammonia to provide real time information thus forecasting potential
nitrite/nitrates requires oxygen and may therefore be a duration and intensity of pollution accidents. In this context,
significant control on oxygen availability in the water. biogeochemical modelling of the water quality includes
• Nitrate/nitrite contains nitrogen and are hence essential different combinations of water quality parameters and
for algal growth in water. High concentrations of processes.

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C. Sanitary aspects. contaminants are microparticles [24]. The particles size may
Main classes of sanitary pollutants affecting human beings represent a very important factor of direct toxicity and
may be classified as bioorganic (bacteria, spores, etc.,) and pathology. Absence of knowledge on the transport and fluxes
chemical (heavy metals, synthetic molecules with potential of these particles in natural environments leads to a further
endocrine disrupting properties, phosphorous and nitrogen problem, which is exasperated by the fact that biological
compounds and many others). Fish and shellfish bred in systems did not evolved in the presence of nanoparticles now
contact with contaminated waters may have serious ubiquitarian in all water bodies. Moreover, nanoparticles from
consequences on human health. Literature data confirm the volcanic dust and combustion of natural products (e.g., forest
possibility that harmful agents and microorganisms may fires), contribute significantly together with synthetic
accumulate in the sea products thus overcoming the biological derivatives (e.g., automobile and industrial combustion
barrier of the animals themselves. Many of the works published products) since the industrial revolution. Finally,
on this topic report the relevant classes of compounds and the biodegradability may be a further important factor governing
related sanitary effects on man. harmful biological effects [26].

• metal-mercury derivatives (MetHg): influencing the IV. PROPOSED SYSTEM


nervous system, with children more influenced to the
exposure during the critical phases of pre- and post- A. Sensor characterization
natal development [15], limits are 4389-16853 for
10ng/L and 10μg/L MeHg exposure, Table II shows a set of commercial sensors today available
for water quality monitoring and multi-parametric probes. As
• trace elements (e.g., As and Cd): arsenobetaine in fish is mentioned, the main aim of this study is definition of a
considered virtually non-toxic. However, the main combined monitoring approach that relies on the integration of
harmful effects are associated with long-term ingestion an e-nose for water quality monitoring systems. The main idea
of inorganic arsenic thus leading to skin lesions, is that both a multi-parametric probe and a e-nose may be
tumours, developmental toxicity, neurotoxicity, cardio- synergistically used with their respective sensitivities and
vascular diseases, abnormal glucose metabolism and operating principles to give a more comprehensive and precise
diabetes (EFSA). Carcinogenic cadmium, may induce evaluation of the chemical status of the water body.
kidney, bone and reproductive dysfunctions [16], limit
for Cd is 0.27 mg/kg and As 55 to 95 μg/L; In the following, the data from experiments carried-out on
seawater with the VPeN commercial device configured for this
• persistent halogenated compounds and dioxine (PCBs, specific application are presented.
dioxins, PB-DEs): dioxins and dioxin-like PCBs’,aryl
VPeN is an e-nose in vapour phase developed at the
receptor agonists, effects on the reproductive, immune
AeFLab - Politecnico di Bari and myHermes Srl laboratories.
and nervous system developement, immunotoxic, IE
The e-nose integrates several solid-state sensors with other
[17],limits is PCBs 514,32 pg/g;
devices, specifically designed to transfer volatile compounds
• endocrine interferers or disrupters) influencing sex from the liquid phase to the gaseous phase [26]. The ultimate
functions and thyroid activity by the presence of objective is to monitor the related volatile pollutants emitted in
steroids like (mimicking) compounds [18]; a distinct expansion chamber. The device architecture provides
a hydraulic system with variable temperature thermostatic
• polychlorobiphenyls (NDL-PCB): influencing thyroid chamber and mechanical separator of steam from the liquid. An
and liver, brain biochemistry, immunotoxin, estrogenic, expansion chamber brings the steam into contact with the gas
reproductive effects and neurobehavioral effects for sensors. Cleaning phases of the chamber and sensors alternate
exposure to the uterus [19]; with reading phases [27].
• polybromodiphenyl ethers (PBDEs) after binding and The main problem with VPeN is that it may detect only
deactivating the AhR aryl receptor, beyond effects on components that are easily transferred from the liquid to the
the expression of CYP1A1, aryl receptor biomarker gas/vapour phase at low temperatures (between 20 and 80°C).
(AhR, dioxin-like), and CYP2B and CYP3A, androstate It is evident that appropriate chemical reagents can cause
androstat bioindicators [20]; selective reactions involving the emission of gases and/or
• nuclear pregnane X (’xenobiotic nuclear receptor’ CAR vapours in the presence of specific elements present in water.
and PXR) in the rat, in vivo. Effects on the homeostasis Only seawater test results without reagents additions will be
and thyroid homeostasis [21]; presented. The aim is to identify a specific signature of
seawater suitable for aquaculture that allows the continuous
• hydroxylated: powerful agonist hydroxylated receptor and safe identification of the presence of common pollutants
agonists estrogenic (a and b -ER) [22]; (organic, hydrocarbons, ammonium compounds etc.) typical of
marine coastal waters [28].
Bacterial strains may be identified, among others, like the
well-known Escherichia coli, but also many other pathogens Experiments with the addition of reagents for the
may be detected in food of marine origin. In addition, spores identification of pollutants, both chemically and biological, are
and mycelia of algae and/or plants may contaminate fish currently underway. Real testing samples were taken from a
products with a wide variety of agents. e.g., the well-known mussel purification plant (Mytilus galloprovincialis) along the
harmful algal blooms (HABs) [23]. An emerging class of northern Adriatic shoreline (Gulf of Venice). Natural seawater

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was preliminarily UV-irradiated together or artificial seawater
was used according to a cycle defined by Italian legislation.
The different response of the system to different types of
120 tests were carried out according to the table to follow, water is clear. The first 4 tests were carried out with a known
the VPeN was equipped with 11 sensitive solid-state sensors standard compound to set-up the efficiency of the sensors. The
(Propan, H2, ethanol alcohol, methyl alcohol, Methane, CO2, two tests to follow were carried-out with demineralized water
NH3, Toluene, SOx). Fig.1 summarizes the complex of all for setting the system. 36 tests, sampled at sea in authorized
experimental results which were reported by the use of a 3D areas, were carried-out at temperatures between 30 and 60
model. The y axis reports single sensors, the x axis reports the degrees. The same tests were repeated with the water from the
experimental tests, the z axis reports the amplitude of the mussel purification plant after 5 hours of mussel housing.
response from the single sensors. Specifically, single groups of Finally, 36 tests were carried out with synthetic seawater
11 figures from different sensors represents the specific (demineralised water with the addition of salts) not
“signature” of the sensor for different pollutants. contaminated by mussels (Fig. 1).
It is evident how in the first and third series of tests sensors
show comparable response. The seawater contaminated by
mussels has a completely different and recognizable signature.
Experimental data were subsequently correlated by cluster
formation with results shown in Fig. 2. The samples from the
first and third tests form a compact and convex cluster with a
small exception (see Fig. 1). Mussels contaminated samples
form a recognisable compact cluster as compared to clean
water. The samples labelled DEM are demineralised water.

B. Data fusion and aggregation


The use of multi-sensor systems offers several advantages,
in consideration that the measured quantities which are not
always independent of each other. A trivial example is the
variation of salinity linked to the variation of resistivity. It is
therefore possible to say that the multi-value measurement
increases the robustness of the measurement and reduces
uncertainty due to the high number of low precision
Fig. 1. 3D model of measurements realized during tests with VPeN. Y axis
represents sensors; X axis tests; Z axis is for representation of each sensor
measurements. In addition, measurements carried out in
output different geographic positions are useful to generate diffusion
patterns (e.g., pollutants). The increase in the number of

Fig. 2. Clusters of data acquired during tests. Each color is related to a specific class of sample as shown in Fig. 1. The number near each class symbol
represent the temperature of the thermostatic chamber

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sensors, however, has a cost in terms of data exchange, depends on the use of marine resources and that fishing is one
increases the amount of measurements collected from the of the most important.
environment and makes it more difficult to manage the
increased amount of data (many times heterogeneous). This Starting from these considerations and from the pre-
case is well-known as big-data. established or automatic methods of structuring the information
on the quality of marine waters in the relevant field of fish
In the case of seawater, it is therefore of economic and farming, we have obtained the following table highlighting the
scientific interest the combination of data and the identification devices and the parameters currently detectable.
of correlations to get real-time response of the systems with the
final aim of obtaining reliable data on the status of the water In the case of VPeN it can be possible to exploit chemical
body. reactions, even complex ones, to indirectly highlight the
presence of elements that are not directly measurable. We are
The research area is of paramount interest and an currently carrying out activities prior to the creation of a
unprecedented number of scientific archives and data services widespread multi-sensorial system for the speditive and
are currently published and made accessible. Remote and in- continuous monitoring of the quality of marine waters with a
situ sensors carry out large amounts of historical observations special emphasis on closed or enclosed basins such as the
combined with real-time data, as well as simulations modelled Adriatic Sea and the Ionian Sea.
in ever finer spatial and temporal resolutions.
With the increasing availability of complex and TABLE II. LIST OF COMMERCIALLY AVAILABLE SENSORS
heterogeneous data, the need for formats adapted to their INTEGRABLED IN THE PROPOSED SYSTEM
Name Type Analytes
representation, access, understanding and integration also VPeN E-nose COD, NH4, NOx, mercaptans, sulphides
increases. An example is reported by the eReefs project, Multi-
aiming to creation of an interoperable coastal information SeaBird parametric conductivity, depth, temperature, dissolved
platform for the management of data collected from the Great SBE19 probe oxygen, chlorophyll
Barrier Reef in the North-Eastern Australia [29]. Multi-
AquaTroll parametric conductivity, depth, temperature, dissolved
400 probe oxygen, pressure, turbidity,
In the computer area, another example is represented by the pH
exchange of WaterML 2.0 XML data for time series of
hydrological observation data [30]. The NetCDF format, which
is a “de facto” standard for output models in many scientific
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