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TUM School of Engineering and Design

Chair of Urban Water Systems Engineering

Water and Wastewater Treatment Engineering


- Introduction -

Prof. Dr.-Ing. Jörg E. Drewes


26 October 2023

1
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Biggest challenge ahead


– for water supply and sanitation in
cities of the future?

2
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

An Historic Perspective

3
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Think about the attributes…


• To get from A to B
• Limited transport capacity
• Requires (paved) roads
• Runs with a gasoline/diesel engine or electric
• Limited fuel capacity/range
• Generates exhausts/emissions
• Kills people
• …

The automobile

4
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

The Sanitation Paradigm of the 1st Century


Water supply during the Roman Empire (~600 B.C.)

Ancient Rome

uImported water
uUse it once
uFlush away urban
waste
Cloaca
uDischarge to streams
maxima

River Tiber
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Sanitation during the Roman Empire (~600 B.C.)

Sewer systems implemented

Cloaca maxima
Public toilet arrangement
(latrinae), 20 seats with continuous 600 B.D.
flushing in Ostia/Italy (100 A.D.)
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TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Public Water Supply in the Middle Ages until 1850

Fountains/Public Wells
Supply from shallow groundwater
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TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

From Middle ages to 1848


Poor hygenic conditions led to major
diseases and tremendous loss of human life

• Pest
• 75 million from 1340-1771
• Typhus
• 3 million between 1918-1922
• Small pox
• 60 million in 18th Century Europe
• Cholera
• Still today 3-5 million cases/yr, 100,000-120,000
deaths

8
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

United Kingdom Royal Commission, 1848

...suggests installation of
buried sewers:
• to carry sewage out of human settlements
• to stop human beings of getting in contact with their own feces

9
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Public Sewer Systems


Hamburg

Boat trip through Hamburgs sewer system

Sewer installation since 1848 in England, Germany


and other industrialized countries
Munich, 1885
10
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

The Sanitation Paradigm of the 20th Century


‘Contemporary Water Supply and Sanitation’

Long-distance supply from


Lake Constance, 1,700
km, 753 m above sea level
1.25 kWh/m3
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

The Attributes of ’contemporary’ Water Supply

sewage
Water
Water Water
Water Wastewater Rivers Water
in
in Treatment
Treatment Treatment
runoff out

Energy Energy
in
generation • Dependence on imported water

• Water is only used once

• Water is used as transport media; water is mixed and diluted

• Little attention given to energy aspects

• Discharge to streams
Source: wasserfluesse.de; swm.de
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Water Supply and Sanitation in Germany


- The status quo

13
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

State of Bavaria

Source: BMBF FONA 2012


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Water Supply in Germany


Öffentliche Wassergewinnung nach Wasserarten1) in Deutschland 2013

Flusswasser
See- und 1,2%
Talsperrenwasser
12,2%

angereichertes
Grundwasser
8,8%

Uferfiltrat Grundwasser
8,6% 60,9%

Quellwasser
8,4%

1) Einschließlich Wasser, dass durch Unternehmen gewonnen wird, die Wasser ausschließlich weiterverteilen.

Source: Statistisches Bundesamt, 2015


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Nature-based Drinking Water Abstraction in Germany

Biological
Rapid sand
wastewater
filtration
treatment

Bank
Wastewater filtration/Artificia Aeration/
l groundwater Filtration
recharge
Relative contribution?
Drinking water
Surface water

Groundwater
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Per capita water consumption in Germany


ddd

Drinking water

Wastewater

17
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Wastewater Treatment in Germany (2007)


Population total 82,261,000

Population connected to Population not connected


sewerage system to sewerage system
79,052,000 3,209,000
96.1 % 3.9 %

with without with without


centralized centralized decentralized decentralized
Wastewater Wastewater Wastewater Wastewater
Treatment Treatment Treatment Treatment
78,158,000 894,000 3,166,000 43,000
95.0 % 1.1 % 3.8 % 0.1 %

Population with Population without


wastewater wastewater
treatment treatment
81,324,000 937,000
98.9 % 1.1 %
Source: Statistisches Bundesamt 18
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Utility structure in Germany: Water Treatment

Source: Statistisches Bundesamt, 2013 19


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Utility structure in Germany: Wastewater Treatment

Source: Statistisches Bundesamt, 2013 20


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Global Challenges and Trends


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Urbanisation

Source: United Nations, 2006


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Top 10 Megacities over time


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Top 10 Megacities over time


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Top 10 Megacities over time


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Migration to Urban Centers by Region, Germany - 2005 and 2030

Quellen: Statistische Ämter des Bundes und der Länder (2011)


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Aging Infrastructure/Investment Gap


— Aging infrastructure:
— Water losses (<5% bis >25%)
— Leaking sewers (groundwater contamination)

Cost breakdown for wastewater treatment

Source: Leptien et al. 2012


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Multiple Crisis are the New Norm

• Water crisis
• Ukraine war
• Energy crisis
• Supply chain crisis
• Economic crisis
• Pandemic crisis…

• Pollution crisis
• Biodiversity crisis
• Climate crisis
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Expected Temperature Changes in Arctica

Sources: AMAP 2021; Fettweis et al. 2013; Kaufman et a.. 2009


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Temperature- and Climate Changes

Source: Stockholm Resilience Center 2022


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

More frequent Droughts and Heatwaves in Europe

https://www.ufz.de/export/data/2/270352_rissbach800x450px.jpg

https://www.spiegel.de/wissenschaft/natur/duerre-in-deutschland-und-weltweit-der-rueckzug-des-
Source: Süddeutsche Zeitung Oktober 2022 wassers-a-380be8ea-f523-46aa-8ba4-78ce3843c2e6
PhD Seminar 4
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Severe Drought Condition in Europe, Summer 2022

Source: JRC Global Drought Observatory 2022; Augsburger Allgemeine; Bundesministerium für Ernährung und Landwirtschaft; Frankfurter Rundschau
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Impact on Soil Moisture


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Glacier Retreat and Changes in Stream Discharge

Source: European State of the Climate Report 2023; BUND Bayern 2021; Info24service, National Geographic
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Changes in Discharge of Streams in Europe


Rhine River, Summer 2022

Source: European Environment Agency 2022; dw.de; FAZ.de


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Impact of Climate Change – State of Bavaria

Source: StMUV, 2013; Disse 2016


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Recent Drought Conditions in Germany

Source: dpa/hka kde; Helmholtz Zentrum; MARCCOPHOTO / GETTY IMAGES / ISTOCK


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Increasing Percentage of Wastewater Discharge in Streams


Mean median discharge Mean median
minimum
discharge
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Wastewater Contributions in Receiving Streams

Mean minimum discharge


– Main river

Decline by 20 % for mean minimum discharge conditions

Increasing stress on receiving streams

Source: Drewes et al. (2018), UBA-Berichte 59/2018


SCHWEIZ Inn
SCHWEIZ Inn

i
Rhe

Rhe
Salzach Salzach
Mittlere Änderung der Grundwasserneubildung 0 50 km Mittlere Änderung der Grundwasserneubildung 0 50 km
TUM School of Engineering and Design
auf Basis von WETTREG2006 auf Basis von WETTREG2010
Chair of Urban Water SystemsAbsolute
Engineering
Mittlere Änderung
Änderungder Grundwasserneubildung
2021-2050 0
gegenüber 1971-2000 [mm/a]50 km Mittlere Änderung
Absolute Änderungder Grundwasserneubildung
2021-2050 0
gegenüber 1971-2000 [mm/a]50 km
auf Basis von WETTREG2006 auf Basis von WETTREG2010
Absolute Änderung 2021-2050 gegenüber 1971-2000 [mm/a] Absolute Änderung 2021-2050 gegenüber 1971-2000 [mm/a]

Impacts on Groundwater Recharge


1 Rates
0 -10 -20 -50 0 -10 -20 -50

0 Grenze
-10 naturräumlich
-20 -50 Fachdaten: 0 Grenze
-10 naturräumlich
-20 -50 Fachdaten:
Kooperation KLIWA
WASSERWIRTSCHAFT
Kooperation KLIWA
hydrogeologischer Einheit hydrogeologischer Einheit
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H e ss en Grundwasserneubildung
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Th ü r i n ge n

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k. Sa än änk
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Bayreuth bis 2010 (unten), äund
nk. S mittlere Änderung

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Zukunft 2021 bis Oh e
. Saa TS CH E CH IS C H E nk. S
änk Bayreuth
Bayreuth 2050 gegenüber ädem Referenzzeitraum Bayreuth

Fr

Fr
Main Main RE P U B L IK Main
Würzburg
Würzburg
Bayreuth TS CH ETS CHCHISE H EIS C H E 1971 bis 2000 in mm/aWürzburg
CCH (Änderungssignal
Bayreuth TS CH E CH IS C H E
Nürnberg RE P U BRE
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P U B L IK auf Basis von
MainWETTREG2006/ECHAM5/ RE P U B L IK

b
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b
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Alt
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au au Regensburg au Regensburg
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in

ns ns ns
ee ee ee
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de
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in

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Salzach Salzach Salzach
Mittlere jährliche Grundwasserneubildung 0 50 km
SCHWEIZ Inn
SCHWEIZ Inn
in

in
1971-2000 [mm/a] Salzach Salzach
Mittlere Änderung der Grundwasserneubildung
Mittlere jährliche Grundwasserneubildung 0 0 50 km 50 km Mittlere Änderung der Grundwasserneubildung 0 50 km
1971-2000auf [mm/a]
Basis von WETTREG2006 auf Basis von WETTREG2010 13
25 50 100 200 300 400 500 750
Mittlere Änderung
Absolute Änderungder Grundwasserneubildung
2021-2050 0
gegenüber 1971-2000 [mm/a]50 km Mittlere Änderung
Absolute Änderungder
2021-2050 Das Niederschlagssignal
Grundwasserneubildung
gegenüber 1971-2000 0
[mm/a]der
50 km
auf Basis von WETTREG2006
25 50 100 200 300 400 500 750
auf Basis von WETTREG2010 Projektion WETTREG2006
Absolute Änderung 2021-2050 gegenüber 1971-2000 [mm/a] Absolute Änderung 2021-2050 gegenüber 1971-2000
lässt sich eher im [mm/a]
Mittelfeld
0 -10 -20 -50 0 -10 -20 -50
des verwendeten Ensembles
Grenze naturräumlich Fachdaten: Grenze naturräumlich Fachdaten:
0 -10 -20 -50
Kooperation KLIWA
0 -10 -20 -50 einordnen, während die Pro-
Kooperation KLIWA
hydrogeologischer Einheit hydrogeologischer Einheit
Grenze naturräumlich Fachdaten: Grenze naturräumlich jektion WETTREG2010
Fachdaten: trocken
Source: Landesamt für Umwelt 2017 hydrogeologischer Kooperation KLIWA bis sehr trocken ausfällt.KLIWA
Kooperation
Th üEinheit hydrogeologischer Einheit
Saale
r i n ge n Sa ch s e n
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Impacts on Groundwater Recharge Rates


Messungen: 2011 - 2020

-17
%

-19
%
-26
%

-18
%

Bayerisches Staatsministerium für


Source: Prof. Martin Grambow, Bay. StUMV, November 2022 Umwelt und Verbraucherschutz
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Impacts for Public Water Supply


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Altered Land Use in Cities and Rural Areas

Source: infosperber.ch; erwerbsimkerbund.at; Süddetusche Zeitung 2021; Transforming Cities 2022


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Impacts on Groundwater Quality from Agricultural Activities

• Approx. 43% of groundwater supplies exceed


25-50 mg/L nitrate

Source: BMBF – FONA, 2012; UBA 2013


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Most frequently detected pesticides and metabolites in


shallow groundwater

Source: LAWA 2015


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Water Quality Challenges


Relevant contaminants and risiks
• Pathogens
– Bacteria, Viruses, Protozoa
– Antibiotic resistance (Bacteria and genes) Human health
Crops
• Microparticles (e.g. microplastic)

• Trace organic chemicals


– Pharmaceuticals
Groundwater Relevant
endpoints
– Personal care products and household chemicals
Soil
– Endocrine disrupting chemicals

– Transformation products
Surface water
– Per- und polyfluorinated alkyl substances (PFAS)

• Nitrogen (nitrate) and salinity


20.10.23 19
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Challenges for the Water Sector

• Aging water infrastructure

• Availability of water resources

• Impact of climate change

• Water-Energy Nexus

• Demographic change

• New contaminants in the environment


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Increasing Number of Conflicts

• Increasing demand for agricultural irrigation

• Increasing demand for urban landscape irrigation

• Public water supply

• Cooling and process water demand

• Maintaining ecological base flows/ecosystem needs

• Fit-for-Purpose: Do we need drinking water quality for all purposes?

Source: MainPost 2017, bild.de, BR24


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

More of the same or reinvent?


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Increasing Infrastructure Resilience


• Motivated by the worst drought in Australian history

• Designed and built Australia’s largest water


recycling (indirect potable reuse) scheme (232
ML/day) at AUD$2,500,000,000

• Followed by a series of flood events in 2010-2011

• Advanced water plants were mothballed


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Increasing Infrastructure Resilience


Exceptional droughts… Exceptional floods...

• Need infrastructure that can cope with these swings


• More resilient, more flexible, easier to adopt, and easier to fix
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Increasing Infrastructure Resilience


Rethinking underlying assumptions…
Colorado River Annual Flow (NRC 2011)
• Ques%on the historic water supply
es%mates

• Per capita water consump%ons are


declining – less revenue

• Water rates are increasing


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Genesis of Urban Water Engineering


Present time – since 1830: 2 primary gaols
§ Hygiene/public health à „human waste “, in particular feces
§ Protection against floods and moisture à Stormwater

Sanitation since 1830:


§ Goals: city hygiene & flood protection
§ Concept: (subsurface) collection and conveyance of black and stormwater

20th century: Expansion of targets and duties


„Protection of streams by limiting discharge from sewers “
§ Wastewater treatment – construction of WWTPs
§ Limiting combined sewer overflows à CSO treatment
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Genesis of Urban Water Engineering

sewage Water
Water Water Wastewater Rivers
in Treatment Treatment
runoff out

Energy Energy
generation
in

Since 1990: new conceptual approaches


§ (decentralized) management of stormwater
§ Resource focused sanitation
-> Concept of separating different streams
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Municipal Wastewater = Resource Recovery


— Water and energy closely connected

— Recovery of energy

— Recovery of nutrients
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Contemporary Municipal Water Management Concepts


REPLENISH
• Multiple use of water; closing local and regional water cycles

RECOVER
• Recovery of energy and nutrients

REUSE
• Source separation of different waste streams
• Establishing decentralized and semi-decentralized treatment facilities closer to residential
areas (shorter sewers, less pumping, opportunities for water reuse)

Definition of wastewater (DIN 1085)


„Water composed of any combination of water discharged
from domestic, industrial or commercial premises, surface
run-off and accidentally any sewer infiltration water“
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Paradigm Shift – Wastewater is Part of the Solution


Paradigm shift from ‘treatment and disposal’ to ‘reuse, recycle and resource recovery’

United Nations

EU Circular Economy

International Water Association (IWA)


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

The 2030 Agenda for Sustainable Development

Source: United Nations, 2015


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Relationship to Water

Source: Stockholm Resiliency Center, 2015


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Goal 6: Targets by 2030


6.1 Achieve universal and equitable access to safe and affordable drinking water for all
6.2 Achieve access to adequate and equitable sanitation and hygiene for all and end open
defecation, paying special attention to the needs of women and girls and those in vulnerable situations
6.3 Improve water quality by reducing pollution, eliminating dumping and minimizing release of
hazardous chemicals and materials, halving the proportion of untreated wastewater and substantially
increasing recycling and safe reuse globally
6.4 Substantially increase water-use efficiency across all sectors and ensure sustainable withdrawals
and supply of freshwater to address water scarcity and substantially reduce the number of people
suffering from water scarcity
6.5 Implement integrated water resources management at all levels, including through transboundary
cooperation as appropriate
6.6 Protect and restore water-related ecosystems, including mountains, forests, wetlands, rivers,
aquifers and lakes
6.a Expand international cooperation and capacity-building support to developing countries in water-
and sanitation-related activities and programmes, including water harvesting, desalination, water
efficiency, wastewater treatment, recycling and reuse technologies
6.b Support and strengthen the participation of local communities in improving water and sanitation
management
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

European Green Deal – Circular Economy Action Plan


Drinking Water DirecNve
2020/2184

Revision of the
Urban Waste Water
Treatment Directive
Oct. 2022

Water Reuse Regulation


2020/741

Source: Bio by Deloitte (2013)


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Structure of the German Water Management


– Thinking and acting in silos

Discharge management
Wastewater management
Discharge • Flood protection
• Wastewater treatment
Flooding
• Drainage
• Stormwater management
• Restoration

Re

e
ch
Dr

ag
Re ag

ar
ain

in
te e w

e
ra

rg
ge
nt

ha
ion ate

ec
, r

R
Groundwater management
• Infiltration
• Abstraction

Source: Dr. Heiko Gerdes, BGS Umwelt GmbH


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Take Home Messages


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Traditional Municipal Water Management Concepts


The traditional concepts,

• are simple, comfortable, reliable

• have been working very well in countries where scarcity regarding financial, natural and
water resources is not considered a major challenge

• have been built up over a long time period (almost 150 years), keeping the financial
burden at a reasonable level

However,

• In water shortage areas, the amount of potable water required to transport pollutants to a
wastewater treatment facility is hardly affordable

• Investments in water supply and sanitation must urgently be made worldwide, however, the
costs and time to replace and build infrastructure are huge
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

What’s next?
Some of these trends are inevitable..., but

the world does have choices in terms of quantity and quality of discharges to
rivers and oceans if a sustainable link is made from agriculture, rural areas and
urban settings to the ecosystems surrounding them

Crisis + Opportunity = Reinvention

Without urgent action to better manage wastewater the


situation is likely to get worse !
Serving the world population with adequate drinking water and
sanitation is an important prerequisite, for hygienic safety,
prosperity, political stability...
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Towards a Water-wise Water Cycle


§ Understanding trends that will influence environment, science and technology as well as society and
impact the water sector (Thinking ahead)

§ How can we sustainably manage the water cycle? How can we achieve a climate-neutral water cycle
in a circular economy (Sustainable water cycle)

§ Taking advantage of the latest developments in technology, materials, information technology, and
genomics (Enabling technologies)

§ Supply safe and healthy water of high quality (Health)

§ How to design a resilient water cycle? What factors promote and hold back the necessary
transformations? (Societal aspects)
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Water in Cities of the Future:


Towards an Integrated Urban Water/Energy Management Concept

non-potable reuse Managed


aquifer

Food supply Evapo-


Transpiration sewage
Resource Freshwater
recovery / systems
potable
Water energy
treatment efficiency
Infiltration

recovered Energy
generation

recovered
Substances

Urban Health
Information recovered
Source: Drewes & Horstmeyer, Österr Wasser- und Abfallw (2016) 68:99–107
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Urban Water Engineering in the 21st Century


§ Demographic developments
§ Urban centers; demographic shifts
§ Economic developments
§ Water-Energy-Food Nexus
§ Technological advancements
§ Engineering informed by science; new technologies; internet of things
§ Availability of conventional and unconventional freshwater resources
§ Reliability; water recycling
§ Water infrastructure
§ More of the same or reinvent
London’s
§ Impacts from climate change wastewater
future.
§ Managing extreme events; cope with uncertainty London 2100: The case for change.

§ Agriculture
§ Water and land use; use of pesticides and fertilizers
§ Social, institutional, political issues and barriers
§ Legal requirements and governance; affordability
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Water Quality and Key Constituents

Prof. Dr.-Ing. Jörg E. Drewes


26 October 2023

Slides with background information, review on your own


1
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Constituents in Natural Water


Constituents

Dissolved Species Particles Gases

Metals & Ligands Inorganic: clay Oxygen


(Turbidity) Carbon dioxide

Organics Organic: bacteria, Ammonia, chlorine,


protozoa, virus ozone, et al.

Important Properties: Important Properties: Important Properties:


Charge Size, shape, Solubility
Hydrophobicity density Volability
Solubility, volatility surface charge Interface (G/L)
2
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Physical Measures: Stream Flow


• Water flow impacts water quality, living organisms, and habitats in
the stream
• Large, swiftly flowing rivers can receive pollution discharges and be
minimally affected
• Small streams have less capacity to dilute and degrade waste inputs
• Oxygen level increases with flow
• Sediment transport affected by flow

3
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Physical Measures: Temperature


• Generally increases with stream size & open water surface area
• Rates of biological and chemical processes
• Oxygen content of the water
• Rate of photosynthesis by aquatic plants
• Sensitivity of organisms to toxic wastes, parasites, and diseases
• Temperature influenced by:
– weather
– shading / stream bank vegetation
– impoundments
– discharges / urban storm water
– groundwater inflows

4
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Physical Measures: Turbidity / Suspended Sediment


• A measure of water clarity (Nephelometric
Turbidity Units – NTU)
• Size range of 0.004 mm (clay) to 1.0 mm (sand)
• Suspended materials include soil particles (clay, silt, and sand), algae, plankton,
microorganisms, and more
• Sources of turbidity include: soil erosion, waste discharge, urban runoff, eroding stream
banks, large numbers of bottom feeders (such as carp), excessive algal growth
• Can affect the color of the water
• Higher turbidity increases water temperatures; suspended particles absorb more heat
à reduces DO concentration
• Higher turbidity reduces the amount of light penetrating the water à reduces
photosynthesis and the production of oxygen
• Affects the health of aquatic life

5
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Physical Measures: Turbidity / Suspended Sediment

6
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Physical Measures: Turbidity / Color

7
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Physical
Measures:
Turbidity / Color
A ligand is an ion or molecule which
donates a pair of electrons to the
central metal atom or ion to form a
coordination complex.

8
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Constituents in Natural Water


Constituents

Dissolved Species Particles Gases

Metals & Ligands Inorganic: clay Oxygen


(Turbidity) Carbon dioxide

Organics Organic: bacteria, Ammonia, chlorine,


protozoa, virus ozone, et al.

Important Properties: Important Properties: Important Properties:


Charge Size, shape, Solubility
Hydrophobicity density Volability
Solubility, volatility surface charge Interface (G/L)
9
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Common Constituents

10
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Major Inorganic Constituents


(Primarily derived from rocks and soils)
Cations Anions
Calcium (Ca2+) Bicarbonate (HCO3-) and Carbonate (CO32-)
Magnesium (Mg2+) Chloride (Cl-)
Sodium (Na+) Sulfate (SO42-)
Potassium (K+) Nitrate (NO3-)
Iron (Fe2+) Fluoride (F)
Manganese (Mn2+) Phosphate (PO43-)
AsO3-3, AsO4-3

11
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Expressions of Concentrations
• Weight Concentration: g/L, mg/L (ppm), μg/L (ppb), ng/L (ppt)

• Molarity (M) : mol/L, mmol/L (x mole of A dissolved in water to make 1 liter


(volume) of solution)
Molarity is a unit of concentration
expressed as the number of moles of
• Normality (N): eq/L, meq/L, dissolved solute per liter of solution

normality as the number of grams


– Equivalent weight: MW equivalent to solute that is present in a
EW =
Z one-liter solution. S

• Z is:

– The absolute value of the ion charge
– The number of H+ or OH¯ ions a species can react with or yield in acid-base reaction

12
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Examples
• What is the equivalent weight of calcium?
MWCa = 40 g/mol; EW = 40 g/mol/ 2 = 20 g/eq

• What is the equivalent weight of calcium carbonate (CaCO3)?


MW = 100 g/mol; EW = 50 g/eq

• What concentration is 40 mg/L Ca2+ when expressed as CaCO3?


c = 0,040 g/L / 40 g/mol * 100 g/mol = 0,1 g/L = 100 mg/L
13
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Classwork #1

mg/L mmol/L meq/L mg/L mmol/L meq/L


Ca2+ 180 HCO3¯ 300
Mg2+ 65 CO32– 40
Na+ 60 SO42– 60
K+ 20 Cl¯ 348
Fe(II) 0.5 NO3¯ 35
Cd(II) 0.5
SUM SUM

Calculate molarity and normality…


14
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Classwork #1
mg/L mmol/L meq/L mg/L mmol/L meq/L
Ca2+ 180 4.49 HCO3¯ 300 4.92
Mg2+ 65 CO32– 40
Na+ 60 SO42– 60
K+ 20 Cl¯ 348
Fe (II) 0.5 NO3¯ 35
Cd (II) 0.5
SUM SUM

15
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Classwork #1
mg/L mmol/L meq/L mg/L mmol/L meq/L
Ca2+ 180 4.49 8.98 HCO3¯ 300 4.92 4.92
Mg2+ 65 2.67 5.34 CO32– 40 0.66 1.3
Na+ 60 2.61 2.61 SO42– 60 0.625 1.25
K+ 20 0.51 0.51 Cl¯ 348 9.94 9.94
Fe (II) 0.5 0.009 0.018 NO3¯ 35 0.56 0.56
Cd (II) 0.5 0.0044 0.0089
SUM 17.47 SUM 17.83

Total Ions Sum, meq/L Acceptable % Difference


0 – 3.0 ± 0.2
Principle of Electroneutrality 3.0 – 10.0 ± 2
10 - 800 ± 2–5
16
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Water Quality Indicators


1
4
basic
• pH 1
3
1
– good indicator of natural water quality 2
1
1
– important for aquatic life 1
0
– sandstone/shale watersheds ~6.0-7.0 neutral
9
8 ßUnpolluted
– limestone watersheds ~7.0-8.0 7 rain
ßAcid Rain
– impacted by acid rain, mine drainage 6
5
acidic
4
• Alkalinity 3
2
– measure of resistance to pH change 1
– high in limestone streams
– lower in headwater areas
– sometimes measured as Acid Neutralizing Capacity (ANC)

17
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Alkalinity

AlkT = [HCO3−] + 2[CO32-] + [B(OH)4−] + [OH−] + 2[PO43-]

[HPO42-] + [SiO(OH)3−] − [H+] − [HSO4−]

[Alk] = [HCO3-] + 2 [CO32-] + [OH-] – [H+] (mol/L)


[Alk] = [HCO3-] + [CO32-] + [OH-] – [H+] (eq/L)

18
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Classwork #2
mg/L mmol/L meq/L mg/L mmol/L meq/L
Ca2+ 180 HCO3¯ 300
Mg2+ 65 CO32– 40
Na+ 60 SO42– 60
K+ 20 Cl¯ 348
Fe (II) 0.5 NO3¯ 35
Cd (II) 0.5
SUM SUM

What is the total alkalinity as CaCO3?


19
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Classwork #2
mg/L mmol/L meq/L mg/L mmol/L meq/L
HCO3- 300 4.92 4.92
CO32- 40 0.66 1.3

SUM 5.58 6.24


[Alk] = [HCO3-] + 2 [CO32-] + [OH-] – [H+] (mol/L) = 6.24 mmol/L
[Alk] = [HCO3-] + [CO32-] + [OH-] – [H+] (eq/L) = 6.24 meq/L
or
[Alk] = 6.24 meq/L * 50 mg CaCO3/mmol = 312 mg/L as CaCO3 20
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Water Quality Indicators


• Total hardness (mg/L as CaCO3): Ca2+, Mg2+

• Total dissolved solids (TDS)

• Conductivity: TDS = k * EC

• Dissolved oxygen

• Turbidity (NTU)

• Particle count

• Stability of water: Langelier Saturation Index (LSI)


21
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Classwork #3
mg/L mmol/L meq/L mg/L mmol/L meq/L
Ca2+ 180 HCO3– 300
Mg2+ 65 CO32– 40
Na+ 60 SO42– 60
K+ 20 Cl– 348
Fe (II) 0.5 NO3– 35
Cd (II) 0.5
SUM SUM

What is the total hardness as CaCO3?

22
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Classwork #3
mg/L mmol/L meq/L mg/L mmol/L meq/L

SUM SUM

Ca2+, Mg2+

23
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Classwork #3
mg/L mmol/L meq/L mg/L mmol/L meq/L
Ca2+ 180
Mg2+ 65

SUM SUM

Ca2+, Mg2+

24
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Classwork #3
mg/L mmol/L meq/L mg/L mmol/L meq/L
Ca2+ 180 4.49
Mg2+ 65 2.67

SUM SUM

Ca2+, Mg2+

25
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Classwork #3
mg/L mmol/L meq/L mg/L mmol/L meq/L
Ca2+ 180 4.49 8.98
Mg2+ 65 2.67 5.34

SUM 14.32

Ca2+, Mg2+

Total hardness = 14.32 meq/L * 50 mg CaCO3/meq = 716 mg/L as CaCO3 26


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Classwork #3
Total hardness = 14.32 meq/L * 50 mg CaCO3/meq = 716 mg/L as CaCO3
• Is it hard water?
– Soft: 0 – 20 mg/L as calcium
– Moderately soft: 20 – 40 mg/L as calcium
– Slightly hard: 40 – 60 mg/L as calcium
– Moderately hard: 60 – 80 mg/L as calcium
– Hard: 80 – 120 mg/L as calcium
– Very Hard >120 mg/L as calcium

– Soft: 0 – 60 mg/L as CaCO3


– Moderately hard: 60 – 120 mg/L as CaCO3
– Hard: 120 – 180 mg/L as CaCO3
– Very Hard >180 mg/L as CaCO3

27
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Constituents in Natural Water


Constituents

Dissolved Species Particles Gases

Metals & Ligands Inorganic: clay Oxygen


(Turbidity) Carbon dioxide

Organics Organic: bacteria, Ammonia, chlorine,


protozoa, virus ozone, et al.

Important Properties: Important Properties: Important Properties:


Charge Size, shape, Solubility
Hydrophobicity density Volability
Solubility, volatility surface charge Interface (G/L)
28
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Issues Associated with Organic Compounds

• Turbidity and color formation


• Dissolved oxygen (DO) depletion
• Taste and odor problems
• Interference with water treatment processes
• Formation of disinfection by-products (DBPs)

29
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Natural Organic Matter (NOM)

• Derived from natural decomposition of plants and animal materials

30
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Natural Organic Matter (NOM)

MacCarthy, 2001, Soil Science., 166, 738-751 31


TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Major Chemical Classes of NOM Compounds and Associated


Water Quality Problems
Chemical Associated Compliance Problems
Class of
Compounds DBP, DBP, Biological Color Transport of Taste and
Chlorination Ozonation Activity Heavy Metals Odor
Humic species Major role Major role Little impact Major role Major role Secondary
importance
Carbohydrates Not known, Probably Major role None Insignificant Insignificant
probably not
insignificant significant
Amino Acids important May be Major role Major Secondary Insignificant
significant importance
Proteins important important Major role Major May be Insignificant
significant
Carboxylic important Generated Secondary None Insignificant Insignificant
acids by importance
ozonation
Others Primarily
Geosmin and
2-MIB
32
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Major Chemical Classes of NOM Compounds and Associated


Water Quality Problems
Chemical Name Acronym Odor Threshold Conc.
(ng/L)
2-methylisoborneol MIB 4 – 10
trans-1,10-dimethyl-trans-9-decalol Geosmin 1.3 – 10

MIB Geosmin
33
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

NOM and Disinfection By-products (DBPs)


Class of DBP Class of NOM Compounds
Humic Species Carbohydrates Amino Acids Proteins Carboxylic Acids
Trihalomethanes (THM) Primary source Not known, minor Important Secondary source
probably minor
Haloacetic Acids (HAA) Primary source Not known, Not known, Not known, may Secondary source
probably minor probably be significant
insignificant
Chlorophenols Primary source Insignificant Insignificant Insignificant Insignificant
Haloketones Primary source Not known, may Not known, Not known, may Insignificant
be significant probably be significant
insignificant
Chloral Hydrate Primary source Not known, Not known, Not known, Insignificant
probably probably probably
insignificant insignificant insignificant
Haloacetonitriles Important Not known, Important Important Insignificant
probably
insignificant
Trihalonitromethane Important Not known, Important Important Insignificant
probably
insignificant
Cyanogen halide Important Not known, Important Important Insignificant
probably
insignificant
Aldehdes Primary source Not known, may Not known, Important
be significant probably
insignificant 34
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Synthetic Organic Compounds (SOC)

• surfactants

• pesticides (i.e., herbicides, insecticides)

• cleaning solvents

• polychlorinated biphenyls (PCBs)

• disinfections by-products (i.e., THM, HAA)

35
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Direct Characterization of Organic Substances


Total Organic Carbon (TOC):

DIN EN 1085:
„Concentration of carbon present in the organic matter which is dissolved or
suspended in water“
- concentration of organic carbon in total

- The organic bound carbon is the characteristic fraction of all organic substances. The sum
of organic carbon in total (lumped parameter) is therefore a measure for the sum of all
organic substances
- In the TOC test the organic carbon is directly measured, in an instrumental test, determined
through the conversion of organic carbon into carbon dioxide (measures all carbon released
in the form of CO2).
- The TOC test takes only 5 to 10 min to complete.

36
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Direct Characterization of Organic Substances


Classification of TOC
TOC

Dissolved Particulate
organic carbon organic Carbon
(DOC) (POC)

• Measure for the sum of all


• Measure for the concentration
non-filterable organic
of all dissolved (filterable)
substances
organic substances

37
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Direct Characterization of Organic Substances


Theoretical Calculation TOC by using the chemical oxidation equation

Example – TOC of glucose:


Chemical formula : C6 H12 O6

6 C + 6 O2
6 CO2
Molar weight:

C = 12 g / mol C: 12 . 6 = 72
H = 1 g / mol H: 1 . 12 = 12
O = 16 g / mol O: 16 . 6 = 96
180 g / mol

Specific TOC = 72 / 180 = 0.40 g TOC / g glucose

38
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Direct Characterization of Organic Substances


Calculation TOC by using the chemical oxidation equation

Example – TOC of glucose:

Chemical formula : C6 H12 O6

Specific TOC = 72 / 180 = 0.40 g TOC / g glucose

E.g.: 1 tea spoon of sugar (5 g glucose) dissolved


in 1 Liter of water

TOC = 5 g/L*0.4 = 2.0 g / L

39
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Microorganisms
• Bacteria: 0.1-10 μm

• Viruses: 0.01-0.1 μm

• Protozoa (i.e., giardia, cryptosporidium):


2-15 μm

• Fungi and molds

• Algae
• Helminths (parasitic worms)
40
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Waterborne Bacterial Diseases

41
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Waterborne Human Enteric Viruses

42
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Waterborne Human Enteric Viruses

43
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Human Parasitic Protozoans

44
TUM School of Engineering and Design
Chair of Urban Water Systems Engineering

Lessons learned

• Understand key groups of water constituents in natural water sources

• Be able to assess different water types based on typical water constituents

• Determine an ion balance based on a water quality analysis

• Calculate alkalinity

• Calculate total hardness

45
Chair of Urban Water Systems Engineering
Technical University of Munich

Drinking Water Regulations

Prof. Dr.-Ing. Jörg E. Drewes


2 November 2023

Slides with background information, review on your own


1
Chair of Urban Water Systems Engineering
Technical University of Munich

Considerations for Water Quality Criteria

• Public health protection


• Environmental concerns
• Specific use requirements
• Aesthetics
• Economics
• Technical feasibility

-> Regulations
-> Guidelines

2
Chair of Urban Water Systems Engineering
Technical University of Munich

EU Drinking Water Regulations

Drinking Water Directive (DWD)


• Water supply – EU Directive on the quality of water for
human consumption (98/83/EC) to limit the amount of
contamination entering water bodies/systems and the
final concentration of contaminants
• Amendment Regulation (EC) No. 596/2009
• does not contain any concentration of microorganisms,
parasites or any other substance which constitutes a
potential human health risk;
• meets the minimum requirements (microbiological and
chemical parameters and those relating to
radioactivity)

• Revised Drinking Water Directive – Dec. 2020


• Additional values regulated
• Risk management approach adopted

3
Chair of Urban Water Systems Engineering
Technical University of Munich

EU Drinking Water Directive (2020)


Microbial Parameter (Part A)
Parameter Parametric Value
(number/100 mL)
Escherichia coli (E. coli) 0
Intestinal enterococci 0

Chemical Parameter (Part B)


Parameter Parametric Value
Bisphenol A 2.5 µg/L
Boron 1.5 mg/L
Haloacetic acids (HAAs) 60 µg/L
Lead 5 µg/L
Sum of PFAS 0.1 µg/L
4
Chair of Urban Water Systems Engineering
Technical University of Munich

Drinking Water Regulations Germany


Relevant regulations:
• EU Drinking Water Directive (2020)
• Trinkwasserverordnung
Revised version 8 Jan. 2018 Öffentliche Wassergewinnung nach Wasserarten1) in Deutschland 2013

Revised version 23 June 2023 See- und


Talsperrenwasser
Flusswasser
1,2%

12,2%

Sources: angereichertes
Grundwasser

- Springs 8,8%

- Groundwater Uferfiltrat
8,6%
Grundwasser
60,9%

- Surface water Quellwasser

- Bankfiltration 8,4%

Philosophy of Supply (Bavaria): 1) Einschließlich Wasser, dass durch Unternehmen gewonnen wird, die Wasser ausschließlich weiterverteilen.

- Derived from protected resources


- Maintain natural state
- Close to consumers
- New concept: Water Safety Plans based on risk management
5
Chair of Urban Water Systems Engineering
Technical University of Munich

WHO Drinking Water Guidelines

6
Chair of Urban Water Systems Engineering
Technical University of Munich

Understanding the Risks


• Health risks remain difficult to fully characterize and quantify
through epidemiological or toxicological studies
• However, well-established methods exist for estimating the
risks of various water applications
– The occurrence of a contaminant at a detectable level does not
necessarily indicate a significant risk.
– Risk assessment screening methods can be used to estimate human
health effects where dose-response data are lacking.

7
Chair of Urban Water Systems Engineering
Technical University of Munich

Risk Assessment and Management


• Virtually every aspect of life involves risk
• Public health concerns are among the main constraints
associated with drinking water supply
• Risk assessment is an important basis for assessing the
acceptability of a drinking water project

Risk Characterization

Risk Assessment Risk Management


8
Chair of Urban Water Systems Engineering
Technical University of Munich

Risk Assessment: Five Steps


1. Problem identification and formulation

2. Hazard identification

3. Exposure assessment

4. Dose-response assessment

5. Risk characterization

9
Chair of Urban Water Systems Engineering
Technical University of Munich

Hazard Identification
• …the process of determining whether exposure to a chemical or
microbial agent can cause an increase in the incidence of a
particular adverse health effect
– e.g., cancer, birth defects, gastroenteritis

• Acute health effects are characterized by sudden and severe


illness after exposure to the substance

• Chronic health effects are long-standing and tend to occur after


prolonged or repeated exposures over many days, months or
years, and symptoms may not be immediately apparent

10
Chair of Urban Water Systems Engineering
Technical University of Munich

Water Quality Constituents


Relevant contaminants and risiks
• Pathogens
– Bacteria, Viruses, Protozoa
– Antibiotic resistance (Bacteria and genes)

• Microparticles (e.g. microplastic)

• Trace organic chemicals


– Pharmaceuticals

– Personal care products and household chemicals

– Endocrine disrupting chemicals

– Transformation products

– Per- und polyfluorinated alkyl substances (PFAS)

• Nitrogen (nitrate) and salinity


20.10.23 11
Chair of Urban Water Systems Engineering
Technical University of Munich

Exposure Assessment
• …exposure is defined as contact between a person and a chemical,
physical, or biological agent
• The amount of exposure (or dose) is a product of two variables –
concentration of a substance in a medium (e.g., potable water)
and the amount of that medium to which an individual is exposed
(e.g., via ingestion or inhalation)

12
Chair of Urban Water Systems Engineering
Technical University of Munich

Dose-Response Assessments
• …the process of characterizing the relationship between the
dose of an agent received and the incidence of an adverse
health effect in the exposed population

• Two approaches
– Certain chemicals: Cancer health effect Carcinogen

Risk
– Microbial constituents and certain chemicals: Potency
Non-cancer health effect Non-Carcinogen

Threshold

Dose

13
Chair of Urban Water Systems Engineering
Technical University of Munich

Dose-Response Assessments for Chemicals


• Cancer risk is generally estimated by a linear, non-threshold dose-
response method

• Non-cancer effects have been thought to result from multiple


chemical reactions within multiple cells of a tissue, organ or
system, so that threshold effects would pertain to non-cancer risk
assessment dose-response analyses

14
Chair of Urban Water Systems Engineering
Technical University of Munich

Dose-Response Assessments for Chemicals

Carcinogen Region with


Risk

Risk
available data

Potency

Non-Carcinogen
Region with data is required
Threshold but not available

Dose Dose

15
Chair of Urban Water Systems Engineering
Technical University of Munich

Probability Models for Dose-Response at


Low Concentrations
• Single-Hit Model
Pinf = 1 – e(-rd)
– Pinf = probability of infection
– r = empirical parameter, constant for any given host and given pathogen
– d = mean ingested dose

• Multi-stage Model
• Linear multi-stage Model
• Multi-hit Model
• Beta-Poisson Model
• Probit Model 16
Chair of Urban Water Systems Engineering
Technical University of Munich

Possible health implications of human


exposure to threshold chemicals
1. Establishment of a health-based guidance value, such
as a Reference Dose (RfD), Acceptable Daily Intake
(ADI) or Tolerable Daily Intake (TDI), which is a daily
intake over a lifetime that is considered to be
without appreciable health risk
2. Estimation of a Margin of Exposure (MOE), which is
the ratio between the dose–response output and the
estimate of human exposure
3. Quantitative estimation of the magnitude of the risk
at the level of human exposure, derived from
modeled dose–response data

17
Chair of Urban Water Systems Engineering
Technical University of Munich

Possible health implications of human


exposure to threshold chemicals
RfD = NOAEL (mg/kg d) x Weight (70 kg/person)/safety factor

RfD: Reference dose (mg/ person d)


NOAEL: no observable adverse effect level
Safety (uncertainty) factor:
- no indication of carcinogenicity: 10; 100; 1,000

Safe Drinking Water Concentration (DWEL) = (RfD/IR) x PF

DWEL: Drinking water equivalent level


Ingestion rate: 2 L/person d
Proportionality factor (relative source contribution): 0.2
18
Chair of Urban Water Systems Engineering
Technical University of Munich

Possible health implications of human


exposure to non-threshold chemicals
• Dose–response curves for carcinogenic chemicals are generally characterized
in terms of a ‘Cancer Slope Factor’ (CSF)
• The CSF is expressed in units of cancer risk per dose, or (mg/kg/day)-1
Safe Drinking Water Concentration = (Risk level x PF x BW)/(CSF x IR)

Risk level = 10-4, 10-5, 10-6


PF = proportionality factor (typically 1 or 0.1)
BW = body weight
Carcinogen

Risk
CSF = slope factor
Potency

Dose
19
Chair of Urban Water Systems Engineering
Technical University of Munich

Take Home Messages


• Assess drinking water sources based on regulatory requirements to provide
safe potable water

• Understand international, European, and German regulatory framework for


drinking water

• Understand key elements of risk management framework

20
Chair of Urban Water Systems Engineering
Technical University of Munich

Basic Design Considerations

Prof. Dr.-Ing. Jörg E. Drewes


2 November 2023
1
Chair of Urban Water Systems Engineering
Technical University of Munich

Water Treatment Projects


• Source of raw water and treatability
• Regulatory requirements
• Intake location
• Plant siting
• Plant capacity
• Process selection and design, including equipment selection
• Storage
• Distribution

2
Chair of Urban Water Systems Engineering
Technical University of Munich

Raw Water Quality and Source Selection


• “Raw water supply should come from the highest-quality source
of supply available!”
• Factors to consider:
– Quantity
– Quality
– Reliability
– Safety of source
– Water rights
– Environmental impact
– Capital and operation costs

3
Chair of Urban Water Systems Engineering
Technical University of Munich

Typical Rates of Water Use from Various Devices


Device Range of Flow
Household faucet 10-20 L/min
Wash basin 4-8 L/use
Shower head 90-110 L/use: 19-40 L/min
Tub bath 60-190 L/use
Toilet flush, tank-type 19-27 L/min
Toilet flush, valve-type 90-110 L/min
Dishwasher 15-30 L/load
Washing machine 110-200 L/load
Lawn sprinkler 6-8 L/min
Continuous flowing drinking fountain 4-5 L/min
Garbage disposal 600-7,500 L/week
4-8 L/person/day
Dripping or leaking faucet 10-1,000 L/d
4
Chair of Urban Water Systems Engineering
Technical University of Munich

Typical Breakdown of Residential Water Use


Type of Water Use Percentage

Toilet flush, including toilet leakage 33

Shower and bathing 28

Wash basin 11

Kitchen 9a

Drinking, cooking (2-6 percent)

Dishwashing (3-5 percent)

Garbage disposal (0-6 percent)

Laundry and washing machine 16b

Lawn sprinkling and miscellaneous 3

a. Dishwasher is 3% and the remaining is faucet use


b. Higher percentage because of increased use of washing machines and reduced
total demand.

5
Chair of Urban Water Systems Engineering
Technical University of Munich

Components of Municipal Water Demand

6
Chair of Urban Water Systems Engineering
Technical University of Munich

Plant Capacity
• Predicting water demand for all users:

– Residential
– Commercial Liters per capita per day (Lpcd)
– Industrial
– Public uses
– Water loss

Average daily amount of water required per person during a


period of one year

7
Chair of Urban Water Systems Engineering
Technical University of Munich

Plant Capacity – Summary of Factors

• Factors to consider:
– Climate
– Geographic location
– Size, population, and economic conditions of the community
– Degree of industrialization
– Metered water supply
– Cost of water
– Supply pressure
– Water conservation efforts

8
Chair of Urban Water Systems Engineering
Technical University of Munich

Fluctuations in Municipal Water Demand

9
Chair of Urban Water Systems Engineering
Technical University of Munich

Design Parameters
• Annual average day demand (“average demand”)
• Maximum day demand
– Max. day demand under drought conditions for plant capacity projection
• Peak hour demand
– peak capacity of distribution system
– elevated reservoirs
– high-pressure service pumps
• Safety factors
– Commercial customers
– Needs of water plant itself
– Losses in distribution system

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Design Parameters:
Fluctuations in Water Demand
Percent of annual
Condition average day
Range Typical
Daily average in max. months 110-140 120

Daily average in max. week 120-170 140

Maximum day in a year 160-220 180

Peak hour within a day 225-320 270

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Procedure to Project Water Demand


1. Estimate future population of service area
2. Develop annual water-consumption data and population served; determine
average Lpcd
3. Plot annual average per capita demand vs. the year (for drought and normal
conditions)
4. Considering water-conservation efforts
5. Develop ratio of maximum day to average day
6. Establish a desirable maximum day/average day ratio
7. Establish ratio of peak hour to maximum day demand
8. Determine projected average day, maximum day, and peak hour demands for
drought and normal conditions

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Process Selection and Design Elements


State design Plant economics (O&M)
criteria
Constituents treated
Raw water quality
Hydraulic
requirements
Chlorine

Raw BR TS Rapid Mix Floc Sedi GF CW HSP


water

FP
Finished water
Cake
quality
Topography and geology Equipment selection

Sludge disposal Energy requirements


13
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Technical University of Munich

Take Home Messages

• Understand public water demand

• Design parameter (water quantity) of public water systems

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Water Treatment Technologies

Prof. Dr.-Ing. Jörg E. Drewes


9 November 2023
Slides with background information, review on your own
1
Chair of Urban Water Systems Engineering
Technical University of Munich

Treatment Driven by Characteristics of


Water Contaminants or Treatment Objectives
Dissolved constituents Particles: Gases:
Ø Oxidation/reduction Ø Coagulation/Flocculation Ø Aeration
Ø Precipitation Ø Sedimentation Ø Stripping
Ø Ion Exchange Ø Filtration
Ø Membranes Ø Flotation
Ø Biological Treatment Ø Membranes
Ø Softening
Ø Adsorption
Ø Aeration

2
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Unit Operations and Unit Processes: Definitions

Unit Operations (UO) Unit Processes (UP)


Sedimentation Aeration
Flotation Coagulation
Granular bed filtration Flocculation
Ultrafiltration Granular Activated Carbon (GAC) adsorption
Nanofiltration Ion exchange
Reverse Osmosis Chlorination
Biological activated carbon filter (BAC)

Physical Chemical
Biological
3
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Conceptional Design of Water Treatment Schemes


• Conventional Water Treatment Processes for Surface Water Treatment

• Advanced Water Treatment Processes

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Raw Water Intake and Pre-sedimentation


• Intakes withdraw water from a river, lake, or reservoir
• Submerged intake pipe or tower-like structures
• Raw water pumping stations are generally located near or within the intake
structure
• Gravity feed into the facility is always preferred

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Technical University of Munich

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Technical University of Munich

Screening and Aeration


Unit Unit operation Description
Abbreviation and process
TR Trash rack Removal of floating debris and ice
FS Coarse screen or Protect fish and remove small solids and frazil ice
fish screen
MSt Micro-strainer Removes algae and plankton from raw water
Aer Aeration Strips and oxidizes taste and odor causing volatile
organics and gases, and oxidizes iron and manganese
Mix Mixing Provides uniform and rapid distribution of chemicals and
gases into the water

Micro-strainer

Fish screen 8
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Aeration
• Removes gases and volatile organics
• Oxidizes taste and odor causing compounds and iron and
manganese

Cascades
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Coagulation/Flocculation
Unit Unit operation Description
Abbreviation and process
Coag Coagulation Destabilization of colloidal particles
Floc Flocculation Aggregation of destabilizing turbidity and color
causing particles

Rapid mix Flocculator 11


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Coagulation/Flocculation

Rapid Mix 12
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Coagulation/Flocculation

Flocculation 13
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Technical University of Munich

Sedimentation
Unit Unit operation Description
Abbreviation and process
Sed Sedimentation Gravity separation of suspended solids

Sedimentation Basins
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Sedimentation (cont.)

Plate settlers

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Sedimentation (cont.)

Plate settlers 17
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Filtration
Unit Unit operation Description
Abbreviation and process
Filtr Filtration Removal of particulate matter by percolation
through granular media

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Composition of a Conventional Gravity Filter

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https://www.youtube.com/watch?v=UmzR3TRTz2U 21
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Disinfection – Chlorine/ClO2

• Inactivate pathogenic microorganisms

Chlorine contact basin

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Disinfection – Ozone

Ozone generator

Reactor

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Technical University of Munich

Conceptional Design of Water Treatment Schemes


• Conventional Water Treatment Processes for Surface Water Treatment

• Advanced Water Treatment Processes


– Activated carbon: SOC, NOM
– UV irradiation: Cryptosporidium, Giardia
– Advanced oxidation processes (AOP): SOC, CECs
– Membranes: SOC, NOM, Cryptosporidium, CECs

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Activated Carbon
• Most active carbon is made from coconut shell or coal materials
• Heated to over 2,000 °C under high pressure
• Creates fissures that results in a large surface area

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Technical University of Munich

Activated Carbon

• Pore sizes:
– Micropores (pore diameter less than 20 nm)
– Mesopores (pore diameter 20-200 nm)
– Macropores (200 nm & above)

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Technical University of Munich

Activated Carbon
• Removes a broad spectrum of organic substances
– Pesticides
– Taste and odor causing compounds
– NOM

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Powdered Activated Carbon (PAC)


• Powdered activated carbon (PAC): taste, odor
– Common dosage: 1 to 5 mg/L
– Used on a one-time basis, no recovery or reuse
– Typically used seasonally
– Can easily be added to existing conventional plants
– Only PAC dosing and mixing facilities required

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Technical University of Munich

Granular Activated Carbon (GAC)


• Granular activated carbon (GAC): SOC, NOM
– Greater dosages and contact times required than PAC
– Requires carbon filters
– Requires reactivation or replacement
– Facilities need to backwash GAC beds

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Technical University of Munich

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Advanced Water Treatment Processes


• Activated carbon: SOC, NOM
• UV irradiation: Cryptosporidium
• Advanced oxidation processes (AOP): SOC, CECs
• Membranes: SOC, NOM, Cryptosporidium, CECs

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UV Irradiation

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Technical University of Munich

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Technical University of Munich

Advanced Water Treatment Processes


• Activated carbon: SOC, NOM
• UV irradiation: Cryptosporidium
• Advanced oxidation processes (AOP): SOC, CECs
• Membranes: SOC, NOM, Cryptosporidium, CECs

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Technical University of Munich

Advanced oxidation processes (AOP)


• Combining ozone with UV irradiation
• Combining ozone with hydrogen peroxide (H2O2)
• Hydrogen peroxide (H2O2) with UV irradiation
• Ozonation at elevated pH (8-10)

• Applications:
– Regulated organic compounds
– Emerging chemicals of concern (CECs)
– Taste- and odor-causing compounds
– Priority pollutants (SOC)

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Technical University of Munich

Hydroxyl Radical Formation


• AOPs involve two stages:
– The formation of hydroxyl radicals (.OH)
– The reaction of hydroxyl radical with
organic contaminants

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Technical University of Munich

Advanced Water Treatment Processes


• Activated carbon: SOC, NOM
• UV irradiation: Cryptosporidium
• Advanced oxidation processes (AOP): SOC, CECs
• Membranes: SOC, NOM, Cryptosporidium, CECs

39
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Technical University of Munich

Why membranes are so attractive?

• Can remove NOM, SOC, turbidity, and emerging organic contaminants


(additional barrier)
• Can remove inorganic constituents
• Can remove Cryptosporidium, Giardia, and viruses
• Integration into (retrofitting of) existing conventional plants
• Alternative to conventional treatment for new plants

40
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Technical University of Munich

Membrane Separation
Membrane

Feed
Permeate

Particle or Solute Solvent


Molecule 41
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Technical University of Munich

Pressure-driven Membrane Processes


• High Pressure Membrane Processes:
– Reverse Osmosis (RO)
– Nanofiltration (NF)

• Low Pressure Membrane Processes:


– Ultrafiltration (UF)
– Microfiltration (MF)
– Vacuum Immersed/Submerged UF and MF

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Application of Pressure-driven Membrane Processes

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Ranges of Pressure and Flux


Membrane Pore Size Pressure Flux
Class or MWCO
psi kPa gfd LMH
(μm or
(gal/ft2·day (L/m2·hr)
Dalton)
)
MF 0.1 – 0.5 µm 1.4 - 14 10-100 60 – 120 100 – 200
UF 1 – 100 kD 7.0 - 70 50-500 30 – 60 50 – 100
NF 100 – 500 D 100 - 400 700-2,800 15 – 30 20 – 50
RO n/a 200 - 1,000 1400- 15 – 30 20 – 50
7,000
MF (sub.) 0.2 µm -1.4 -10 >59 >100
UF (sub.) 0.04 µm -7.0 -50 20 - 50 35 – 85
conversions
1 atm = 101.3 kPa (kN/m2) = 14.7 psi LMH = GFD x 1.7
1 kPa = 0.145 psi or 1 psi = 6.90 kPa
1 psi = 0.068 atm 44
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Flow Configuration
Cross Flow vs. Dead End Filtration

Cross Flow Operation


Feed Concentrate

Permeate

Dead End Operation


Feed

Permeate
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Spiral Wound Modules


- Membrane Bank or Rack

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Technical University of Munich

Hollow Fiber Membrane (Pall Corp.):


Single Fiber (left) vs. Module (right)

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Technical University of Munich

Hollow Fiber Membranes: Module (left) vs.


array (right) (Memcor/US Filter)

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Technical University of Munich

Immersed Membrane
Cassette (left) vs. System (right)

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Processes Driven by Electric Current

• Electrodialysis (ED)
• Electrodialysis reversal (EDR)

http://www.gewater.com/images/multimedia/edr/index_flash.html 50
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Target Contaminants/Constituents

Ø MF: Microbes (Protozoa and Bacteria), Turbidity (Particles and Colloids)


Ø UF: Same as MF + Viruses, “Some” NOM
Ø NF: Same as UF + NOM, SOCs (e.g., Atrazine),
Ø Divalent Cations (Ca2+, Mg2+, Zn2+, Cd2+, etc.),
Ø Polyvalent Anions (SO42-, PO43-, AsO43-, CrO42-, etc.)

Ø RO: Same as NF + Simple Ions (TDS, NO3-, ClO4-)


Ø MF + Coagulant: Viruses, NOM (also Fouling Reduction)
Ø UF + PAC: SOCs, NOM (also Fouling Reduction)
Ø Submerged MF and UF: Fe and Mn (Aeration), NOM (with coagulant), SOCs
(with PAC)

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Typical Process Train for Removal of


Turbidity and Color from Surface Water

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Typical Process Train for Treatment of Surface Water by


Direct and In-line Filtration

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Typical Process Train for Treatment of


Surface Water by Membrane Filtration

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Typical Process Train for Treatment


of Surface Water by Reverse Osmosis

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Technical University of Munich

Typical Process Train for Removal of Hardness from


Groundwater with Lime-Soda Softening Process

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Technical University of Munich

Typical Process Train for Treatment of Groundwater


with Nanofiltration Softening Process

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Typical Process Train for Removal of Dissolved Gases and/or


Volatile Constituents from Groundwater

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Typical Process Train for Removal of Iron


and Manganese from Groundwater

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Coagulation/Flocculation

Dr.-Ing. Benedikt Aumeier


Prof. Dr.-Ing. Jörg E. Drewes
16 November 2023
Slides with background information, review on your own
1
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Technical University of Munich

Coagulation Theory

2
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What do we find in surface waters?


• Inorganic Particles
– Clay, silt, mineral oxides
• Organic Particles
– Viruses, Bacteria, Algae NOM
– Detritus litter that falls into water
• Colloidal and Dissolved Organics
– Humic acids, Fulvic acids
• Dissolved Inorganics
– Contributors to water hardness (e.g., Ca2+, Mg2+)

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Size of Particles Present in Source Water


Particle Diameter (micron)
Virus 0.005-0.01
Bacteria 0.3-3.0
Small colloids 0.001-0.1
Large colloids 0.1-1.0
Soil 1-100
Sand 500
Floc 100-2,000

• > 1 mm will usually settle in quiescent water


• Smaller particles will not settle readily
• Suspension of particles that will not settle is known as
a stable suspension (causing turbidity)

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Stable Suspension

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Why do particles remain in suspension?


• Electrostatic force
– principal force contributing to stability of suspension
– electrically charged particles

Why are particles charged???

6
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Sources of Primary Surface Charge


• Preferential adsorption of specific ions
– Adsorption usually VDW or H-bonding
– e.g., humic acid on silica, hydroxyl on minerals
– Charge that results as f(conc., ion, pH)

7
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Sources of Primary Surface Charge


• Isomorphous substitution

• Ionization of inorganic groups on particle


surfaces
– Contain ionizable surface groups (carboxyl, amino,
hydroxyl,…) – pH dependent!

8
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If we put a charged particle in suspension


with ions…
– Primary charge attracts counterions (oppositely
charged) – electrostatic attraction
– Primary charge can’t attract an equal amount
of counterions b/c gradient
– Gradient drives counterions away from surface
– Electric Double Layer (EDL) forms via
attraction of oppositely-charged counterions by
primary surface charge and gradient
– Counter ions are mobile, primary charge not
9
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Why do particles remain in suspension?


(particle stability)

Satisfy
Electroneutrality

10
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Why do particles remain in suspension?


(particle stability)
• Electrostatic force
– principal force contributing to stability of suspension
– electrically charged particles

• Van der Waals force


– attraction between any two masses
– opposing force to electrostatic forces

11
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Why do particles remain in suspension?


(particle stability)
• As a result of EDL there is a net
electrostatic repulsion/attraction that
develops between particles/colloids

• Stability depends on balance between:


– Repulsive electrostatic forces and
– Attractive VDW forces

Goal ® magnitude of electrostatic forces must be reduced


12
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Forces Acting on Colloids:


Particle-Particle Interactions

13
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Surface Phenomena
• Electrostatic force
– principal force contributing to stability of suspension
– electrically charged particles

• Van der Waals force


– attraction between any two masses
– opposing force to electrostatic forces

• Particle-Particle Interactions
– Brownian motion
– insignificant

14
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How to Destabilize Particles:


Mechanisms of Coagulation
1. Compression of EDL
2. Adsorption and Charge Neutralization
3. Adsorption and Interparticle Bridging
4. Enmeshment in a Precipitate (“sweep floc”)

All have disadvantages à use multiple strategies

15
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Destabilization Mechanisms:
#1 EDL Compression
• Increasing the ionic
strength
• Counter ions pushed
closer to surface
• Repulsion forces become
easier to negate with
VDW forces
Increasing the
ionic strength
**Not practical b/c exceed accepted values for drinking water!!

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Destabilization Mechanisms:
#1 EDL Compression

17
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Destabilization Mechanisms:
#2 Adsorption and Charge Neutralization

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Destabilization Mechanisms:
#3 Interparticle Bridging

àpolymers

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Technical University of Munich

Destabilization Mechanisms:
#3 Interparticle Bridging

– Overdose of synthetic organic polymer

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Interparticle Bridging

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Destabilization Mechanisms:
#4 Sweep-Floc Coagulation

– Also known as “enmeshment in a precipitate”


– high coagulant dose added (metal salt)
– coagulant forms insoluble precipitates
– dominant mechanism applied (pH 6-8)
– Doesn’t depend on type of particle
à same coagulant dosage required regardless
of particle

22
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Destabilization Mechanisms:
#4 Sweep-Floc Coagulation
Al2(SO4) 3

Al2(SO4) 3
+ +

colloids are
enmeshed

23
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Analysis of Coagulation Process:


Jar Tests

p Determination of optimum pH
p Fill jars with raw water sample
(500 or 1000 mL) – usually 6 jars
p Adjust pH of the jars while mixing
using H2SO4 or NaOH/lime (pH:
5.0, 5.5, 6.0, 6.5, 7.0, 7.5)
p Add same dose of the selected
coagulant (alum or iron) to each
jar (coagulant dose: 5 or 10
mg/L…) Jar Tester 24
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Analysis of Coagulation Process:


Jar Tests
• Batch tests to simulate
coagulation/flocculation process
• Vary pH, coagulant dosage to get
optimal dosage
• Optimal dosage = lowest residual
turbidity

25
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Jar Testing: Determine Optimal pH

• Rapid mix each jar at 100-150 rpm for 1 minute


• Reduce stirring speed to 25-30 rpm and continue mixing
for 15 to 20 minutes
• This slower mixing speed helps promote floc formation
by enhancing particle collisions which lead to larger
flocs - FLOCCULATION
• Turn off mixers and allow flocs
to settle for 30-45 minutes
• Then measure the final residual
turbidity in each jar
• Plot residual turbidity against pH
Jar Testing set-up
26
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The pH with the lowest residual turbidity will be the


optimum pH

Optimum pH: 6.3

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Jar Testing: Determine Optimal Dose


• Repeat all previous steps
• This time adjust pH of all jars to optimal pH (6.3 found from first
test) while mixing using H2SO4 or NaOH/lime
• Add different doses of the selected coagulant (alum or iron) to each
jar (coagulant dose: 5, 7, 10, 12, 15, 20 mg/L)
• Rapid mix each jar at 100-150 rpm for 1 minute. Rapid mix helps in
dispersing the coagulant throughout each container
• Reduce stirring speed to 25-30 rpm and continue mixing for 15-20
minutes: FLOCCULATION

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• Turn off mixers and allow flocs to settle for 30-45


minutes
• Measure the final residual turbidity in each jar
• Plot residual turbidity against coagulant dose
• The coagulant dose with the lowest residual turbidity
will be the optimum coagulant dose
Optimum coagulant dose:
12.5 mg/L

29
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Technical University of Munich

Restabilization

30
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Enhanced Coagulation
• Used to achieve removal DBP precursors
• Practically, sweep floc coagulation
• Key mechanisms: precipitation and
adsorption
• Removal of NOM, color, arsenic, heavy
metals
• Bonds between adsorbent and adsorbate
include van der Waals interaction,
chemical bonds, hydrophobic bonds, ionic
bonds, or dipole interactions 31
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Enhanced Coagulation
• Co-precipitation is the main mechanism in
coagulation of NOM and arsenic
– Surface of coagulation precipitate covered by functional groups
(hydroxyl, carboxylic…)
– The hydroxyls are the actual “reactive” sites
– Covalent or ionic bonds between hydroxyls and adsorbate ions
– Factors affecting co-precipitation: site-specificity, pH, surface of the
hydrous metal oxide

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Technical University of Munich

Coagulation Practice

33
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Design of Coagulation Processes


The design of coagulation process involves:
1. Selection of proper coagulants and their
dosage
2. Design of rapid mix and flocculation
basins
q Coagulation (“chemical conditioning”)

q Flocculation (“physical conditioning”)

q Chemical precipitation
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Coagulation Practice
• Type and dose of coagulant depends on:
– Characteristics of coagulant
– Concentration and type of particulates
– Concentration and type of NOM
– Water temperature
– Water quality

35
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Inorganic Metallic Coagulants


• Principle inorganic coagulants for
destabilization:
– Aluminum ion salts (alum = aluminum sulfate)
– Ferric ion salts (ferric sulfate, ferric choride, ferrous
sulfate)
– Prehydrolyzed salts of these two metals

36
Table 9.5: Common inorganic
coagulants, coagulation aids, and pH
Technical University of Munich

and Alkalinity Adjusting Chemicals


Chair of Urban Water Systems Engineering

133.3

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Coagulating Power of Inorganic


Electrolytes

38
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Metal Salt Chemistry and Coagulation


• Main metal salts = Al or Fe sulfate
• Both, Fe and Al are “hydrolyzing metals” –
pH dependent

39
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Technical University of Munich

Metal Salt Chemistry and Coagulation


FeCl3 Fe3+ + 3Cl
1. Initially when added to water dissociation
occurs:
3+ 2
Al2 (SO4 )3 2Al + 3SO4
3+
FeCl3 Fe + 3Cl
1. The trivalent metal ions then hydrate and
form:
3+ 3+
Al (H2 O)6 and Fe (H2 O)6
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Technical University of Munich

Metal Salt Chemistry and Coagulation


cont.
3. The aquometal complexes go thru series
3+
of hydrolytic
3+
reactions and variety of
O)6 andsoluble
Fe (H2 O)
metal
6 species form such as:
2+ 7+
(H2 O)5 or Al13 O4 (OH)24 or Al (OH)3 (s)

**Speciation is highly pH dependent**

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Al(III) Solubility Diagram @ 25 °C

42
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Fe(III) Solubility Diagram @ 25 °C

43
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Technical University of Munich

Solubility of aluminum hydroxide solubility of iron hydroxide

44
3+ 3+
Al (H2 O)6 and Fe (H2 O)6
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Stoichiometry
Al (OH) (H2 O)5oforMetal
2+ Ion7+
Al13 O4 (OH) Coagulants
24 or Al (OH)3 (s)
3+ 3+
Al (H2 O)6 and Fe (H2 O)6
Al3+ + 3H2 O Al (OH)3 (am) # +3H+
2+ 7+
5 or+
Al (OH) (H2 O)Fe 3+ Al13 O4 (OH)24 or Al (OH)3 (s)
3H2 O Fe (OH) (am) # +3H+ 3

Al3+ + 3H2 O Al (OH)3 (am) # +3H+


Fe3+•+Hydrogen
3H2 O released
Fe (OH) during
3 (am) # +3H
+ metal hydroxide
Fe3+ +formation
3H2 O reacts
Fe (OH) with
3 (am) # +3H
+ alkalinity:
Al2 (SO4 )3 · 14H2 O + 6(HCO3 ) ! 2Al(OH)3 (am) # +3SO24 + 14H2 O + 6CO2
Fe2 (SO4 )3 · 9H2 O + 6(HCO3 ) ! 2Fe(OH)3 (am) # +3SO24 + 9H2 O + 6CO2

**1 mole of alum or ferrous sulfate consumes 6 moles of alkalinity (HCO3-)**

45
2 5 13 4 24 3
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2+ 7+
O5 3+or or Al+(OH)3 (s)
Technical University of Munich
Al 3+
Al(OH)+ (H
3H22O) AlAl 13 O4 (OH)
(OH) (am)24# +3H
Al + 3H2 O3 Al (OH)3 (am) # +3H+
Fe Stoichiometry of Metal
3+
3+ + 3H2 O 3+Fe (OH)3 (am) # +3H +
+ Ion Coagulants
Al + 3H2 O Fe Al+ (OH) # +3H
(am) Fe
3H23 O (OH)3 (am) # +3H+
3+ +
Fe + 3H O
Fe• If+alkalinity Fe (OH) (am) # +3H
not sufficient, pH drops
# +3H+due to
3+ +
3H2 O
2 Fe+
Fe3+ (OH) (am)
3H23 O3 # +3H
Fe (OH)3 (am)
Fe3+sulfuric
+ 3H2 O acid or3 (am)
Fe (OH) hydrochloric
# +3H+ acid formation:
Al2 (SO4 )3 · 14H2 O + 6H2 O 2Al(OH)3 (am) # +3H2 SO4 + 14H2 O
Al2 (SO4 )3 · 14H2 O 2Al(OH)3 (am) # +3H2 SO4 + 14
2
Al (SO44)3)3· 14H
Fe22(SO · 9H22OO++6H 2O
6(HCO 3
2Al(OH)
) ! (am)
2Fe(OH)
3 #
3 +3H
(am) #
2 SO
+3SO
4 + 14H
4 +O9H2 O
2
Fe2 (SO4 )3 · 9H2 O + 6(HCO3 ) ! 2Fe(OH)3 (am) # +3S
2
Fe (SO ) · 9H
Fe22 (SO443)3 · 9H O + 6(HCO
2 2 O + 6H2 O 3 ) ! #
2Fe(OH)33(am) # +3H24SO+
2Fe(OH) (am) +3SO 9H2 O2+
4 + 9H O 6C
Fe2 (SO4 )3 · 9H2 O 2Fe(OH)3 (am) # +3H2 SO4 + 9H
Fe 2 (SO+
FeCl 4 )33H· 9HO2 O +Fe(OH)
6H2 O (am) 2Fe(OH) 3 (am) # +3H2 SO4 + 9H2 O
# +3HCl
3 2 3
FeCl3 + 3H2 O Fe(OH)3 (am) # +3HCl
FeCl3 + 3H2 O Fe(OH)3 (am) # +3HCl

46
Al (H2 O)6 and Fe (H2 O)6
Chair of Urban Water Systems Engineering
Technical University of Munich

2+ 7+
Al (OH) (H2 O)5 or Al13 O4 (OH)24 or Al (OH)3 (s)
Stoichiometry of Metal Ion Coagulants
Al3+ + 3H2 O Al (OH)3 (am) # +3H+
•3+If+not
Fe 3H2 Oenough
Fe (OH)alkalinity,
3 (am) # it can be added in
+3H+

form of: lime,


Fe3+ + 3H O
soda ash, or caustic soda:
Fe (OH) (am) # +3H+
2 3

Al2 (SO4 )3 · 14H2 O + 3Ca(OH)2 ! 2Al(OH)3 (am) # +3CaSO24 + 14H2 O


Fe2 (SO4 )3 · 9H2 O + 6(HCO3 ) ! 2Fe(OH)3 (am) # +3SO24 + 9H2 O + 6CO

47
Chair of Urban Water Systems Engineering
Technical University of Munich

Alkalinity Calculation
If 200 mg/L of alum is to be added to achieve complete coagulation, how
much alkalinity is consumed in mg/L as CaCO3?

Al2(SO4)3·14 H2O + 6 HCO3¯ à 2 Al(OH)3(am)¯+ 6 CO2 + 14 H2O + 3 SO4-2

48
Chair of Urban Water Systems Engineering
Technical University of Munich

Alkalinity Calculation
If 200 mg/L of alum to be added to achieve complete coagulation. How
much alkalinity is consumed in mg/L as CaCO3?

Al2(SO4)3·14 H2O + 6 HCO3¯ à 2 Al(OH)3(am)¯+ 6 CO2 + 14 H2O + 3 SO4-2

594 mg/mmol 366 mg/6 mmol


594 mg alum consumes 366 mg HCO3-

200 mg alum will consume ((366/594) x 200) mg HCO3-

= 123 mg HCO3-

Alkalinity in mg/L as CaCO3 = 123 x (50/61)

=101 mg/L as CaCO3


49
Chair of Urban Water Systems Engineering
Technical University of Munich

Iron Chemistry
Exercise: Alkalinity calculation
If 200 mg/L of ferric chloride are to be added to achieve complete
coagulation, how much alkalinity is consumed in mg/L as CaCO3?

50
Application Guidance for Al(III) and Fe(III)
as Coagulants in Water Treatment
Technical University of Munich
Chair of Urban Water Systems Engineering

51
Chair of Urban Water Systems Engineering
Technical University of Munich

Take Home Messages


• Why do particles remain in suspension?

• How to destabilize particles in solution?

• Coagulation chemicals and alkalinity


requirements

52
Chair of Urban Water Systems Engineering
Technical University of Munich

Coagulation/Rapid Mixing

Dr.-Ing. Benedikt Aumeier


Prof. Dr.-Ing. Jörg E. Drewes
16 November 2023
Slides with background information, review on your own
1
Chair of Urban Water Systems Engineering
Technical University of Munich

Rapid Mixing

• Provide sufficient agitation to


disperse the coagulant or
softening chemicals
homogeneously

• Design Considerations:
– Design for short period of vigorous
agitation
– Chemicals being added at the point of
greatest turbulence
2
Chair of Urban Water Systems Engineering
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Rapid Mixing
Example Reactions Mixing Time, Is rapid initial Comments
sec mix
important?

Coagulation (Al, Fe) <0.3 Yes Fast, poorly reversible, competitive, consecutive

pH adjustment <<1 No Fast, easily reversible

CaCO3 nucleation ~20 Perhaps Somewhat fast, poorly reversible

HOCl/NOM to DBPs ~90,000 No Very slow, not reversible, competitive,


consecutive

Chlorine hydrolysis 0.06 Yes Fast, easily reversible, Cl2 solubility

Cl2/Ammonia ( Cl2/N) <0.1-2,000 Yes Fast in early stage, poorly reversible

Cl2/Ammonia ( Cl2/N) 104-106 No Extremely slow, poorly reversible

HOCl/coliform ~10 No Fast, persistent residual kill

HOCl/Giardia ~200 No Fast, persistent residual kill

HOCl/Crypto ~90,000 No Fast, persistent residual kill

3
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Technical University of Munich

Types of Mixers
• Static mixer
• Pumped flash mixer
• Mechanically agitated mixer

4
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Technical University of Munich

Static Mixer

6
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Technical University of Munich

Static Mixer

Koch Static Mixer


7
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Technical University of Munich

In-line Static Mixers

• Mixing time: 1 - 3 seconds


• Maximum headloss: 0.6 m is OK
• Intake fine screen is important
• It is important that the mixing elements
are removable for maintenance

11
Chair of Urban Water Systems Engineering
Technical University of Munich

In-line Static Mixers


• Very effective
• Advantages:
– Lack of moving parts
– No requirement for external energy input
– Fewer clogging problems

• Disadvantages
– Degree of mixing and mixing time is a function of flow rate
– Proprietary items. Need to rely on manufacturer claimed performance

12
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Technical University of Munich

• Hydraulic Jump: creates turbulence and


promotes mixing

14
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Technical University of Munich

Mechanical mixing

Back mix impeller flat-blade impeller

Inflow
Chemical
feeding
Chemical
feeding
Inflow

15
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Technical University of Munich

Mechanical Mixer

Rapid-Mixing Basin
16
Chair of Urban Water Systems Engineering
Technical University of Munich

Mechanical Mixers/Impellers
Mixer Type Advantages Disadvantages
Mechanical mixers • Agitation independent of flow • Additional equipment
rate required for maintenance
• Agitation is adjustable • Reliability subject to
• High flexibil ity in operation equipment failure
Static mixers • Little or no maintenance • Agitation dependent on flow
• Very reliable rate
• High head loss
• Less flexibility in operation

17
Chair of Urban Water Systems Engineering
Technical University of Munich

Mixing and Power


➢ The degree of mixing is measured by velocity gradient (G)
➢ The higher the G value, the more intense the mixing
➢ Velocity gradient is the relative velocity of the two fluid particles
at a given distance

G = dv/dy = 1.0/0.1 = 10 sec-1

0.1 m
➢ In mixer design, the Camp-Stein equation is used:

P 1 m/s
G=
m ×V
G = velocity gradient, s-1; P = Power input, Watt (J/sec)
V = Tank volume, m3;  = Dynamic viscosity, (Pa·sec)
18
Chair of Urban Water Systems Engineering
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Mixing and Power Requirement


• G can range from 700 to 1,000 s-1
• Detention time ranges from 30 to 60 seconds
• Total number of particle collisions is proportional to
G·t
• Effective G·t values for flash mixing:
– General value ~30,000
• Power consumption is defined empirically for different
mixers by different manufacturers
• Disadvantages:
– Lack of instantaneous mixing characteristics
– Significant flow short-circuiting
– Long mixing time for most coagulants
– Back mixing adversely affect coagulation

20
Chair of Urban Water Systems Engineering
Technical University of Munich

21
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Technical University of Munich

Mechanical Flash Mixing

22
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Technical University of Munich

Mixing and Power


➢ Power consumption is defined empirically for different
mixers by different manufacturers
➢ Power consumption for impellers in baffled tank:
➢ For turbulent flow (Re > 10,000)
➢ P = KTn3Di5r P = Power input, Watt (J/sec)
KT = impeller constant
➢ For laminar flow (Re < 20) n = rotational speed, rps
Di = impeller diameter, m
➢ P = KLn2Di3 r = density (=g/gc)
g = specific weight (N/m3)
gc = acceleration of gravity (9.81 m/s2)
➢ Re = Di2nr/
 = viscosity (N-sec/m2)

➢ In an un-baffled square tank, the power imparted is about 75%


of that imparted in baffled square tank or a baffled circular tank
25
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Technical University of Munich

Mixing and Power

26
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Technical University of Munich

Example
A cylindrical rapid-mixing tank having a diameter of 1.37 m is
to be designed for a flow of 1.85 m3/s. The value of G*t should
be set at 1,000. The mixing time is set at 3 sec and the
operating temperature is 20°C. Please determine the size of
the tank and the power requirement.

Hint: @T= 20°C, density of water = 998.2 kg/m3; dynamic viscosity of water=
1.002*10-3 N s/m2

27
Chair of Urban Water Systems Engineering
Technical University of Munich

Example
Given:
• Q = 1.85 m3/sec
• Tank diameter = 1.37 m
• G·t = 1,000
• Mixing time = 3 sec @ 1.85 m3/sec
• Operating temperature = 20 °C
Find:
• Size of tank? How much power is required?
28
Chair of Urban Water Systems Engineering
Technical University of Munich

Example
G = Gt / t = 1000/3 = 333 1/s
V = Q * t = 1.85 m3/s *3 s = 5.55m3
V = p * h * d2/4 = Q * t
h = Q * t *4/p*d2 = 1.85 * 3 *4 / p * 1.372
=3.76 m
G = (P /  * V)1/2 => P = G2 *  * V
P = 3332 s-2 *1.002 *10-3 N s/m2 * 5.55 m3 =
616.7 Nm/s (W)
Punbaffled square tank = P * 0.75 = 463 W
29
Chair of Urban Water Systems Engineering
Technical University of Munich

Example
A square rapid-mixing basin, having a water depth equal to
1.25 times the width, is to be designed for a flow of 7,570
m3/d. The velocity gradient is to be 790 rps, the detention time
is 40 sec, the operating temperature is 10°C, and the turbine
shaft speed is 100 rpm. Determine:

• The basin dimensions


• The power required
• Impeller diameter? (vane disc / 6 flat blades / 4 vertical
baffles / impeller D = 30-50% of tank width)
• Impeller diameter if no baffles used?

Tip: @T= 10°C, density of water =999.2 kg/m3; dynamic viscosity of water=
1.317*10-3 N s/m2

30
Chair of Urban Water Systems Engineering
Technical University of Munich

GIVEN:
Example
• Square rapid mix basin
• Depth = 1.25 x width
• Q = 7,570 m3/d
• Velocity gradient required = 790 s-1
• Detention time = 40 sec
• Operating temp = 10°C (999.2 kg/m3 // 1.317*10-3 Ns/m2)
• Turbine shaft speed 100 rpm

• Basin dimensions?
• Power required?
• Impeller diameter? (vane disc / 6 flat blades / 4 vertical
baffles / impeller D = 30-50% of tank width)
• Impeller diameter if no baffles used?
31
Chair of Urban Water Systems Engineering
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Example
Q = 7.570 m3/d = 0.0876 m3/s
V = Q t = 0.0876 m3/s * 40 s = 3.5 m3

Square basin: V = x2 * 1.25 x


x = (V/1.25)1/3 = 1.41 m

Power: P = G2 *  * V = 7902 * 1.37 *10-3 * 3.5 1/s2 NS/m2 m3


= 2.83 *103 Nm/s (2.880 W)

Diameter: P = KT * n3 * D5 r = KT * n3 * D5 r
D = 0.65 m

32
Chair of Urban Water Systems Engineering
Technical University of Munich

Take Home Messages


• Requirements for rapid mixing

• Design options

• Calculations for power demand/tank size

39
Chair of Urban Water Systems Engineering
Technical University of Munich

Flocculation

Dr.-Ing. Benedikt Aumeier


Prof. Dr.-Ing. Jörg E. Drewes
16 November 2023
Slides with background information, review on your own
1
Chair of Urban Water Systems Engineering
Technical University of Munich

Flocculation Theory

• Rapid Mix (coagulation) followed by flocculation


• Slow, enhanced contact between destabilized
(coagulated) particles
• Flocculation basins used to promote growth of
destabilized flocs by promoting particle-particle
contact

2
Chair of Urban Water Systems Engineering
Technical University of Munich

Flocculation Theory

• There are 2 modes of particle-particle


contact:
1. Perikinetic flocculation (a.k.a. microscale
flocculation)
2. Orthokinetic flocculation (a.k.a. macroscale
flocculation)

3
Chair of Urban Water Systems Engineering
Technical University of Munich

Flocculation Theory

1. Perikinetic Flocculation
– For small particles (<0.1 µm) primary mechanism
of aggregation is Brownian Motion or microscale
flocculation
– As small particles aggregate, larger particles are
formed (microflocs ca. 1-100 µm)

4
Chair of Urban Water Systems Engineering
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Flocculation Theory
2. Orthokinetic Flocculation
– Major mechanism for flocculation in water treatment for
particles larger than 1 µm = gentle mixing
– Mixing causes velocity gradients which increasing # of
particle collisions
– Mechanical mixing applied to accelerate flocculation
– Flocs subjected to unequal shearing – causes
erosion/break-up
– Eventually steady-state floc size distribution reached

5
Chair of Urban Water Systems Engineering
Technical University of Munich

Flocculation Practice

• Installations divided into 2 groups: Power


imparted by either mechanical agitation or
hydraulic agitation
• Degree of completion depends on ease and
rate by which small micro-flocs aggregate
• It’s a function of floc characteristics, G and
G*t
6
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Technical University of Munich

7
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Technical University of Munich

8
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Technical University of Munich

9
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Technical University of Munich

10
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Technical University of Munich

Flocculation
• Hydr. Flocc.: Flocs nearly always settleable
• Mech. Flocc: Tapered power needed
– Decreasing G
– Rapid build-up of small, dense floc →
→aggregation at lower G to large, dense floc
– Typical values: 50, 20, 10 sec-1
• All mechanical flocculation devices should
be equipped with variable-speed drives
having a range of up to 1:4 to meet
variation in quality of feed water
12
Chair of Urban Water Systems Engineering
Technical University of Munich

Flocculation Mixing
G Mixing time
20-80 sec-1 20-60 min

• In flocculator design, G·t is commonly used as a design parameter.


Typical G·t for flocculation is 2x104 to 105
• Large G and small t gives small but dense floc
• Small G and large t gives big but light flocs
• We want big and dense flocs which can be obtained by designing
flocculators with different G values

• Coagulation: 700-1,000 30-60 sec

• Flocculation:

G1=50 G2=20 G3=10

13
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Technical University of Munich

Typical Design Criteria for


Mechanical Flocculators

14
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Vertical Turbine Flocculators


• Impeller attached to
vertical shaft rotated
by an electric motor
• Types of Impellers:
– Radial flow
– Axial flow
• Axial flow impellers
– Pump downward
– Rotate clockwise

15
Chair of Urban Water Systems Engineering
Technical University of Munich

Impeller Design Criteria


• Important design considerations for vertical turbine
impellers:
– Displacement capacity: rate at which impeller pumps water
– Power consumption
– Pumping head
**Together they determine the nature of flow in tank**

• All flocculation impellers work in turbulent flow regime


(full turbulence at Re>10,000) 2
D Nr
Re =
• D = impeller diameter (m) m
• N = impeller’s rotational speed (sec-1)
 r = water density (kg/m3)
 m = dynamic viscosity of water (N·sec/m2)

16
Chair of Urban Water Systems Engineering
Technical University of Munich

Example
• Vertical turbine is 1.6 m in diameter
• Flocculation tank diameter is 4 m
• Rotational speed is 20 rpm
• Viscosity of water 1.31·10-3 kg/m·sec

• Re = ?

D Nr 2
Re =
m
17
Chair of Urban Water Systems Engineering
Technical University of Munich

Other Design Considerations


Besides the impeller choice, the following should also be considered:
• Baffling
– Important in preventing vortices around the impeller shaft
– For circular tanks: 4 baffles, each 10% of tank diameter
• Impeller depth ≈ 2/3 tank depth

21
Chair of Urban Water Systems Engineering
Technical University of Munich

Hydraulic Flocculation
• Three types:
– Baffled channels (most common)
– Hydraulic-jet flocculators
– Coarse-media flocculators
• Main design issue:
– available head in the plant profile for the required
power input

• Hydraulic flocculators operate well at low flow


conditions (even at G=10 sec-1)
• Around-the-end baffled channels preferred over the
under-and-over baffled flocculators
22
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Technical University of Munich

Hydraulic Flocculation

23
Chair of Urban Water Systems Engineering
Technical University of Munich

Baffled Channel Hydraulic Flocculation


❑ Plug flow devices but because of the turns they are actually
closer to a series of Continuous Flow Mixed Reactor (CFMR)
❑ Energy dissipation is achieved by changing flow direction (either
over-under or around-the-end baffles)
❑ Greatest strengths:
❑ Outstanding compartmentalization and

❑ Nearly no short-circuiting

❑ RMS velocity gradient can be determined from:

r = water density (kg/m3)


r gDH g = acceleration of gravity, 9.81 (m/sec2)
G= ΔH = head loss through basin (m)
mt m = dynamic viscosity (N-sec/m2) (kg/m-sec)
t = detention time (sec)

24
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Technical University of Munich

Design Criteria for Hydraulic Flocculation

26
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Technical University of Munich

Important Design Features in Flocculation


• Size of Flocculation Basin
– Detention time: 20-45 (60) minutes for conventional
and plate-and-tube settling
– Function of:
• feed water characteristics
• temperature
• type of coagulant
– For low turbidity and cold regions: at least 30 minutes
– For direct filtration: 15 minutes flocculation is typical
– For Dissolved Air Flotation (DAF): 5-10 minutes is
typical

27
Chair of Urban Water Systems Engineering
Technical University of Munich

Important Design Features in Flocculation


• Inlets and Outlets
– Uniform hydraulic loading to each basin
– Three types of inlets:
• simple pipe connection to basin
• weir inlet
• submerged orifice inlet
– Plant layout (symmetry of basin and inlet lines) and
appropriate flow velocity in distribution
pipe/channel will minimize uneven flow distribution
to each basin regardless of inlet type
– Same width of sedimentation basin

28
Chair of Urban Water Systems Engineering
Technical University of Munich

Important Design Features in Flocculation


• Diffuser Walls
– Used to divide flocculation basins into compartments
– Also used between flocculation basin and sedimentation
basin
– Major task: establish uniform velocity profile across the
entrance to the sedimentation tank
– In conventional settling, flocculation and sedimentation
tanks are coupled (diffuser wall separate the two)
– The diffuser wall must have enough head loss to establish
uniform discharge profile without creating turbulence and
floc breakage

29
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Diffuser Walls

30
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31
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Technical University of Munich

Diffuser Walls – Design Guidelines

32
Chair of Urban Water Systems Engineering
Technical University of Munich

Example: Design of vertical turbine flocculator


Vertical turbines are to be used for flocculation in a water treatment
plant with a design flow rate of 75,000 m3/d. Flocculation is to be
designed with four parallel trains and each train is to be made of four
compartments in series. The total detention time in flocculation is to be
20min. Make the following design decisions for the first compartment in
each flocculation train.

1. Determine compartment dimensions


2. Determine impeller diameter (assume 3-blade hydrofoil)
3. Power required to achieve G of 80 sec-1
4. Maximum rotational speed
5. Estimate pumping capacity of the impeller
6. Estimate circulation time in the tank (compartment volume /
impeller pumping rate)

33
Chair of Urban Water Systems Engineering
Technical University of Munich

Example
GIVEN:
• Capacity of water treatment facility 75,000 m3/d
• Flocculation basin: 4 parallel trains, 4 compartments in series in
each train
• Total detention time: 20 minutes
• Viscosity = 1.31x10-3 kg/m-sec, density = 998 kg/m3
FIND:
1. Determine compartment dimensions
2. Determine impeller diameter (assume 3-blade hydrofoil)
3. Power required to achieve G of 80 sec-1
4. Maximum rotational speed
5. Estimate pumping capacity of the impeller
6. Estimate circulation time in the tank (compartment volume /
impeller pumping rate)

MWH, Example 5-3, p. 179 34


Chair of Urban Water Systems Engineering
Technical University of Munich

Take Home Messages


• Key features of flocculators

• Design calculations (G-values, tank dimensions,


power requirements)

35
Chair of Urban Water Systems Engineering
Technical University of Munich

Sedimentation

Prof. Dr.-Ing. Jörg E. Drewes


23 November 2023

Slides with background information, review on your own


1
Chair of Urban Water Systems Engineering
Technical University of Munich

Pre-sedimentation

Sludge Thickening

2
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Technical University of Munich

Sedimentation Basins

3
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Empty Sedimentation Basin


Rakes on bottom move sludge into drain

4
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Technical University of Munich

Mechanism and Types of Sedimentation


• Physical treatment process that utilizes gravity to separate
solids from liquids

• Types of sedimentation
– Type I: discrete settling (i.e., settling of silt; pre-sedimentation)
– Type II: flocculent settling (i.e., coagulated surface water)
– Type III: hindered settling/zone settling (i.e., upper portion of sludge
blanket in sludge thickener)
– Type IV: compression settling (i.e., lower portion of a gravity sludge
thickener)

5
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Type I: Discrete Settling

• Silt and Sand

6
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Type II: Floc Settling

7
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Type III: Hindered Settling/Zone Settling

8
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Technical University of Munich

Type IV: Compression Settling

9
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Type I vs. Type II Sedimentation

Top of tank

Bottom of
tank

10
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Technical University of Munich

Ideal Tank Theory

Freeboard

Ho vf

vs

Sludge Zone

Inlet Zone L Outlet Zone


11
Chair of Urban Water Systems Engineering
Technical University of Munich

Gravity Settling Tanks


• All sedimentation tanks are modeled as plug flow reactors
• Rectangular or circular design
• Their design is determined by settling velocity (vs) of the particles to be
removed
θ = Ho/vs = L/vf
– vs = Stokes’ settling velocity
– Ho = effective tank height = water depth – sludge depth
– L = tank length
– vf = horizontal velocity a.k.a. fluid velocity
– Θ = detention time

12
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Technical University of Munich

Settling Characteristics

13
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Technical University of Munich

Type I: Discrete Settling

14
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Technical University of Munich

Type I Sedimentation: Discrete Settling


Particle settling unhindered at constant velocity through water
Newton’s Law

Terminal Settling Velocity = vs =?

Ø Non-spherical shape

Ø Temperature

15
F = Fg Fb Fd
Chair of Urban Water Systems Engineering
Technical University of Munich

Type I: DiscreteFgSettling
= ma = ⇢p Vp g

P P
F = Fg Fb Fd Fb = F
ma==
Fg⇢w V
Fpb g Fd
Fb+Fd
Fg = ma = ⇢p Vp g Fd F=g C
=dma =p⇢vp2Vp g
⇢w A s

Fb = ma = ⇢w Vp g
Vp F=b =
⇡ ma3 = ⇢w Vp g⇡ 2
6 d p ; Ap = 4 d p
Fg
Fd = Cd ⇢w Ap vs2 P Fd = Cd ⇢w Ap vs2 /2
F =0
Vp = ⇡ 3
6 dp ; Ap = ⇡ 2
4 dp Vp = ⇡6qd3p
4g(⇢p ⇢w )dp
P ) vs = 3Cd ⇢w
F =0 Ap = ⇡ 2
4 dp
q
Constant P
vs = velocity when the gravitational
F = 0 and drag
4g(⇢ ⇢ )d p w p
3C ⇢ d w
forces are equal 16
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Technical University of Munich

Type I: Value of CD
(for spherical particles)

17
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Technical University of Munich

Type I: Value of CD
(for spherical particles)
Laminar range 24
Re < 1
CD =
Re

Transition range 24 3
Re = 1-104
CD = + + 0.34
Re Re

Turbulent range C D ~ 0.4


Re > 104

υ s dρ
Reynolds number Re =
µ
18
Chair of Urban Water Systems Engineering
Technical University of Munich
Type I Sedimentation:
Discrete Settling
for spherical particles under laminar flow conditions
4 d ⋅ g (ρs − ρ ) 24
υs = CD =
3 CD ρ Re

g ⋅ €d 2 ( ρ s − ρ )
Stokes Law: υs =
18µ
where vs = settling, m/s
g = acceleration of gravity, m/sec2
rs = density of particle, kg/m3
r = density of water, kg/m3
µ = dynamic viscosity, kg/m∙sec velocity,
m/sec
d = particle diameter 19
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Example
Calculate the terminal settling velocity for a sand particle in water at 10 °C. Assume that the
sand particle has a diameter of 25 µm and a density of 2,650 kg/m3. For water at 10 °C:
µ = 0.001307 N∙s/m2 and r = 999.7 kg/m3
Check again with particle 200 µm in size.

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Example
g ⋅ d 2 (ρs − ρ )
υs =
18µ
vs = 9.81m/s2 (2.5 10-5 m)2 (2.65 - 1) * 1000 3600 s/h / 18 * 0.0013 m2/a

vs = 1.55 m/h

Check Reynolds:

Re = dp * vs/ n = 2.5 * 10-5 m * 1.55 m/h * 1h/3600 s / 1.306 * 10-6 m2/s

= 0.0082 (laminar!)

b.) vs = 99 m/h for 200 µm

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Ideal Settling of Discrete Particles


Settling of particles is predominantly Type I
Assumptions made:
1. Plug flow conditions exist in the settling zone
2. Uniform horizontal velocity in the settling zone
3. Uniform concentration of all size particles across a vertical plane at the inlet
end of the settling zone
4. Particles are removed once they reach the bottom of the settling zone
5. Particles settle discretely without interference from other particles at any
depth

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Fd = Cd ⇢w Ap vs2
Technical University of Munich

Rectangular
Vp = ⇡6 d3p ; ASedimentation
⇡ 2
p = 4 dp
Basin
P
F =0
Q vf W Q
q
4g(⇢p ⇢w )dp
) vs = 3Cd ⇢w
Inlet Outlet
Settling Zone, L
Zon g(⇢p ⇢w )dp 2 Zone
)e vs = 18µ (laminar flow)
H
Q h 1.6 i1/1.4 Q
g(⇢p ⇢vwf )dp
) vs = 13.9⇢0.4 0.6 (transition flow)
w µ
Sludge Zone
Q
vf = W ·H v f = fluid velocity (m/h)
Q
vs = W ·L v s = settling velocity (m/h)
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) vs = 18µ (laminar flow)
Technical University of Munich

Rectangular hSedimentation i 1/1.4


Basin:
g(⇢p ⇢w )d1.6
Critical
) vs = Settling Velocity(transition flow)
p
13.9⇢0.4 µ0.6 w

Q
vf = W ·H v f = fluidvfvelocity (m/h)
H
Q
vs = W v·L v s = settling velocity (m/h)
s= vc

vf vs Q vs Q
L  H ) W ·H·L  H ) W ·L = vs  vc
L

H H Q
vc = = H·W ·L
= = OR
⌧ Q
A
Not influenced by depth
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Rectangular Sedimentation Basin


Q = flow rate through basin
W = width of the basin Q Q
L = Length of the basin υc = =
Ap = surface area of settling basin WL Ap
vc = settling velocity of smallest particle
that is fully removed

‘Settling velocity’, ‘Terminal velocity’, ‘Hydraulic loading’,


‘Design overflow rate’, ‘Surface loading rate’
• Designed OFR is independent of the depth
• Designed OFR is independent of the detention time
• For pre-sedimentation basins:
– vc = 200 – 400 m3/m2-d (m/d)
– 3 – 5 m depth

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Rectangular Sedimentation Basin


vs > vc – all particles settle completely
vf
vs

vs = vc – all particles settle completely

vf
vs

vs < vc – some of the particles settle completely

vf
vs

L 26
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Rectangular Sedimentation Basin


• vs < vc particles will be partially removed
• Fraction that will be removed = hs/ho = vs/vc

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) vs = 18µ (laminar flow)
Technical University of Munich

hExample1.6 i1/1.4
g(⇢p ⇢w )dp
• Small Water
) vs =plant:
treatment 13.9⇢0.4 0.6 (transition flow)
w µ

• Qin = 0.6 m3/sec


• vs = 0.004 m/sec v(not
= a good
Q assumption
v = fluid for floc) (m/h)
velocity
f f
• Effective settling zone,WL·H
= 20 m, H = 3 m, W = 6 m
Q
vs = W ·L v s = settling velocity (m/h)
Can 100% removal be expected?
vf vs Q vs Q
L  H ) W ·H·L  H ) W ·L = vs  vc

H H Q
vc = = H·W ·L
= = OR
⌧ Q
A

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Rectangular Sedimentation Basins

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Rectangular Sedimentation Basins

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Rectangular Sedimentation Basins

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Rectangular Sedimentation Basins:


Design Criteria Horizontal Flow

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Rectangular Sedimentation Basins: Inlet

• Uniform distribution of water from flocculation basin


• Flow velocity to maintain floc in suspension - 0.15 - 0.60
m/sec
• Diffuser wall openings 0.1 - 0.2 m diameter circular or
equivalent

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Settling Zone - Basic Design Criteria


• Surface loading rate (a.k.a. overflow rate)
– relationship to settling velocity
• Effective water depth
– can be shallow but practical minimum of 2.5-3 m (due to sludge removal equip)
– Flow velocity, wind and sun effects make shallow basin less practical
– 70% floc settle in first 1/3 of basin
– 0.5 m freeboard – offer protection from wind
• Horizontal flow velocity
– Re = vfRhr/µ < 20,000 and Fr = vf2/gRh > 10-5
• Longitudinal baffles
– Reduce hydraulic radius and à turbulence
• Minimum length-to-width ratio
– Long, narrow, deep (5 m)
– Minimum length-to-width ratio of 4:1 or 5:1 à promotes plug flow
– Minimize short circuiting
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Troughs and Weirs

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Outlet Structure
• Launders/troughs (usually) parallel to length of tank

• Water should be collected uniformly across the width of basin

• Long weirs are commonly used as outlet structures


– Gradually reduce flow velocity at end of tank
– Minimize wave action from wind

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Rectangular Sedimentation Basin


with Various Outlet Types

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Typical Trough Layouts

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V-Notch Weir

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Trough and Weir

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Trough and Weir

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Type II Sedimentation:
Flocculent Settling
t=t0 t=t1 t=t2 t=t3

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Type II Sedimentation:
Flocculent Settling
• Floc settling is much more complicated than discrete settling, so NO simple
mathematical basis for floc settling has yet been developed for design purposes

• Unlike discrete settling, the water depth is the most important parameter
affecting the particles removal efficiency in floc settling

• For a selected water depth, hydraulic loading rate and detention time must be
determined by batch settling tests or from experience with existing plants
treating similar water

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settling time equals
detention time of the basin

Type II Sedimentation:
Floc Settling

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Example Batch Settling Test Results for Sampling


Port #1
Time, min Measured TSS, TSS Removed, % Removal
mg/L mg/L
0 200 0 0
10 134 66 33
20 75 125 62.5
30 51 149 74.5
40 20 180 90

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Type II Sedimentation:
Floc Settling

Design for water depth of 3.5 m


% removals; Suspended Solids
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Settling Depth and Removal Efficiency


• Percent removal is plotted on a graph of depth (of sample) vs. time
• Interpolations are made between plotted points and curves of equal
percent removal are drawn

H2
RT = RC + (RD − RC )+ H1 (RE − RD )
H H 49
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For desired removal of 80%

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Settling Depth and Removal Efficiency

For design purposes:


• Scale-up factor of 0.60 – 0.80 for overflow rate
• Scale-up factor of 1.25 – 1.75 for detention time

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Circular Sedimentation Basins


• Opportunity to use a relatively trouble-free circular sludge removal equipment

• Lower capital cost per unit surface area (small plants)

• Need more piping

• Diameter is calculated based on overflow rate – same criteria as rectangular


tanks

• Square sedimentation tanks: combined advantages of common-wall


construction and circular sludge collector mechanism

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Circular Sedimentation Basins

Q
vf =
2π (r − ri )ho

π (r 2 − ri 2 )ho
h = tv c = vc
Q

ho hoQ Q Q
vc = = 2 2
= 2 2
= = OR
τ hoπ (ro − ri ) π (ro − ri ) A
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Alternative Sedimentation Processes

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Sedimentation Tanks with Settlers


• High rate clarifiers are needed to accommodate growth

• Conventional sedimentation basins can be easily modified

• High rate sedimentation can be achieved by:


– Increase particle size – coagulation / flocculation
– Decrease distance particle must fall prior to removal – shallower basin à parallel plates
or tube in sedimentation basin

• Horizontal plates or tubes à bad, will be clogged with sediments

• Inclining the surfaces à good, solid will slide from the plates
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Tube Settlers

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Table 10-6: Design Criteria for


Horizontal-flow Rectangular Tank
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With Plate or Tube Settlers

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High-rate Settlers: Design Criteria


• Design criteria provided in Table 10-6 are for lamella settlers (inclined plate
settlers) in rectangular sedimentation basins

• The surface loadings presented in Table 10-6 are based on footprint area and
not top area of the plates (projected area)

• In cold regions where alum floc is to be removed, maximum surface loading


rate should be limited to 150 m3/m2·d (6.25 m/hr)

• Pilot test helps in establishing design criteria

• Reynolds and Froude numbers are more critical in the design


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Detention Time in High-Rate Clarifiers


• For a basin of depth ho and a theoretical detention time of τ,
particles with settling velocity vs will be removed if:
vs ≥ ho
τ

• If plate settlers are added, τ is the same and ho is smaller à


removal efficiency is higher

• Parallel plates and tube settlers have a typical detention time of


20 minutes with settling efficiency comparable to rectangular
settling tank with a minimum detention time of 2 hours!!!

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(a) Counter-current

(b) Co-current

(c) Cross-flow

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Countercurrent Settlers
d
t = settling time (sec) =
vs cos θ
Lp
t p = particle time spent in plate (sec) =
v fθ − vs sin θ

Q Q
v fθ = =
Ndw A sin θ

v fθ d
vs ≥
L p cos θ + d sin θ

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Co-current Settlers
d
t = settling time (sec) =
vs cos θ
Lp
t p = particle time spent in plate (sec) =
v fθ + vs sin θ

Q Q
v fθ = =
Ndw A sin θ

v fθ d
vs ≥
L p cos θ − d sin θ

67
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Cross-current Settlers
d
t = settling time (sec) =
vs cos θ
Lp
t p = particle time spent in plate (sec) =
v fθ

Q Q
v fθ = =
Ndw A sin θ

v fθ d
vs ≥
L p cos θ

68
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Example
• Sedimentation basin retrofitted with 2 m square inclined plates
spaced 50 mm apart. Angle of inclination varies between 0° and
80°. Which flow pattern is more efficient for particle removal?

vs d
=
v fθ Lp cos θ + d sin θ
vs d
=
v fθ Lp cos θ − d sin θ
€ vs d
=
v fθ Lp cos θ

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Example
• Sedimentation basin retrofitted with 2 m square
inclined plates spaced 50 mm apart. Angle of
inclination varies between 0° and 80°
Inclination angle

vs d
=
v fθ Lp cos θ + d sin θ
vs d
=
v fθ Lp cos θ − d sin θ
€ vs d
=
v fθ Lp cos θ
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Take Home Messages

• Understand design concepts of clarifiers

• Stokes Law (type I sedimentation)

• Determine dimensions of clarifiers

• Understand advantages of plate settlers

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Filtration

Prof. Dr.-Ing. Jörg E. Drewes


30 November 2023
Slides with background information, review on your own
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Flocculation/Sedimentation

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Overview
1. Introduction
2. Removal Mechanisms
3. Classification of Filters
4. Filter Media
5. Filter Components
6. Hydraulics
7. Rapid-Filter Design

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1. Introduction to Filtration
• Removal of particulate matter from water including algae, sediments, clay,
organic and inorganic particulate, microorganisms

• Nearly all surface water treatment facilities use filtration

• Historically:
– Has been used to clarify water for thousands of years
– First modern slow sand filtration in London (1852)
– Interest in filtration grew as people realized it can prevent waterborne diseases
– Rapid filtration originated in the U.S. during the 1880s

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Cholera Outbreak Hamburg 1892


• Drinking water abstraction from the
river Elbe
• No filtration
• 9,000 deaths
• Very limited impacts in Altona

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William Philipps Dunbar

…a pioneer in

public health,

bacteriology,

allergology, and

sanitation engineering

*27.10.1863, +19.03.1922

www.wikipedia.com
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Relevant Regulations
• European Union (2020/2184) – Drinking Water Directive
– Turbidity for surface water treatment should be below 0.3 NTU and
never exceed 1 NTU in the finished water

• Trinkwasserverordnung (TrinkwV) 2023


– Turbidity for finished water should be below 0.3 NTU and never exceed
1.0 NTU in the finished water

• U.S. EPA - Surface Water Treatment Rule


– As of January 1, 2002, for systems servicing >10,000, and January 14,
2005, for systems servicing <10,000, turbidity may never exceed 1 NTU,
and must not exceed 0.3 NTU in 95% of daily samples in any month
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Common Filtration Processes


• Three common types:

– Rapid filtration – most common in Europe and the United States

– Slow sand filtration – small utilities / high quality feed water

– Pre-coated filtration – specific applications (green sand filtration)

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Comparison between Granular Filtration


Technologies for Water Treatment

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Rapid Granular Media Filtration


• Replaced slow sand filtration
• Up to 100 times faster due to:
– Granular media processed to have uniform size
– Coagulation is used for pretreatment
– Mechanical and hydraulic systems to efficiently remove solids from
the bed

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Rapid Filtration – Process Flow


• Filter bed is contained in a deep structure (concrete, open)

• Two-stage cycles:
– Filtration cycle
• water flows downward through the filter
• particles accumulate
• typically lasts 1-4 days

– Backwash cycle – accumulated material is flushed from the system


• water flows upward
• efficient removal of solids is a key component of rapid filtration
• typically lasts 15-30 minutes

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https://www.youtube.com/watch?v=UmzR3TRTz2U 15
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2. Mechanism of Filtration

• Physical treatment process to remove colloidal particles

• Removal mechanisms during filtration


– Straining (i.e., removal due to size)
– Sedimentation (i.e., particles in low-velocity zones)
– Impaction (i.e., particle removal due to inertia)
– Interception (i.e., particle contact with media grain)
– Diffusion (i.e., removal due to Brownian motion)

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Straining
• Capture of spherical particle by spherical media
grains

• If the ratio of particle diameter to media


diameter is greater than 0.15, the particle will be
strained by the media

• If the ratio is smaller, straining is not possible and


particle capture occurs by other means

• For typical rapid filtration, straining is limited to


particles with diameter of 80 µm and larger
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Sedimentation
• Particles in low-velocity zones

• Particles with a density significantly greater


than water tend to deviate due to
gravitational forces

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Impaction
• Particles with an inertia greater than the
hydrodynamic force will tend to deviate

• Insignificant in water treatment!

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Interception

• Particles that pass the collector surface by a


distance of half the particle diameter will
contact the collector and be intercepted

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Diffusion
• Particles influenced by Brownian motion
will deviate from the fluid streamlines
due to diffusion

• Diffusion is most significant for particles


< 1 µm in diameter

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Removal Mechanisms During Filtration


Particle transport mechanisms in fundamental
filtration theory:
1. Interception: particle A follows a streamline but
collides with the collector

2. Inertia, sedimentation: particle B deviates from the


streamline and collides with the collector because of
inertial or gravitational forces

3. Diffusion: particle C collides with collector due to


random Brownian motion

particle diameter < 80 µm


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Attachment efficiency
• Transport efficiency depends on particle
size and density
– Small particles removed by diffusion
– Larger particles removed by
sedimentation and interception

• Lowest efficiency for particles of 1-2 µm

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Principal Attraction Forces

• Chemical Bonding

• Physical Attraction
– Electrostatic forces
– van der Waals forces

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Filtration Dynamic
• As filtration continues, pore spaces between media grains
become smaller
– enhance straining
– increased velocity of water through the pore spaces
– increased shear forces of the water flowing through the media bed
– increased head loss

I decrease in filtration rate, filter performance, and


efficiency

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3. Classification of Filters
• Filtration rate
– slow sand filters
– rapid filters
– high-rate filters
• Driving force
– gravity
– pressure (up to 1 MPa (10,3 bar))
• Direction of flow
– downflow – most commonly used in water treatment
– upflow – rarely used in granular filters
• Pretreatment level
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Slow Sand Filter


• Hydraulic loading rate < 10 m3/m2-day
• Does not utilize chemical coagulation
• Removal occurs in the upper layers of the filter

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Slow Sand Filter

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Slow Sand Filter

• River bank filtration (RBF)

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Rapid and High-Rate Sand Filters

• Hydraulic loading rate ~120 m3/m2·day (rapid)

• Hydraulic loading rate >240 m3/m2·day (high-rate)

• Designed for removals throughout the entire depth of


the filter bed

• Most of these filters have multiple layers

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Filters Classified by Driving Force


Gravity filters: Pressure filters:
• 2-3 m head • higher head
• housed in open concrete • housed in closed steel vessels
or steel tanks • costly; small systems
• large and small systems

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Rapid Filtration – Pretreatment


• Coagulation is required for high removal efficiency

• Destabilization of particles will reduce repulsion forces between


the filter media and the particles

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Classification of Rapid Filtration


Systems by Pretreatment Level
Conventional filtration

Direct filtration

In-line filtration

Two-stage filtration

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Classification of Rapid Filtration


Systems by Pretreatment Level

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4. Filter Media

• Media characterization
– Effective Size
– Uniformity coefficient

• Materials for Rapid-Filtration

• Filter classification
– single-medium
– dual media
– mixed media
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Media design parameters


• Size distribution determined by sieve analysis

• effective size (d10)

𝐸𝑆 = 𝑑!"

• uniformity coefficient
𝑑#"
𝑈𝐶 =
𝑑!"

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Example 1: Determine ES and UC


• Determine effective size and uniformity coefficient of
granular materials

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Stratification/reverse gradation

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Rapid Filtration – Typical Media


Properties

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Sand
• worn or crushed sand
0.4 – 0.8 mm

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Anthracite

0.5 – 2 mm

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Garnet

0.3 – 0.8 mm
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Filter classification

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Single-Medium Filter
• stratification/reverse gradation

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Ideal Filter

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Dual-Media Filter
• Anthracite coal (1.55) and quartz sand (2.65)
• More depth is utilized

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Dual-Media Filter

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Mixed-Media Filter
• anthracite coal (1.55), quartz sand (2.65), garnet (4.05)

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Filter Media
• Typical Media Design Values

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Filter Media Selection

Kawamura relationships 50
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5. Filter Components

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Filter Support Media and Underdrains

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Filter Components

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Filter Components

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Filter Components

Filter Backwash 55
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6. Hydraulics of Flow Through Granular


Media
• Flow regime in granular media identified
by Reynolds number for flow around
spheres: r vd
Re = W
µ
rW = fluid density, kg/m3
v = filtration rate (superficial velocity), m/s
d = media grain diameter, m
µ = dynamic viscosity, kg/m·s

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Hydraulics of Flow Through Granular Media

• Steady, laminar flow


– Re < 1 : Darcy flow or creeping flow – viscous flow
behavior (HL=f(v))
– 1 < Re < 100 : Forchheimer flow – viscous and
inertial (HL=f(v2)) behavior

• 100 < Re < 600-800 : Transition flow

• Re > 800 : Turbulent flow


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Ranges of Reynolds Number in Granular


Filtration Technologies

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Headloss Through Clean Granular Filters


• Net available head = filter design headloss –
clean-bed headloss

• Insignificant in slow sand and pre-coat


filtration, but important in rapid filtration
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Headloss Through Clean Granular Filters


• Henry Darcy (1856) – relationship between
velocity, hL, and bed depth in granular media
under creeping-flow conditions:
kp = hydraulic permeability, m/s
hL v = filtration rate (superficial velocity), m/s
v = kp hL = headloss across media, m
L L = depth of granular media, m

• Not taking into account media properties…


• Poiseuille’s Law and Kozeny development:
hL 32 µv k k µS 2v
= =
L rW gd 2
rW ge 3
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Headloss Through Clean Granular Filters


• Forchheimer flow regime – nonlinear relationship for viscous and
inertial effects:
hL k1 = permeability coefficient (viscous), s/m
= k1v + k 2v 2 k2 = permeability coefficient (inertial), s2/m2
L
• Later development with correlations to measurable properties:

hL = kV
(1 - e )2 µLv 1 - e Lv 2
+kI 3
Ergun
Equation
e3 rW gd 2
e gd
kV = headloss coefficient (viscous), unitless
kI = headloss coefficient (inertial), unitless

61
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Headloss Through Clean Granular Filters


• Effects of porosity and velocity

62
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Example 2
Calculate the clean-bed headloss through a deep-bed filter with 1.5 m
anthracite coal (ES=1.1 mm) over 0.3 m sand (ES=0.5 mm) at a
filtration rate of 15 m/hr and temperature of 15 °C

Ø rW = 999 kg/m3, µ = 1.14·10-3 kg/m· s


Ø midpoints from Table 11-5:
anthracite coal: kV = 228, kI = 4.4, e = 0.50
sand: kV = 112, kI = 2.2, e = 0.42

hL = kV
(1 - e )2 µLv 1 - e Lv 2
+ kI 3
e3 rW gd 2
e gd

63
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Example 2

64
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Backwash Hydraulics

• Backwash flowrate must be great enough to flush


captured material from bed
• …but not to the point that filter media is flushed out of
the filter box…

• To prevent loss of media, need determine Bed Expansion

65
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Rapid Filtration – Backwashing


1. Filter influent and effluent lines closed
2. Backwash supply and waste wash water valves opened
3. Backwash water (potable water) is directed upward
4. Backwash supplemental systems:
– Surface wash systems – nozzles blast surface of bed
– Pressurized air under the
media – reduces water usage
5. Valves positions reversed
and filter is placed back
in service

66
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Forces on Particles (foulants or grain)


• Backwashing hydraulics occur within the Forchheimer flow
regime

æp ö
• Gravity: FG [N ] = mg = (rP - rW )ç d 3 ÷g
è6 ø

• Upward drag forces: FD [N ] = 3pµvd for Re < 2


2.31
FD [N ] =
0.6
prW v 2 d 2 for 2 £ Re £ 500
Re
• Equating the two allow to determine the fate of individual
particles
é g (r P - rW )d 1.6 ù
0.714

v=ê 0.4 0.6 ú


ë 13 . 9 rW µ û
67
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Example 3

• A filter is backwashed at 40 m/hr at 15°C.


Determine whether a 0.1 mm particle of sand will
be washed from the filter.

68
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Example 3

69
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Bed Expansion and Porosity


• The flow velocity in fixed bed is higher than for isolated particle
because of the presence of media à higher drag forces
• As media rises, porosity increases and velocity decreases until
equilibrium is reached
• Relationship between bed porosity and expansion…

𝐿$ 1 − 𝜀% LE
= LF
𝐿% 1 − 𝜀$

70
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Multi-media Filters
• The media in multi-media filters must be
matched so that all media fluidize at the same
backwash rate
é g (r P - rW )d 1.6 ù
0.714

v=ê 0.4 0.6 ú


ë 13.9 rW µ û

• Equating an equivalent fluidization velocity for


two media and solving for grain size ratio yield
the expression:
0.625 d1 = grain diameter of one filter medium, m
d1 æ r 2 - rW ö d2 = grain diameter of a second filter medium, m
= çç ÷÷ r1 = density of medium with diameter d1, kg/m3
d 2 è r1 - rW ø r2 = density of medium with diameter d2, kg/m3

71
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7. Design of Rapid-Filters
Preliminary design consists of several tasks:
1. Setting performance criteria
n effluent turbidity n length of filter run
n recovery n unit filter run volume (UFRV)

2. Selecting process design criteria


n required level of pretreatment n filter media type, size, and
depth
n filtration rate n available head

3. Selecting method for flow distribution and control

4. Selecting major process components (backwashing systems, underdraines,


wash troughs, process piping)
72
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Rapid Filtration – Filter Run


Effluent turbidity characterized by three distinct
phases:
1. Ripening
– media conditioning (15 min - 2 hr)
– Sometimes consists of two peaks
– Size and duration can be reduced by
proper backwashing procedure
– Filter-to-waste line
2. Effective filtration
– Steady state with turbidity <0.1 NTU
– Gradual increasing in head loss
3. Breakthrough
– Filter bed can’t hold more particles
– Effluent turbidity increases
– Headloss increases

73
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Rapid Filtration – End of Filter Run


Can be triggered by several events and lead to backwash:
1. Breakthrough
n Preventing high-turbidity water from entering
the distribution system
2. Headloss
n Increases beyond the available head through
the process
n Rapid filters are typically designed with
1.8 - 3 m available head
n If in specific cases neither are reached
within several days: utility initiates
backwash after a set period of time

74
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Performance Criteria: Effluent Water Quality


• Turbidity is used as a surrogate for the concentration of particulates in water

• Current US regulation: “…As of January 1, 2002, for systems servicing >10,000,


and January 14, 2005, for systems servicing <10,000, turbidity may never
exceed 1 NTU, and must not exceed 0.3 NTU in 95% of daily samples in any
month”.

• Europe/Germany: “…less than 1.0 NTU”

• Typical goal: 0.1 NTU (close to detection limit)

• Particle counter is a newer method for measuring effluent quality (provides


both number and size distribution of particles in water)
75
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Performance Criteria: Length of Filter Run

• Dictates how often backwash is performed

• Affects water recovery and how much labor involved

• Minimum desirable: 1 day

• Common design length: 1-4 days

76
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Performance Criteria: Recovery


• Ratio between the net and the total quantity of water filtered

• Some product water is used for backwash and some is discharged as filter-to-
waste

• Recovery is evaluated using the concept of


– Unit Filter Run Volume (UFRV)
– Unit Backwash Volume (UBWV), and
– Unit Filter-to-Waste Volume (UFWV)

77
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Recovery
a = filter cross-sectional area, m2
VF VF = volume of water filtered during one filter run, m3
UFRV = = v F tF
a VBW = volume of water for backwashing one filter, m3
VFTW = volume of water discharged as filter-to-waste, m3
VBW
UBWV = = v BW t BW vF = filtration rate (superficial velocity), m/hr (=vFTW)
a vBW = backwashing rate, m/hr
VFTW tF = duration of filter run, hr
UFWV = = v F t FTW
a tBW = duration of backwash cycle, hr
tFTW = duration of filter-to-waste period, hr

VF - VBW - VFTW UFRV - UBWV - UFWV


Re cov ery º r = =
VF UFRV

78
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Recovery
• Effective filtration rate (vEFF) º net volume produced over total
time
UFRV - UBWV
vEFF =
t F + t BW

• Filters should be designed to achieve recovery of at least 95%

• Typical wash water quantities are ~8 m3/m2 à to achieve 95%,


UFRV of at least 200 m3/m2 is required!

79
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Relationship between Recovery, UFRV and UBWV

80
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Example 4
• A filter is operated at a rate of 10 m3/m2-hr for 37.5 hrs, of which 15
minutes was discharged as filter-to-waste. After filtration, the filter is
backwashed at a rate of 40 m/hr for 15 minutes.

• Calculate: UFRV, UBWV, and UFWV, effective filtration rate, and recovery

81
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Example 4

82
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Process Design Criteria


• Filter type
• Filtration rate
• Number and Dimensions of Filters
• Available Head
• Filter Media

83
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Classification of Rapid Filtration


Systems by Pretreatment Level
Conventional filtration

Direct filtration

In-line filtration

Two-stage filtration

84
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Filtration Rate
• Filtration rate influences many aspects of rapid-filter design:
– Clean-bed headloss
– Rate of headloss accumulation
– Distribution of solids collection in bed
– Effluent quality
– Run length

• Also directly related to cost

• Highest filtration rate that yields good filter performance is


recommended
85
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Filtration Rate
• Filtering floc resulting from alum or ferric with polymer aid, up to 25 m/hr

• Filtering weak floc of alum without polymer aid, <12.5 m/hr

• Often subjected to regulatory limits (U.S. west coast states <15 m/hr)

• Most rapid filters are designed to operate at 5 – 15 m/hr

86
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Number & Dimensions of Filters


• Number of filters is influenced by the
– capacity of the plant
– dimensions of a single filter
– effect of filtration rate changes during backwashing
– economic considerations

• Most water treatments have a minimum of 4 filters

• Filters are typically designed to treat the maximum plant capacity at the
design filtration rate with at least one filter out of service

87
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Number & Dimensions of Filters


A (total filter area) = Q (peak day) / v (selected)

• Maximum dimensions of a single filter are generally determined by


the economic size of backwash facility and difficulties in providing
uniform distribution of backwash water

• Typical maximum size of one high-rate gravity filter is ~100 m2

• Extremely large plants sometimes have double this size

88
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Available Head
• Filtration head = available head in the structure – clean-bed headloss

• Rapid filters typically operate by gravity

• Available head depends on upstream and downstream structures

• Selection of available head involves trade-off between longer filter


runs (greater available head) and economics (smaller available head)

• Due to construction costs, available head is rarely more than 2 – 3 m


89
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Backwashing Systems Typical Design Criteria

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Design Criteria for Filters at Typical WTP

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Control of Filtration Rate


• Modulating control valve:
– Flow meter controls a modulating control valve on the effluent piping
from each filter

– Set-point for total flow

– Advantages: flexibility, smooth flow of influent without weirs or orifices

– Disadvantages: complex control system, high maintenance, can cause


variation in filtration rate

92
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Control of Filtration Rate


• Influent weir flow splitting:
– Water flows through a common influent channel to several filters
– Influent weir for each filter
– When filter is removed from service for backwash, flow automatically
distributed to the remaining filters
– The simplest method
– Rate changes are made gradually with no control valves

93
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Hydraulic Modes
• Constant Rate and Constant Head Water Filtration:
– Most common filtration mode
– Water head in the filter box is at highest level throughout the duration of
filter run
– A valve on the effluent line controls filtration rate
• beginning of run – valve almost completely closed
• end of run – valve almost completely open

94
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Hydraulic Modes
• Constant Rate and Rising Head Water Filtration:
– Effluent valve remains open throughout the filter run
– The head water seeks its own level
– Head water should be deep enough to prevent scouring of top layer
when water spills over the overflow launders
– Water head in the filter box rises to its terminal level
– No need for sophisticated control

95
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Hydraulic Modes
• Declining-rate filtration:
– Effluent valve remains open throughout the filter run
– All filters receive water from a common influent channel
– All filters operate at the same head
– Each filter receive a different quantity of influent water based on the
accumulated solids (headloss) in the filter
– The flow through each filter declines as solid accumulate
– The common water level gradually rises as all filters accumulate solids
– Backwash is initiated on a run length basis

96
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Control of Filtration Rate


• Declining-rate filtration (cont’):
– Advantages:
• simplicity, no instrumentation or flow control on individual filter
– Disadvantages:
• no indication of flow rate or headloss in any individual filter
• no method to control filtration rate
• the initial filtration rate can exceed the designed rate

• Discouraged by many state regulating agencies

97
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Take Home Messages


• Filtration principles

• Mechanisms of filtration; attachment theory

• Classification of filtration types

• Media design

• Filter components

• Head loss calculations


98
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Wastewater Characteristics I

Prof. Dr.-Ing. Jörg E. Drewes


7 December 2023

Slides with background information, review on your own


1
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Wastewater Characteristics
- Domestic sewage contains approximately 99.9% water!
- The remaining portion includes organic and inorganic matter, as well as suspended and
dissolved solids (incl. microorganisms)

water

treatment solids
pollution

because of this 0.1% that water pollution occurs and wastewater


needs to be treated prior to discharge to the environment

adapted from von Sperling (2005) 2


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Wastewater Characteristics
Origin of wastewater – input
material flux analysis rain water
settlement

input output

- water - wastewater
- food Suspended solids;
-chemicals organic pollutants;
-consumer goods, etc. inorganic pollutants;
heavy metals;
bacteria;
viruses
output …
(roof, courtyard and road runoff)
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Transformation Processes in the Environment

Input

Growth:
• Plants
Sedimentation
• Algae
Erosion
• Fish
input • Protozoa
• Bacteria
Advective transport Self purification

-Nitrification,
Flow -Denitrification,
Diffuse inputs -transformation of
organic matter, … 4
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Introduction to Biological Treatment


However, in natural water bodies: Self purification is slow

big reactor volumes (ponds)

Often more advantageous: Optimization of reaction rates

Increasing biomass in a reactor

Increasing oxygen

Enabling optimal contact between biomass, pollutants and oxygen

5
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Introduction to Biological Treatment


Objectives of (traditional) wastewater treatment:
• Protection of the receiving waters with minimal costs
• Transformation into substances that have no or little damaging effect on the receiving
system or can be separated from the wastewater effluent

River

Solution:
Transforming the natural conversion
processes into engineered systems

Biofilm reactor Reactor with biomass in suspension


Source: Mudrack und Kunst, 2003 6
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Municipal Wastewater Treatment Plants

Source: Marcus Östman; CC0 Public Domain 7


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Conventional Activated Sludge (CAS) Treatment

Source: Marcus Östman 8


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Technical University of Munich

Introduction to Biological Treatment


• In biological wastewater treatment the transformation is achieved by
microorganisms

• The microorganisms used in the system are a


complex mix of different types of
microorganisms with (very) different
characteristics regarding their activity (function)

• The composition and properties of this complex mixed biomass depends on


the conditions characterized by the technological system and the
characteristics of the wastewater and is subject to dynamic processes

9
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Dominant Bacterial phyla and domain Archaea


of Activated Sludge

Vuono et al. (2016), ES&T


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Introduction to Biological Treatment


• The task of biological wastewater process engineering is to design the system in a way
that the conditions within the system promote the stable growth of those
microorganisms that have the desired properties/function

• Desired properties include:


- Organisms being able to degrade / transform specific undesireable wastewater
constituents at a reasonable rate

- Organisms must easily be separated from the


effluent (e.g. easily settleable)

+++++++

+++++++++ +++++
+++++++ ++++++
+++

++
+
++++

++
+++

++

+
+

+++++++++
+++++
++++ ++++

++
+++
+
+
++++

++
+

+
+++

+++++++
++
+
+++

++
11
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Introduction to Biological Treatment


Fundamental processes:

Solid-liquid separation suspension clarified effluent

concentrate

Reaction unit; educts products


biochemical transformation

reactor
12
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Introduction to Biological Treatment


Example activated sludge system:
• Co-existense of aerobic, anoxic, and anaerobic bacteria
Objectives:
Elimination of organic matter (COD), elimination of N (Nitrification, Denitrification),
and phosphorus (Bio-P-Elimination)
NO3
COD

Denitrification Nitrifikation

Creation of alternating conditions for the microorganisms in the system in order to


control the composition and transformations of the types of organisms present

13
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Technical University of Munich

Changes in effluent
quality over time

14
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Fundamental Transformation Processes

Degradation of organic carbon (aerated à aerobic conditions)


e.g. methanol: 2 CH3OH + 3 O2 è 2 CO2 + 4 H2O
Heterotrophic bacteria

Nitrification (aerated à aerobic conditions)


2 NH4+ + 3 O2 è 2 NO2- + 2 H2O + 4 H+ (nitritation)
2 NO2- + O2 è 2 NO3- (nitratation)
Autotrophic bacteria

Denitrification (not aerated à anoxic conditions)


5 CH3OH + 6 NO3- è 5 CO2 + 7 H2O + 3 N2 + 6 OH-
Heterotrophic bacteria

15
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Transformation of N-species during Biological Treatment

Source: Weißbach, M. Criddle, C.S., Drewes, J.E.., Koch, K. (2016). Environmental Science: Water Research and Technology, 3 (1), 10–17. 16
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Introduction to Biological Treatment


Importance of wastewater characteristics

• Wastewater characteristics influence the microorganisms and microbiological


processes

• Thus, wastewater characteristics determine the optimal design of the system and
are essential for predicting the performance of the system

• To design an (activated sludge) treatment process properly, characterization of the


wastewater is perhaps the most critical step in the process

• Without comprehensive wastewater characterization, facilities may either be


under- or overdesigned, resulting in inadequate or inefficient treatment

17
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Sink 3

gases

effluent
influent
Sources WWTP Sink 1

waste sludge

Sink 2

18
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Bulk, Group or Lumped Parameters

19
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Lumped Parameter
• wastewater is a complex mixture of different compounds that are only partially known

• There is a vast amount of different biochemical and microbiological processes that are carried
out in a reactor in biological wastewater treatment

• However,

- typically many fundamental aspects of the processes and their performance are characterized by
the behaviour of substances, that can be described by means of lumped parameters (e.g., oxygen
consumption, sludge production)

- considerung the day-to-day operations at a wastewater treatment plant, usually there are no
resources for a detailed analysis of single substances

20
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Lumped Parameters

• The „backbone“ of biological wastewater treatment processes can be described by


means of ‚lumped parameters‘

• Lumped parameters represent a group of single substances that are characteristized


by a specific common property. The property chosen depends on the problem to be
solved

• Thus, lumped parameters represent only a specific aspect of the sum of the
substances

• If a statement regarding single substances is required, these lumped parameter can


serve as a basis for a more detailed description of single substances

21
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Lumped Parameters
An illustrative example
All wastewater
constituents

Lumped parameter: Single substance:


a subset one element

Set of Set of
particulate dissolved
substances substances

Separation, e.g., membrane filtration


Gujer, 1999 22
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Main classification of constituents

23
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Main Classification of Constituents


Characterization by size,
Characterization by settleability
chemical characterisitics
• non-
settleable
• inorganic
compounds •
settleable
• organic • dissolved
compounds (soluble)
• colloidal
• suspended
(particulate)

Characterization by
biological degradability
• biodegradable
• non
biodegradable
24
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Main classification of constituents


Physical Characteristics

solid
s

temperature

Metcalf & Eddy 25


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Main classification of constituents


Inorganic Chemical Characteristics

nitrogen,
phosphorus

Metcalf & Eddy 26


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Main classification of constituents


Organic Chemical Characteristics

carbonaceous matter,
oxygen demand

Metcalf & Eddy 27


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Representation of Wastewater Constituents


Chemical Characterization Physical Characterization

- - size
volatilization
- settleability

Biological Characterization
- biodegradability

28
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Solids

29
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Solids
• All the contaminants in water, with the exception of dissolved gases, contribute to the solids load

Suspended solids coarse material i.e., plastic bags, sanitary napkins


settleable material i.e., sand, grit
suspended matter i.e., bacteria
floating matter i.e., fats / oil

Why treating? development of sludge deposits and anaerobic conditions in


aquatic environment

30
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Solids
Classification of solids
Solids

Classification by size Classification by Classification by


chemical settleability
characteristics

Volatile Fixed
(organic) (inorganic)
Dissolved colloidal Suspended
(soluble) (particulate settleable non-
) settleable

31
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Solids
Classification by size SS: dry solid on filter at 105 oC

TDS: dry filtrate at 105 oC


Dissolved solids (soluble solids):
• particles of small dimensions
• capable of passing through a filter paper of a specific size
(dissolved solids = filterable solids)

Suspended solids (particulate solids):


• particles with larger dimensions
• retained by the filter (suspended solids = non-filterable solids).

colloidal solids:
• in an intermediate range
• of importance in water treatment, but
• difficult to identify by the simple method of paper filtration.
• the major part of colloidal solids is separated as filterable
(dissolved) solids.

Total solids = suspended solids + dissolved solids

32
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Solids
Basic procedure for classification by size Wastewate
r sample

Filter

filtrate solids on filter


105°C
evaporation evaporation

dissolved suspended
solids solids
• Filterable • Non-filterable

Total solids = suspended solids + dissolved solids

33
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Solids
Particle Size Ranges
algae

bacteria

Bacterial flocs
cell fragments

viruses
protein
DNA Visible to the naked eye
fatty acids
ammonium,
nitrate, etc..
settleable
dissolved colloidal
suspended

10-6 10-5 10-4 10-3 10-2 10-1 100 10+1 10+2 µm


1 µm=0.001 mm
34
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Solids
Basic procedure for classification by organic Wastewater
matter sample

105°C
evaporation

Total solids
550°C
Volatile
solids
(volatilized, Fixed solids
oxidized) (inert fraction,
• Representation of unoxidised)
organic matter
• Representation of inorganic
Total solids = Volatile solids + Fixed solids or mineral matter

35
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Solids
Classification by Settleability
Standard test for settleable solids:
• Placing a wastewater sample in a 1-liter Imhoff cone
• Noting the volume of solids in millimeters that settle after a specified time period.
• The volume of solids accumulated in the bottom of the Imhoff Cone is measured and expressed as mL/L

Settleable solids:
are considered those that are able to settle in a specified period.
(typically approx. 60%)

Non-settleable solids:
The fraction that does not settle represents the non-settleable
solids.

Total solids = settleable solids + non settleable

36
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Solids
Classification I TOTAL SOLIDS (TS)
The residue remaining after a wastewater
sample has been evaporated and dried at a
specified temperature (103 to 105°C)

TOTAL TOTAL DISSOLVED


SUSPENDED „Abfiltrierbare SOLIDS (TDS)
SOLIDS (TSS) Stoffe“ Those solids that can pass through the
filter, and are then evaporated and dried
Portion of the TS retained on a filter
at a specified temperature. Consists also
with a specified pore size,
of colloidal besides the “truely” dissolved
measured after being dried at a
solids!
specified temperature (105°C)

VOLATILE FIXED TOTAL VOLATILE FIXED


SUSPENDED SUSPENDED DISSOLVED DISSOLVED
SOLIDS (VSS) SOLIDS (FSS) SOLIDS (VDS) SOLIDS (FDS)
Those solids that can be The residue that Those solids that can be The residue that remains
volatilized and burned off remains after TSS are volatilized and burned off when TDS are ignited
when the TSS are ignited (500 ignited (500 +/- 50°C) when TDS are ignited (500 +/- (500 +/- 50°C)
+/- 50°C) 50°C)

„Glühverlust der „Glührückstand der


abfiltrierbaren Stoffe“ abfiltrierbaren Stoffe“

37
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Solids
TOTAL SOLIDS (TS)
Classification II The residue remaining after a
wastewater sample has been
evaporated and dried at a specified
temperature (103 to 105°C)

TOTAL VOLATILE SOLIDS TOTAL FIXED SOLIDS (TFS)


(TVS) The residue that remains after TS are
ignited (500 +/- 50°C)
Those solids that can be volatilized and
burned off when the TS are ignited (500
+/- 50°C)

VOLATILE TOTAL VOLATILE


FIXED FIXED
SUSPENDED DISSOLVED
SUSPENDED DISSOLVED
SOLIDS SOLIDS (VDS)
SOLIDS (FSS) SOLIDS (FDS)
(VSS) Those solids that can be
The residue that remains The residue that remains
Those solids that can volatilized and burned off
after TSS are ignited (500 when TDS are ignited
be volatilized and when TDS are ignited (500
+/- 50°C) (500 +/- 50°C)
burned off when the +/- 50°C)
TSS are ignited (500
+/- 50°C)
„Glührückstand der
„Glühverlust der abfiltrierbaren Stoffe“
abfiltrierbaren Stoffe“

38
Chair of Urban Water Systems Engineering
Technical University of Munich

Solids
Overlapping of Classification
Approaches

39
Chair of Urban Water Systems Engineering
Technical University of Munich

Solids
Example 1
The following test results were obtained for a wastewater sample taken at the headworks to a wastewater
treatment plant. All of the tests were performed using a sample size of 50 mL. Determine the concentration of
-Total solids (TS),
-Total volatile solids (TVS),
-Suspended solids (TSS),
-Volatile suspended solids (VSS),
-Total dissolved solids (TDS)
-Total volatile dissolved solids (VDS).

The samples used in the solids analysis were all either evaporated, dried, or ignited to constant weights.
-Tare mass of evaporating dish = 53.5433 g
-Mass of evaporating dish plus residue after evapor. at 105°C=53.5794 g
-Mass of evaporating dish plus residue after ignition at 550°C = 53.5625g
-Tare mass of filter after drying at 105°C = 1.5433 g
-Mass of filter and residue after drying at 105°C = 1.5554 g
-Mass of filter and residue after ignition at 550°C = 1.5476 g

40
Chair of Urban Water Systems Engineering
Technical University of Munich

Solids
Solution to example 1
Given: -Tare mass of evaporating dish = 53.5433 g
-Mass of evaporating dish plus residue after evapor. at 105°C=53.5794 g
-Mass of evaporating dish plus residue after ignition at 550°C = 53.5625g
-Tare mass of filter after drying at 105°C = 1.5433 g
-Mass of filter and residue after drying at 105°C = 1.5554 g
-Mass of filter and residue after ignition at 550°C = 1.5476 g
Total solids (TS) = residue after evaporation at 105°C / 0.05 l
= (tare mass of evaporating dish + residue – tare mass of evaporating dish ) / 0.05 l
53.5794 g – 53.5433 g = 0.0361 g
à TS = 0.0361 g / 0.05 l = 0.722 g / l = 722 mg/l
Total volatile solids (TVS) = TS – TFS
TFS = (residue after ignition at 550°C ) / 0.05 l
TVS = TS - (tare mass of evaporating dish + residue after ignition at 550°C ) / 0.05 l + (tare mass of
evaporating dish) / 0.05 l
TVS = 722 mg/l - 53562.5 mg / 0.05 l + 53543.3 mg/ 0.05 l
à TVS = 338 mg/l

41
Chair of Urban Water Systems Engineering
Technical University of Munich

Solids
Solution to example 1
Given: -Tare mass of evaporating dish = 53.5433 g
-Mass of evaporating dish plus residue after evapor. at 105°C=53.5794 g
-Mass of evaporating dish plus residue after ignition at 550°C = 53.5625g
-Tare mass of filter after drying at 105°C = 1.5433 g
-Mass of filter and residue after drying at 105°C = 1.5554 g
-Mass of filter and residue after ignition at 550°C = 1.5476 g
Calculated: TS, TVS
Total suspended solids (TSS) = residue on filter after filtering / 0.05 l
= (tare mass of filter + mass of residue)/0.05 l – (tare mass of filter) / 0.05 l
= 1.5554 g / 0.05 l - 1.5433 g / 0.05 l
à Total suspended solids = 0.0361 g / 0.05 l = 242 mg/l

Volatile suspended solids (VSS) = TSS – FSS


FSS = The residue (of what stayed on filter) that remains after TSS are ignited / 0.05 l
VSS = TSS + tare mass of filter / 0.05 l - (residue on filter after ignition + tare mass of filter) / 0.05 l
= 242 mg/l + 1543.3 / 0.05 l - 1547.6 mg / 0.05 l
à Volatile suspended solids = 156 mg/l

42
Chair of Urban Water Systems Engineering
Technical University of Munich

Solids
Solution to example 1
Given: -Tare mass of evaporating dish = 53.5433 g
-Mass of evaporating dish plus residue after evapor. at 105°C=53.5794 g
-Mass of evaporating dish plus residue after ignition at 550°C = 53.5625g
-Tare mass of filter after drying at 105°C = 1.5433 g
-Mass of filter and residue after drying at 105°C = 1.5554 g
-Mass of filter and residue after ignition at 550°C = 1.5476 g
Calculated: TS, TVS, TSS, VSS

Total dissolved solids (TDS) = TS – TSS


Total dissolved solids = 722 mg/l - 242 mg/l = 480 mg/l

Volatile dissolved solids (VDS) = TVS – VSS


àVDS = 338 mg/ l – 156 mg/l = 182 mg/l

43
Chair of Urban Water Systems Engineering
Technical University of Munich

Solids
+tare mass of
Overlapping of filter
Classification Approaches

+tare mass of
dish

+tare mass of
filter

+tare mass of
dish

44
Chair of Urban Water Systems Engineering
Technical University of Munich

Organic Substances

45
Chair of Urban Water Systems Engineering
Technical University of Munich

Organic Substances
Classification and measurement of carbonaceous organic matter

• Direct :
Based on measurement of organic carbon:
- Total Organic Carbon (TOC)

• Indirect :
Based on theoretical considerations:
- Theoretical Oxygen Demand (ThOD)
Based on measurement of oxygen consumption:
- Chemical Oxygen Demand (COD)
- Biochemical Oxygen Demand (BOD)
- Ultimate Biochemical Oxygen Demand (UBOD)
46
Chair of Urban Water Systems Engineering
Technical University of Munich

Direct Characterization of Organic Substances


Total Organic Carbon (TOC):

DIN EN 1085:
„Concentration of carbon present in the organic matter which is dissolved or
suspended in water“

- concentration of organic carbon in total

- The organic bound carbon is the characteristic fraction of all organic substances. The sum of
organic carbon in total (lumped parameter) is therefore a measure for the sum of all organic
substances

- In the TOC test the organic carbon is directly measured, in an instrumental test, determined through the
conversion of organic carbon into carbon dioxide (measures all carbon released in the form of CO2)

- The TOC test takes only 5 to 10 min to complete.

47
Chair of Urban Water Systems Engineering
Technical University of Munich
Das Messprinzip basiert auf dem Hochtemperaturaufschluss Probevolumen bzw. Gewicht und Detektorsignal, auf Basis

Direct Characterization of Organic Substances


der Probe im Luft/O2 Strom bei 850 °C. Für thermisch stabile einer Kalibrationskurve, den Kohlenstoffgehalt.
Feststoffe können Aufschlusstemperaturen von permanent Ist in einer Probe anorganischer Kohlenstoff (Karbonat)
bis zu 1200 °C oder kurzzeitig 1800 °C erreicht werden. Dabei enthalten, kann er nach Ansäuern und Freisetzen im Spar-
wird der gesamte gebundene Kohlenstoff in CO2 überführt, ger separat als TIC bestimmt werden. Der TOC errechnet
das mit einem NDIR Detektor quantitativ bestimmt wird. Vor-

- TOC Analyzer
sich dann aus TC-TIC. Eine TOC bzw. NPOC Direktbestim-
teil dieser Methode gegenüber dem nasschemischen UV/ mung ist nach externer TIC Entfernung ebenfalls möglich.
Persulfataufschluss ist die absolute Sicherheit, dass selbst Der Sparger kann auch unmittelbar zur Direktbestimmung
stabilste Verbindungen, Partikel oder salzhaltige Lösungen flüchtiger Kohlenstoffverbindungen (POC) genutzt werden.
vollständig erfasst werden und zusätzlich die Bestimmung Dazu ist lediglich ein zusätzlicher CO2 Absorber erforderlich.
von gebundenem Stickstoff (TNb) möglich ist. Damit sind mit einem Gerät und ohne aufwändige Umbauten
Die flüssige Probe wird über eine Dosierspritze angesaugt alle relevanten Parameter der TOC-Analytik zugänglich.
und direkt in das Verbrennungsrohr injiziert, wo die kataly- Der Einsatz NO spezifischer Detektoren erweitert den
tische Oxidation erfolgt. Alternativ werden Feststoffproben Anwendungsbereich auch auf die TNb Analytik von gebun-
über einen Kugelhahn zugeführt. Nach dreistufiger Trock- denem Stickstoff. Das Gesamtkonzept ist geprägt von
nung des Verbrennungsgases und Ausgleich von Druck- kürzesten Gas- und Flüssigkeitswegen und einem Minimum
schwankungen durch einen elektronischen Durchflussregler an Ventilen mit Vorteilen für die Analysengeschwindigkeit,
erfolgt die Messung des Gesamtkohlenstoffgehaltes (TC) Nachweisstärke oder Messung partikel- und salzhaltiger
am NDIR Detektor. Ein angeschlossener PC errechnet aus Proben.

H3PO4
Luft

Probe Sparger Verbrennung Trocknung Detektion

48
Chair of Urban Water Systems Engineering
Technical University of Munich

Direct Characterization of Organic Substances


Theoretical Calculation TOC by using the chemical oxidation equation
Example – TOC of glucose:
Chemical formula : C6 H12 O6

6 C + 6 O2
6 CO2
Molar weight:

C = 12 g / mol C: 12 . 6 = 72
H = 1 g / mol H: 1 . 12 = 12
O = 16 g / mol O: 16 . 6 = 96
180 g / mol

Specific TOC = 72 / 180 = 0.40 g TOC / g glucose

49
Chair of Urban Water Systems Engineering
Technical University of Munich

Direct Characterization of Organic Substances


Calculation TOC by using the chemical oxidation equation

Example – TOC of glucose:

Chemical formula : C6 H12 O6

Specific TOC = 72 / 180 = 0.40 g TOC / g glucose

E.g.: 1 tea spoon of sugar (5 g glucose) dissolved


in 1 Liter of water

TOC = 5 g/L*0.4 = 2.0 g / L

50
Chair of Urban Water Systems Engineering
Technical University of Munich

Direct Characterization of Organic Substances


Classification of TOC present in wastewater

TOC

Dissolved Particulate
organic carbon organic Carbon
(DOC) (POC)

• Measure for the concentration of all • Measure for the sum of all non-
dissolved (filterable) organic substances filterable organic substances

51
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances- ThOD


Theoretical Oxygen Demand (ThOD)

• The main ecological effect of organic pollution in a water body is the decrease in the
level of dissolved oxygen

• The ThOD is the theoretical calculation of the oxygen demand if the chemical formula
of the organic matter present is known

• Organic matter of animal or vegetable origin in wastewater is generally a combination


of carbon, hydrogen, oxygen, and nitrogen (present in carbohydrates, proteins, oils and
grease)

52
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances- ThOD


ThOD
What can be oxidized?

C CO2
H H2O
N NO2-, NO3-
S SO42-

53
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances


Calculation ThOD by using the chemical oxidation equation
Example 1 – ThOD of glucose:

Chemical formula : C6 H12 O6

6 C + 6 O2 6 CO2
Molar mass:

C = 12 g / mol C: 12 . 6 = 72
H = 1 g / mol H: 1 . 12 = 12
O = 16 g / mol O: 16 . 6 = 96
180 g / mol

54
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances


Calculation ThOD by using the chemical oxidation equation

Example 1 – ThOD of glucose:


Chemical formula : C6 H12 O6

C6 H12 O6 + 6 O2 6 CO2 + 6 H2 O + energy

Molar mass O2 : 32 g / mol


6 . 32 g / mol = 192 g O2 / mol glucose

Molar mass glucose: 180 g glucose /mol glucose

specific ThOD = 192 / 180 = 1.067 g O2 / g glucose

55
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances


Calculation ThOD by using the chemical oxidation equation
Example 1 – ThOD of glucose:

Chemical formula : C6 H12 O6

E.g.: 1 tea spoon of sugar (5 g glucose) dissolved


in 1 Liter of water

specific ThOD = 192 / 180 = 1.067 g O2 / g glucose

ThOD = 5 . 1.067 = 5.3 g O2 / L

56
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances


Calculation of the ThOD
Example 2 – ThOD of glycine:
Chemical formula Glycine (CH2(NH2)COOH )

1. Conversion of organic carbon and nitrogen to carbon dioxide and ammonia:

CH2(NH2)COOH + 1.5 O2 à NH3 + 2 CO2 + H2O

2. Oxidation of ammonia to nitrite and nitrate:

NH3 + 1.5 O2 à NO2- + H2O + H+


NO2- + 0.5 O2 à NO3-

57
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances


Calculation of the ThOD
Example 2 – ThOD of glycerine:
Chemical formula Glycine (CH2(NH2)COOH )

ThOD = (1.5 + 2) mol O2 / mol glycine

Molar mass: 32 g/ mol O2

Specific ThOD (per mol) = 3.5 * 32 = 112 g O2 / mol glycine

Molar Mass glycine: 75.07 g glycine /mol glycine

Specific ThOD = 112 / 75.07 = 1.49 g O2 / g glycine

58
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances


• The ThOD is a measurement for the pollution potential of a wastewater by the theoretical
calculation of the oxygen consumption that it would cause, that is, an indirect
quantification of the potential to generate an impact.

• However, in practice, wastewater has a great heterogeneity in its composition

• Trying to establish all its constituents in order to calculate the oxygen demand based on
the chemical oxidation reactions of each of the components is impossible and an
extrapolation of the data to other conditions is not possible

Measuring in the laboratory the consumption of oxygen exerted


by a standard volume of wastewater:
COD, UBOD, BOD

59
Chair of Urban Water Systems Engineering
Technical University of Munich

Take Home Messages

• Understand function of a municipal wastewater treatment facility

• Understand composition of municipal wastewater

• Target parameters and values for wastewater treatment

• Parameter for suspended solids

• Parameter for dissolved organic substances

60
Chair of Urban Water Systems Engineering
Technical University of Munich

Wastewater Characteristics II

Dr.-Ing. Benedikt Aumeier & Prof. Dr.-Ing. Jörg E. Drewes


14 December 2023

Slides with background information, review on your own


1
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances


- Chemical Oxygen Demand (COD) -

2
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - COD


DIN EN 1085:
Chemical Oxygen Demand (COD) „Concentration of oxygen equivalent to the amount of dichromate consumed
when a water sample is treated with that oxidant under defined conditions“

• Equivalent for the concentration of all organic substances, independent from their composition
and biodegradability

• The COD is a lumped parameter, expressing, how much oxygen is needed for a complete
oxidation of organic substances to CO2 and H2O. Therefore, it is an indirect indication of organic
substances

• The COD is especially useful because:


• it captures the organic substances almost completely,
• can be determined at wastewater treatment plants relatively easily
• Corresponds to an electron balance for which laws of conservation hold
• directly reflects the oxygen consumption in biochemical oxidation reactions

• The COD test can be completed in about 2.5 h. To reduce the time further, a rapid COD test that
takes only about 15 minutes has been developed
3
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - COD

COD - what can be oxidized?

C CO2
H H2O
N NO2-, NO3-
S SO42-

4
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - COD


Theoretical calculation of COD by using the chemical oxidation equation (=ThOD)

Example 1 – COD of glucose:


Chemical formula : C6 H12 O6

C6 H12 O6 + 6 O2 6 CO2 + 6 H2 O + energy

Molar mass O2 : 32 g / mol


6 . 32 g / mol = 192 g O2 / mol glucose

Molar mass glucose: 180 g glucose /mol glucose

specific COD = 192 / 180 = 1.067 g O2 / g glucose

5
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - COD


Theoretical calculation of COD by using the chemical oxidation equation (=ThoD)

Example 1 – COD of glucose:


Chemical formula : C6 H12 O6

E.g.: 1 tea spoon of sugar (5 g glucose) dissolved


in 1 Liter of water

Specific COD = 192 / 180 = 1.067 g O2 / g glucose

COD = 5 . 1.067 = 5.3 g O2 / L

6
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - COD


COD Test
Chemical oxidation using potassium dichromate (K2Cr2O7) as oxidizing agent
- Heat for 2 hours at 148 °C

- Titrate non-consumed potassium dichromate with ferrous ammonium


sulfate or photometric detection of non used potassium dichromate

- Calculate the oxygen consumed during digestion

7
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - COD


Classification of COD present in wastewater I Total COD

Biodegradable Non-biodegradable
COD (bCOD) COD (nbCOD)

Readily Slowly Non- Non-


biodegradable biodegradable biodegradable biodegradable
(soluble) (particulate) soluble particulate
(rbCOD) (sbCOD) COD COD
(nbsCOD) (nbpCOD)
• can be quickly • particulate and colloidal
• Organic material,
assimilated by • must first be dissolved by • For domestic
biomass nbpCOD
extracellular enzymes wastewater the WWTP
corresponds to
• “true” dissolved • are thus assimilated at influent nbsCOD ≈
sCODe (sCODe = non-biodegradable
much slower rates
volatile suspended
activated-sludge
process effluent) when solids (nbVSS)
operated at an SRT >
4d
8
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - COD


Classification of COD present in wastewater II Total COD

Particulate (pCOD) Soluble (sCOD)

•Colloidal and sCOD = rbCOD +


suspended solids part of colloidal
COD + nbsCOD

non non-
biodegradable biodegradable
biodegradable biodegradable
particulate soluble
particulate soluble
(bpCOD) (bsCOD)
(nbpCOD) (nbsCOD)
• slowly
biodegradable • rbCOD + part of colloidal COD
• rbCOD is “true” soluble COD
• Biodegradable colloidal COD is
slowly biodegradable
9
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - COD


Particle Size Ranges
algae

bacteria

Bacterial flocs
cell fragments

viruses
protein
DNA Visible to the naked eye
fatty acids
ammonium, *Filter pore size
nitrate, etc.. 0.45 µm* if 0.45 µm is
used to
settleable distinguish
dissolved colloidal between
suspended particulate and
dissolved
10-6 10-5 10-4 10-3 10-2 10-1 100 10+1 10+2 µm fraction

1 µm=0.001 mm 10
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - COD


Importance of readily and slowly biodegradable fractions
(illustated by an example of a 3 staged cascade):

tank 1 tank 2 tank 3 Secondary clarifier

rate mg/L h
Relative oxygen

rbCO • in case tank 1 is aerated: High rbCOD in


D the influent causes higher oxygen demand
(more aeration needed)
uptake

• in case tank 1 is anoxic (preanox


denitrification): High rbCOD causes higher
uptake rate mg/L h
Relative oxygen

sbCOD denitrification rates

11
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - COD


Importance of readily and slowly biodegradable fractions

• Carbonaceous constituents measured by BOD or COD analyses are critical to the activated-sludge
process design. Higher concentrations of degradable COD may e.g. result in
1. a larger aeration basin volume,
2. more oxygen transfer needs, and
3. greater sludge production

• Especially the rbCOD fraction of the COD has a direct effect on the biological process performance

• The biodegradable fractions of the COD are important for biological treatment and must be evaluated

Biochemical oxygen demand (BOD)

12
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances


- Biomass -

13
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - Biomass


Biomass
• The biological treatment of municipal wastewater is achieved by using mixed cultures of microorganisms
composed of different types of microorganisms, the exact composition of the different types being
unknown

• The term „biomass“ therefore describes a very complex mix of different types of microorganisms, having
(very) different characteristics regarding their activity

• The properties of this complex mixed biomass depends on the conditions characterized by the process
type and the characteristics of the wastewater

• Biomass is mostly organic material and can be represented by

• volatile suspended solids (VSS)

• particulate COD (pCOD)

Other parameters to represent biomass include DNA, ATP, protein content, ….


14
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - Biomass


Importance of biomass for biological treatment process design

• Requires an understanding of the biochemical activities of microorganisms

• Microorganisms
- consume substrate,
- carry out oxidation-reduction reactions,
- are subject to growth (by the production of additional cells), and decay processes

• Therefore, biomass is produced continuously (by consumption of the substrate in the wastewater) and
decomposted (biodegraded)

15
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - Biomass


Characterization of biomass

BIOMASS
(part of pCOD and VSS)

active inactive

• e.g. • resulting from decay


- Heterotrophic bacteria, processes of biomass
- Autotrophic bacteria (cell debris)
- ….

16
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - Biomass


Fundamental transformation processes:
Degradation of organic carbon (aerated à aerobic conditions)
e.g. methanol: 2 CH3OH + 3 O2 è 2 CO2 + 4 H2O
Heterotrophic bacteria

Nitrification (aerated à aerobic conditions)


2 NH4+ + 3 O2 è 2 NO2- + 2 H2O + 4 H+ (nitritation)
2 NO2- + O2 è 2 NO3- (nitratation)
Autotrophic bacteria
Denitrification (not aerated à anoxic conditions)
5 CH3OH + 6 NO3- è 5 CO2 + 7 H2O + 3 N2 + 6 OH-
Heterotrophic bacteria

17
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances


- BOD -

18
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances – BOD


• Biochemical Oxygen Demand (BOD)

DIN EN 1085:
„Concentration of dissolved oxygen consumed under specified conditions (t days at 20°C
with or without nitrification inhibition) by the biological oxidation of organic and/or
inorganic matter in water“

• Equivalent for the concentration of the biological degradable fraction of organic substances

• The BOD is a lumped parameter, expressing, how much oxygen is needed to stabilize, through
biochemical processes, the carbonaceous matter. Therefore, it is an indirect indication of the
biodegradable organic carbon present

19
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances – BOD


Biochemical Oxygen Demand after 5 days (BOD5)
• If sufficient oxygen is available, the aerobic biological decomposition of an organic waste will continue until
(nearly) all of the waste is consumed
• (Nearly) complete stabilization takes, in practical terms, various days (around 20 days of more for domestic
sewage)

• However, to shorten the time for the laboratory test, and to allow a comparison of the various results,
some standardizations were established:
- The determination is undertaken on the 5th day
- The BOD test is carried out at a temperature of 20°C

• The most widely used parameter of organic pollution applied to both wastewater and surface water is
the 5-day BOD (BOD5 or BOD520)

• The 5 day duration has mainly historical background

20
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances – BOD


Fundamental transformation processes:
Degradation of organic carbon (aerated à aerobic conditions)
e.g. methanol: 2 CH3OH + 3 O2 è 2 CO2 + 4 H2O
Heterotrophic bacteria

Nitrification (aerated à aerobic conditions)


2 NH4+ + 3 O2 è 2 NO2- + 2 H2O + 4 H+ (nitritation)
2 NO2- + O2 è 2 NO3- (nitratation)
Autotrophic bacteria

Denitrification (not aerated à anoxic conditions)


5 CH3OH + 6 NO3- è 5 CO2 + 7 H2O + 3 N2 + 6 OH-
Heterotrophic bacteria

21
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances – BOD


BOD test; dilution method
• prepare dilution water (20 °C, oxygen saturated)
• measure dissolved oxygen concentration at time zero (= D1)

• incubate for 5 days (dark, 20 °C)


• measure dissolved oxygen concentration after 5 days (= D2)
• calculate BOD5 = (D1 – D2) / volume

22
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances – BOD


Example for a BOD test for a domestic wastewater:

Oxygen
[mg/l]

time [d]

23
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances – BOD


Example for a BOD test for a domestic wastewater

Oxygen demand
[mg/l]
BOD5

5d time [d]

24
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances – BOD

Typical BOD 5 Water


Concentrations [mg/L]
3-30 River water
3-60 Biologically treated ww
40-600 Low polluted industrial ww
100-300 Municipal untreated
wastewater (ww)
400-1,200 Polluted industrial ww
1,000-6,000 Highly polluted industrial
wastewater

25
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances – BOD


Analysis of the BOD- test

Oxygen [mg/l]
Oxygen
consumed until
time t (BOD
measured)

time [d]

- During the test three more or less distinct activities occur:


(1) a portion of the waste is oxidized to end products to obtain energy for cell maintenance and the synthesis of new cell tissue
(2) Simultaneously, some of the waste is converted into new cell tissue using part of the energy released during oxidation
(3) decay of cells
26
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances – BOD


What happens after 5 days?

- At the end of the fifth day the stabilization of the organic material is still not complete. If the test was
continued, degradation will go on (however, continuing at slower rates).

- Biochemical oxidation theoretically takes an infinite time to go to completion (the rate of oxidation is assumed
to be proportional to the amount of organic matter remaining).

Ultimate biochemical oxygen demand (UBOD or BODu)

27
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances


- Ultimate BOD -

28
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - UBOD


Ultimate biochemical oxygen demand
(BODu)

Oxygen demand [mg/l]


BODu

• Depending on the type of wastewater in


the 5 day period, 60 to 70% of oxidation BOD5
95 – 99%
is complete and oxidation will still go on.
Within a 20 day period, the oxidation of
the carbonaceous organic matter is about
95 to 99 % complete.
5d time [d] 20 d

• For domestic sewage, it is considered that after 20 days of the test the stabilization is practically
complete. Therefore, in practice the BODU can be determined at 20 days, or estimated by following the
BOD course as a function of time and calculating the UBOD.

• The concept of the test is similar to the standard BOD of 5 days, varying only with the final period of
determination of the dissolved oxygen concentration (e.g. 20 days).
29
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - UBOD

Analysis of the BOD - test

substrat
e

biomass

Cell debris

time

30
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - UBOD


Analysis of the BOD - test

31
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - UBOD


Modelling biochemical oxygen demand (highly simplified!)

• Degradation is assumed to be proportional to BOD remaining:


dBODr
= -k1 × BODr
dt

Analytical solution after integration between t=0 and t=t:

BODr = UBOD × (e - k1t )


BODt = UBOD - BODr
BODt = UBOD × (1 - (e - k1t ))
BODr = amount of waste remaining at time t (expressed in oxygen equivalents, [mg/l]
k1 = first-order reaction rate constant (usually base e), [1/d]; typical (at 20°C): 0.23 1/d; untreated WW
(at 20°C): 0.12 to 0.46 1/d; effluents (at 20°C): 0.12 to 0.23 1/d
UBOD = total or ultimate carbonaceous BOD, [mg/l]
t = time [d]

32
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - UBOD

Modelling biochemical oxygen demand (highly simplified !)

Temperature adjustment:

- if the temperature is not 20°C, k can be adjusted:

k1,T = k1, 20 ×q (T -20)


θ = 1.056 between 20 and 30°C, and 1.135 between 4 and 20”C

33
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - UBOD


Example for a fitted BOD curve for the determination of k, UBOD and bCOD

Source: Roeleveld and van Loosdrecht (2002) 34


Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - UBOD


Average results of the performed wastewater characterization for 21 different WWTP in the
Netherlands

kmin = 0.33
kmax = 0.7

Source: Roeleveld and van Loosdrecht (2002) 35


Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - UBOD


Example for the relation between the measured k value and the slowly biodegradable COD fraction

SS = readily biodegradable COD


XS = slowly biodegradable COD
SS+XS = total biodegradable COD

Source: Roeleveld and van Loosdrecht (2002) 36


Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - UBOD

Example 2: Determine the 1-day BOD and ultimate BOD for a wastewater
whose 5-day BOD (20°C) is 200 mg/L. The reaction constant k
(base e) = 0.23 1/d.
What would have been the 5-day BOD if the test had been
conducted at 25°C ?

37
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - UBOD


Solution to Example 2 (Calculating UBOD):
given: k1, BOD5, T
BODt = UBOD - BODr BODr = UBOD × (e - k1t )
At t = 5d BOD = 200 mg/l

BOD5 = UBOD -UBOD × (e - k1t )


- k1t
BOD5 = UBOD(1 - (e ))
k1, 20 = 0.23

200 = UBOD(1 -(e -0.23×5 ))


à UBOD = 293mg / l

38
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - UBOD


Illustration of Example 2:

BODt = UBOD × (1 - (e - k1t ))


BODr

UBO
D
BOD5

39
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - UBOD


Solution to Example 2 (Calculating BOD1):
given: k1, BOD5, T, t=1d
calculated: UBOD
BODr = UBOD × (e - k1t ) BODt = UBOD × (1 - (e - k1t ))
At t = 1d :
- k1t
BODt = UBOD(1 - (e ))

BOD1 = 293(1 - 0.795)


à BOD1 = 60mg / l

40
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - UBOD


Illustration of Example 2:

BODt = UBOD × (1 - (e - k1t ))

BOD1

41
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - UBOD


Solution to Example 2 (Calculating BOD5 at 25°C):
given: k1 at 20°C, T
calculated: UBOD
BOD5 at T= 25°C :
(T -20 )
k1,T = k1, 20 ×q
θ = 1.056
k1, 25 = 0.23 ×1.056(25-20)
à k1, 25 = 0.302
BOD5 = UBOD(1 - (e - k1t ))
à BOD5 = 228mg / l

42
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - UBOD


Illustration of the influence of k1

k1=0.46
BODt

k1=0.23
k1=0.12

43
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - UBOD


Illustration of Example 2 (temperature change):

T=25°C BODt = UBOD × (1 - (e - k1t ))


T=20°C

Time [d]
44
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - UBOD


Illustration of Example 2 (extreme temperature change):

T=30°C, k1,20 =0,23 BODt = UBOD × (1 - (e - k1t ))

T=4°C, k1,20 =0,23

Time [d]

45
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Matter


Nitrification in the BOD test

46
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances – BOD


Nitrification during the BOD-test

• Non-carbonaceous matter, such as ammonia, is produced during the hydrolysis of proteins and
nitrification may occur during the BOD test

• The oxygen demand associated with the oxidation of ammonia to nitrate is called the nitrogenous
biochemical oxygen demand (NBOD)

• When nitrification occurs in the BOD test, erroneous interpretations of treatment operating data
are possible

• When nitrification occurs in the BOD test, the measured BOD value will be higher than the true
value due to the oxidation of carbonaceous matter

47
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances – BOD


Fundamental transformation processes:
Degradation of organic carbon (aerated à aerobic conditions)
e.g. methanol: 2 CH3OH + 3 O2 è 2 CO2 + 4 H2O
Heterotrophic bacteria

Nitrification (aerated à aerobic conditions)


2 NH4+ + 3 O2 è 2 NO2- + 2 H2O + 4 H+ (nitritation)
2 NO2- + O2 è 2 NO3- (nitratation)
Autotrophic bacteria

Denitrification (not aerated à anoxic conditions)


5 CH3OH + 6 NO3- è 5 CO2 + 7 H2O + 3 N2 + 6 OH-
Heterotrophic bacteria

48
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances – BOD


Influence of nitrification on oxygen demand in a BOD test for a municipal wastewater

Oxygen demand [mg/l]


The reproductive rate of the
nitrifying bacteria is slow. It
NBOD
normally takes from 6 to 10
days for them to reach
significant numbers to exert
a measureable oxygen
Carbonaceous BOD
demand
A sufficient number of nitrifying
bacteria is present initially
5 days time [d]
BOD due to oxidation of carbonaceous material. When it is referred to the
oxygen demand by the oxidized carbon in the test (when nitrification is
suppressed) the oxygen demand is called carbonaceous BOD (CBOD)

49
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances – BOD


Overcoming the effects of nitrification in a BOD test
- by using various chemicals to suppress the nitrification reactions, or
- by treating the sample to eliminate the nitrifying organisms.

original sample
BOD [mg/L]

Sample with inhibitor for nitrification

1 2 3 4 5
time [d]

Source: BSB-Fibel, Fa. WTW 50


Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of
Organic Matter Interrelationships

51
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - Interrelationships


Interrelationship between representatives of organic matter in a WWTP
influent
non biodegradable remaining biomass,
and organic matter remaining cell
COD
after 5d debris
(nbCOD)
(additional
nbCOD)

COD remaining
cell debris
bCOD (additional UBOD
BOD5 nbCOD)
after 5d

• The ratios vary as the wastewater passes along the various units of the treatment plant (the tendency is for
the ratio COD/xxx to increase); xxx= bCOD, BOD5 or UBOD

• The higher the treatment efficiency, the higher the value of the ratio of COD to the other values becomes

52
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - Interrelationships

Relationship between UBOD and COD

• The value of the ultimate carbonaceous UBOD value is usually not the same as the COD, because

1. Some organic substances are difficult to oxidize biologically, but can be oxidized chemically

2. Some inorganic substances can be oxidized by dichromate (in the COD-test this increases the
apparent organic content of the sample

3. certain organic substances may be toxic to the microorganisms used in the BOD test

4. Some of the biomass can still remain as cell debris (and active cells) in the UBOD test (even after 20
days)

53
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - Interrelationships


UBOD and BOD5

Origin UBOD/BOD5

High concentration sewage 1.1 – 1.5 a value of 1.6 is


Low concentration sewage 1.2 – 1.6 commonly used
Primary effluent 1.2 – 1.6

Secondary effluent 1.5 – 3.0

Source: von Sperling (2005)

Origin UBOD/BOD5

Untreated 1.1 – 2.2


(k1 = 0.12 – 0.46)
Effluent from biological treatment 1.46 – 2.2
(k1 = 0.12 – 0.23)
Calculated via UBOD/BOD = 1/(1-e^(-k1*5))

54
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - Interrelationships


Relationship between COD and BOD5
Oxygen – used by microorganisms for energy
BOD5 generation

CODtotal
CODresidual
residual-COD
- biomass (growth of microorganisms that use part of
Municipal wastewater: the organic substances to build up their biomass
Typical proportion:
- refractory organic substances (non biodegradable
COD / BOD5 : ≈ 1.7 - 2 matter)
(However, for industrial wastewater,
the ratio can vary widely).

COD / TOC : ≈ 2.5

55
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - Interrelationships

COD and BOD

Origin BOD/COD

Untreated 0.3 – 0.8

After primary settling 0.4 – 0.6

Final effluent 0.1 – 0.3*

*CBOD/COD

Source: adapted from Metcalf & Eddy (2003) 56


Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - Interrelationships


Evaluation of wastewater by the ratio of COD and BOD5
BOD5 / COD ratio Evaluation

BOD5 / COD > approx. 0.4 to 0.5 biodegradable fraction is high,


good indication for biological treatment

approx 0.3 < BOD5 / COD poor biological degradability, waste may
have some toxic components or
< approx 0.5 acclimated microorganisms may be
required in its stabilization, treatability
studies are recommended to verify
feasibility of biological treatment
BOD5 / COD < approx 0.25 non-biodegradable fraction is high,
possible indication for physical-chemical
treatment

57
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - Interrelationships

TOC and BOD5

Origin BOD/TOC

Untreated 1.2 – 2.0

After primary settling 0.8 – 1.2

Final effluent 0.2 – 0.5*

*CBOD/COD Source: Metcalf & Eddy (2003)

58
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - Interrelationships

Example 3: Determine the theoretical TOC/COD ratio for the following compound C5H7NO2.

59
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - Interrelationships

Solution to Example 3:
C5H7NO2 + 5 O2 à 5 CO2 + NH3 + 2H2O
C5H7NO2 : mw = 113
O2 : mw = 32
COD = 5 * 32/113 = 1.42 mg O2 / mg C5H7NO2

TOC = (5 * 12)/113 = 0.53 mg TOC / mg C5H7NO2

TOC 0.53 COD


à = = 0.37 = 2.7
COD 1.42 TOC

Note: C5H7NO2 is often assumed to be a typical composition of biomass.

60
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances


Possible properties of COD Bio- Non-bio- dissolved Suspended
fractions degradable degradable (soluble) (particulate
)
organic

inorganic

dissolved
(soluble)

Suspended
(particulate
)

61
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances


Properties of some COD Bio- Non-bio- dissolved Suspended
fractions degradable degradable (soluble) (particulate
)
bCOD = biodegradable COD
bCO nbCOD rbCOD pCO
organic
D
rbCOD nbsCOD D
nbpCOD rbCOD=readily biodegradable COD
nbsCOD
bpCO nbpCOD bpCO
D D nbpCOD = nonbiodegra-dable
inorganic particulate COD
bpCOD=biodegradable particulate COD

dissolved
rbCOD nbsCOD nbsCOD=nonbiode-gradable soluble
(soluble)
COD
pCOD=particulate COD
Suspended nbpCOD nbCOD=nonbiodegradable COD
(particulate) bpCO
D

Note: soluble COD (sCOD) = rbCOD + colloidal COD + nbsCOD); due to the method used (filter with 0.45 μm pore size); but
only the rbCOD is quickly assimilated by the biomass
62
Chair of Urban Water Systems Engineering
Technical University of Munich

Nitrogenous Compounds

63
Chair of Urban Water Systems Engineering
Technical University of Munich

Nitrogenous Compounds

Plant nutrients
- ammonium NH4 +

-
- nitrite NO2

-
- nitrate NO3

- phosphate PO43-

64
Chair of Urban Water Systems Engineering
Technical University of Munich

Nitrogenous Compounds in the Environment


• The elements nitrogen and phosphorous are essential nutrients for algae leading, under
certain conditions, to eutrophication of lakes and reservoirs

• Nitrogen can lead to dissolved oxygen consumption in the receiving water body due to
the processes of nitrification

• Nitrogen in the form of free ammonia is directly toxic to fish. At high pH-values, a high
amount of ammonia is produced

• Nitrite is an intermediate product in the nitrification process and usually low in concentration,
however highly toxic to fish

• Nitrate is associated with illnesses, therefore undesirable in water and is only in limited
amounts tolerable in drinking water

65
Chair of Urban Water Systems Engineering
Technical University of Munich

Nitrogenous Compounds in a Treatment Plant

• As nitrogen and phosphorous are essential nutrients for the growth of microorganisms,
they are needed for the treatment of wastewater by biological processes

• Nitrogen in the process of nitrification leads to oxygen consumption

• Nitrogen in the process of denitrification can lead to the deterioration in the settleability
of the sludge in the secondary clarifier

66
Chair of Urban Water Systems Engineering
Technical University of Munich

Nitrogenous Compounds
Characterization of nitrogen found in wastewater

• The most common and important forms of nitrogen in wastewater are Ammonia (NH3), Ammonium (NH4+),
Nitrogen gas (N2), Nitrite ion (NO2-) and Nitrate ion (NO3-)

• Urea, also present in fresh wastewater, is converted rapidly to ammonium carbonate, and is seldom found in
untreated municipal wastewaters
• Nitrite is an intermediate product of microbial processes and is usually not present in high concentrations.
In the presence of O2 nitrogen usually accumulates to nitrate

• N2 has poor solubility in water

• The age of wastewater is indicated by the relative amount of ammonia that is present

• The determination of the prevailing form of N in a water body can provide indications about the stage of
pollution caused by an upstream discharge of sewage

67
Chair of Urban Water Systems Engineering
Technical University of Munich

Nitrogenous Compounds
Relative distribution of the forms of nitrogen under different conditions
Condition Prevailing form of N
Raw wastewater • Organic N
• Ammonia
Recent pollution in a water course • Organic N
• Ammonia
Intermediate stage in the pollution of a water course • Organic N
• Ammonia
• Nitrite (low)
• Nitrate
Remote pollution in a water course • Nitrate
Effluent from a treatment process without nitrification • Ammonia
Effluent from a treatment process with nitrification • Nitrate
Effluent from a treatment process with nitrification and • Low concentrations of all
denitrification forms of nitrogen
Source: von Sperling (2005)
68
Chair of Urban Water Systems Engineering
Technical University of Munich

Nitrogenous Compounds N
Characterization of nitrogen
present in wastewater TKN nitrite nitrate
• usually
low
Organic N ammonium,
ammonia

non - bio-
biodegradable degradable

Soluble Particulate Soluble Particulate

• usually • Associated with the •Quickly • slowly


negligible non-biodegradable biodegradable biodegradable
carbonaceous matter,
involved in the
biomass
69
Chair of Urban Water Systems Engineering
Technical University of Munich

Nitrogenous Compounds
Nitrogen distribution in raw (untreated) domestic sewage

NOx NOx NOx

Total
Ammonia TKN soluble inorganic
60 to 70% of nitrogen
TKN the influent
N total (TIN)
TKN

N org N
org
TKN
particulate

(adapted from von Sperling, 2005 and IAWQ, 1995) 70


Chair of Urban Water Systems Engineering
Technical University of Munich

Nitrogenous Compounds - Ammonia


• The inorganic nitrogenous matter is represented by ammonia, both in the form of NH3 and as NH4+

• Ammonia in the influent wastewater is mainly derived from urea, which is rapidly hydrolyzed and rarely found
in raw sewage

• Hydrolysis and ammonification reactions begin in the collection and interception sewerage system

• In the usual range of pH, near neutrality, the ammonia present is practically in the form of NH4+

Source: Metcalf & Eddy (2003) 71


Chair of Urban Water Systems Engineering
Technical University of Munich

Phosphorous

72
Chair of Urban Water Systems Engineering
Technical University of Munich

Phosphorous
• Total phosphorus in domestic sewage is present in the form of phosphates

• Phosphorus is an essential nutrient for the growth of the microorganisms responsible for
the stabilization of organic matter

• Phosphorus is an essential nutrient for the growth of algae, eventually leading, under
certain conditions, to the eutrophication of lakes and reservoirs

73
Chair of Urban Water Systems Engineering
Technical University of Munich

Phosphorous
Characterization of phosphorous P total
species present in wastewater

Organic P Inorganic P
Bound to organic Main source from detergents
compounds, and other household
physiological origin products

Particulate P Soluble P Soluble P

orthophosphates
polyphosphates Available for biological
Subject to hydrolysis metabolism without
further breakdown

74
Chair of Urban Water Systems Engineering
Technical University of Munich

Phosphorous
Phosphorus in raw (untreated) domestic sewage

P inorg (poly +
P orthophosphate)
soluble
P
total

P P
particulate org

(adapted from IAWQ, 1995) 75


Chair of Urban Water Systems Engineering
Technical University of Munich

Example 4: Given the wastewater characteristics in the table, determine the concentrations for
- bCOD (biodegradable COD)
- nbpCOD (nonbiodegradable particulate COD)
- sbCOD (slowly biodegradable COD)
- FSS
- the fraction of organic nitrogen in VSS

Constituent (influent) Concentration mg/l

BOD 195

COD 465

rbCOD 80

TSS 220

VSS 200

TKN 40

NH4-N 26

Constituent (effluent)

sCODe 30

sON (soluble org N) 1.2

76
Chair of Urban Water Systems Engineering
Technical University of Munich

Solution to Example 4:
Determine the concentrations for
bCOD, nbpCOD,sbCOD, FSS, the fraction of organic nitrogen in VSS
table.: BOD, COD, rbCOD, TSS, VSS, TKN, NH4-N, sCODe, sON

bCOD = UBOD + 1.42 × f d × (YH ) × bCOD


bCOD / BOD = UBOD / BOD + 1.42 × f d × (YH ) × bCOD / BOD
bCOD/BOD = 1.6 (under the assumption that UBOD/BOD=1.46)
à bCOD/BOD =1.6 is often assumed à bCOD = 1.6 * BOD = 1.6*195 = 312 mg/l
nbpCOD = nbCOD – nbsCOD
For domestic wastewater nbsCOD ≈ sCODe (sCODe = activated-sludge
process effluent) when operated at an SRT > 4d
à nbpCOD = nbCOD – sCODe
nbCOD = COD – bCOD = 465 – 312 = 153 mg/l
à nbpCOD = nbCOD – sCODe = 153 - 30 = 123 mg/l
sbCOD = bCOD – rbCOD = 312 -80 = 232 mg/l
FSS = TSS – VSS = 220 - 200 = 20 mg/l

77
Chair of Urban Water Systems Engineering
Technical University of Munich

Solution to Example 4:
Determine the concentrations for
bCOD, nbpCOD, sbCOD, FSS, the fraction of organic nitrogen in VSS
table.: BOD, COD, rbCOD, TSS, VSS, TKN, NH4-N, sCODe, sON

TKN = orgN + NH4-N


orgN = sON + pON ( = particulate organic N)
TKN = sON + pON + NH4-N
àpON = TKN - sON – NH4-N = 40 – 26 -1.2 = 12.8 mg/l
àfraction of organic N in VSS = pON / VSS = 0.064 gN/gVSS

78
Chair of Urban Water Systems Engineering
Technical University of Munich

Temperature

79
Chair of Urban Water Systems Engineering
Technical University of Munich

Temperature and Temperature Effects


• Temperature is a crucial factor in biological processes

• Temperature effects include effects on chemical reactions, equilibrium constants,


solubility constants, biological reaction-rate constants, etc. (all of them are dependent on
temperature)

• Different (mean) temperature can tremendously influence the performance and the design of
wastewater treatment plants:
- tank volumes
- sludge production
- oxygen demand

80
Chair of Urban Water Systems Engineering
Technical University of Munich

Temperature
Temperature Effects, e.g. tank volume in the design of a WWTP
(15 design models from eight countries)

Tank volume [m³]

Temperature [°C] Wichern et al. (2004)


With the data set used:
• Differences of more than 200% between models at 10°C were observed
• 10°C Temperature increase could result in a decrease of about 50%
• it is recommended to use design procedures for other countries / conditions only if they have
been tested for these conditions
81
Chair of Urban Water Systems Engineering
Technical University of Munich

Temperature
Wastewater temperature variations

• Temperature of wastewater is commonly higher than that of the local water supply, because of the
addition of warm water from household and industrial activities.

• The temperature variation of the water over a year is delayed compared to the time of the year and the
temperature of the air. Seasonal heating and cooling is delayed.

• Observed wastewater temperatures are higher than the local air temperatures during most of the year
and are lower only during the hottest summer months.

• Variations of wastewater temperature over one day are caused by the change of the portion of warm
water in the wastewater.

• Knowing the temperature extreme values is very important for wastewater treatment plant design. If
the plant is big, often daily mean values are sufficient (due to the temperature equalization of the
variations over one day in big tank volumes).

82
Chair of Urban Water Systems Engineering
Technical University of Munich

Wastewater Temperature Variations


Daily mean temperature of raw wastewater in a WWTP in Switzerland (in °C) over one year:

Seasonal variations are lower and delayed compared to air temperature and season

83
Chair of Urban Water Systems Engineering
Technical University of Munich

Temperature
Wastewater temperature ranges based on an international study

Country Wastewater Temperature BOD BOD N


Influent [°C] [mg/l] [g/ capita d] [mg/l]
[l/(capita d)]
Brasil 120 - 180 10 - 28 108 - 299 29 27 - 64

China - 5 - 25 44 - 386 - 35
Indonesia - - - 27 - 70 -

Morocco - - - 32 - 40 9

South Africa 10 - 800 10 - 30 250 - 400 - 35 - 80

Thailand - 26 - 33 20 - 400 - 17 - 20

USA - 1 - 25 160 - 360 - -

http://www.ptka.kit.edu/downloads/ptka-wte-w/WTE-W-Berichte-2010_Leitfaden_Abwassertechnologie_Laendern.pdf
84
Chair of Urban Water Systems Engineering
Technical University of Munich

Fundamentals of Microbial Metabolism, Stoichiometry,


Process Kinetics, and Biological Process Models

Prof. Dr.-Ing. Jörg E. Drewes


11 January 2024
Slides with background information, review on your own
1
Chair of Urban Water Systems Engineering
Technical University of Munich

Fundamentals of Microbial Metabolism,


Stoichiometry, Process Kinetics and Biological
Process Models

- Microbial Metabolism -

2
Chair of Urban Water Systems Engineering
Technical University of Munich

Microbial Metabolism
The Role of Microorganisms
• Biological processes in wastewater treatment consist of mixed communities with a wide variety of
microorganisms, including

• bacteria,
• protozoa,
• fungi,
• rotifiers,
• and possibly algae

• Bacteria constitute the largest


and most important group in
biological wastewater treatment
systems

3
Chair of Urban Water Systems Engineering
Technical University of Munich

Microbial Metabolism

EP
S

adapted from von Sperling (2005)

Simplified schematic representation of a bacterial cell


Genetic material • DNA and plasmides
Ribosome • location of enzyme synthesis
Cell membrane • external boundary,
• has an important role in selecting the substances that can leave or enter the cell,
• location where energy is gained
Cell wall • another external layer, keeps the form of the cell,
• protection against mechanical impacts and osmotic alterations
Extracellular matrix • composed of polysaccharides and polypeptides that is often found around the cell
(EPS) • plays an important role in e.g. the formation of bacterial flocs that are important in
wastewater treatment
4
Chair of Urban Water Systems Engineering
Technical University of Munich

Microbial Metabolism
Sources needed for microbial growth
Reproduction and proper functioning of an organism require sources of
• energy

• carbon
• nutrients
- inorganic elements
- organic nutrients (growth factors)

Carbon source New cells

Electron donor other products

5
Chair of Urban Water Systems Engineering
Technical University of Munich

Microbial Metabolism
Energy sources for microorganisms
• Microorganisms require chemically available energy, to
• carry out synthesis,
• enable mobility, a big portion of this energy is supplied by
• maintain inner structure and osmotic barriers • redox reactions, or
• light

Carbon sources for microorganisms


• obtained from
• organic matter, or
• carbon dioxide

Nutrients
• Nutrients may at times be the limiting factor for microbial cell synthesis and growth
• Principal inorganic nutrients: N, S, P, K, Mg, Ca, Fe, Na, Cl
• Minor nutrients

6
Chair of Urban Water Systems Engineering
Technical University of Munich

Microbial Metabolism
Metabolism of microorganisms and enzymes
• Metabolism: the chemical processes that simultaneously take place in the cell

• The chemical transformations occur in a sequence of diverse and complex intermediate reactions, each catalyzed by
a specific type of enzyme

• Enzyme types:

- Intracellular enzymes
Most of the enzymes, located inside the cell, aid in the consumption of soluble matter

- Extracellular enzymes
Some enzymes are released into the external medium,
lead to hydrolysis that converts large and complex substrate molecules in order to make them
available for passing through the cell membrane

7
Chair of Urban Water Systems Engineering
Technical University of Munich

Microbial Metabolism

Carbon source New cells

Electron donor other products

aerobic, aerobic, anaerobic,


heterotrophic autotrophic heterotrophic

8
Chair of Urban Water Systems Engineering
Technical University of Munich

Simplified Scheme of Microbial Metabolism


The reaction sequences within the cell can be divided into the following four interrelated steps:

Decomposition, synthesis, energy production, and storage

Storage

Nutrients,
carbon sources Synthesis
Decom
pos. New cells
Electron Energy
donor e-

Electron acceptor
Products

Metabolism works only if substrate AND electron acceptors are available ! 9


Chair of Urban Water Systems Engineering
Technical University of Munich

Microbial Metabolism
Decomposition
Serves for the retrieval of material for the synthesis
of cell components and electrons that are needed
for gaining energy

e-

Energy production,
Stepwise transfer of electrons to the electron
acceptor to gain energy

Synthesis
Supplied with the energy
Production of the components of the new cells (reproduction)
Production of substances, that are needed to build up the storage
Production of substances, that serve to repair cell components

Storage: Serves for building up reserves for a survival in periods of shortage

10
Chair of Urban Water Systems Engineering
Technical University of Munich

Microbial Metabolism
Classification of Microorganisms

Sources Microorganism type


Energy source

a) Radiation (light) Phototrophic

b) Chemical reactions Chemotrophic

Electron donor (substrate being oxidized)

a) Inorganic (e.g. NH4+, NO2-,H2,…) Lithotrophic

b) Organic compounds Organotrophic

Carbon source for biomass synthesis

a) Carbon dioxide, CO2 as main source Autotrophic

b) Organic compounds Heterotrophic

11
Chair of Urban Water Systems Engineering
Technical University of Munich

Microbial Metabolism
Conditions in the environment
Energy production Prevalent Conditions in
the environment

Available electron acceptor being reduced

Respiration

a) O2 Aerobic

b) Nitrate, NO3-, nitrite, NO2-, no oxygen Anoxic

c) Sulfate, SO42-, CO2, no oxygen, no nitrate Anaerobic

Fermentation

d) Organic compounds, no oxygen, no nitrate Anaerobic

• In biological wastewater treatment almost the whole spectrum of microorganisms is engaged in transformations

12
Chair of Urban Water Systems Engineering
Technical University of Munich

Microbial Metabolism
Example
• A microorganism, oxidizing ammonium to nitrite that needs (obligatory) oxygen as electron
acceptor to synthesize its biomass from carbon dioxide is called:

Obligate aerobic, chemo-litho-autotrophic

13
Chair of Urban Water Systems Engineering
Technical University of Munich

Microbial Metabolism
Examples
chemo-organo-heterotrophic aerobic bacteria
(coh-aerobic)
responsible for the elimination of organic wastewater constituents

chemo-organo-heterotrophic anoxic bacteria


(denitrifiers)

responsible for the transformation of nitrate into nitrogen gas (N2)

chemo-litho-autotrophic aerobic bacteria


(nitrifiers)
responsible for the transformation of ammonium into nitrate (or nitrite)

14
Chair of Urban Water Systems Engineering
Technical University of Munich

Microbial Metabolism
Preferences of organic matter decomposition

• The objective of the energetic metabolism is to conserve as much energy as possible in a form available to a cell

• When various electron acceptors are available in the medium, the microorganisms use the one that produces the
highest quantity of energy:

(1) Dissolved oxygen is used first under aerobic conditions, after it is exhausted

(2) When dissolved oxygen is not available and nitrate is available, the organism that are capable of using nitrate start to
take over (anoxic conditions)

(3) When there is no nitrate, strict anaerobic conditions occur, where sulfates are used and reduced to sulfides, and
CO2 is converted into CH4 (methane) (anaerobic conditions)

• Since more energy is released through aerobic reactions than through anaerobic reactions, the aerobic organisms
reproduce faster than the anaerobic organisms

15
Chair of Urban Water Systems Engineering
Technical University of Munich

Microbial Metabolism
Main routes of organic matter decomposition in the presence of different electron acceptors:

CO2 H2O
aerobic conditions
O2

CxHyOz
Energy gain

Organic matter
anoxic conditions NO3 -

CO2 N2

SO4 2-
CO2
anaerobic conditions
CO2 H2S
CO2 CH4

Source: von Sperling (2005) 16


Chair of Urban Water Systems Engineering
Technical University of Munich

Microbial Metabolism/Biochemical Pathways

17
Chair of Urban Water Systems Engineering
Technical University of Munich

Detection of SARS-CoV-2 by Biomarker Project


- In silico tests - - Primerauswahl -
A B C D E F G H I J K L M N O P Q Targetgen Sequenz Referenzen
FSSRFSSRFSSRFSRFSRFSRFSSRFSRFSRFSSRFSRFSRFSRFSRFSRFSRFSR
Corona_229E ORF6-8 GACCCCAAAATCAGCGAAAT CDC 2020; Nemudryi et al. 2020; Wu
SARS-CoV-2 Genome
Corona_avian M Nukleocapsid FAM-ACCCCGCATTACGTTTGGTGGACC- et al. 2020; Medema et al. 2020;
Corona_bat E QYS Rimoldi et al. 2020; Peccia et al.
Corona_HKU1
Corona_mers ORF1a ORF1ab S
ORF3 N
ORF10
N TCTGGTTACTGCCAGTTGAATCTG 2020; Randazzo et al. 2020a;
Corona_murine
Randazzo et al. 2020b
5`UTR Corona_NL63
3`UTR ACAGGTACGTTAATAGTTAATAGCGT Corman et al. 2020; Wurtzer et al.
Corona_pigeon
Hüllprotein
0 10000
Corona_porcine
enterovirus
20000 30000 FAM-ACACTAGCCATCCTTACTGCGCTTCG- 2020; Bar Or et al. 2020
norovirus E QYS
SARS 2020 ATATTGCAGCAGTACGCACACA
SARS before 2016
SARS Africa
Replikase-Polyprotein TGGGGYTTTACRGGTAACCT Chu et al. 2020; Etievant et al. 2020;
SARS Brazil (Open Reading Frame) VIC-TAGTTGTGATGCWATCATGACTAG- Curti et al. 2020; Sah et al. 2020
SARS Canda QYS
SARS China
SARS France
ORF AACRCGCTTAACAAAGCACTC
SARS Germany RNA-abhängige RNA- GTGARATGGTCATGTGTGGCGG Corman et al. 2020; Wurtzer et al.
SARS India
SARS Italy
Polymerase CAGGTGGAACCTCATCAGGAGATGC 2020; Alpaslan Kocamemi et al.
SARS Peru CARATGTTAAASACACTATTAGCATA 2020b; Alpaslan Kocamemi et al.
SARS Russia
SARS Spain
RdRP 2020a; Westhaus et al., 2020
SARS USA
SARS Reference

No Missmatch
1 Missmatch
→ The detection is based on 3-4 gene fragments
2 Missmatches
3-4 Missmatches
5+ Missmatches

Ho et al. (2022), Water Research 210, 117977


Chair of Urban Water Systems Engineering
Technical University of Munich

Biomarker Results Berchtesgaden (21.906 PE)


– rolling average
12/1/20 1/1/21 2/1/21 3/1/21 4/1/21 5/1/21
120 140
SARS-CoV-2
Neuinfektionen in 7 Tagen
Biomarker: E-Gen 120
100

SARS-CoV-2 Biomarker Konzentration


pro mL Abwasser
Biomarker: Durchschnitt aus 3 Zielgenen

Genkopien pro mL Abwasser


100
Neuinfektionen in 7 Tagen

pro mL Abwasser
80 Gleitender Mittelwert (Durchschnitt)
80
60
60

40
40

20
20

0 0
12/2020 1/2021 2/2021 3/2021 4/2021 5/2021

• Sampling 2x/week provides reasonable representation of infection pattern


• Biomarker abundance approx. 7 days ahead of official case data

Rossmann et al. (2021), Detusches Ärztebaltt 19


Chair of Urban Water Systems Engineering
Technical University of Munich

Biomarker Results in Karlsruhe


01.06.2020 Infection 18.12.2020
number ddPCR (E, ORF)
01.06.2020 Infektionszahle
18.12.2020
500
0 10
0
50
40
30
20

0…
0…
0…
0…
1…
1…
1…
0…
0…
0…
0…
0…
0…
0…
n

o…
350 50

cti

RS
-…
fe
In

A
S
Aktive Fälle pro 100.000 Einwohner

RNA proconcentration
Infections per 100,000 inhabitants

mL Abwasser
300 A
Infection data not shifted 40
250 Not corrected
(original data)

per mL sewage
200 30

Biomarker
150 20

SARS-CoV-2
100

SARS-CoV-2
10
50

0 0
06/20 07/20 08/20 09/20 10/20 11/20 12/20 01/21 02/21 03/21 04/21 05/21 06/21 07/21
01.06.2020 18.12.2020
350 50

mLconcentration
Infections per 100,000 inhabitants

B
Aktive Fälle pro 100.000 Einwohner

300

Abwasser
InfectionCase
data shifted by 40
250 16 days
numbers

per m L sewage
200 shifted by 16 30

arker
days

RNA pro
150

SARS-CoV-2 Biom
20
100

SARS-CoV-2
10
50

0 0
06/20 07/20 08/20 09/20 10/20 11/20 12/20 01/21 02/21 03/21 04/21 05/21 06/21 07/21

Ho et al. (2022), Water Research 210, 117977


20
Chair of Urban Water Systems Engineering
Technical University of Munich

Detection of Variants of Concern (VoCs) - Karlsruhe

Anteil Alpha, Beta, Gamma, Mu, (Omikron) - S:N501Y (S:N501Y / Wildtyp) Anteil Alpha
50Diagrammtitel
ddPCR 50
Anteil
0 Delta und OmikronDiagrammtitel
- S:T478K (S:T478K / Wildtyp) RKI 0 Anteil Delta
Anteil Omikron (Omikron /1E, ORF) Anteil
1 Omikron

120%

100%

80%
Anteil Variante

60% Alpha Delta Omikron


40%

20%

0%
11/20 12/20 01/21 02/21 03/21 04/21 05/21 06/21 07/21 08/21 09/21 10/21 11/21 12/21 01/22 02/22 03/22 04/22

Ho et al. (2022), Water Research 210, 117977 21


Chair of Urban Water Systems Engineering
Technical University of Munich

Detection of Variants of Concern in Bavaria

Source: https://www.bay-voc.lmu.de/abwassermonitoring 22
Chair of Urban Water Systems Engineering
Technical University of Munich

Microbial Metabolism
Environmental factors

• Environmental conditions have an important effect on the selection, survival, and growth of microorganisms

• Important environmental factors are


- Temperature
- pH
- Presence of toxic substances (i.e. heavy metals)

- Quality of the substrates (wastewater constituents)

• The environmental requirements for the bacteria vary with the species. E.g. chemo-autotrophic bacteria
are much more sensitive to environmental conditions than are heterotrophic bacteria

23
Chair of Urban Water Systems Engineering
Technical University of Munich

Microbial Metabolism
Environmental factors
• In general, optimal growth for a particular microorganism occurs within narrow ranges of temperature and pH

• Temperatures below the optimal level have a greater influence on the growth rate compared to temperatures
above the optimum

Type Temperature range Optimum range


°C °C
Psychrophilic 10 - 30 12 - 18

Mesophilic 20 - 50 25 - 40

Thermophilic 35 - 75 55 - 65

• The pH of the environment is also a key factor in the growth of microorganisms. Most bacteria cannot tolerate
pH levels above 9.5 or below 4.0

• Generally the optimum pH range for bacterial growth lies between 6.5 and 7.5

24
Chair of Urban Water Systems Engineering
Technical University of Munich

Fundamentals of microbial metabolism,


stoichiometry, process kinetics and biological
process models

- Stoichiometry of microbial reactions -

25
Chair of Urban Water Systems Engineering
Technical University of Munich

Stoichiometry of Microbial Reactions


Stoichiometry

Quantifies the relative quantities of reactants and products in chemical and biochemical reactions

here:

• Which amounts of material are to be used in the calculations performed for biological processes?

• Thereby, how can the different types of organisms be distinguished from one another?

26
Chair of Urban Water Systems Engineering
Technical University of Munich

Stoichiometry of Microbial Reactions


General form of a process equation for a growth process:

Biomass Examples
+ substrate (energy source, electron donor)

+ electron acceptor O2, NO3-, CO2, org. substances,…


+ nutrients P, N, …
=
more biomass
+ metabolites H2O, CO2, …
+ products Org. substances

27
Chair of Urban Water Systems Engineering
Technical University of Munich

Stoichiometry of Microbial Reactions


Cell composition and stoichiometry
• Composition of bacteria: ≈ 80% water; ≈ 20% dry material (90% of which is organic and ≈ 10% is inorganic)

• The most important chemical elements in organisms are:


C N P S H O
• The elemental composition of a bacteria cell the following proportions are typical:

C 51% 250 atoms


H 10% 611 atoms
O 21% 77 atoms
N 13% 55 atoms
P 3% 6 atoms
S 1% 1 atom
plus trace elements

28
Chair of Urban Water Systems Engineering
Technical University of Munich

Stoichiometry of Microbial Reactions


Cell composition and stoichiometry
• The most widely used empirical formula for the organic fraction of cells is

C5H7O2N
• When phosphorus / sulfur are also considered:

C60H87O23N12P
• or

C250H611O77N55P6S

• these cumulative chemical formulations are approximations only and may vary with time and species

• all of these components should be obtained from the medium and the absence of any of them could
limit the growth of the bacterial population

29
Chair of Urban Water Systems Engineering
Technical University of Munich

Stoichiometry of Microbial Reactions


Wastewater composition and stoichiometry
• Based on a „typical composition“ of domestic sewage, wastewater may be expressed with the formula

C500H1327O532N142P16S19

considering, however, only the compounds used by chemo-organo-heterotrophic bacteria

• These formulas are cumulative chemical formulas and enable a stoichiometric calculation of
transformations, occuring in cell metabolism

30
Chair of Urban Water Systems Engineering
Technical University of Munich

Stoichiometry of Microbial Reactions


Some important metabolic process in wastewater treatment (anoxic and aerobic):

Wastewater Components Products


constituents coh cla -
bacteria bacteria O2 NO3 Me

COD X X Biomass

NH4+ X X NO3-
NO2-

NO3- X X N2

3- X X (PO43- )n in biomass
PO4
X Me PO43-

31
Chair of Urban Water Systems Engineering
Technical University of Munich

Stoichiometry of Microbial Reactions


Fundamental transformation processes:

Degradation of organic carbon (aerated → aerobic conditions)


e.g. methanol: 2 CH3OH + 3 O2 ➔ 2 CO2 + 4 H2O
Heterotrophic bacteria

Nitrification (aerated → aerobic conditions)


2 NH4+ + 3 O2 ➔ 2 NO2- + 2 H2O + 4 H+ (nitritation)
2 NO2- + O2 ➔ 2 NO3- (nitratation)
Autotrophic bacteria

Denitrification (not aerated → anoxic conditions)


5 CH3OH + 6 NO3- ➔ 5 CO2 + 7 H2O + 3 N2 + 6 OH-
Heterotrophic bacteria

32
Chair of Urban Water Systems Engineering
Technical University of Munich

Stoichiometry of Microbial Reactions


Scheme of metabolism of chemo organo heterotrophic bacteria:

wastewater Syn- biomass


thesis

waste

decom waste
position

oxygen Energy waste


prod.

energy

33
Chair of Urban Water Systems Engineering
Technical University of Munich

Stoichiometry of Microbial Reactions


Fundamental transformation processes:

Degradation of organic carbon (aerated → aerobic conditions)


e.g. methanol: 2 CH3OH + 3 O2 ➔ 2 CO2 + 4 H2O
Heterotrophic bacteria

Nitrification (aerated → aerobic conditions)


2 NH4+ + 3 O2 ➔ 2 NO2- + 2 H2O + 4 H+ (nitritation)
2 NO2- + O2 ➔ 2 NO3- (nitratation)
Autotrophic bacteria

Denitrification (not aerated → anoxic conditions)


5 CH3OH + 6 NO3- ➔ 5 CO2 + 7 H2O + 3 N2 + 6 OH-
Heterotrophic bacteria

34
Chair of Urban Water Systems Engineering
Technical University of Munich

Scheme of metabolism of chemo organo heterotrophic bacteria (Denitrification)

wastewater Syn- Biomass


thesis

waste

decompo waste
sition

Nitrate Energy
prod.

energy
35
Chair of Urban Water Systems Engineering
Technical University of Munich

Stoichiometry of Microbial Reactions


Fundamental transformation processes:
Degradation of organic carbon (aerated → aerobic conditions)
e.g. methanol: 2 CH3OH + 3 O2 ➔ 2 CO2 + 4 H2O
Heterotrophic bacteria

Nitrification (aerated → aerobic conditions)


2 NH4+ + 3 O2 ➔ 2 NO2- + 2 H2O + 4 H+ (nitritation)
2 NO2- + O2 ➔ 2 NO3- (nitratation)
Autotrophic bacteria

Denitrification (not aerated → anoxic conditions)


5 CH3OH + 6 NO3- ➔ 5 CO2 + 7 H2O + 3 N2 + 6 OH-
Heterotrophic bacteria

36
Chair of Urban Water Systems Engineering
Technical University of Munich

Scheme of metabolism of chemo-litho autotrophic bacteria (nitrosomonas,


nitritation)

wastewater
Syn- biomass
thesis

waste

waste

oxygen Energy
prod.

energy

37
Chair of Urban Water Systems Engineering
Technical University of Munich

Scheme of metabolism of chemo-litho autotrophic bacteria


(nitrobacter/nitrospira, nitratation)

wastewater
Syn- biomass
thesis

waste

waste
oxygen Energy
prod.

energy

38
Chair of Urban Water Systems Engineering
Technical University of Munich

Fundamentals of microbial metabolism, stoichiometry,


process kinetics and biological process models

- Bacterial Growth and Biomass Yield -

39
Chair of Urban Water Systems Engineering
Technical University of Munich

Bacterial Growth and Biomass Yield


Biomass yield Y
• The ratio of the amount of biomass produced to the amount of substrate consumed is defined as

g biomass produced
Biomass yield Y =
g substrate utilized

• Y is typically defined relative to the electron donor. E.g.

Heterotrophic reactions with organic substrates:


g biomass / g organic substrate

Nitrification:
g biomass / g NH4-N oxidized

40
Chair of Urban Water Systems Engineering
Technical University of Munich

Bacterial Growth and Biomass Yield


Example for a biomass yield: YH for aerobic heterotrophic growth
(see also Lecture 12 Wastewater Characteristics II)

Y: The ratio of the amount of biomass g biomass produced


produced to the amount of substrate Y=
consumed
g substrate utilized

biodegradable
organic
material
New cells
(COD produced)
Y
utilized by
heterotrophs 1
(biodegradable
O2 consumption
COD utilized)
(for energy
production)
1-Y
Typical values for heterotrophs : Y = 0.5 to 0.67 g COD of Biomass / g COD substrate
41
Chair of Urban Water Systems Engineering
Technical University of Munich

Bacterial Growth and Biomass Yield


Yield coefficients of relevant microorgansims in wastewater treatment

• The biomass synthesis yield is related to the energy produced by the electron transfer

• The energy production that occurs from the oxidation reduction reactions is reduced as the electron acceptor is
changed from oxygen to nitrate to sulfate and CO2

• Moreover, conversion of CO2 to cellular carbon compounds requires more energy. Autotrophic bacteria must therefore
spend more of their energy for synthesis than do heteroptrophs

• These aspects are reflected in the synthesis of yield coefficient!


42
Chair of Urban Water Systems Engineering
Technical University of Munich

Bacterial Growth and Biomass Yield


Estimating Biomass Yield and Oxygen Requirements from Stoichiometry

Example for the stoichiometric meaning of the biomass yield

Degradation of organic matter assumed to be in the form of glucose (C6H12O6)

New cells are assumed here to be represented by C5H7NO2

→ 3 C6 H12 O6 + 8 O2 + 2 NH3 2 C5H7NO2+ 8 CO2 + 14 H2 O


3(180) 8(32) 2(17) 2(113)

→ ΔC5H7NO2 2(113) g/mol


Y= = = 0.42 g cells / g glucose used
ΔC6 H12 O6 3(180) g/mol

43
Chair of Urban Water Systems Engineering
Technical University of Munich

Bacterial Growth and Biomass Yield


Estimating Biomass Yield and Oxygen Requirements from Stoichiometry
Example for the stoichiometric meaning of the biomass yield
When COD is used to represent the organic matter and cells :

C6 H12 O6 + 6 O2 6 CO2 + 6 H2 O
180 6(32)

→ specific COD = 192/ 180 = 1.067 g O2 / g glucose


The theoretical yield expressed in terms of COD therefore is (with 1.42 g COD/g biomass VSS) (see example 3,
Wastewater Char. II) :

ΔC5H7NO2 2(113) g/mol 1 g glucose


Y= = = 0.39 g cells / g COD used
ΔC6 H12 O6 (3(180) g/mol ) 1.07 g COD
and

Y = (0.39 g cells / g COD used) 1.42 gCOD / g cells = 0.56 g COD / gCOD used

44
Chair of Urban Water Systems Engineering
Technical University of Munich

Indirect Characterization of Organic Substances - Interrelationships


Solution to Example 3 (from Lecture 12):

C5H7NO2 + 5 O2 → 5 CO2 + NH3 + 2 H2O


C5H7NO2 : mw = 113 g/mol
O2 : mw = 32 g/mol
COD = 5 * 32/113 = 1.42 mg O2 / mg C5H7NO2

TOC = (5 * 12)/113 = 0.53 mg TOC / mg C5H7NO2

TOC 0.53 COD


→ = = 0.37 = 2.7
COD 1.42 TOC

Note: C5H7NO2 is often assumed to be a typical composition of biomass.

45
Chair of Urban Water Systems Engineering
Technical University of Munich

Bacterial Growth and Biomass Yield


Estimating Biomass Yield and Oxygen Requirements from Stoichiometry

Example for the stoichiometric meaning of the biomass yield:

1 - Y = 1 – 0.56 = 0.44 g O2 / g COD used

46
Chair of Urban Water Systems Engineering
Technical University of Munich

Bacterial Growth and Biomass Yield


Estimating Biomass Yield and Oxygen Requirements from Stoichiometry
Example for the stoichiometric meaning of the biomass yield:

The same result is obtained by using the stoichiometry directly (see slide 43):
8 (32) g O2
= 0.44 g O2 / g COD used
(3(180) g/mol ) 1.07 g COD/g glucose

or by a mass balance:

COD utilized = COD cells produced + COD of oxidized substrate

Oxygen consumed = COD utilized - COD cells produced

(3(180) g glucose/mol )1.07 g O2/g glucose - (2(113) g cells/mol) 1.42 g O2/g cells

= 577.8 - 320.9 = 256.9 g O2


256.9 g O2
= 0.44 g O2 / g COD used
(3(180) g/mol ) 1.07 gCOD/g glucose

47
Chair of Urban Water Systems Engineering
Technical University of Munich

Fundamentals of microbial metabolism,


stoichiometry, process kinetics and biological
process models

- Kinetics of microbial reactions -

48
Chair of Urban Water Systems Engineering
Technical University of Munich

Kinetics of microbial reactions


Definition
Kinetics: decription of the velocity at which a chemical reaction proceeds

= mathematical description

with consideration of the relevant


boundary conditions (e.g. temperature, pressure, concentrations

dc
Velocity: M L-3 T-1 kg m-3 h-1
dt
• The degradability of substrate and activity of the organisms determine the velocity at
which a substrate is degraded and its behavior

Both aspects together have to be considered

49
Chair of Urban Water Systems Engineering
Technical University of Munich

Kinetics of microbial reactions


Some basic reaction types
Hypothesis The rate is directly dependent on the substrate concentration

rate = f ( cs )

with k :reaction constant

rate = k cs0 0 (zero) order reaction

rate = k cs1 1st order reaction

rate = k cs2 2nd order reaction

50
Chair of Urban Water Systems Engineering
Technical University of Munich

Kinetics of microbial reactions


Graphical representation of the reaction order

rate Reaction First Order cs

-ks Cs1
Reaction Zero Order
-ks Cs0

cs t

rate – cs - Diagram c - t - Diagram

51
Chair of Urban Water Systems Engineering
Technical University of Munich

Kinetics of microbial reactions


Enzyme-Catalyzed Reaction

Enzyme • chemically: protein

• Symbol: E

• substrate specific catalyst

Hypothesis Each reaction within a cell requires a specific enzyme

52
Chair of Urban Water Systems Engineering
Technical University of Munich

Enzyme-Catalyzed Reaction
• The metabolism processes within the organisms are understood as a chain of enzyme-catalyzed reactions

• Mathematically, enzyme-catalyzed reactions are usually described by a model based on the work of
Michaelis and Menten (1913)

• Reaction equation to describe the formation and decay of the enzyme-substrate-complex:

Principle

enzyme + substrate  enzyme-substrate-complex  enzyme + product

S Substrate
r1 r3
E + S ES E + P E Enzyme
r2 ES Enzyme-substrate-complex
P Product
r1,r2,r3 reaction rates
53
Chair of Urban Water Systems Engineering
Technical University of Munich

Single reactions and rate expressions


r1 r3
E + S ES E + P
r2

r1
E + S ES r1 = k1cEcS
cE , cS , cES =
concentrations [mol /L³];
r2
ES E + S r2 = k2cES k1 [L³ mol-1 T-1],k2,k3 [T-1]
= rate constants,

r3 r = partial reaction
ES E + P r3 = k3cES

54
Kinetics of microbial reactions
Chair of Urban Water Systems Engineering
Technical University of Munich

r1 r3
Rate of change for the components E + S ES E + P
dcS r2
= -r1 + r2 = - k1cEcS + k2cES
dt
dcE
= -r1 + r2 + r3 = -k1cEcS + k2cES + k3cES
dt
dcES
= r1 - r2 - r3 = k1cEcS - k2cES - k3cES
dt

dcP
= r3 = k 3cES
dt

Also, the following balance holds: cE(t) = cE0 - cES (t)

This is a type of a non-linear ordinary differential equation system that can not be solved in a closed form.
However, …
55
Chair of Urban Water Systems Engineering
Technical University of Munich

Solution
…. under certain additional assumptions, the following expression is obtained

dcS k3 cE0 cS
- =
dt k2 + k 3
cS +
k1

k 3   k 1, k 2

k2 + k 3 k2 k2
≈ Km =
k1 k1 k1

dcS cS
with rmax = k3cE0
- = r = rmax and
dt cS + Km k
Km = 2
k1
56
Chair of Urban Water Systems Engineering
Technical University of Munich

Summary
Principle
enzyme + substrate  enzyme-substrate-complex  enzyme + product

Reaction equation
r1 r3
E + S ES E + P
r2

kinetic equation dcs cs


= k3 cE0
(Michaelis & Menten) dt k2
+ cs
k1

k 3   k 1, k 2

57
Chair of Urban Water Systems Engineering
Technical University of Munich

Monod Kinetics
Monod (1949) investigated the influence of the concentration of a dissolved nutrient on the velocity of
division of microorganisms and found a simple empirical mathematical way to describe the phenomenon
which is used until today:

dX 1 S Monod
+ = µ = μ max
dt X kinetics
Ks + S
This relation is very similar to the relation that Michaelis and Menten (1913) reported based on enzymatic
considerations.

Monod and Michaelis & Menten are therefore often confused with each other in literature.

Nevertheless, the theory of Michaelis & Menten and the resulting equations can describe the complex
reaction sequences, as they are present in organism cells, and are also related to the change of substances
outside the cell when certain assumptions are valid.

58
Chair of Urban Water Systems Engineering
Technical University of Munich

Kinetics of microbial reactions


Kinetics of substrate utilization
• The theory of Michaelis & Menten and the resulting equations can be used to describe complex reaction
sequences in organism cells.

• However, certain assumption must be valid

• If these assumptions hold, the following relation results:

dS S
- = rSXmax X
dt S + KS

with
rSXmax = maximum substrate utilization rate related to biomass [M/(M T)]
KS = Half saturation constant [M/V]
S = Substrate concentration outside the organism [M/V]
X = Biomass concentration (all species X = Σ Xspecies j ) [M/V]

59
Chair of Urban Water Systems Engineering
Technical University of Munich

Kinetics of microbial reactions


Kinetics of biomass growth

dS - dX dX S
- = = rSXmax YXS X
dt dS dt S + KS

with YXS = Yield coefficient [M/M]

dX 1 S
= rSXmax YXS
dt X S + KS

S
μ = μmax
S + KS

μ = growth rate [1/T]; μmax = maximum growth rate [1/T]

60
Chair of Urban Water Systems Engineering
Technical University of Munich

Kinetics of microbial reactions


Resulting reaction equations

dS 1 S
dt = μ X
YXS max
Ks + S

rsx max

dX S µ : growth rate, T-1


+ = µX = μ max X
dt - dX
Ks + S = const = YXS
dS

S
r = µX = μ max X
Ks + S
61
Chair of Urban Water Systems Engineering
Technical University of Munich

Kinetics of microbial reactions


Graphical representation
S S
S << KS ρ = μ max X ≈ μ max X
KS + S KS
S
S >> KS : ρ = μ max X ≈ μ max X
KS+ S
ρ
S→0

S→

μ max X
2

Ks S
62
Chair of Urban Water Systems Engineering
Technical University of Munich

Fundamentals of microbial metabolism,


stoichiometry, process kinetics and biological
process models

Model expressions for important


biological processes

63
Chair of Urban Water Systems Engineering
Technical University of Munich

Model expressions for important biological processes


Representation of biomass
• Biomass in the reactors are mixed cultures (unknown detailed composition)

• Therefore, biomass is described as a whole, without considering the detailed structure in the cell and
the detailed composition

• It is usually measured in pCOD or VSS

64
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Technical University of Munich

Model expressions for important biological processes


Representation of processes

• The mathematical description of the process rates depends on the properties of the substances used
(e.g., dissolved, colloidal, particulate) and the mechanisms in the process (e.g., inhibition, surface
limitation, …)

• The following expressions are examples of simple descriptions that have been proven to be of value

• However, there are many different formulations of empirical and theoretical nature in the literature that
may be used alternatively and lead to similar results!

• The expressions used, the substances incorporated, and the way the phenomena are described depend
on the situation and the question to be answered!

65
Chair of Urban Water Systems Engineering
Technical University of Munich

Model expressions for important biological processes


Growth of microorganisms
• The growth rate μ, depends on a number of factors such as temperature, pH, substrate- and nutrient concentration, toxicity,…

• Very often the empricial equation of Monod is used to describe the dependency of μ on the substrate concentration

ρ =μX

S
ρ = μmax X
KS + S
µ : growth rate, T-1
ρ = process rate [M L-³ T-1]
μmax = maximum growth rate at the given conditions (temperature, pH,..) [T-1]
KS= Half saturation coefficient for the substrate [MS L-³]
S = substrate concentration [MS L-³]
X = Biomass concentration [MX L-³]

66
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Technical University of Munich

Model expressions for important biological processes


Growth of microorganisms
• The value of μmax is e.g. dependend on the type of organism and on temperature

• Temperature dependency is often described by

μmax(T) = μmax(T0) exp[θ (T-T0)]

T = Temperature [°C]
T0 = reference Temperature [°C]
Θ = Temperature coefficient [°C-1]
μmax(T), μmax(T0) = μmax at T and T0

67
Chair of Urban Water Systems Engineering
Technical University of Munich

Model expressions for important biological processes


Decay and maintenance of microorganisms
• Decay processes describe a number of different processes that result in a loss of biomass. Therefore, decay is a
lumped process consisting of several single processes

• a living organism needs energy independently of growth, for

- renewing macromolecules (without synthesis of new cells)


- mobility
- maintaining inner structure and osmotic barriers
- etc.

• Under aerobic conditions the required energy is e.g. obtained through respiration of cell internal reserves (endogenous
respiration), this results in oxygen consumption independently of growth (reproduction)

• Additional losses of biomass result from predation by protozoa

68
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Technical University of Munich

Model expressions for important biological processes


Decay and maintenance of microorganisms
• Three different main concepts for the description of these processes may be distinguished:

- Endogenous Respiration

- Lysis

- Maintenance

• Each of these processes can describe phenomena regarding the decay and energy requirements of
biomass (all of them contribute to the whole „truth“). However, often just one process is chosen.

69
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Technical University of Munich

Model expressions for important biological processes


Endogenous Respiration:

Direct respiration of endogenous substances (cell internal reserves) to gain energy independently from growth /
reproduction

• Educts: Biomass, oxygen or an alternative electron donor


• Products: Metabolites (CO2, H2O, etc.), nutrients, inert particulate matter (nbpCOD)
• Direct oxygen consumption
- +
electron donor (e.g. O2)

-
Non biodegradable
biomass Endogenous
particulate matter
respiration
(nbpCOD)

nutrients
metabolites

70
Chair of Urban Water Systems Engineering
Technical University of Munich

Model expressions for important biological processes


Endogenous Respiration:
The rate of endogenous respiration is proportional to the biomass present

ρ∼ X

ρ = process rate [M L-³ T-1]


X = concentration of biomass [MX L-³]
bend = endogenous respiration rate [T-1]

The rate expression depends on the situation. If aerobic endogenous respiration is considered the rate may be
expressed as
O2
ρ = bend X
KO2 + O2

KO2 = half saturation constant for oxygen [M L-³ ]


O2 = dissovled oxygen concentration [M L-³]

to express that oxygen is needed

71
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Technical University of Munich

Model expressions for important biological processes


Lysis
• Break up of cells
• Educts: Biomass
• Products: Several products, e.g. biodegradable organic matter, and nonbiodegradable particulate matter (nbpCOD), nutrients
• No direct oxygen consumption, however, it results in indirect oxygen consumption through use of lysis products (bCOD)

non biodegradable
particulate organic
matter (nbpCOD)

biomass lysis Biodegradable


organic matter
- (bCOD)

nutrients
+

72
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Technical University of Munich

Model expressions for important biological processes


Lysis
The process is usually described by a first-order reaction:

ρ = blysis X

ρ = process rate [M L-³ T-1]


X = concentration of biomass [MX L-³]
blysis = decay rate for lysis [T-1]

73
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Technical University of Munich

Model expressions for important biological processes


Maintenance
• Utilization of external substrate to gain energy independently from growth / reproduction (without synthesis of new cells)
• Educts: Substrate, oxygen
• Products: None, energy
• Direct oxygen consumption

electron donor (O2)


-
substrate Maintenance No products (only energy)

74
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Technical University of Munich

Model expressions for important biological processes


Maintenance
The process is proportional to the biomass

ρ∼ X

ρ = process rate [M L-³ T-1]


X = concentration of biomass [MX L-³]

Oxygen and substrate are needed. The process rate may therefore e.g. be expressed as

O2 S
ρ = bmaint X
KO2 + O2 KS + S

KO2 = half saturation constant for oxygen [M L-³ ]


O2 = dissolved oxygen concentration [M L-³]
S = substrate concentration [MS L-³]
X = Biomass concentration [MX L-³]
bmaint = decay rate maintenance [T-1]
75
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Model expressions for important biological processes


Hydrolysis of colloidal and particulate organic matter
• Usually, microorganisms can utilize only dissolved material (e.g. rbCOD)

• Exoenzymes (released in the external medium ) lead to hydrolysis reactions outside the cell, in the
liquid medium, converting large and complex substrate molecules into smaller and simpler molecules,
which can then pass through the cell membrane to become available for consumption by the cell.

Hydrolysis makes particulate or colloidal organic material available for microbial


metabolism

76
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Technical University of Munich

Model expressions for important biological processes


Hydrolysis
• Converts particulate matter into smaller compounds
• Educts: particulate matter
• Products: dissolved matter (sometimes also non-biodegr. may be included)
• No oxygen consumption

Dissolved non biodegradable organic


matter (nbsCOD)

Particulate Dissolved biodegradable organic


organic Hydrolysis matter (rbCOD)
matter

Dissolved nutrients

77
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Technical University of Munich

Model expressions for important biological processes


Hydrolysis
• Hydrolysis is a surface limited reaction and requires contact between heterotrophic organisms and particulate
substances. The rate can be described by a rate often used for surface limited reactions:

C/X
ρ = khyd X
KX + C/X

ρ = process rate [M L-³ T-1]


kH = hydrolysis rate constant [MC MX-1 T-1]
K = hydrolysis saturation constant [MC M-1]
C = concentration of particulate substances [MC L-³]
X = heterotrophic biomass [MX L-³]

• Hydrolysis is a process, that is characterized by the interrelation of many different factors, microorganism types and
different particulate and colloidal substances.

• It is a sum of several processes and the described equations allow only for a very simplified description and are mainly
of empirical nature.

78
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Technical University of Munich

Model expressions for important biological processes


Hydrolysis extreme cases Microorganisms (X)
Microorganisms (X)

C/X >> KX : The amount of microorganisms limits the reaction. The process rate
simplifies to:

C/X C/X
ρ = khyd X ≈ khyd X= khyd X
KX + C/X C/X

79
Chair of Urban Water Systems Engineering
Technical University of Munich

Model expressions for important biological processes


Hydrolysis extreme cases
Microorganisms (X) Microorganisms (X)

C/X << KX : The supply of particulate matter is the limiting factor. The process rate simplifies to:

C/X C/X khyd


ρ = khyd X ≈ khyd X= K C
KX + C/X KX X

80
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Technical University of Munich

Model expressions for important biological processes


Inhibition
• Microbiological processes are often inhibited by certain substances (i.e. run more slowly). These substances can be:

(1) Substances not involved in the reaction but being toxic or in competition with the reacting substances
(competitive inhibition)

(2) High concentrations of substrates (substrate inhibition)

(3) High concentrations of products of the reaction (product inhibition)


• It is usually described by:

KI
ρinhibited = ρnot inhibited
KI + Si

KI = Saturation coefficient for inhibition [M L-³]


Si = concentration of inhibiting substance [M L-³]
ρnot inhibited = reaction rate e.g. described by one of the expressions mentioned before

81
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Note:

• The kinetic parameters (and especially the maximum growth rate µmax and the half saturation constants K)
are no unique parameters!

• They represent the net effect of certain factors of microbial kinetics on the simultaneous degradation of a
variety of different wastewater constitutents

• They depend on:

- conditions in the environment (temperature, pH, …), and


- the type and composition of the microbial population and the substrate

and, therefore have to be determined experimentally (or have to be calibrated/fitted for a certain situation)!

82
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Technical University of Munich

Values of kinetic and stoichiometric expressions in


different design procedures
procedure µN bA bH YN YH GV KN
[ 1/d ] [ 1/d ] [ 1/d ] [ gTS/gNH4 ] [ kg/kg ] [-] [ mg/l ]
EPA 0,288 − 0,06 − 0,7 oTS/BSB 0,6 1
Eckenfelder 0,276 0,034 0,068 0,2 TS/BSB 0,7 1 ) oTS/BSB 0,75 0,5
0,55 1 b) oTS/BSB

Sen 0,210 0,075 0,104 0,133 TS/CSB 0,45 2 ) 0,75 0,22


oTS/CSB
0,272 2 b) oTS/CSB
Denmark − − − − 0,7 - 0,8 TS/BSB − −
Japan − − 0,025 - 0,035 − 0,5 - 0,6 TS/BSB − −
Austria 0,342 0,050 0,180 −  − 1
Switzerland 0,29 − − −  − −
Barnard 0,202 0,050 0,180 − 0,45 oTS/CSB 0,83 −
WRC 0,113 0,03 0,180 0,10 0,45 oTS/CSB 0,83 0,31
A 131 0,319 3 ) 0,031 0,057 − 0,6  0,7 −
TS/BSB
Denika ‘89 0,319 0,032 0,056 0,15 TS/BSB 0,6  0,7 1
TS/BSB
range 0,11-0,34 0,03-0,075 0,025-0,18 − − 0,6-0,83 0,22 - 1,0
Wichern (1996) 83
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Range of kinetic and stoichiometric parameters of


the design procedures

Souce: Wichern et al. (2004) 84


Chair of Urban Water Systems Engineering
Technical University of Munich

Examples for the use of kinetic expressions in the calculation of


the aerobic Sludge Age in design procedures for AS systems
pH influence
no decay rate

no decay rate

pH influence

Source: Wichern et al. 2004 85


Chair of Urban Water Systems Engineering
Technical University of Munich

Limitation by more than one substance

• In biological processes, a multitude of different substances are transformed that are needed as
reactants (substrate, nutrients, biomass)

• The Monod kinetics has turned out to be useful to describe the substrate limitation for microbial growth
in biochemical processes

• To describe that more than one substance is needed for a process to run, often multiplication of different
Monod terms is applied

• Although this multiplication is not based on biochemical fundamental considerations it has turned out to be
a useful possibility to describe kinetic relationships in a mathematically easy way

86
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Limitation by more than one substance


Example for a description of aerobic growth of heterotrophs as used in ASM1 (activated sludge model No 1, a
dynamic simulation model)

Metabolism works only if

substrate and electron acceptors are available:

S O2
Aerobic growth of heterotrophs ρ = μH,max XH
KS + S KO2 + O2

ρ = process rate [M L-³ T-1] electron donor electron


μH,max =maximum growth rate of heterotrophs [T-1] and carbon acceptor
KS , KO = Half saturation coefficients [M L-³] source
S, O2 = concentration of rbCOD, Oxygen [MS L-³]
X H= active heterotrophic biomass concentration [MX L-³]

87
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Technical University of Munich

Limitation by more than one substance


Example for a description of anoxic growth of heterotrophs as used in ASM1 (activated sludge model No 1, a
dynamic simulation model)

Anoxic growth of heterotrophs (Denitrification)


S NO KO2
ρ = μH,max η XH
KS + S KNO + NO KO2 + O2

electron donor Electron Inhibition


and carbon acceptor by oxygen
source
ρ = process rate [M L-³ T-1]
μH,max =maximum growth rate of heterotrophs [T-1]
KS , KNO , KO = Half saturation coefficients [M L-³]
S, O2, NO = concentration of rbCOD, Oxygen, Nitrate and Nitrite [MS L-³]
X H= active heterotrophic biomass concentration [MX L-³]
η = correction factor for anoxic growth
88
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Technical University of Munich

Fundamentals of microbial metabolism,


stoichiometry, process kinetics and biological
process models

Process Model Equation Systems

89
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Technical University of Munich

Process Matrix Representation


Simplified example: Process equation:
• Growth of heterotrophic biomass 0 = -a Ss – (-b) O2 + XH
• Decay of heterotrophic biomass
• Aerobic conditions
-: represents used components
• No nitrification
+: represents generated components

Component i XH SS O2 Process rate rj

Process rate j

1 Growth 1 -1/YH 1-1/YH μmax (SS/(SS+KS)) XH

2 Decay -1 0 bH XH

Reaction rate
ri = Sr =Sv
ij ij rij

Substrate
Biomass

demand
Oxygen
90
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Process Matrix Representation


Component i XH SS O2 Process rate rj

Process rate j

1 Growth 1 -1/YH 1-1/YH μmax (SS/(SS+KS)) XH

2 Decay -1 0 bH XH

Substrate
Biomass

demand
Oxygen
Biomass production dXH/dt = rXH = μmax (SS/(SS+KS)) XH - bH XH

Substrate utilization dSs/dt = rS = - 1/YH μmax (SS/(SS+KS)) XH

Oxygen demand dO2/dt = rO2 = (1-1/YH) μmax (SS/(SS+KS)) XH


91
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SI

Soluble inert organic matter (nbsCOD) -1

Readily biodegradable substrate (rbCOD) YH


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SS XI

Particulate inert organic matter (nbpCOD)

Slowly biodegradable substrate (sbCOD)


1

Active heterotrophic biomass


XS XH

Active autotrophic biomass


XA

Particulate products arising from biomass


XP

decay (nbpCOD)

Oxygen
SO

YH
-(1-YH)
O

Nitrate and nitrite


SN

NH4 and NH3 nitrogen


-ixB
SNH

Soluble biodegradable organic nitrogen


SND

Particulate biodegradable organic nitrogen


XND

Alkalinity
SALK

-ixB/14

Note: XI and XP may also be modelled together using one expression only
ρ = μH,max XH
Process rate

KS + S
O2
Example: The process matrix of the ASM1 (one row)

KO2 + O2

92
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Example 1 for a simple dynamic model (not the ASM)


Heterotrophic growth in a batch reactor (e.g. BOD-test, neglecting nitrification)

Biodegradable COD is considered as fully readily biodegradable

dXH
= Biomass growth rate + (-1) Biomass decay rate
dt
dSS
= - (1/YH) Biomass growth rate + 0
dt
dXI
= 0 + (f) Biomass decay rate
dt

dO2
= (1-1/YH) Biomass growth rate + (-1+f) Biomass decay rate
dt

93
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Technical University of Munich

Example 1 for a simple dynamic model (not the ASM)

XH = Heterotrophic Biomass [mg COD/l];


SS = readily biodegradable organic substances (rbCOD) [mg COD/l]
O2 = dissolved Oxygen [mg O2/l];
SI = non-biodegradable soluble organic material (nbsCOD) [mg COD/l]
XI = non-biodegradable particulate organic material (nbpCOD) [mg COD/l]
YH = Biomass Yield of Heterotrophic Biomass;
f = Production of XI in the decay process

Matrix
Process rate XH SS XI O2 SI

μmax (SS/(SS+KS)) (O2/(O2+KO2)) XH 1 -1/YH 0 1-1/YH 0

bH (O2/(O2+KO2)) XH -1 0 f f-1 0

94
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Example 1 for a simple dynamic model (not the ASM)


Resulting ODE system (if no in - or outflow is considered)

dXH
= μmax (SS/(SS+KS)) (O2/(O2+KO2)) XH - bH (O2/(O2+KO2)) XH
dt

dSS
= -(1/YH) μmax (SS/(SS+KS)) (O2/(O2+KO2)) XH
dt
dXI
= f bH (O2/(O2+KO2)) XH
dt

dO2
= (1-1/YH) μmax (SS/(SS+KS)) (O2/(O2+KO2)) XH + (f-1) bH (O2/(O2+KO2)) XH
dt

95
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Technical University of Munich

Example 1 for a simple dynamic model


Simulation results (organic material)

XI and SI

0
t

96
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Technical University of Munich

Example 1 for a simple dynamic model

Simulation results (Oxygen)

0 t

The term O2/(O2+KO2) could be neglected in the given simulation, since O2 is >> KO2

97
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Technical University of Munich

Example 1 for a simple dynamic model (not the ASM)

Accumulated organic material remaining (i.e. COD remaining)

O2
O2 consumed
rbCOD consumption until t

COD nbCOD
total biomass produced
until t

nbCO Biomass
D remaining
at t
0 t

98
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Technical University of Munich

Example 2 for a simple dynamic model (not the ASM)


Heterotrophic growth in a batch reactor (e.g. BOD-test, neglecting Nitrification)
Biodegradable COD is considered as rbCOD and sbCOD

dXH
= Biomass growth + (-1) Biomass decay + 0
dt
dSS
= (-1/YH) Biomass growth + 0 + Hydrolysis
dt
dXI
= 0 + (f) Biomass decay
dt
dXS
= 0 + 0 + (-1) Hydrolysis
dt
dO2
= (1-1/YH) Biomass growth + (-1+f) Biomass decay
dt
dSI
= 0
dt

99
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Technical University of Munich

Example 2 for a simple dynamic model (not the ASM)


XH = Heterotrophic Biomass [mg COD/l];
SS = readily biodegradable organic substances (rbCOD) [mg COD/l]
XS = slowly biodegradable organic substances (sbCOD) [mg COD/l]
O2 = dissolved Oxygen [mg O2/l];
SI = non-biodegradable soluble organic material (nbsCOD) [mg COD/l]
XI = non-biodegradable particulate organic material (nbpCOD) [mg COD/l]
YH = Biomass Yield of Heterotrophic Biomass;
f = Production of XI in the decay process

Process rate XH SS XI O2 XS SI

μmax (SS/(SS+KS)) (O2/(O2+KO2)) XH 1 -1/YH 0 1-1/YH 0 0

bH (O2/(O2+KO2)) XH -1 0 f f-1 0 0

kHyd ((XS /XH)/(XS/XH +KX)) XH 0 1 0 0 -1 0

parameter values were not changed compared to the first model to show the effect of the new
process and COD fraction

100
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Example 2 for a simple dynamic model (not the ASM)


Resulting ODE system (if no in- or outflow is considered)

dXH
= μmax (SS/(SS+KS)) (O2/(O2+KO2)) XH + (-1) bH (O2/(O2+KO2)) XH
dt
dSS
= (-1/YH) μmax (SS/(SS+KS)) (O2/(O2+KO2)) XH + kHyd ((XS /XH)/(XS/XH +KX)) XH
dt
dXI
= (f) bH (O2/(O2+KO2)) XH
dt
dX (-1) kHyd ((XS /XH)/(XS/XH +KX)) XH
S =
d
t
dO2
= (1-1/YH) μmax (SS/(SS+KS)) (O2/(O2+KO2)) XH + (f-1) bH (O2/(O2+KO2)) XH
dt

dSI
= 0
dt

101
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Example 2 for a simple dynamic model (not the ASM)

Simulation results (organic material)

XI and SI

0 t

102
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Example 2 for a simple dynamic model (not the ASM)


Simulation results (Oxygen)

0 t

The term O2/(O2+KO2) could be neglected in the given simulation, since O2 >> KO2

103
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Example 2 for a simple dynamic model (not the ASM)


Accumulated organic material remaining (i.e. COD remaining)

O2
rbCOD
consumed
until t
sbCOD nbCOD
COD
total biomass produced
until t

nbCO Biomass
D remaining
t at t
0

104
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Biological Nutrient Removal (BNR) Facilities

Dr.-Ing. Benedikt Aumeier


Prof. Dr.-Ing. Jörg E. Drewes
18 January 2024
Slides with background information, review on your own
1
Chair of Urban Water Systems Engineering
Technical University of Munich

The Activated Sludge Process

https://www.youtube.com/watch?v=R9R9jYUvgSI 2
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Technical University of Munich

Reactor Configurations – Complete mix

Source: Suez Degremont Handbook 3


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Technical University of Munich

Reactor Configurations – Plug-flow

Source: Suez Degremont Handbook 4


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Technical University of Munich

Reactor Configurations – Step feed

Source: Suez Degremont Handbook 5


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Technical University of Munich

Reactor Configurations – Ditch type

Source: Suez Degremont Handbook 6


Two (2) Stage with Internal Recycle (IR)
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Technical University of Munich

Modified Ludzack-Ettinger (MLE) Process

Source: Hazen and Sawyer 2016 7


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Technical University of Munich

Anaerobic / Anoxic and Oxic (A 2/O) Process 3 Stage/1 IR


Anaerobic/anoxic and oxic (A2/O) Process

Sedlak: 1991
Source: Hazen and Sawyer 2016 8
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Biological Nutrient Removal (BNR) Processes


• Modified Ludzack-Ettinger (MLE) Process – continuous-flow suspended-growth process with an initial anoxic stage followed by an
aerobic stage; used to remove TN

• A2/O Process – MLE process preceded by an initial anaerobic stage; used to remove both TN and TP

• Step Feed Process – alternating anoxic and aerobic stages; however, influent flow is split to several feed locations and the recycle
sludge stream is sent to the beginning of the process; used to remove TN

• Bardenpho Process (Four-Stage) – continuous-flow suspended-growth process with alternating anoxic/aerobic/anoxic/aerobic stages;
used to remove TN

• Modified Bardenpho Process – Bardenpho process with addition of an initial anaerobic zone; used to remove both TN and TP

• Sequencing Batch Reactor (SBR) Process – suspended-growth batch process sequenced to simulate the four-stage process; used to
remove TN (TP removal is inconsistent)

• Modified University of Cape Town (UCT) Process – A2/O Process with a second anoxic stage where the internal nitrate recycle is
returned; used to remove both TN and TP

• Rotating Biological Contactor (RBC) Process – continuous-flow process using RBCs with sequential anoxic/aerobic stages; used to
remove TN

• Oxidation Ditch – continuous-flow process using looped channels to create time sequenced anoxic, aerobic, and anaerobic zones; used
to remove both TN and TP.

9
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Average of COD and NH4-N Effluent Concentrations


of WWTPs across Germany

DWA (2018). Leistungsvergleich 2017 10


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Technical University of Munich

Average of Total N and Total P Effluent


Concentrations of WWTPs across Germany

DWA (2018). Leistungsvergleich 2017 11


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Technical University of Munich

Average Influent and Effluent Concentrations and


Performance of WWTPs across Germany

DWA (2018). Leistungsvergleich 2017 12


Chair of Urban Water Systems Engineering
Technical University of Munich

Activated Sludge Processes I


- Modeling Suspended and Attached Growth Systems

Prof. Dr.-Ing. Jörg E. Drewes


25 January 2024

Slides with background information, review on your own


1
Chair of Urban Water Systems Engineering
Technical University of Munich

Suspended and attached growth


Suspended growth treatment processes:
• The active biomass is suspended in and transported with the liquid phase

• The technologies that use suspended biomass mimic natural systems where biomass is suspended
and transport through advection, turbulence, and others dominates (e.g., lakes, lagoons, rivers)

Attached growth treatment processes:


• The active biomass is attached to a surface and the water flows
relative to the biomass

• Biofilm technologies mimic natural systems where the attached biomass dominates the processes (e.g.,
in shallow rivers)

2
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Technical University of Munich

Suspended and attached growth


Suspended growth treatment processes

Example: Activated sludge system

3
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Technical University of Munich

Suspended and attached growth


Bacterial - Floc
(green: EPS , red: Bacteria)

CLSM image CLSM image

Source: Christian Staudt, Thomas Neu, UFZ, Department Fließgewässerökologie 4


Chair of Urban Water Systems Engineering
Technical University of Munich

Suspended and attached growth


Attached growth treatment processes

Example: Trickling filter

5
Chair of Urban Water Systems Engineering
Technical University of Munich

Suspended and attached growth


Biofilm
(green: EPS , red: Bacteria)

150
100
50
0

z [µm]
-50
-100
-150
-200
100 µm -250
-300
0 5 10
Oxygen concentration
[mg/l]
6
Chair of Urban Water Systems Engineering
Technical University of Munich

Suspended and attached growth


Biofilm
(green: EPS , red: Bacteria)

Biofilm 3 D
Area: 500 x 500 µm

7
Chair of Urban Water Systems Engineering
Technical University of Munich

Mass balances for dynamic and steady-state conditions


Important (ideal) reactor types
Batch reactor:
• No inflow
• No outflow

Inflow
Ideal continuous completely stirred tank reactor
(CSTR) (Durchlauffermenter):
• with suspended biomass Outflow

Plug Flow reactor:


Inflow Outflow

8
Chair of Urban Water Systems Engineering
Technical University of Munich

Mass balances for dynamic and steady state conditions


Important reactor types
Inflow
Activated sludge system:
• Reactor with suspended biomass and organism
recycling

Sludge Recycling

Biofilm-fixed bed-reactor: Inflow

Outflow

9
Chair of Urban Water Systems Engineering
Technical University of Munich

Mass balances for dynamic and steady state conditions


Ideal continuous flow completely stirred tank

with suspended biomass


Q,
Outflow
Cin
Q, Cout
biological reactions ri

C Inflow
C is everywhere the same in the reactor Czu
and Creactor = Cout
Reactor Outflow
C Cout

Location

10
Chair of Urban Water Systems Engineering
Technical University of Munich

Mass balances for dynamic and steady state conditions


Mass balance of a CSTR

Assumption: Perfect Mixing (CSTR, Completely stirred tank reactor)

System boundary

Qi
n
Ci
n
Qout
Cout
V
C

11
Chair of Urban Water Systems Engineering
Technical University of Munich

Mass balances for dynamic and steady-state conditions


General written statement for a mass balance :

Time variation of Mass of the Mass of the Mass of the


the mass of the = component that - component that component
+-
component in the goes into the leaves the system produced or
system system per time per time consumed by
reactions per time

accumulation = inflow - outflow + generation


(Positive or negative sign)

The input and output terms are transport terms and depend upon the physical
characteristics of the system being modeled (and the reactor type)

12
Chair of Urban Water Systems Engineering
Technical University of Munich

Mass balances for dynamic and steady-state conditions


The Notion of Mass balances
General written statement for a CSTR :

Time variation of Mass of the Mass of the Mass of the


the mass of the = component that - component that component
+-
component in the goes into the tank leaves the tank produced or
tank per time per time consumed by
reactions per time

d(VC)
dt = Σ Qin Cin – Σ Qout Cout + V ri

13
Chair of Urban Water Systems Engineering
Technical University of Munich

Mass balances for dynamic and steady-state conditions


Mass balance of a CSTR
d(VCi)
dt = Qin Ci,in – Qout Ci,out + V ri

dCi dV
V + Ci = Qin Ci,in – Qout Ci,out + V ri
dt dt

If the volume does not change:


dCi Qin Qou
dt = Ci,in – t Ci,out + ri
V V ri: reaction rate of component i (sum of reactions or
net reaction rate if there are more reactions) [M / L³ T]

transport conversion V: Volume [L³]

By defining the dilution rate D=Qin/V : Qin,Qout : flow [L³ / T]

dCi Cin, Cout, C: Concentrations of component i [M/L³]


= D Ci,in – D Ci,out + ri
dt
14
Chair of Urban Water Systems Engineering
Technical University of Munich

Mass balances for dynamic and steady-state conditions


Steady-state simplification

If only the steady-state (long-term) concentration is of interest :

accumulation = inflow + outflow + generation

=0

0 = inflow + outflow + generation

15
Chair of Urban Water Systems Engineering
Technical University of Munich

Mass balances for dynamic and steady-state conditions


Mass balances for conservatives
Examples for conservatives gas N2
(in an aerated tank) System boundary

influent Biological effluent


processes
N P N
COD or ThoD*
COD or
ThoD* P

*ThoD (Theoretical Oxygen demand) is the


conservative form of COD (COD analysis input waste N
recovers only a fraction of the ThOD, typically O2 (sludge) COD or ThoD*
95% in domestic wastewater) (negative P
COD or ThOD)

16
Chair of Urban Water Systems Engineering
Technical University of Munich

Mass balances for dynamic and steady-state conditions


Mass balances for conservatives
Examples for conservatives gas N2
System boundary
(in an aerated tank)

influent Biological effluent


processe
Flow: Qin Flow: Qout
s V
Substrate: Sin Substrate: Sout
XB,H, XD

input waste
O2 (sludge) Flow: QW

17
Chair of Urban Water Systems Engineering
Technical University of Munich

Mass balances for dynamic and steady-state conditions


Continuity in the processes for conservatives
Processes j Components i Process
equations
Component 1 Component 2 Component 3 Component n
1
2 ʋ ji ρj
3
m
ri

ρj : Process equation for process j m m


ri : summed up reaction equation for component i ri = Σ j=1 rji = Σj=1 ʋji ρ j
ʋji : stoichiometric constant

The continuity can be checked by moving across the matrix

Providing consistent units have been used, the sum of the stoichiometric coefficients must be zero
! 18
Chair of Urban Water Systems Engineering
Technical University of Munich

Mass balances for dynamic and steady-state conditions


Continuity: Example for a simple kinetic model
(heterotrophic bacteria growth in an aerobic environment)

Process Components Process


equations
Substrate Nutrient Het. Oxygen Non biodegr.
ρ
S SNH4-N Biomass O2 part. org. matter
X XI

(rbCOD, (NH4 (het. (O2, (measured as


measured measured organisms negative COD)
as COD) as N) measured COD)
as COD)
growth - 1 / YH -iN,BM 1 1-1/YH µmax (S/(S+KS))X
decay iN,BM - -1 -(1-fXI) fXI bX
iN,XI*fXI
fXI : Portion that generates XI in endogenous respiration (port. of inert org. products) [gCOD/gCOD]
iN,BM : N content of biomass [gN / gCOD]
iN,XI : N content of XI [gN / gCOD] à See also example 4 in Lecture 12 (but rel. to COD)
YH : Aerobic synthesis Yield of heterotrophic biomass [g COD / g COD]

19
Chair of Urban Water Systems Engineering
Technical University of Munich

Mass balances for dynamic and steady state conditions


Continuity: Example for a simple model
(heterotrophic bacteria growth in an aerobic environment)
Process Components Process
equations
Substrate Nutrient Het. Oxygen Non biodegr.
ρ
S SNH4-N Biomass O2 part. org. matter
X XI

(rbCOD, (NH4 (het. (O2, (measured in


measured measured organisms negative COD)
as COD) as N) measured COD)
as COD)
growth - 1 / YH -iN,BM 1 1-1/YH µmax (S/(S+KS))X
decay iN,BM - -1 -(1-fXI) fXI bX
iN,XI*fXI
COD in growth : 1*(-1/YH) + 1*(1) +(-1)*(1-1 / YH) = 0
COD in decay : 1*(-1) + (-1)*(-(1-fXI)) + 1*fXI = 0
N in growth : (1)*(-iN,BM) + iN,BM*(1) = 0
N in decay : (1)*(iN,BM-iN,XI*fXI) + iN,BM*(-1) + iN,XI* fXI = 0

20
Chair of Urban Water Systems Engineering
Technical University of Munich

Continuous flow systems with suspended biomass (a simple AS system)


A simple activated sludge system

Activated sludge tank


oxygen
Secondary clarifier
Inflow (prim. effl.)
effluent

Excess sludge
Return sludge

21
Chair of Urban Water Systems Engineering
Technical University of Munich

Continuous flow systems with suspended biomass (a simple AS system)


A simple activated sludge system
oxygen

Q
Q+QR
Q-QW
XT,0 XT,e Ce Se
C0 V
XT C S QW+QR
S0
QW
QR XT,R CR SR XT,w Cw Sw

XT : Total suspended solids concentration

C : concentration of pollutants (dissolved and particulate)

22
Chair of Urban Water Systems Engineering
Technical University of Munich

Continuous flow systems with suspended biomass (a simple AS system)


Mass balance around the aeration tank
oxygen System
boundary

Q
Q+QR
XT,0
C0 V
S0 XT
CS

QR
SR CR XT,R

V dX
dt = Q XT,0 – (Q+QR ) XT + QR XT,R + rXT V
T XT : Total suspended solids concentration

V dC
dt = Q C0 – (Q+QR ) C + QR CR + rC V
C : concentration of pollutants (dissolved and particulate)

23
Chair of Urban Water Systems Engineering
Technical University of Munich

Continuous flow systems with suspended biomass (a simple AS system)


Mass balance around the secondary clarifier
• It is assumed that there are no biological reactions in the secondary clarifier
• The sludge blanket level in the secondary clarifier is assumed to remain constant, i.e. the storage of
XT in the secondary clarifier is negligible System
boundary
XT (Q+QR)
(Q-QW) XT,e

(QW+QR) XT,w
QW XT,w
QR XT,R

0 = (Q+QR) XT – (Q-QW) XT,e – (QR+QW) XT,W

24
Chair of Urban Water Systems Engineering
Technical University of Munich

Continuous flow systems with suspended biomass (a simple AS system)


Mass balance around the whole system

System
boundary

Q XT
(Q-QW) XT,e

XT,0

QW XT,w

V dX
dt = Q XT,0 – [(Q-QW ) XT,e + QW XT,R ] + rXT V
T XT : Total suspended solids concentration

V dC
dt = Q C0 – [(Q-QW ) Ce + QW CT,R ] + rC V
C : concentration of pollutants (dissolved
and particulate)

25
Chair of Urban Water Systems Engineering
Technical University of Munich

Continuous flow systems with suspended biomass (a simple AS system)


Total suspended solids Mass Balance (alternative view)

V dX
dt = Q XT,0 – (Q+QR ) XT + QR XT,R + rXT V
T

0 = (Q+QR) XT – (Q-QW) XT,e – (QR+QW) XT,W

0 +V dXT = (Q+QR) XT – (Q-QW) XT,e – (QR+QW) XT,W +Q XT,0 – (Q+QR ) XT + QR XT,R + rXT V
dt
dXT = – (Q-Q ) X – (Q ) X +Q X + r V Which is the same expression as obtained with the total mass
à dt W T,e W T,W T,0 XT balance (XT,R = XT,w )

26
Chair of Urban Water Systems Engineering
Technical University of Munich

Continuous flow systems with suspended biomass (a simple AS system)


Total suspended solids mass balance
Many models of the simple activated sludge process assume that
• the amount of sludge in the secondary clarifier is negligible,
• there are no biological reactions in the secondary clarifier,
• the volume of the secondary clarifier is negligible

With these assumptions, the secondary clarifier does not appear in the mass balance:
V dX
dt = Q XT,0 – [(Q-QW ) XT,e + QW XT,R ] + rXT V
T

With the assumption that the concentration of biomass in the influent is negligible (XT,0 = 0) :

1 dXT (Q-QW ) XT,e + QW XT,R rXT


= +
XT dt V XT XT
Definitions:
XT : Total suspended solids concentration
(Q-QW ) XT,e + QW XT,R DX : Dilution rate of XT
DX =
V XT
μn : net production rate of XT
rXT
µn =
XT 27
Chair of Urban Water Systems Engineering
Technical University of Munich

Continuous flow systems with suspended biomass (a simple AS system)


With

V dX
dt = Q XT,0 – [(Q-QW ) XT,e + QW XT,R ] + rXT V
T

1 dXT = D + µ
X n
XT dt
The operation of the AS system often aims at keeping the concentration of XT constant by adjusting QT,W * XT,w to the
production of XT,w in the system.

Over long periods this gives:

∫ (1/XT) (dXT / dt) dt = 0


∫ DX dt = ∫ µn dt
or

DX ,mean = µn, mean

28
Chair of Urban Water Systems Engineering
Technical University of Munich

Continuous flow systems with suspended biomass (a simple AS system)


DX determines whether, a specific organism group can exist in the system

Therefore, DX (or more often its inverse value SRT) is considered the most important design
parameter for activated sludge systems

1/DX = SRT (solids retention time or sludge age)

Solids mass in the reactor


SRT =
Solids removed from system

29
Chair of Urban Water Systems Engineering
Technical University of Munich

Continuous flow systems with suspended biomass (a simple AS system)


Hydraulic retention time 𝝉 vs. solids retention time (SRT)

Systems with sludge recycling 𝝉 < SRT

Systems without sludge recycling


𝝉 = SRT

1 Volume of liquid in the system


= HRT = 𝝉 =
Dh Volume of liquid removed from the system

1 Solids mass in the reactor


DX = SRT =
Solids removed from system

30
Chair of Urban Water Systems Engineering
Technical University of Munich

Continuous flow systems with suspended biomass (a simple AS system)


Effect of SRT on the performance of an activated sludge system
(red Substrate, blue Biomass)

gVSS/m³

gCOD/m³
gCOD/m³

Wash out Wash out


Values used:
Si ∞= KS (1+kd (1/DX) )/((1/DX) (µmax-kd)-1) Y=0.4 gVSS/gCOD
μmax = 5 gVSS/gVSS d
X∞ = (Dh/Dx)Y (Si,in – Si,∞ )/(1+kd*(1/DX) ) kd = 0.1 gVSS/gVSSd
Ks = 10 gCOD/m³
Sin Substrate (bsCOD) Sin =192 gCOD/m³
wash out at DX >= µmax - Xin = 0
S in+ KS kd V = 197 m³
Q = 1000 m³/d
31
Chair of Urban Water Systems Engineering
Technical University of Munich

Continuous flow systems with suspended biomass (a simple AS system)


Effect of SRT on the performance of an activated sludge system
(red Substrate, blue Biomass)

gVSS/m³
gVSS/m³

gCOD/m³
gCOD/m³

Wash out Wash out


Values used:
Y=0.4 gVSS/gCOD
Si ∞= KS (1+kd (SRT) )/((SRT) (µmax-kd)-1) μmax = 5 gVSS/gVSS d
kd = 0.1 gVSS/gVSSd
X∞ = (SRT/𝝉)Y (Si,in – Si,∞ )/(1+kd*(SRT) )
Ks = 10 gCOD/m³
Substrate (bsCOD) Sin =192 gCOD/m³
Xin = 0
V = 197 m³
Q = 1,000 m³/d
32
Chair of Urban Water Systems Engineering
Technical University of Munich

Simple activated sludge system, design equations using simple rate expressions

Terminology used in the following expressions


• In the following formulation of kinetic expressions biodegradable soluble COD (bsCOD) will be used to
quantify the fate of biodegradable organic compounds because it relates easily to the stoichiometry of
substrate oxidized or used in cell growth

• For complete-mixed suspended growth designs if the SRT is 3 d or more, essentially all of the
degradable particulate COD will be converted to bsCOD

• The biomass solids in a bioreactor are commonly measured as total suspended solids (TSS) and
volatile suspended solids (VSS). The mixture of solids resulting from combining recycled sludge with
influent wastewater in the bioreactor is termed mixed liquor suspended solids (MLSS) and mixed liquor
volatile suspended solids (MLVSS)

• Besides the organic (volatile) fractions of solids the influent wastewater contains inorganic total
suspended solids (iTSS or termed FSS in former lectures)

33
Chair of Urban Water Systems Engineering
Technical University of Munich

Simple activated sludge system, design equations using simple rate expressions
Mass balances for soluble substrate and biomass

dS = Q S – QS + r V
V dt 0 SU

V dX
dt = Q X0 – [(Q-QW ) Xe + QW XR ] + rg V
where
dX
= rate of change of biomass concentration in the reactor measured as gVSS/m³ d
dt
V : reactor volume (i.e. aeration tank), [m³]
Q : influent flowrate, [m³/d]
X0 : concentration of biomass in influent, [g VSS/m³]
S0 : influent soluble substrate concentration, [g/m³]
QW : waste sludge flowrate [m³/d]
Xe : concentration of biomass in effluent, [gVSS/m³]
XR : concentration of biomass in return line from clarifier [gVSS/m³]
rg : net rate of biomass production, [ gVSS/m³ d]
rSU : rate of substrate concentration change due to utilization, [g/m³ d]

34
Chair of Urban Water Systems Engineering
Technical University of Munich

Simple activated sludge system, design equations using simple rate expressions
Kinetic Process Matrix However, other
The simple process matrix below can be used to describe the aerobic system (X in the matrix is expressions may
described in COD units): be equally valid

Process Soluble Biomass O2 Xinert


Substrates
growth - 1/Y 1 -1/Y+1 µmax S
X
S + KS
decay -1 fd-1 fd kd X

Note: The soluble substrate can e.g. be


organic substances if X are heterotrophs
or e.g. ammonia, nitrite if X are autotrophs
α=1 for heterotrophic growth

Xinert : non biodegradable part. org. matter


35
Chair of Urban Water Systems Engineering
Technical University of Munich

Simple activated sludge system, design equations using simple rate expressions
Ranges of kinetic coefficients often used (VSS based)

µmax/Y

Remember: the kinetic parameters are not unique and may change
depending on the specific loal condition!
36
Chair of Urban Water Systems Engineering
Technical University of Munich

Simple activated sludge system, design equations using simple rate expressions
Rate of Utilization of Soluble Substrates Corresponds to:

37
Chair of Urban Water Systems Engineering
Technical University of Munich

Simple activated sludge system, design equations using simple rate expressions
Net production rate of biomass Corresponds to:

μ is defined here such that it corresponds to a


net growth rate of growth - decay

When biomass is expressed in VSS :

38
Chair of Urban Water Systems Engineering
Technical University of Munich

Simple activated sludge system, design equations using simple rate expressions
Corresponds to:
Rate of Oxygen Uptake

However, the term f kd is not


included in the equation for ro

(given earlier in example Biomass is expressed here in VSS


in former lecture, and in
lecture notes)

(defined earlier)

(defined earlier)

39
Chair of Urban Water Systems Engineering
Technical University of Munich

Simple activated sludge system, design equations using simple rate expressions
Rate of nbVSS production from cell debris
Corresponds to:

40
Chair of Urban Water Systems Engineering
Technical University of Munich

Important Yield Expressions


Yield Expressions
Besides the synthesis yield two other yield terms are important in the design and analysis of biological
treatment processes:

• Synthesis Yield (or true Yield)


The amount of biomass produced during cell synthesis relative to the amount of substrate degraded

• Net Biomass Yield


The ratio of the net biomass growth rate to the substrate utilization rate

• Observed Yield
Accounts for the actual solids production that would be measured for the system

41
Chair of Urban Water Systems Engineering
Technical University of Munich

Important Yield Expressions


Synthesis Yield (defined in earlier lectures)

The amount of biomass produced during cell synthesis relative to the amount of substrate degraded

• Typically defined relative to the electron donor

• affected by
the energy that can be derived from the oxidation reduction reaction,
by the growth characteristics of the carbon source,
by the nitrogen source, and
by environmental factors such as temperature, pH, and osmotic pressure.

42
Chair of Urban Water Systems Engineering
Technical University of Munich

Important Yield Expressions


Net Biomass Yield

The net biomass yield is the ratio of the net biomass growth rate to the substrate utilization rate

(defined earlier)

(defined earlier)

43
Chair of Urban Water Systems Engineering
Technical University of Munich

Important Yield Expressions


Observed Yield
The observed yield accounts for the actual solids production that would be measured for the system (calculated as
gTSS/g bsCOD or gBOD, or as gVSS/g bsCOD or g BOD)

(defined earlier)

(defined earlier)

44
Chair of Urban Water Systems Engineering
Technical University of Munich

Important Yield Expressions


Observed Yield

VSS production PX,VSS


Yobs =. =
Substrate removed Q(S0-S)

(defined earlier)

if there is no nbVSS in the influent

45
Chair of Urban Water Systems Engineering
Technical University of Munich

Important Yield Expressions


Observed yield vs synthesis yield
Synthesis yield (or true yield) Observed yield

• amount of biomass produced • Includes also cell loss concurrent with cell
immediately upon consumption of the growth
growth substrate or oxidation of the electron
donor

• takes into account only the biomass • Contains other organic solids from the
(cells) produced wastewater that are measured as VSS, but
are not biologically degradable

• Seldom measured directly and often • Based on actual measurements of


interpreted frome evaluating biomass biomass production and substrate
production data for reactors operating under consumption
different conditions or based on theoretical
considerations

46
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions

Biomass Mass Balance

System
boundary
Q X0 rg V
(Q- Xe
QW)
VX

QW Xw

47
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions
Biomass Mass Balance

48
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions
Biomass mass balance and solids retention time
At steady state and with X0 = 0 :

and

VX
= (defined earlier)
rg V

49
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions
Substrate effluent concentration

50
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions
Substrate Mass Balance

System
boundary
Q S0 rSU V
(Q- Se
QW)
VS

QW Sw

51
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions
Substrate Mass Balance and Biomass concentration

At steady state :

and with

52
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions
Mass Balance of nbVSS

V dXi = Q Xi,0 – [(Q-QW ) Xi,e + QW Xi,R ] + rX,i V


dt

System
boundary
Q Xi,0 rX,i V
(Q- Xi,e
QW)
V Xi

QW Xi,w

53
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions
Mass Balance of nbVSS

V dXi = Q Xi,0 – [(Q-QW ) Xi,e + QW Xi,R ] + rX,i V


dt

At steady state :

0 = Q Xi,0 – V Xi + fd kd X V because
SR
T (and SRT is valid for all fractions of the mixed liquor)

(given earlier)

54
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions
Total Volatile Suspended Solids in the tank
• In general :

total VSS = biodegradable VSS + non biodegradable VSS


total VSS = bVSS + nbVSS
• The biomass in the aeration tank is measured here as VSS
• The total VSS in the aeration tank equals the biomass concentration plus the nbVSS concentration:

total VSS in the tank = biomass + nbVSS

• The kinetic expressions used to describe the biological processes are related to the active biomass
concentration (microorganisms) in the treatment reactor (X).
• the fraction of active biomass can vary depending on the wastewater characteristics and operating
conditions.

55
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions
Mixed liquor suspended solids (MLSS) and Mixed liquor volatile suspended solids (MLVSS)

• The mixture of solids resulting from combining recycled sludge with influent wastewater in the bioreactor is termed
MLSS and MLVSS, respectively.

Biomass + nonbiodegradable Volatile Suspended Solids nbVSS + inert inorganic total suspended solids (iTSS or FSS)

MLSS = Biomass + nbVSS + FSS


MLVSS = Biomass + nbVSS

MLSS = VSS in the tank + FSS in the tank


MLVSS = VSS in the tank

56
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions
Mixed liquor volatile suspended solids concentration (MLVSS)
• The total MLVSS in the aeration tank equals the biomass concentration plus the non biodegradable VSS (nbVSS)
concentration:

XT = X + Xi
With the expressions for X and Xi (given earlier):

57
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions
Effect of SRT on the performance of an activated sludge system

58
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions
Production rate of total VSS in the tank
total VSS in the tank = biomass + nbVSS
or XT = X + Xinert

and d(VSS) = d(biomass) + d(nbVSS)


d d d
t t t
or dXT dX dXinert
dt = dt + dt
with
V dXi = Q Xi,0 – [(Q-QW ) Xi,e + QW Xi,R ] + rX,i V
dt

and

àV dX T = – [(Q-QW ) Xi,e + QW Xi,R ] – [(Q-QW ) Xe + QW XR ] + Q Xi,0 + rX,i V + rg V


dt

Production 59
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions
Production rate of total VSS in the tank
With the expressions for rg and rXi (given earlier), and the nbVSS in the influent:

fd may vary from 0.1 to 0.15 gVSS/gVSS

= rXi

60
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions
Solids Production
The amount of VSS produced and wasted daily is determined as follows:

Note: 1/SRT represents the fraction of solids wasted per day


Because the mixed liquor is a homogeneous mixture, the expression can be
used to calculated the amount of solids wasted of any of the mixed liquor
components
PX component * SRT = V*Xcomponent

with
(given earlier)

à PXT,VSS

61
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions

Solids Production
with (given earlier)

62
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions
Active Biomass

because: X/XT = PX / PXT,VSS

(defined earlier)

(defined earlier)

(defined earlier)

63
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions
Solids Production
To calculate the solids production in terms of TSS the influent inorganic solids are added and the biomass is calculated in
terms of TSS by assuming a VSS/TSS ratio of 0.85:

However, the VSS/TSS ratio may vary from 0.8 to 0.9

64
Chair of Urban Water Systems Engineering
Technical University of Munich

The simple activated sludge system, design equations using simple rate expressions
MLSS, MLVSS and aeration tank volume

(given earlier)

This equation allows for a

determination of the aeration volume

by selecting an appropriate

MLSS concentration in the range of 2,000 to 4,000 mg/L

(must be compatible with the sludge settling characteristics and the clarifier design)
65
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The simple activated sludge system, design equations using simple rate expressions
COD mass balance and oxygen requirements
Oxygen used = CODin - CODout

oxygen System
boundary
Q
(Q-QW) CODeffluent
CODinfluent

QW CODwaste

66
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The simple activated sludge system, design equations using simple rate expressions
PX,bio includes active biomass and cell debris from cell growth and is the sum of terms A and B in:

(given earlier)

67
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Design and Operating Parameters


Important design and operating parameters for activated sludge systems

• Solids retention time (SRT) German: „Schlammalter “


• Food to microorganism ratio (F/M) German: „Schlammbelastung BTS“
• Volumetric (organic) loading rate (Lorg)

68
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Design and Operating Parameters


Food to microorganism ratio (F/M)

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Design and Operating Parameters


F/M ratio and Efficiency
The F/M ratio can be related to the specific substrate utilization rate by the process efficiency :

U: Specific Substrate Utilization rate

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Design and Operating Parameters


F/M ratio, SRT, and Efficiency
Furthermore with and :

and

And with the relation between U, F/M and E :

71
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Design and Operating Parameters


Discussion of the F/M ratio
• The F/M ratio is historically the most important design parameter to design simple activated sludge systems.

• However, the F/M ratio is based on a highly simplified consideration of the process.

• Effects of loading variations e.g. over a day are only considered by experience.

• The F/M ratio is problematic if more complex processes are to be designed (e.g. if chemical elimination of P is
included, a big portion of the return sludge consists of precipitates, changing the relation between process performance
and F/M ratio.

• The F/M ratio only considers the BOD and is therefore not suitable if other aspects besides the BOD elimination
have to be considered

72
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Design and Operating Parameters


• High sludge ages are associated with low F/M ratios, and vice versa

• High F/M ratio: can mean a larger offer of biodegradable organic matter than the consumption capacity of the biomass
in the system, resulting in surplus substrate in the final effluent

• Low F/M ratio: can mean that the substrate offer is lower than the microorganisms‘ capacity to use it in the activated
sludge system. As a consequence, they will consume practically all the organic matter from the influent wastewater,
as well as their own cellular material

73
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Design and Operating Parameters


Organic Volumetric Loading rate (Lorg)

74
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Design and Operating Parameters


Solids Retention Time (SRT)

• The SRT is more suitable than the F/M ratio especially when Nitrification and Denitrification is to be incorporated. The
SRT is based on the growth rate of microorganisms in the aerated tank independently of the type of e.g. P-Elimination

• The SRT is based on a steady state consideration and effects of loading variations e.g. over a day are only
considered by experience

• For given values of the kinetic coefficients, the effluent substrate concentration from the reactor is a direct function of
the SRT. Setting the SRT value fixes the values of U and μ and also defines the efficiency of biological waste
stabilization

75
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Design and Operating Parameters


Process Performance and Stability
• The critical SRT at which the cells are washed out of the system is the minimum SRT SRTmin. When washout occurs S = S0.

• Using the simple expressions introduced earlier SRTmin is given by :

If S0 is much greater than KS (which is often encountered in wastewater treatment) :

To ensure adequate treatment and avoid system failure, biological treatment processes are operated with a design SRT
value from 2 to 20 times SRTmin

à Corresponds to a Safety Factor SF = SRTdesign/SRTmin

76
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Activated Sludge Processes II


- Modeling Suspended Growth Systems for Biological Nutrient
Removal (BNR)

Prof. Dr.-Ing. Jörg E. Drewes


1 February 2024

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Biological Nitrogen Removal

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Example for a single sludge suspended growth system


Example for a single sludge suspended growth system:
• Bacteria: Aerobic autotrophic bacteria in suspended or attached growth systems

3
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Example for a two sludge suspended growth system

effluent

• In cases where there is a significant potential for toxic and inhibitory substances in the
wastewater,
• First aeration tank/clarifier unit: Operated at a short SRT for BOD removal.
Removal of BOD and toxic substances
• Second unit:
Nitrification can proceed unhindered.

4
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Example for a two sludge suspended growth system


WWTP Munich II – Gut Marienhof

Born and Ermel, 2022 5


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Example for the concentration change along the flow axis in an


attached growth reactor (nitrifying trickling filter)
Nitrification starts only,
when COD degradation is lower Competition for oxygen !
concentration

àmost of the BOD must be removed


before nitrifying organisms can be
established

The heterotrophic bacteria dominate


the surface area of fixed-film systems
over nitrifiying bacteria

NH4-N COD NO3-N


distance
à Nitrifying trickling filters are often designed with 50% of the load (resulting in a
doubling of the volume) and the upper and lower part may be designed separately
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Nitrification – Stoichiometry (suspended or attached)


The two-step process is involving two groups of bacteria:

Nitrosomonas: Ammonia à nitrite;

Nitrospira, nitrobacter: Nitrite à Nitrate

• The stoichiometry of the growth of nitrifiers is based on


- the conservation of COD (1 g NO3--N corresponds to - 4.57 g COD) - and the conservation
of nitrogen

• The yield coefficient of the nitrifiers is often defined as the nitrifiers produced per nitrogen oxidized to nitrate

7
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Nitrification – Dominant Bacteria


ARTICLE doi:10.1038/nature16461 LETTER doi:10.1038/nature16459

Complete nitrification by Nitrospira Complete nitrification by a single microorganism


bacteria Maartje A. H. J. van Kessel1, Daan R. Speth1, Mads Albertsen2, Per H. Nielsen2, Huub J. M. Op den Camp1, Boran Kartal1,3,
Mike S. M. Jetten1,4 & Sebastian Lücker1
Holger Daims1, Elena V. Lebedeva2, Petra Pjevac1, Ping Han1, Craig Herbold1, Mads Albertsen3, Nico Jehmlich4,
Marton Palatinszky1, Julia Vierheilig1, Alexandr Bulaev2, Rasmus H. Kirkegaard3, Martin von Bergen4,5, Thomas Rattei6,
Nitrification is a two-step process where ammonia is first oxidized removed ammonium and nitrite from the medium (Extended Data
Bernd Bendinger7, Per H. Nielsen3 & Michael Wagner1 to nitrite by ammonia-oxidizing bacteria and/or archaea, and Fig. 1). The culture showed anaerobic ammonium-oxidizing (anam-
subsequently to nitrate by nitrite-oxidizing bacteria. Already mox) activity (Fig. 1a), and fluorescence in situ hybridization (FISH)
described by Winogradsky in 18901, this division of labour between revealed that anammox organisms of the genus Brocadia constituted
the two functional groups is a generally accepted characteristic of the approximately 45% of all FISH-detectable bacteria. Surprisingly,
Nitrification, the oxidation of ammonia via nitrite to nitrate, has always been considered to be a two-step process catalysed biogeochemical nitrogen cycle2. Complete oxidation of ammonia to Nitrospira-like nitrite-oxidizing bacteria accounted for approximately
by chemolithoautotrophic microorganisms oxidizing either ammonia or nitrite. No known nitrifier carries out both nitrate in one organism (complete ammonia oxidation; comammox) 15% of the community and co-occurred with the Brocadia species in
steps, although complete nitrification should be energetically advantageous. This functional separation has puzzled is energetically feasible, and it was postulated that this process flocs (Fig. 2a). This tight clustering with anammox bacteria was unex-
microbiologists for a century. Here we report on the discovery and cultivation of a completely nitrifying bacterium could occur under conditions selecting for species with lower pected as both microorganisms require nitrite for growth. Together
from the genus Nitrospira, a globally distributed group of nitrite oxidizers. The genome of this chemolithoautotrophic growth rates but higher growth yields than canonical ammonia- with the presence of Nitrospira at very low oxygen concentrations, this
organism encodes the pathways both for ammonia and nitrite oxidation, which are concomitantly expressed during oxidizing microorganisms3. Still, organisms catalysing this process indicated that there could be a functional link between these organisms.
growth by ammonia oxidation to nitrate. Genes affiliated with the phylogenetically distinct ammonia monooxygenase and have not yet been discovered. Here we report the enrichment and To determine the function of Nitrospira in the community, we
hydroxylamine dehydrogenase genes of Nitrospira are present in many environments and were retrieved on Nitrospira- initial characterization of two Nitrospira species that encode all extracted and sequenced total DNA from the enrichment culture bio-
contigs in new metagenomes from engineered systems. These findings fundamentally change our picture of nitrification the enzymes necessary for ammonia oxidation via nitrite to nitrate mass. In total 4.95 gigabase pairs of trimmed metagenomic sequence
and point to completely nitrifying Nitrospira as key components of nitrogen-cycling microbial communities. in their genomes, and indeed completely oxidize ammonium to were obtained and used for de novo assembly. By differential coverage
nitrate to conserve energy. Their ammonia monooxygenase (AMO) and sequence composition-based binning5 it was possible to extract
enzymes are phylogenetically distinct from currently identified high-quality draft genomes of two Nitrospira species. The two strains
Nitrification is catalysed by ammonia-oxidizing bacteria (AOB)1 The globally distributed genus Nitrospira represents the most AMOs, rendering recent acquisition by horizontal gene transfer had genomic pairwise average nucleotide identities (ANI)6 of 75%
or archaea (AOA)2 and nitrite-oxidizing bacteria (NOB)1. Since diverse known group of NOB. Nitrospira members have been found from known ammonia-oxidizing microorganisms unlikely. We and thus clearly represented different species (Nitrospira sp.1 and sp.2,
the pioneering studies by Winogradsky more than a century ago3, in terrestrial8 and limnic habitats 9,10, marine waters11, deep sea also found highly similar amoA sequences (encoding the AMO Extended Data Fig. 2 and Extended Data Table 1). Surprisingly, both
nitrifying microorganisms are generally perceived as specialized sediments, sponge tissue12, geothermal springs13, drinking water subunit A) in public sequence databases, which were apparently genomes contained the full set of AMO and hydroxylamine dehy-
chemolithoautotrophs that obtain energy for growth by oxidizing distribution systems14, corroded iron pipes15, and wastewater treat- misclassified as methane monooxygenases. This recognition of a drogenase (HAO) genes for ammonia oxidation, in addition to the
either ammonia or nitrite. The known ammonia-oxidizing microbes ment plants (WWTPs)10,16. At least six phylogenetic sublineages of novel amoA sequence group will lead to an improved understanding nitrite oxidoreductase (NXR) subunits necessary for nitrite oxidation
(AOM) and NOB are phylogenetically not closely related, and none Nitrospira exist, of which lineage II seems to be most widely distrib- of the environmental abundance and distribution of ammonia- in Nitrospira7. In both species all these genes were localized on a sin-
of these organisms can oxidize both substrates. This separation of the uted in both natural and engineered ecosystems10. The ecological suc- oxidizing microorganisms. Furthermore, the discovery of the long- gle contiguous genomic fragment, along with general housekeeping
two nitrification steps in different organisms leads to a tight cross- cess of Nitrospira has been linked to an economical pathway for nitrite sought-after comammox process will change our perception of the genes that allowed reliable phylogenetic assignment. Consequently,
feeding interaction and the frequently observed co-aggregation of oxidation17 and a substantial metabolic versatility, which includes nitrogen cycle. these Nitrospira species had the genetic potential for the complete
AOM with NOB in nitrifying consortia4. However, the functional the utilization of various organic compounds in addition to nitrite Nitrification, the aerobic oxidation of ammonium to nitrate is oxidation of ammonia to nitrate. No AMO of canonical ammonia-
separation is a puzzling phenomenon since complete nitrification and CO210,11,17–19, cyanate or urea degradation and nitrification by divided into two subsequent reactions: ammonium oxidation to oxidizing bacteria or archaea could be detected in the trimmed
would yield more energy (∆G°′ = −349 kJ mol−1 NH3) than either reciprocal feeding with AOM19,20, and chemolithoautotrophic aerobic nitrite (equation (1)) and nitrite oxidation to nitrate (equation (2)). metagenomic reads or by amoA-specific PCR8,9 on DNA extracted
single step (∆G°′ = −275 kJ mol−1 NH3 for ammonia oxidation hydrogen oxidation21. These two reactions are catalysed by physiologically distinct clades of from reactor biomass, and no other indications for the presence of
to nitrite and ∆G°′ = −74 kJ mol−1 NO2− for nitrite oxidation to microorganisms. ammonia-oxidizing microorganisms were found in the metagenome
nitrate). Thus, an organism catalysing complete nitrification should Enrichment of conspicuous Nitrospira or by FISH analyses. The AMO structural genes (amoCAB) of both
have growth advantages over the ‘incomplete’ AOM and NOB. Based A microbial biofilm developing on the walls of a pipe under the flow NH 4+ + 1.5O2 → NO2− + H2O + 2H+ (∆G°′ = − 274.7 kJ mol –1) (1) Nitrospira species, along with the putative additional AMO subunits
on kinetic theory of optimal pathway length5,6, Costa et al.7 argued of hot water (56 °C, pH 7.5) raised from a 1,200 m deep oil exploration amoEDD210,11, formed one gene cluster with haoAB-cycAB (encoding
that a hypothetical complete nitrifier would likely be outcompeted well (Aushiger, North Caucasus, Russia) was sampled and incubated NO2− + 0.5O2 → NO3− (∆G°′ = − 74.1 kJ mol−1) (2) HAO, the putative membrane anchor protein HaoB, electron trans-
by incomplete, cross-feeding AOM and NOB in many environments. at 46 °C in ammonium-containing mineral medium to enrich mod- NH 4 + + 2O −
2 → NO3 + H2O + 2H
+
(∆G°′ = − 348.9 kJ mol –1) (3) fer protein cytochrome c554 and quinone-reducing cytochrome cm552,
However, the same authors7 also pointed out that a complete nitrifier erately thermophilic AOM. After a series of subcultivation steps, we respectively)12 and showed highest similarities to their counterparts
might be competitive under conditions that favour the maximiza- obtained enrichment culture ‘ENR4’ that oxidized ammonia to nitrate Even though the existence of a single microorganism capable of oxidiz- in betaproteobacterial ammonia-oxidizing bacteria (60% average
tion of growth yield rather than growth rate and coined the term and contained a dense population of cells morphologically resem- ing ammonium to nitrate (equation (3)) was not previously reported, amino acid identity to the Nitrosomonas europaea genes; Fig. 3 and
“comammox” (complete ammonia oxidizer) to describe such a bling described Nitrospira species13,15 (Extended Data Fig. 1a, b). it was proposed that such a microorganism could have a competitive Supplementary Table 1). The same genomic region also contained
hypothetical microbe. Conditions selecting for comammox may A second abundant population consisted of rod-shaped cells, but advantage in biofilms and other microbial aggregates with low substrate genes for copper and haem transport, cytochrome c biosynthesis, and
be characterized by slow, substrate-influx-limited growth with a no organism in ENR4 displayed the typical morphologies of known concentrations3. iron storage. These accessory genes were highly conserved in ammonia-
spatial clustering of biomass in microbial aggregates and biofilms7. AOM. Inspection by fluorescence in situ hybridization (FISH) with In this study, to characterize the microorganisms responsible for oxidizing bacteria but not in other Nitrospira7,13, indicating their
A prerequisite for the existence of comammox would also be that any nitrifier-specific ribosomal RNA-targeted probes10,22 confirmed that nitrogen transformations in an ammonium-oxidizing biofilm, we involvement in AMO and HAO biosynthesis or activation. Nitrospira
biochemical incompatibilities of ammonia and nitrite oxidation can ENR4 contained Nitrospira (Extended Data Fig. 1c) but no other sampled the anaerobic compartment of a trickling filter connected sp.1 encoded three discrete amoC genes, one of which was clustered
be overcome by adaptations of enzymes or cellular compartmentali- detectable nitrifiers. Moreover, known bacterial or archaeal genes to a recirculation aquaculture system4 with an ammonium effluent of with a second, almost identical copy of amoA (97.7% amino acid
zation7. Aside from these theoretical considerations, the old question of ammonia monooxygenase (AMO) subunit alpha (amoA) and 16S less than 100 µM. To enrich for the N-cycling community, a bioreactor identity). Nitrospira sp.2 lacked the second amoA, but contained four
of whether comammox exists in nature has not been resolved. rRNA genes of AOA were not detected by PCR in ENR4. Considering was inoculated and supplied with low concentrations of ammonium, additional amoC and a second haoA gene (Supplementary Table 1).
nitrite and nitrate under hypoxic conditions (≤3.1 µM O2). Within Unlike other Nitrospira7,13, both species lacked enzymes for assimila-
1
Department of Microbiology and Ecosystem Science, Division of Microbial Ecology, University of Vienna, Althanstrasse 14, 1090 Vienna, Austria. 2Winogradsky Institute of Microbiology, Research 12 months, we obtained a stable enrichment culture that efficiently tory nitrite reduction, indicating adaptation to ammonium-containing
Center of Biotechnology of the Russian Academy of Sciences, Leninsky Ave. 33, bld. 2, 119071 Moscow, Russia. 3Center for Microbial Communities, Department of Chemistry and Bioscience,
Aalborg University, Fredrik Bajers Vej 7H, 9220 Aalborg, Denmark. 4Helmholtz-Centre for Environmental Research - UFZ, Department of Proteomics, Permoserstrasse 15, 04318 Leipzig, Germany. 1
Department of Microbiology, IWWR, Radboud University, Heyendaalseweg 135, 6525 AJ Nijmegen, the Netherlands. 2Center for Microbial Communities, Department of Chemistry and Bioscience,
5
Helmholtz-Centre for Environmental Research - UFZ, Department of Metabolomics, Permoserstrasse 15, 04318 Leipzig, Germany. 6Department of Microbiology and Ecosystem Science, Division
Aalborg University, Fredrik Bajers Vej 7H, 9220 Aalborg, Denmark. 3Laboratory for Microbiology, University of Gent, K. L. Ledeganckstraat 35, 9000 Gent, Belgium. 4Department of Biotechnology,
of Computational Systems Biology, University of Vienna, Althanstrasse 14, 1090 Vienna, Austria. 7DVGW-Forschungsstelle TUHH, Hamburg University of Technology, Am Schwarzenberg-Campus 3,
TU Delft, Julianalaan 67, 2628 BC Delft, the Netherlands.
21073 Hamburg, Germany.

2 4 / 3 1 D E C E M B E R 2 0 1 5 | VO L 5 2 8 | NAT U R E | 5 5 5
5 0 4 | NAT U R E | VO L 5 2 8 | 2 4 / 3 1 D E C E M B E R 2 0 1 5
© 2015 Macmillan Publishers Limited. All rights reserved
© 2015 Macmillan Publishers Limited. All rights reserved
8
Chair of Urban Water Systems Engineering
Technical University of Munich

Nitrification – Stoichiometry (suspended or attached)


Energy yielding two-step oxidation process from ammonia to nitrate :

Nitrification (aerated à aerobic conditions)


2 NH4+ + 3 O2 è 2 NO2- + 2 H2O + 4 H+ (nitritation) Nitrosomonas
2 NO2- + O2 è 2 NO3- (nitratation)
Autotrophic bacteria Nitrobacter, Nitrospira

If summed up (mostly sufficient)

2 NH4+ + 4 O2 è 2 NO3- + 2 H2O + 4 H+ „Nitrifiers“

(4 ∙ 32) / (2 ∙ 14.01) = 4.57 g O2/g N oxidized


with
à 3.43 g O2/g N used for nitrite production and
1.14 g O2/ g NO2-N oxidized

9
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Sequencing batch/MBR Process Overview


• Hybrid system coupling:
– Sequencing Batch Reactor (SBR)
– Membrane Bioreactor (MBR)
• Time managed, sequential process
• Provides flexibility to easily change
operational set points MBR
Membrane
Qi Qrecirculation Qpermeate
n
React Fill Stage React Draw Stage
SBR
Anaerobi Aerobic Anoxi Aerobi Anoxic Anoxi
c c c c
0 1 2
Cycle Time [hours]

Vuono et al. (2013). J. Membrane Science 446, 34


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Impact of SRT on Microbial Diversity


• Amplicon sequencing of the
SSU rRNA (Phylogenetics)

• Disturbance followed by
recovery of SRT can restore
MLSS concentrations and
desired functions (COD- and N-
removal)

• Shortest SRT exhibits lowest


degree of diversity (Hill number)

• Same SRTs can result in


different degrees of diversity
while preserving general
function
(“functional redundancy
hypothesis” – Allison and Martiny,
Vuono et al. (2015), ISME 9, 425 2008)
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Major Bacterial Phyla

Vuono et al. (2015), ISME 9, 425


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Nitrification – Stoichiometry (suspended or attached)


Estimation of the amount of alkalinity required to carry out the reaction by rewriting the equation (neglecting
cell tissue):

NH4+ + 2 HCO3- + 2 O2 è NO3- + 2 CO2 + 3 H2O

For each g of ammonia nitrogen (as N) converted,

7.14 g of alkalinity as CaCO3 will be required (2 ∙ 50 g CaCO3 / 14)

13
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Nitrification – Stoichiometry (suspended or attached)


Biomass synthesis reaction (using C5H7NO2 as an expression for bacterial cell synthesis):

4 CO2 + HCO3- + NH4+ + H2O è C5H7NO2 + 5 O2

Expression of an equation for the overall nitrification reaction (biomass synthesis and energy production):

NH4+ + 1.863 O2 + 0.098 CO2 è 0.0196 C5H7NO2 + 0.98 NO3- + 0.0941H2O + 1.98 H+

For each g of ammonia nitrogen (as N) converted,

à 1.863∙32 / 14 = 4.25 g of O2 are utilized and

0.0196 ∙ 113/14 = 0.16 g of new cells are formed

14
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Nitrification – Stoichiometry (suspended or attached)


The oxygen required to oxidize 1.0 g of ammonia nitrogen (= 4.258 g) is
à less than the theoretical value of 4.57 g

à The alkalinity required for nitrification is 7.07 g/g instead of 7.14 g

The Yield coefficient (Ya = 0.23 g COD biomass/nitrate-N produced) of the nitrifiers expressed as the nitrifiers produced per
nitrogen oxidized to nitrate using the above equation:

Ya = (0.0196 ∙ 113 ∙ 1.42 ) / (0.98 *14.01) = 0.23 g/g

Nitrification causes a significant oxygen consumption (4.3 to 4.5 kg O2 / kg NH4-N, see above), which may vary strongly
during the day

The design of the aeration equipment has to take these aspects into account (adaption of the aeration rate along the
reactor length)

15
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Nitrification – Stoichiometry (suspended or attached)


Matrix representation

With the Yield coefficient YA the growth process can be described by a kinetic matrix, such as:

Process Autotrophic O2 Nutrients Nitrate


Biomass [O2,-COD] [NH4-N] [NO3-N]
[COD]

Autotrophic 1 (YA-4.57)/YA -iN-1/YA 1/YA ρautotrophic


growth growth

Where
iN = nitrogen content of the COD fractions, 0.065 g N/g COD
YA = Yield coefficient for autotrophs

Biomass is expressed here in COD

Decay processes can be taken into account similar to heterotrophic decay

16
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Nitrification – growth kinetics (suspended or attached)


The rate expression for growth ρautotr. Growth and decay ρend respiration (or ρdecay in general) may incorporate all limiting substances
(e.g., by a multiplication of Monod type terms and biomass, see previous lectures)

Rate expression as defined in the design procedure applied in this lecture (Metcalf & Eddy):

If dissolved oxygen is assumed to be present in excess and alkalinity is also not rate-limiting, the kinetic rate (growth and
decay) can be expressed as:

However, if dissolved oxygen is considered (nitrification rates increase up to DO concentrations of 3 to 4 mg/L):

17
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Nitrification – some aspects


• Bacteria responsible for nitrification grow much more slowly than heterotrophic bacteria (μmax)

• Nitrification is pH sensitive and rates decline significantly at pH values below 6.8. At pH values near 5.8 to
6.0, the rates may be 10 to 20% of the rate at pH 7.0

• Nitrifiers tentatively inhibit themselves (if the buffer capacity of the water is not sufficient) because their
reactions set free protones, which reduces the pH of water

• Toxicity: Nitrifiying organisms are sensitive to a wide range of organic and inorganic compounds (at
concentrations well below the concentrations that would affect aerobic heterotrophic organisms)

• Systems designed for nitrification generally require much longer hydraulic and solids retention times
than those for systems designed only for BOD removal !!!

• Typical design SRT values for nitrifiying systems may range from 10 to 20 d at 10°C to 4 to 7 d at 20°C

18
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Comparison of kinetic parameters for design purposes


Activated sludge kinetic coefficients
for heterotrophic bacteria at 20°C

Activated sludge nitrification kinetic


coefficients at 20°C

Source: Metcalf & Eddy (2000) 19


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Comparison of growth rates


6.0

Wachstumsgeschwindigkeit [1/d]
autotrophe Bakterien

5.0 heterotrophe Bakterien

4.0

3.0

2.0

1.0

0.0
0 10 20 30 40 50 60 70 80 90 100
Substratkonzentration [mg/l]
20
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Example for Concentration Profiles in a Simple Nitrifying System

O2

BOD5

NH4+

NO3-

(qualitative schematics! No CSTR, profiles simplified) 21


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Nitrification: Required Environmental Conditions


Nitrification

aerobic

O2 ●
Nitrifiers ●
NH4+ ●
NO3- Product
HCO3- ●
Sludge age 7-10 d

Souce: Gujer, 1999 22


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Biological Denitrification

23
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Biological Denitrification – Process description


• Bacteria: heterotrophic bacteria in suspended and attached growth processes

• Denitrification is the biological reduction of nitrate to nitric oxide, nitrous oxide, and nitrogen gas:

NO3- à NO2- à NO à N2O à N2


• Heterotrophic growth of facultative aerobic organisms in the anoxic zones with nitrate as electron acceptor
instead of oxygen

• Denitrification therefore requires:

(1) At least two different environmental conditions (aerobic for nitrification and anoxic for denitrification)

(2) Nitrate gets into contact with organic degradable substances

24
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Pre-anoxic Denitrification
Pre-anoxic denitrification (Modified Ludzak-Ettinger (MLE) Process)
Nitrate feed

Aerobic /
Anoxic nitrification

• Most common process used for biological nitrogen removal in municipal wastewater treatment
• Organic substrate in the influent wastewater provides the electron donor for oxidation reduction reactions using nitrate

• Nitrate concentration in the effluent ≈ nitrate concentration in the recirulation à no complete denitrification possible, but
the higher the recirculation, the better the denitrification

25
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Pre-anoxic Denitrification
Pre-anoxic Denitrification

Gujer (2012) 26
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Pre-anoxic Denitrification

7-10

DAFT
Underflow
Superna-
tant Return
Gravity
Thickener

27
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Post-anoxic Denitrification
Post-anoxic denitrification

Aerobic /
nitrification Anoxic

• BOD removal has occured first and is not available to drive the nitrate reduction reaction

• Denitrification occurs after nitrification and the electron donor source is from (anoxic) endogenous decay (however,
uptake by this process is relatively slow)

• Often, an exogenous carbon source, such as methanol or acetate, is added to provide sufficient BOD for nitrate
reduction

28
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Denitrification – Stoichiometry
Energy-yielding reaction (expressed here using e.g. C10H19O3N as an representation for biodegradable organic matter in
wastewater):

Denitrification (not aerated à anoxic conditions)


For wastewater:
C10H19O3N + 10 NO3- è 5 N2 + 10 CO2 + 3 H2O + NH3 + 10 OH-
Heterotrophic bacteria

Or for methanol:
5 CH3OH + 6 NO3- è 5 CO2 + 7 H2O + 3 N2 + 6 OH-

Or acetate:

5 CH3COOH + 8 NO3- è 10 CO2 + 6 H2O + 4 N2 + 8 OH-

29
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Technical University of Munich

Denitrification – Stoichiometry

C10H19O3N + 10 NO3- è 5 N2 + 10 CO2 + 3 H2O + NH3 + 10 OH-

1 equivalent of alkalinity is produced per equivalent of NO3-N reduced, which equates to 3.57 g of alkalinity (as CaCO3)
production per g of nitrate nitrogen reduced

In nitrification, 7.14 g alkalinity (as CaCO3) was consumed per g of NH4-N oxidized

à By denitrification about 50% of the amount transformed by nitrification can be recovered

30
Chair of Urban Water Systems Engineering
Technical University of Munich

Denitrification – Stoichiometry
Oxygen equivalent of using nitrate as electron acceptors

Metabolism of anoxic and aerobic growth of heterotrophs differs only in the energy yielding process. Per mole e- transferred
the following equivalents hold:
For oxygen:
0.25 O2 + H+ + e- è 0.5 H2O
For nitrate:
0.20 NO3- + 1.2H+ + e- è 0.1 N2 + 0.6 H2O
à 0.25 mole of O2 is equivalent to 0.2 mole of nitrate for electron transfer in oxidation reduction

Thus, the oxygen equivalent of nitrate is:


(0.25 ∙ 32 g O2 / mole)/(0.2 ∙ 14 g N / mole) ) = 2.86 g O2/g NO3-N

à Part of the oxygen that has to be put into the system can be saved because of denitrification

31
Chair of Urban Water Systems Engineering
Technical University of Munich

Denitrification – Stoichiometry
Oxygen equivalent of using nitrite as electron acceptors

For oxygen:

0.25 O2 + H+ + e- è 0.5 H2O

For nitrite:
0.33 NO2- + 1.33 H+ + e- è 0.67 H2O + 0.17
N2
The oxygen equivalent of nitrite is:

(0.25 ∙ 32 g O2 / mole)/(0.33 ∙ 14 g N / mole) ) = 1.71 g O2/g NO2-N

32
Chair of Urban Water Systems Engineering
Technical University of Munich

Estimating COD needed for Denitrification


The principal design goal in biological denitrification is the biological reduction of nitrate!

Thus, an important design parameter for denitrification processes is the amount of bsCOD or BOD needed to provide a
sufficient amount of electron donor for nitrate removal.

As a general rule, 4 g of BOD is needed per g of NO3 reduced!

The actual value will depend on the system operating conditions and the type of electron donor used for denitrification.

E.g., activated sludge process according to DWA A131:


Denitrification:

requirement for external carbon Þ 5 kg COD per kg of nitrate nitrogen to be denitrified

33
Chair of Urban Water Systems Engineering
Technical University of Munich

Estimating COD Needs for Denitrification


bsCODr = bsCODsyn + bsCODo
where

bsCODr = bsCOD utilized, g bsCOD/d


bsCODsyn = bsCOD incorporated into cell synthesis, g bsCOD/d
bsCODo = bsCOD oxidized, g bsCOD/d

bsCODsyn = 1.42 Yn bsCODr

Yn = net biomass yield, g VSS/g bsCODr (defined in previous lecture)


1.42 = conversion factor as introduced in previous lectures

Y
and Yn =
1 + (kdn) SRT

34
Chair of Urban Water Systems Engineering
Technical University of Munich

Thus,

bsCODr = bsCODo + 1.42 Yn bsCODr

and after rearrangement:

bsCODo = (1 - 1.42 Yn ) bsCODr

bsCODo is the COD oxidized and is equal to the oxygen equivalent of the NO3-N used for
bsCOD oxidation. Hence,

bsCODo = 2.86 NOx


with 2.86 being the O2 equivalent of NO3-N [g O2/g NO3-N] as given earlier

and NOx = NO3-N reduced [g/d]

à 2.86 NO3-N reduced = (1 - 1.42 Yn ) bsCODr


or 2.86
bsCOD 2.86
= and thus g bsCOD / g NO3-N =
NO3-N 1-1.42Yn 1-1.42Yn

35
Chair of Urban Water Systems Engineering
Technical University of Munich

Biological Denitrification – Stoichiometry


Matrix representation:
The process can be described by a kinetic matrix such as:

Process Substrate Hetero- O2 Nutrients NO3-N


[COD] trophic [O2,-COD] [NH4-N]
Biomass
[COD]

Heterotr. - 1/YH 1 - iN (-1/YH+1) / ρanox heterotr


anoxic growth 2.86 growth
(Denitrification)

Where iN = nitrogen content of the COD fractions, gN/gCOD

Biomass is expressed here in COD

Moreover, anoxic decay processes can be taken into account (see also postanoxic denitrific.) and are similar to aerobic
decay processes, but are typcially slower than aerobic processes.

36
Chair of Urban Water Systems Engineering
Technical University of Munich

Denitrification – Growth Kinetics


The rate expression for growth ρanox autor. Growth and decay ρend respiration (or ρdecay in general) may incorporate all limiting
substances (e.g., by a multiplication of Monod type terms and biomass, see previous lectures)

Rate expression as defined in the design procedure applied in this lecture (Metcalf & Eddy):

η = anoxic correction factor, gVSS/gVSS

η : 0.2 to 0.8 for pre-anoxic denitrification reactors fed domestic wastewater; takes
into account that
- only a portion of X is capable of dentrification (that fraction of denitrifiying bacteria
in the biomass), and that
- the maximum specific substrate utilization rate may be lower when nitrate is used
as an electron acceptor instead of oxygen

If the effect of nitrate and dissolved oxygen concentrations is to be incorporated into the rate expression :

Ko‘ = DO inhibition coefficient for nitrate reduction, mg/l


KS,NO3 = half velocity coefficient for nitrate limited reaction, mg/l
Other terms defined earlier

37
Chair of Urban Water Systems Engineering
Technical University of Munich

Example for Concentration Profiles in a Denitrifying System (preanoxic)


(qualitative schematics, no CSTR !)

O2

BOD5

NH4+

NO3-

Comment:
In this example denitrification is limited due to the supply of nitrate (concentration is zero whereas organic substances are still available).
This could be improved by an increase of the recirculation rate bringing more nitrate into the denitrification zone

Source: Gujer (2007) 38


Chair of Urban Water Systems Engineering
Technical University of Munich

Denitrification – some aspects


• Denitrification is especially fast, when large amounts of dissolved, readily biodegradable, organic
substances are available

• The volume for nitrification has to be approximatly the same as the nitrification volume without
denitrification

• N2 is only poorly soluble in water. As a result of denitrification gas bubbles can be generated and
massively disturb performance of biological treatment plants (especially when happening in the secondary
clarifier)

39
Chair of Urban Water Systems Engineering
Technical University of Munich

German Technical Design Guideline DWA A 131:

Index
:

40
Chair of Urban Water Systems Engineering
Technical University of Munich

Denitrification: Required Environmental Conditions


Denitrification

anoxic

O2 inhibits
COD ●

Het. Biomass ●
NO3- ●
HCO3- Product
Sludge age 10-20 d

Source: Gujer, 1999 41


ever, appreciable quantities are only released under acidic oxidizing (so-called Anammox) bacteria8 (planctomycetes)
Chair of Urban Water
23 Systems Engineering
conditions
Technical University ofand
Munichsuch conditions are uncommon in BNR or by DB.30 Frequently, these treatments are carried out
systems. simultaneously in single-stage systems.31,32 From a biochemical

Nitrogen Cycle

Fig. 1 Schematic representation of the proposed terminology. The continuously lined arrows indicate microbially catalyzed reaction pathways,
the dashed
Weißbach et al.lined arrows
(2017). Env. Sci.chemical
Wat. Res. &reactions,
Techn. 10, 3reaction pathways are indicted by dash-dotted lines. In yellow: The aerobic and sub-oxic reaction 42
Chair of Urban Water Systems Engineering
Technical University of Munich

Alternative Nitrogen Removal Processes:


Anaerobic Ammonium Oxidation (Anammox) or Deammonification

2 NH4+ + 4 O2 è 2 NO3- + 2 H2O + 4 H+ „Nitrifiers“

à (4 ∙ 32) / (2 ∙ 14.01) = 4.57 g O2/g N oxidized


with
3.43 g O2/g N used for nitrite production and
1.14 g O2/g NO2-N oxidized

2 NH4+ + 3 O2 è 2 NO2− + 2 H2O + 4 H+ „Shannon process“

NH4+ + NO2− è N2 + 2 H2O „Anammox


process“
à (3 ∙ 32) / (2 ∙ 14.01) = 3.43 g O2/g N oxidized

Tomorrowater.com
43
Chair of Urban Water Systems Engineering
Technical University of Munich

Biological Phosphorus Removal

44
Chair of Urban Water Systems Engineering
Technical University of Munich

Biological P Removal – General Process Description


• Chemical treatment to remove phosphorus is still the most commonly used technology

• Biological phosphorus removal has some advantages over the chemical removal (reduced chemical
costs and less sludge production as compared to chemical precipitation)

• Principle:
- Phosphorus in the influent wastewater is incorporated into cell biomass in high amounts
under certain conditions
- P is removed from the system with the waste sludge

• Bacteria: A number of bacteria is capable of storing polyphosphates. The P content of these bacteria
can amount to up to 15% („normal“ bacteria have a P content of 1-2%)

• These bacteria are grown in the treatment system and separated from the wastewater after they have
stored large amounts of P
45
Chair of Urban Water Systems Engineering
Technical University of Munich

Biological P Removal – General Process Description


A simplified way to describe the process is:

Properties of the P-assimilating organisms ( PAOs)

(1) Capable of storing excess amounts of P as polyphosphates in their cells.

(2) Under anaerobic conditions, PAOs assimilate fermentation products (e.g., volatile fatty acids)
into storage products within the cells with the concomitant release of phosphorus from stored
polyphosphates

(3) Under aerobic conditions, PAOs produce energy by the oxidation of storage products and
polyphosphate storage within the cell

46
Chair of Urban Water Systems Engineering
Technical University of Munich

Biological Phosphorus Removal Technology


Simplified biochemical model:
ANOXIC
ANAEROBIC PROCESS AND AEROBIC PROCESS

dissolved ortho- NO3- ortho-


substrate phosphate O2 phosphate

energy cell growth

energy
Poly- Poly- Poly- Poly-
substrate phosphate substrate phosphate

Source: Gujer, 1999 47


Chair of Urban Water Systems Engineering
Technical University of Munich

Biological Phosphorus Removal Technology


• The phosphate accumulating organisms (PAOs) have the possible advantage (different from the
heterotrophic organisms) that they can store substances under anaerobic environmental conditions and
assimilate acetate while other organisms are starved (therefore, a portion of the bsCOD is taken up
by the PAOs)

• These substances then allow them to grow under aerobic conditions

The process must be designed in a way that this property can be used by the organisms as an
advantage in order to grow them in the system

48
Chair of Urban Water Systems Engineering
Technical University of Munich

Biological P Removal – Process Description

effluent

dissolved ortho-
substrate phosphate ortho-
O2 phosphate

energy cell growth

energy

Poly- Poly- Poly- Poly-


substrate phosphate substr phosphate
ate

Source: Metcalf & Eddy (2000) and Gujer (2007) 49


Chair of Urban Water Systems Engineering
Technical University of Munich

Biological Phosphorus Removal Technology


NO3
COD

bio-P DN nitrification

Periodic exposure of the activated sludge organisms to selected process conditions allows control of
structure and function of heterogeneously composed microbial communities.
Note:
The preferred food source of the PAOs (low molecular weight fermentation products) would not be available
without the anaerobic zone!
The anaerobic zone provides for the fermentation of the influent bsCOD to acetate.
50
Chair of Urban Water Systems Engineering
Technical University of Munich

Example for concentration profiles in a system with biological P


elimination (UCT process)

XTSS

NO33--
NO

PO
PO44

bsCOD

(qualitative schematics)
Souce: Gujer (2007) 51
Chair of Urban Water Systems Engineering
Technical University of Munich

Source: Yang Jiang (2011) Polyhydroxyalkanoates production by bacterial enrichments (PhD Thesis TU Delft) 52
Chair of Urban Water Systems Engineering
Technical University of Munich

Fate of soluble BOD and phosphorus in reactor

53
Chair of Urban Water Systems Engineering
Technical University of Munich

Biological P Removal – Stoichiometry


• The amount of phosphorus removed by biological storage can be estimated in a simplified way from the
amount of bsCOD that is available in the wastewater influent (most of the bsCOD will be converted to
acetate in the anaerobic reactor)

• With the following assumptions:


(1) 1.06 g acetate/g bsCOD will be produced (most of the COD fermented will be converted to VFAs due to
the low cell yield of the fermentation process).
(2) A cell yield of 0.3 g VSS/g acetate
(3) A cell phosphorus content of 0.3 gP/g VSS

• Using these assumptions, about 10 g of bsCOD will be required to remove 1 g of phosphorus by the
mechanism of biological storage

• Normal cell synthesis by uptake of bCOD in the activated sludge system will result in additional
phosphorus removal

54
Chair of Urban Water Systems Engineering
Technical University of Munich

Biological P Removal – Growth kinetics


• Biological phosphorus growth kinetics are within the same order of magnitude of other heterotrophic
bacteria
Conditions:

1) Dissolved organic biologically degradable substances (volatile acids),


No Nitrate and No Oxygen must be available !
2) A subsequent reactor (aerobic or anoxic) with enough reaction time
3) The biomass must be adapted to the process (weeks)

4) The phosphorus rich sludge must be taken out of the system under aerobic conditions

For further reading on (dynamic) growth kinetics (simulation) models for biological P removal see:

-ASM 2d (IWA Task Group)


-Bio P-Model of TU Delft and related publications
55
Chair of Urban Water Systems Engineering
Technical University of Munich

Biol. P Removal: Required Environmental Conditions


Biological P Elimination
phase 1 phase 2
anaerobic aerobic

O2 inhibits ●
COD ●
PAO ● ●
NO3- inhibits
PO43- Product ●
HCO3- ●
Sludge age > 15 d
Source: Gujer, 1999 56
Chair of Urban Water Systems Engineering
Technical University of Munich

EXAMPLE
Estimating the amount of phosphorus removal

Given the following influent wastewater characteristics and the corresponding biological
process information, estimate the effluent phosphorus concentration.
•Heterotrophic synthesis yield, Y = 0.40 g VSS/g COD
•Endogenous decay coefficient, kd = 0.08 g VSS/g VSS.d
•SRT = 5 d
•Phosphorus content of PAOs = 0.30 g P/g VSS
•Phosphorus content of other bacteria = 0.02 g P/g VSS
•Clarifier effluent VSS concentration = 8 g/m3

Influent Concentration, g/m3


COD 300
bCOD 200
bsCOD 50
Phosphorus 6

57
Chair of Urban Water Systems Engineering
Technical University of Munich

Estimate the effluent phosphorus concentration. Heterotrophic synthesis yield, Y = 0.40 g VSS/g COD;
Endogenous decay coefficient, kd = 0.08 g VSS/g VSS.d; SRT = 5 d; P content of PAOs = 0.30 g P/g VSS;
P content of other bacteria = 0.02 g P/g VSS; Clarifier effluent VSS concentration = 8 g/m3

Solution

Y
Yn =
1 + (kdn) SRT

Yn = net biomass yield, g VSS/g bsCOD

58
Chair of Urban Water Systems Engineering
Technical University of Munich

Estimate the effluent phosphorus concentration. Heterotrophic synthesis yield, Y = 0.40 g VSS/g COD;
Endogenous decay coefficient, kd = 0.08 g VSS/g VSS.d; SRT = 5 d; P content of PAOs = 0.30 g P/g VSS;
P content of other bacteria = 0.02 g P/g VSS; Clarifier effluent VSS concentration = 8 g/m3

59
Chair of Urban Water Systems Engineering
Technical University of Munich

Estimate the effluent phosphorus concentration. Heterotrophic synthesis yield, Y = 0.40 g VSS/g COD;
Endogenous decay coefficient, kd = 0.08 g VSS/g VSS.d; SRT = 5 d; P content of PAOs = 0.30 g P/g VSS;
P content of other bacteria = 0.02 g P/g VSS; Clarifier effluent VSS concentration = 8 g/m3

60
Chair of Urban Water Systems Engineering
Technical University of Munich

Required Environmental Conditions


Aerobic Nitrification Denitrificatio Biological P
biological n Elimination
oxidation phase 1 phase 2
aerobic aerobic anoxic anaerobi aerobic
c
O2 ● ● inhibits inhibits ●
COD ● ● ●
Het. Biomass ● ●
Nitrifiers ●
PAO ● ●
NH4+ ●
NO3- Product ● inhibits
PO43- Product ●
HCO3- ● Product ●
Source: Gujer, 1999 Sludge age >5d 7-10 d 10-20 d > 15 d 61
Chair of Urban Water Systems Engineering
Technical University of Munich

Required System Configurations


Aerobic Nitrification Denitrification Bio P removal
biological
oxidation

Aerobic
conditions ● ● ● ●
Anoxic
conditions ● ●*
Anaerobic
conditions ●
Sludge age >5d 7-10 d 12-18 d

*Biological phosphorus removal is not used in systems that are designed with nitrification without including a means for
denitrification to minimize the amount of nitrate in the return sludge flow to the anaerobic zone.
62
Chair of Urban Water Systems Engineering
Technical University of Munich

Dynamic Activated Sludge Models

Prof. Dr.-Ing. Jörg E. Drewes


1 February 2024

1
Chair of Urban Water Systems Engineering
Technical University of Munich

Steps to Build a Dynamic WWTP Model


1. Definition of the WWTP model purpose or the objectives of the model application (design, reconstruction,
control, learning)

2. Model selection, which means the selection of appropriate models needed to describe the different
WWTP units that should be considered in the simulation, i.e., selection of the activated sludge model, the
sedimentation model, etc.

3. Hydraulic determination of the models for the whole plant or specific units of WWTP (i.e., hydraulics of
the aeration tanks, secondary settling tanks, etc.)

4. Determination of the wastewater and biomass characterization, including biomass sedimentation (influent
and effluent data, design parameters, etc.)

5. Calibration and verification of the activated sludge model parameters

6. Evaluation of the different WWTP scenarios (i.e., optimization of the WWTP operation, process
improvement, different technical (structure) solution, etc.)

Source: A. Serdarevic & A. Dzubura (2016). Wastewater Process Modeling. Coupled Systems Mechanics 5(1), 21-39 2
Chair of Urban Water Systems Engineering
Technical University of Munich

IWA Activated Sludge Models ASM1, ASM2, ASM3


ftp://ceres.udc.es/Master_en_Ingenieria_del_Agua/master%20antiguo_antes%20del%202012/Segundo_Curso/Programas_Comerciales_en_Ingenieria_Hidraulica_y_Sanitaria/ajacome-aquasim/MODELOS-ASM1-ASM2-ASM3.pdf

3
Chair of Urban Water Systems Engineering
Technical University of Munich

SIMBA# Version 3.0 Process Simulator


for Modeling, Simulation and Optimization

Selected Features:
• Detailed fully dynamic aeration system model library (incl. blowers, pipes,
valves, etc.) Introduction to SIMBA:
• Reactor models for CSTR, MABR, MBBR, MBR, AGSR, trickling filter, etc.
https://www.youtube.com/watch?v=ELjlix04nE8
• Library for process water management and treatment
• Advanced Gujer process matrix editor https://www.youtube.com/watch?v=93MGzC2hxf0
• Tools for result evaluation and LCA studies
• Pollutants in sewers and rivers
Source: www.ifak.eu; inCTRL Solutions, Inc. 4
Chair of Urban Water Systems Engineering
Technical University of Munich

SUMO Wastewater Process Simulator

Selected Features:
• Most extensive calibrated model library for traditional and advanced wastewater resource recovery processes
• Sumo is the only open process source commercial simulator2 (coded in Excel tabular format in SumoSlangTM)
• Virtually unlimited activated sludge/anaerobic digester/sidestream treatment configurations available
• Integrated steady-state and dynamic simulations, book of SumoSlang, extended manual, software in Korean, Chinese,
Japanese, Spanish, Turkish
Source: http://www.dynamita.com/the-sumo/ 5
Chair of Urban Water Systems Engineering
Technical University of Munich

WRc Ltd STOAT


Wastewater Process Simulator

Download request (Freeware):

http://sites.wrcplc.co.uk/freeware/STOAT/downloadform.aspx

Source: http://www.wrcplc.co.uk/ps-stoat 6
Chair of Urban Water Systems Engineering
Technical University of Munich
Example Manual reference:

BIOWIN Wastewater Process Simulator


Model Reference > Chemical Precipitation Reactions > Chemical
Phosphorus Removal with Iron Salts

Introduction to BioWin:
https://www.youtube.com/watch?v=cJ0dGY9w2Gg
Watch a BioWin application for a plant upgrade:
https://www.youtube.com/watch?v=0VgTvumjlpk
Source: https://envirosim.com 7
Chair of Urban Water Systems Engineering
Technical University of Munich

Hydromantis GPS-X Version 6.0

Source: https://www.hydromantis.com/GPSX.html 8
Chair of Urban Water Systems Engineering
Technical University of Munich

Hydromantis GPS-X Lite (open access)

https://www.hydromantis.com/GPS-X-Limited/download.html

Request form for free download (PC only):


https://www.hydromantis.com/GPS-X-Limited/request-form.html
9
Chair of Urban Water Systems Engineering
Technical University of Munich

Energy Recovery and Sludge Handling

Prof. Dr.-Ing. Jörg E. Drewes


8 February 2024

1
Chair of Urban Water Systems Engineering
Technical University of Munich

Solids Handling – Resource Recovery

2
Chair of Urban Water Systems Engineering
Technical University of Munich

Sludge Digesters at the Wastewater Treatment Plant


Munich II, Gut Großlappen

3
Chair of Urban Water Systems Engineering
Technical University of Munich

Environmental Conditions/Terminology

Energy source Conditions in the environment


Available electron acceptor being reduced

Respiration

a) O2 Aerobic

b) Nitrate, NO3-; nitrite, NO2-; no oxygen Anoxic

c) Sulfate, SO42-; CO2; no oxygen; no nitrate Anaerobic

Fermentation

d) Organic compounds, no oxygen, no nitrate Anaerobic

4
Chair of Urban Water Systems Engineering
Technical University of Munich

Anaerobic Digestion
General Process Description
• Microorganisms: facultative and obligate anaerobic bacteria (hydrolysis and fermentation), strict
obligate anaerobic (methane production)

• Primarily used for the treatment of waste sludge and high strength organic wastes

• Characterized by
lower biomass yields (less sludge production), and possibly
energy recovery through methane production (instead of energy used for aeration)

• often used as a pre-treatment step

• mostly operated in the mesophilic temperature range (30 to 40°C)

• Thermophilic fermentation (>50°C) also possible resulting in high pathogen inactivation

5
Chair of Urban Water Systems Engineering
Technical University of Munich

Anaerobic Digestion
General Process Description
Hydrolysis:
• Conversion of particulate matter to soluble compounds

Fermentation (Acidogenesis):
• Further degradation
• Organic substrates serve as both electron donor and acceptor

• Final products of fermentation are acetate, hydrogen, and CO2

Methanogenesis:
• Carried out by methanogens Harvestpower.com

• Two groups of methanogens:


1st: acetate à CH4 and CO2;
2nd: Hydrogen (electron donor) and CO2 (electron acceptor) à methane
6
Chair of Urban Water Systems Engineering
Technical University of Munich

Anaerobic Digestion
General Process Description
Complex Organics
(Carbohydrates, Proteins, Lipids)

Fermentative bacteria
(Hydrolysis)

Monosaccharides, Higher Fatty Acids,


Amino Acids Alcohols
Fermentative bacteria
(Acidogenesis)
Volatile Acids Acetogenic bact.
(Propionic, Butyric, etc.) (Acetogenesis)

Hydrogen-Producing Acetogens

H2 + CO2 Acetate
Hydrogen-utilizing acetogens
Methanogenic organisms (Methanogenesis)

Hydrogen utilizing CH4 + CO2


Aceticlastic
methanogens
methanogens

Von Sperling (2005)


Chair of Urban Water Systems Engineering
Technical University of Munich

Anaerobic Digestion
Process Description
Step 1 Hydrolysis

Step 2 Acidification

Step 3 Acetogenesis

Step 4 Methanogenesis

4 microorganism groups are needed !

4 microorganism groups have to build a


symbiotic community
Chair of Urban Water Systems Engineering
Technical University of Munich

Anaerobic Digestion
Anaerobic systems are characterized by complex interactions
The symbiotic co-existence requires certain conditions (important process parameters:

• Buffer capacity
• pH
• Propionic acid
• Hydrogen
• Acetate
• Redox potential

à Check feed conditions


à Mix, but without introducing extreme local shear forces
Chair of Urban Water Systems Engineering
Technical University of Munich

Anaerobic Digestion
Temperature
• the higher, the faster are the reactions

• as long as enzymes are not harmed Þ Optimal Temperature

• different bacteria types have different optima

Reaction-
rate
psychrophilic
Bacteria
opt.: ca. 16 °C extremophilic
thermophilic Þ Bacteria
Bacteria opt.: über 100 °C
opt.: ca. 57 °C
mesophilic
Bacteria
opt.: ca. 38 °C
Temperature, °C
20 40 60
Chair of Urban Water Systems Engineering
Technical University of Munich

Anaerobic Digestion
Anaerobic Fermentation/Oxidation – Stoichiometry

• A COD balance can be used to account for the changes in COD during fermentation

• Instead of oxygen, the COD loss in the anaerobic reactor is accounted for by the methane production

• The COD equivalent of methane is:

CH4 + 2 O2 à CO2 + 2 H2O

COD per mole of methane : 2 (32 g O2/mole) = 64 g O2/mole

Volume of methane per mole at standard conditions (0°C and 1 atm) = 22.414 L

à CH4 equivalent of COD : 22.414 / 64 = 0.35 L CH4 / g COD

• Synthesis yield coefficients for anaerobic processes are considerably lower compared to aerobic
processes (see also former lectures)

11
Chair of Urban Water Systems Engineering
Technical University of Munich

Anaerobic Digestion
Aerobic vs anaerobic treatment – carbon balance

CO2 Biogas
(40 - (70 -
COD 50%) COD 90%)
(100%) (100%)

Aerobic Anaerobic
Reactor Reactor
effluent effluent
(5 - 10%) (10 - 30%)

sludge sludge
(50 - 60%) (5 - 15%)

Von Sperling
Chair of Urban Water Systems Engineering
Technical University of Munich

Anaerobic Digestion
COD balance throughout the anaerobic degradation process

COD cells COD cells


COD
bCOD removed
Total COD VFA COD CH4
COD

COD VFA COD not


removed
COD rec COD rec COD rec

bCOD = biodegradable COD


CODrec = non biologically degradable COD and COD in complex substrate form treated
in anaerobic reactors containing biomass not yet adapted to the complex substrate
COD VFA = Fraction of COD still present as volatile fatty acids
CODCH4 = COD converted into methane
CODcells = COD converted into cells

Von Sperling (2005)


Chair of Urban Water Systems Engineering
Technical University of Munich

Anaerobic Digestion
Kinetic and stoichiometric parameters
µmax YS
d-1 kg VSS / kg COD

Aerobic bacteria
readily degradable substrate 10 - 20 0.4 – 0.6

Hydrolysers 0.1 – 1.5 0.02 – 0.2

Acidifying organisms 2-4 0.1 – 0.3

Methanogens 0.3 – 0.4 0.03 – 0.04

The weak organisms in the system!


Methanogenic growth kinetics are of main interest in the design of the reactor

Hydraulic detention time of approximately 20 – 30 d (>> 1 / µmax )


Chair of Urban Water Systems Engineering
Technical University of Munich

Anaerobic Digestion
Anaerobic Fermentation/Oxidation – Growth kinetics
• Two rate limiting concepts are important:

- Hydrolysis conversion rate


(can be decisive if compounds are difficult to hydrolyse, affects the total amount of
solids converted)

- Soluble substrate utilization for fermentation and methanogenesis


(affects stability of the process)

à Depending on the conditions (inflow composition), a two-step process can be advantageous to create
optimal conditions for the different stages in the process

15
Chair of Urban Water Systems Engineering
Technical University of Munich

Anaerobic Digestion
Pros and cons of anaerobic treatment
Advantage Disadvantage
Low production of solids Anaerobic bacteria are susceptible to
inhibition by many compounds
Low energy consumption Process start up can be slow
Low land requirements Post-treatment usually necessary
Low construction costs Complex biochemistry and microbiology
Methane production (energy) Possible generation of odours
Tolerance to high organic loads Possible generation of effluents with
unpleasant aspects
Small and large scale application Unsatisfactory removal of nitrogen and
phosphorus
Low nutrient consumption

Combination of aerobic and anaerobic processes to exploit advantages of both processes


(e.g. sludge digestion)
16
Chair of Urban Water Systems Engineering
Technical University of Munich

EXAMPLE
Prediction of methane gas production
An anaerobic reactor, operated at 35°C, processes a wastewater stream with a flow of
3,000 m3/d and bsCOD concentration of 5,000 g/m3. At 95 percent bsCOD removal and a
net biomass synthesis yield of 0.04 g VSS/g COD used, what is the amount of methane
produced in m3/d?

17
Chair of Urban Water Systems Engineering
Technical University of Munich

An anaerobic reactor, operated at 35°C, processes a wastewater stream with a flow of 3,000
m3/d and bsCOD concentration of 5,000 g/m3. At 95 percent bsCOD removal and a net biomass
synthesis yield of 0.04 g VSS/g COD used, what is the amount of methane produced in m3/d?
Solution

18
Chair of Urban Water Systems Engineering
Technical University of Munich

An anaerobic reactor, operated at 35°C, processes a wastewater stream with a flow of 3,000
m3/d and bsCOD concentration of 5,000 g/m3. At 95 percent bsCOD removal and a net biomass
synthesis yield of 0.04 g VSS/g COD used, what is the amount of methane produced in m3/d?

19
Chair of Urban Water Systems Engineering
Technical University of Munich

Anaerobic Digestion
• Anaerobic Processes are cost effective, but only if the influent concentration is relatively
high (> 2,000 mg COD/L)

• At 30°C and at normal pressure (1.0133 bar), approximately 20 g CH4 / m³ are soluble in water.
This corresponds to a COD of approxiately 80 g/m³

à Biogas is only generated, if at least 80 g/m³ of COD are degraded. Wastewaters with low
concentrations will therefore only produce little biogas!

20
Chair of Urban Water Systems Engineering
Technical University of Munich

Gas Collecting Systems


Chair of Urban Water Systems Engineering
Technical University of Munich

Anaerobic Digestion
Digester shapes

Cylindric shape
with flat bottom

Problem: This causes


Sediment accumulation in corners à Vusable < VReactor
qh real < qh required
Chair of Urban Water Systems Engineering
Technical University of Munich

Anaerobic Digestion
Digester shapes

Cylinder shape with


cones

Problem:
Complex reinforcement in the corners
Advantage:
• good mixing
• insensitive to settling
Chair of Urban Water Systems Engineering
Technical University of Munich

Anaerobic Digestion
Digester shapes
Egg-shape

Advantage:
• good mixing
• insensitive to settling
• low radiation losses
• stable structure
Chair of Urban Water Systems Engineering
Technical University of Munich

WWTP Köhlbrandhöft, Hamburg Harbour

25
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Technical University of Munich

Disposal Strategies of Digested Sludge in Bavaria

DWA (2017). Mitgliedermitteilungen 26


Chair of Urban Water Systems Engineering
Technical University of Munich

P-Recovery Strategies from Sludge

DWA (2017). Novellierung der AbfKlärV 27


Chair of Urban Water Systems Engineering
Technical University of Munich

Disinfection

Prof. Dr.-Ing. Jörg E. Drewes


8 February 2024

Slides with background information, review on your own


1
Chair of Urban Water Systems Engineering
Technical University of Munich

Disinfection
Drinking Water Treatment

Wastewater Treatment

2
Chair of Urban Water Systems Engineering
Technical University of Munich

History Recap…
• Koch (Germany, 1881) demonstrated the role of bacteria in waterborne diseases and
demonstrated that chlorine can inactivate pathogenic bacteria
• Filtration for control of waterborne diseases: low efficiency, even when combined with
coagulation
• 1902 – first continuous chlorination for disinfection of drinking water (Middelkerke,
Belgium)
• 1908 – first continuous chlorination in the US in Jersey City, NJ (solid calcium
hypochlorite, Ca(ClO)2)
• Liquefied chlorine gas makes large-scale operation more feasible (first facility in
Philadelphia, 1913)
• By 1941, 85% of drinking water supplies in the US were chlorinated

3
Chair of Urban Water Systems Engineering
Technical University of Munich

History Recap…
• In Germany, almost all water supplies come from protected sources (groundwater,
springs, riverbank filtration) favoring natural filtration and inactivation of pathogens
(“chemical disinfection” is option of last resort)
• Discovery in the US and Europe that DBP are formed when chlorine reacts with NOM
(mid 1970s)
• Limits are set by the EU Drinking Water Directive and the USEPA on THM
concentrations in drinking water
• More DBP are discovered and more regulations follow
• Last two decades of 20th century: questioning the effectiveness of chlorination in
controlling waterborne diseases caused by protozoa

4
Chair of Urban Water Systems Engineering
Technical University of Munich

Disinfection
• Two basic strategies to reduce microbiological contaminants in drinking water:
– removal from the water
– inactivation

• Inactivation ≡ traditionally referred to as disinfection


• Inactivation – still present but harmless to consumer

5
Chair of Urban Water Systems Engineering
Technical University of Munich

Disinfection
• Primary Disinfection: inactivation of microorganisms in the water
• Secondary Disinfection: maintaining a disinfectant residual in the
distribution system
• Five disinfection agents are commonly used in treatment of drinking
water:
– Free chlorine – most common
– Combined chlorine (not allowed in Germany)
– Ozone – strongest oxidant, controls T&O
– Chlorine dioxide
– UV irradiation

6
Chair of Urban Water Systems Engineering
Technical University of Munich

EU Regulations/German Trinkwasser Verordnung


• EU Drinking Water Directive/German TrinkwV
– Escherichia coli 0/100 mL
– Enterococci 0/100 mL
– Coliform bacteria 0/100 mL
– Clostridium perfringens 0/100 mL (only for surface water supply)

• German TrinkwV only


– Heterotrophic plate count (22/36°C) 100 HPC/mL
– Legionella spec. 100 units/100 mL (triggers additional measures)
– Somatic coliphage 50 PFU/100 mL

• Disinfection by-products (EU/German TrinkwV)


– Trihalomethane (THM) – 0.05 mg/L (up to 0.1 mg/L)
– Haloacetic acids (HAA-5) – 0.06 mg/L 7
Chair of Urban Water Systems Engineering
Technical University of Munich

U.S. Regulations
• Surface Water Treatment Rule
– treatment requirements:
• 3-log inactivation of Giardia lamblia cysts
• 4-log inactivation of enteric viruses

• Interim Enhanced Surface Water Treatment Rule


– treatment requirements:
• 2-log inactivation of Cryptosporidium

• Long Term 2 Enhanced Surface Water Treatment Rule


– treatment requirements for Cryptosporidium:
• Bin 1: <0.075 oocysts/L no additional treatment
• Bin 2: 0.075 to <1.0 1.0 log additional
• Bin 3: 1.0 to <3.0 2.0 log additional
• Bin 4: >3.0 2.5 log additional

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Chair of Urban Water Systems Engineering
Technical University of Munich

Long Term 2 Enhanced Surface Water Treatment


Rule (LT2ESWR) – “Toolbox”
• Watershed Control Program (0.5-log)
• Pre-sedimentation basin with coagulation (0.5-log)
• Lime-soda softening (0.5-log)
• Bank Filtration (0.5-log to 1.0-log depending on set-back)
• Combined filter effluent turbidity less than or equal to 0.15 NTU in at least 95 percent of
measurements each month (0.5-log)
• Slow sand filters (2.5-log)
• Membranes
• Chlorine Dioxide (based on CT table)
• Ozone (based on CT table)
• UV (based on UV dose table)
9
Chair of Urban Water Systems Engineering
Technical University of Munich

U.S. Regulations
• Stage 1 Disinfectants and Disinfection Byproducts Rule (Stage 1 D/DBPR)
– Regulates disinfectants: Maximum Residual Disinfectant Level (MRDL)
– Regulates disinfection by-products (DBPs)
• TTHMs (0.08 mg/L)
• HAA5 (0.06 mg/L)
• Chlorite (1.0 mg/L)
• Bromate (0.01 mg/L)

10
Chair of Urban Water Systems Engineering
Technical University of Munich

Emerging Issues
• Chlorination/disinfection byproducts
• Chlorine-resistant organisms
• Both causing reevaluation of chlorine as a primary disinfectant and
reevaluation of the role of inactivation itself in the control of pathogens
• New methods for removal: membrane filtration, UV irradiation

11
Chair of Urban Water Systems Engineering
Technical University of Munich

Chlorine Reactions with Organic Constituents


(AOX - adsorbable organically bound halogens)
Behavior of AOX-subgroups during chlorination

0.59
160
15.8
140
0.17
120 AOI
11.27 AOBr
100 AOCl
AOX (ug/L)

80
134
60
101.2
40
0.78
20 4.79
12.3
0
Val Vista prior Cl2 Val Vista after Cl2 Val Vista finished water

12
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Technical University of Munich

Characteristics of Five Most Common Disinfectants

13
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Technical University of Munich

Characteristics of Disinfectants

• T13-1

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Technical University of Munich

Oxidation Power
Disinfectant Oxidation potential (Volt)
Hydroxyl radical -2.8
Ozone -2.07
Hydrobromous acid -1.59
Hydrochlorous acid -1.49
Chlorine -1.36
Bromine -1.07
Chlorine dioxide -0.95
Monochloramine -0.75
Dichloramine -0.74

15
Chair of Urban Water Systems Engineering
Technical University of Munich

Kinetics of Disinfection
• The specific mechanism of microorganism inactivation during chemical
disinfection is not well understood
• Function of chemical disinfection agent, properties of the
microorganism, and properties of the water
• One simple kinetic model is widely used, but many other models
describe the mechanism of disinfection
– Dr. Harriet Chick - Chick’s Law (1908) – disinfection could be modeled
as a pseudo-first-order reaction with respect to the concentration of
the organisms

16
Chair of Urban Water Systems Engineering
Technical University of Munich

Kinetics of Disinfection – Chick’s Law

dN
= -KN
dt

17
Chair of Urban Water Systems Engineering
Technical University of Munich

Kinetics of Disinfection – Chick’s Law


dN
= -KN
dt
dN/dt = rate of change in # of organisms with time
N = concentration of microorganisms, organisms/volume
K = Chick’s law rate constant, time-1

After integration:

æN ö
lnçç ÷÷ = -Kt
è N0 ø

18
Chair of Urban Water Systems Engineering
Technical University of Munich

19
Chair of Urban Water Systems Engineering
Technical University of Munich

Kinetics of Disinfection – Chick-Watson Law


C n t = constant

n ⋅ log(C) + log(t) = log(constant)

dN
= −k 'C n N
dt
C = concentration of disinfectant, mg/l
n = empirical constant, (-)
t = time required to achieve a constant % of inactivation
constant = value of given % of inactivation
After integration:
!N$ n N −k 'C nt
ln # & = −k 'C t _ or _ =e
" N0 % N0
20
Chair of Urban Water Systems Engineering
Technical University of Munich

Chlorine Disinfectants

• Chlorine
– Most widely used
– Effective at low concentrations
– Inexpensive
– Forms residual if applied in sufficient dosage
– Powerful oxidation properties
– Can be applied as a gas (Cl2(g)) or liquid (hypochlorite (bleach))

21
Chair of Urban Water Systems Engineering
Technical University of Munich

Chlorine Disinfectants
• Chlorine gas
– Liquified at 5-10 bar
– Shipped in steel cylinders (99.8% Cl2) containing 45, 68, 910 kg

Cl2(g) ó Cl2(aq) KH = Cl2(aq)/pCl2

Cl2 + H2O à HOCl +HCl


Hydrochloric acid
Hypochlorous acid
HOCl Û H+ +OCl¯
22
Chair of Urban Water Systems Engineering
Technical University of Munich

Chlorine Disinfectants
• Chlorine gas
– The relative distribution of HOCl and OCl¯ is pH
dependent

23
Chair of Urban Water Systems Engineering
Technical University of Munich

Chlorine Disinfectants

• Hypochlorite salts:
– Calcium hypochlorite – dry
– Sodium hypochlorite – liquid

Ca(OCl)2 à Ca2+ +2 OCl ¯

NaOCl à Na+ + OCl ¯


NaOCl + H2O à HOCl + Na+ + OH-

24
Chair of Urban Water Systems Engineering
Technical University of Munich

Chlorine Disinfectants
• Combined chlorine:
– Ammonia reacted with chlorine (max. 6 mg/L according to TrinkwV):

NH3 + HOCl à NH2Cl + H2O monochloramine


NH2Cl + 2 HOCl à NHCl2 + 2 H2O dichloramine
NHCl2 + 3 HOCl à NCl3 + 3 H2O nitrogen trichloramine

25
Chair of Urban Water Systems Engineering
Technical University of Munich

Chlorine Disinfectants
• Chlorine dioxide (ClO2):
– Three general methods of formation:

– NaClO2 + HCl à ClO2 + NaCl + H+

– (Cl2 +H2O à HOCl +HCl)


HOCl + HCl + 2 NaClO2 à 2 ClO2 + 2 NaCl + H2O

– 2 NaClO2 + NaOCl + 2 HCl à 2 ClO2 + 3 NaCl + H2

26
Chair of Urban Water Systems Engineering
Technical University of Munich

Chlorine Reaction
• As chlorine is added it reacts with constituents until residuals
are produced (Cl2, HOCl, OCl ¯ ≡ free chlorine)

• Residuals composed of chloramines ≡ combined available


chlorine residuals

• Sum of the above ≡ total residual chlorine (TRC)

27
Chair of Urban Water Systems Engineering
Technical University of Munich

Breakpoint Chlorination

28
Chair of Urban Water Systems Engineering
Technical University of Munich

Breakpoint Chlorination
• From point A to B: chlorine reacts with organic compounds, ammonia, and
amines to form chloro-organic species and chloramines. Free Chlorine is NOT
formed.
• From point B to minimum: dichloramine is decomposed to nitrogen
trichloramine and chloramines may also decompose to N2 and N2O
• Breakpoint: the point at which all destructible chloramines and chloro-organic
compounds are decomposed and FREE chlorine residual begins to appear
• Beyond breakpoint: free and combined residual in solution

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Technical University of Munich

Chlorine Demand

30
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Technical University of Munich

Classwork

xxxxxx

31
Chair of Urban Water Systems Engineering
Technical University of Munich

Classwork
The chlorine demand curve on the graph was obtained for a drinking water for a 1-hour contact
time. Determine the daily amount of NaOCl to be applied to this water in order to produce a free
and combined residual of 0.9 mg/L after a contact time of one hour in a flow of 24,000 m3/day.
1
0.9
0.8

Chlorine Residual, mg/L


0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 0.5 1 1.5 2
Chlorine Dose, mg/L

32
Chair of Urban Water Systems Engineering
Technical University of Munich

CT Approach

33
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Technical University of Munich

Residual CT is calculated with a very conservative approach !


4

3
Cl2 (mg/L)

0
0 5 10 15 20

Time (minutes)
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Chair of Urban Water Systems Engineering
Technical University of Munich

Integral CT

Cl2 (mg/L) 3

CT = 70 (mg-min/l)

0
0 5 10 15 20

Time (minutes)
35
Chair of Urban Water Systems Engineering
Technical University of Munich

Residual CT

3
Cl2 (mg/L)

1
CT = 50 (mg-min/l)

0
0 5 10 15 20

Time (minutes)

36
Chair of Urban Water Systems Engineering
Technical University of Munich

Residual CT

3
Cl2 (mg/L)

0
0 5 10 15 20

Time (minutes)

37
Chair of Urban Water Systems Engineering
Technical University of Munich

CT Approach
• “CT Value” used in water treatment – Conservative Estimate
• It is the product of the residual disinfectant concentration C (mg/L) determined at
the end of the process (reactor effluent), with the corresponding disinfectant contact
time T (minutes)
• Appropriate CT value must be satisfied at peak flow
• Best disinfection achieved in plug-flow reactor
• C = 0.2 – 40 mg/L, rarely exceeds 15 mg/L
• T = measure of the time at which 10% of a tracer feed concentration (T10) appears at
the sampling point
• CT has long been used as a basis for disinfection requirements
• Useful way of comparing alternative disinfectants

38
Chair of Urban Water Systems Engineering
Technical University of Munich

CT Approach

Removal of 99%

C*t = important design criteria! 39


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Technical University of Munich

CT Approach
log(C) = -log(t) +log(constant)

40
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Technical University of Munich

CT Approach

41
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Technical University of Munich

TTab for Inactivation of Viruses by Free Chlorine

42
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Technical University of Munich

TTab

43
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Technical University of Munich

TTab for 3-log Inactivation of Giardia Cysts by Free Chlorine

44
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Technical University of Munich

TTab

45
Technical University of Munich

CT Values for Inactivation of Giardia Lamblia


Cysts and Viruses by
Chair of Urban Water Systems Engineering

Chlorine, Dioxide, Chloramine, and UV

46
Chair of Urban Water Systems Engineering
Technical University of Munich

CT Approach

47
Chair of Urban Water Systems Engineering
Technical University of Munich

48
Chair of Urban Water Systems Engineering
Technical University of Munich

Ultraviolet Light (UV) Disinfection


• UV is effective against Cryptosporidium
• UV does not contribute to formation of
regulated DBPs

• Established technology
• Emerging UV-LED
• State of rapid development

49
Chair of Urban Water Systems Engineering
Technical University of Munich

UV Light in the Electromagnetic Spectrum


Gamma
Rays X - Ray UV Visible Infrared
254

Vacuum UV-C UV-B UV-A


UV absorbance

DNA
Water

100 200 300 400


Wavelength (nm)

50
Chair of Urban Water Systems Engineering
Technical University of Munich

Why Mercury Lamps?

• Electron transitions provide energy in the germicidal wavelength


range

• Low vapor pressure is needed for high efficient UV generation

• High vapor pressure can produce high intensity polychromatic light,


but lower efficiency

• Low ionization energy, easily start gas discharge at low voltage

• Hg is stable in the lamp envelope


51
Chair of Urban Water Systems Engineering
Technical University of Munich

Spectra of LP and MP Mercury Lamps

Relative Intensity (mW )cm


200 250 300 350 400
Low Pressure
Wavelength (nm)Hg Medium Pressure Hg

) -2
-2

Relative Intensity (mW )cm


Relative Intensity (mW cm

200 225 250 275 300 200 250 300 350 400

Wavelength (nm) Wavelength (nm)

monochromatic vs. polychromatic


-2

52
Chair of Urban Water Systems Engineering
Technical University of Munich

Low Pressure, High Intensity


• Low Pressure - Higher Wattage Lamps
• 0.13 to 0.79 kW/1,000 m3
• Lamp Life Expectancy greater than 5,000 -
12,000 hours
• Available in vertical, horizontal, and
combined alignment
• Self Cleaning System

53
Chair of Urban Water Systems Engineering
Technical University of Munich

54
Chair of Urban Water Systems Engineering
Technical University of Munich

Mechanism of UV Irradiance in Water

UV lamp
Absorbing
water column Quartz
sleeve
(fouling)

DNA target UV energy

Target
organism Particulates
Enlarged
target
organism
55
Chair of Urban Water Systems Engineering
Technical University of Munich

Calculation of UV Dose
D = Iavg t
Where D = UV dose (fluence), mJ/cm2 (note mJ/cm2 = mW s/cm2)
Iavg = average UV intensity, mW/cm2
t = exposure time, s
"I%
€ log$ ' = −ε( λ )Cx
# Io &

Where I = UV light intensity at distance x from the light source, mW/cm2


Io = UV light intensity at light source, mW/cm2
e(l) – molar absorptivity
€ of the light absorbing solute
C = concentration of light-absorbing solute, mole/L
x = pathway distance, cm
56
Chair of Urban Water Systems Engineering
Technical University of Munich

Inactivation

• First-order reaction:
Nt
ln = -kIt
No

– Nt and No are the number of the viable microorganism at time t and initially, respectively
– k is the inactivation constant
– I is the average UV intensity (irradiance) in the reactor
– t is the average detention time in the irradiated portion of the reactor

57
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Technical University of Munich

Water Quality Effects

Particulate Matter

Dissolved Matter
• iron
• nitrate
• natural organic matter

58
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Technical University of Munich

Short-Circuiting

59
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Technical University of Munich

Characteristics of Three Types of UV Lamps

60
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Technical University of Munich

UV disinfection systems

61
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Technical University of Munich

Lamps in Modules

62
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Technical University of Munich

Modules in a Bank

63
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Technical University of Munich

Flow Control in Serpentine


Contactor

64
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Technical University of Munich

Typical UV Doses Required to Achieve Different Coliform


Disinfection Levels for Different Wastewaters

65
Technical University of Munich
Chair of Urban Water Systems Engineering

Cr
yp UV Dose (mJ/cm2)
to
sp
or

50

0
100
150
200
250

id
iu
E. m
co Gia
li rd
Sa Sh O1 ia
lm ig 57
Le on ell :H
gi el a 7
on la so
el en nn
la t ei
pn eri
eu tid
m is
op
P H hi
ol ep la
io at
Co vir it
u is
xs s A
Typical UV Dose - 40 mJ/cm2

ac Ty
ki pe
R e 1
ot vir
A a us
de v B
UV Doses Required

no iru 5
s
UV Doses for 99.99% removal

vi SA
ru
s 11
ty
pe
41
66
Chair of Urban Water Systems Engineering
Technical University of Munich

Comparison to Other Disinfectants


1000
Bacteria
Viruses
Protozoans
Relative to E. coli
Dose Required -

100
Spores

10

0.1
Chlorine Ozone UV Light

Disinfectant Type
67
Chair of Urban Water Systems Engineering
Technical University of Munich

Summary
• How does UV compare to other current technologies?

68
Chair of Urban Water Systems Engineering
Technical University of Munich

BGU38010
Advanced Water Treatment Engineering and
Reuse
Summer term 2024, Thursdays, 9.45 – 11.15 h

Prof. Dr.-Ing. Jörg E. Drewes


(jdrewes@tum.de)

69
Chair of Urban Water Systems Engineering
Technical University of Munich

BV180004
Modeling of Aquatic Systems
SS 2024

Prof. Dr.-Ing. Konrad Koch


(k.koch@tum.de)

70
Chair of Urban Water Systems Engineering
Technical University of Munich

BGUxxx
Anaerobic Technology and Energy Recovery
Summer term 2024, Thursday afternoon

Prof. Dr.-Ing. habil. Konrad Koch


(k.koch@tum.de)

71
Chair of Urban Water Systems Engineering
Technical University of Munich

BGU xxx
Engineered Natural Treatment Systems
Winter Term 2024/25

Dr.-Ing. Benedikt Aumeier


Prof. Dr.-Ing. Jörg E. Drewes
(jdrewes@tum.de)

72

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