Barriers Against Cyanotoxins in Drinking Water
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Barriers Against Cyanotoxins in Drinking Water
DVGW-Technology Center Water (TZW) Karlsruhe, Dresden branch
TOXIC - EVK1-2001-00182
TOXIC
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TOXIC - EVK1-2001-00182
Consortium of TOXIC
* member of EWRI (European Water Research Institutes)
Institute / Company End-users Country
DVGW-Technology Center Water Karlsruhe(TZW), Dresden branch *
1 Germany
University of Dundee (UDU) 3 UK
Swiss Federal Institute for EnvironmentalScience and Technology (EAWAG)
1 Switzerland
DHI – Institute of Water and Environment 1 Denmark
Universidad de Extremadura (UEX) 1 Spain
Water Research Centre (WRc) * 2 UK
Kiwa N.V. Research & Consultancy * - Netherlands
Abo Akademi University (AAU) 1 Finland
Universidade do Algarve (UAL) 2 Portugal
University of Lodz (ULO) 6 Poland
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TOXIC - EVK1-2001-00182
Content
• Introduction
• Results of work packages
• Published results
• Case studies
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TOXIC - EVK1-2001-00182
Guide lines for drinking water
• WHO: 1.0 µg/L MCYST-LR• Australia: 1.3 µg/L MCYST-LR
Cylindrospermopsin (in discussion)
Anatoxin-a (in discussion)
Saxitoxin (in discussion)• Germany: 0.1 µg/L each single toxic compound • …..
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TOXIC - EVK1-2001-00182
H OCH3
H CH3CH3
H H
HNHH
CH3
HO
YN N X
N
O
O OCO2H
CH3H
H
H H
NN
N
O
O CH2
O
CH3
H
H CO2H
H
H
H
CH3
Mdha
ß-Me-Asp
Glu
AlaAdda
X Y MC-RR Arginin Arginin MC-YR Tryptophan Arginin MC-LR Leucin Arginin MC-LA Leucin Alanin
Figure 2.2: Strukture of Microcystins
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TOXIC - EVK1-2001-00182
Saxitoxin Anatoxin-a
Cylindrospermopsin
N H2+
O
C H3
O
O
N HN H HN+
N H
N
H H OH-O3SO
Me
H
H2N
N N
O
N
H2N
HO
HO HNH2
O
Figure 2.3: Strukture of Anatoxin-a, Saxitoxin and Cylindrospermopsin
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TOXIC - EVK1-2001-00182
Structure of TOXIC
Co-ordination and project management
Sub-groups
Raw water quality
Analysis
Treatment
Exploitation
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TOXIC - EVK1-2001-00182
Detailed Structure of TOXIC
Management and co-ordination
Conventionaltreatment
Raw waterquality
Polishing treatment
Analysis
Final treatment
Alternativetechnologies
Modelling
Cost evaluation and exploitation
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TOXIC - EVK1-2001-00182
Work-segments
• Production of standard materials
• Design of evaluated analytical procedures
• Lab scale experiments
• Pilot scale experiments
• Full scale monitoring
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TOXIC - EVK1-2001-00182
WP 1 - Co-ordination and Project Management
Participants: TZW
Protocols Reports Public presentations
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Data base of cyanobacteria and cyanotoxins in European waterbodies
Establishment of an Internet-Based Platform on cyanobacteria and-toxins in European waterbodies (cyanobacteria-platform.com)
List of suitable methods for early-warning of cyanobacterial bloom
TOXIC - EVK1-2001-00182
WP 2 - Raw Water Quality
Participants: UDU, TZW, AAU, UAL, ULO
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TOXIC - EVK1-2001-00182
WP 3 - Analysis
Participants: AAU, UDU, ULO
Supply of pure cyanotoxin standards Know-how transfer and inter-calibration
exercises Provision of Standard Operational
Precedures (SOPs) for cyanotoxin analysis (PPIA, ELISA, HPLC/UV, MS)
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TOXIC - EVK1-2001-00182
WP 4 - Conventional Treatment
Participants:TZW, UDU, DHI, UEX, UAL, ULO
Test of different treatment trains Cyanotoxin biodegradability and
degradation kinetics (aerobic and anaerobic)
Risk assessment for treatment trains (intra- and extracellular toxins)
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Toxin release - pilot plant studies
0,0
1,0
2,0
3,0
4,0
5,0
6,0
cell
boun
d to
xin
in µ
g/L
0,00
0,10
0,20
0,30
0,40
0,50
0,60
0,70
0,80
0,90
1,00
extr
acel
lula
r to
xin
in µ
g/L
Toxin, intra
Toxin, extra
flocc./filtr.
KMnO4+flocc./filtr.
ozone+flocc./filtr. PAC+flocc./filtr.
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TOXIC - EVK1-2001-00182
WP 5 - Polishing Treatment: activated carbon
The application of activated carbon (PAC !!!) is one of the most efficient measure for dissolved toxin removal
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0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
0 1 2 3 4 5 6 7 8 9 10
Aktivkohlemenge in mg/L
1,2 cis-Dichlorethen (F 300)
(berechnet nach Literaturangaben für destilliertes Wasser)
Atrazin (F 100)(berechnet nach Literaturangaben für destilliertes Wasser)
Trichlorethen (ROW 0,8 S)(berechnet nach Literaturangaben für destilliertes Wasser)
Hepatotoxine (Adsorba N)(Messwerte in Reinwasser)
The efficiency of activated carbon
dichloroethene
trichloroethene
atrazine
Activated carbon in mg/L
MCYST-LR
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TOXIC - EVK1-2001-00182
WP 5+6 - Polishing and Final Treatment: oxidation and disinfection
Participants: EAWAG, UEX, WRc, UAL, ULO
Kinetic data base for oxidation of cyanotoxins by oxidants (chlorine, chlor-amine, chlorine dioxide, permanganate, ozone)
Assessment of the influence of water quality parameters (DOC, alkalinity, pH, temperature, ammonia) on toxin oxidation
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TOXIC - EVK1-2001-00182
WP 5+6 Polishing and Final Treatment
Overall oxidation of dissolved cyanobacterial toxins during oxidation-disinfection
Primary Oxidant + Chlorine
Disinfection
Cyanotoxin Ozone KMnO4 Chlorine
MC-LR ++ ++ +
CYN ++ + ++
ANTX ++ ++ —
Symbols: ++effective oxidation of toxins —ineffective oxidation of toxins Colors: green low DBP risk, where DBPs include Bromate and THMs yellow medium DBP risk red high DBP risk
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TOXIC - EVK1-2001-00182
WP 7 - Alternative Techniques
Participants: Kiwa, UAL
Protocol of optimised membrane filtration procedures (ultrafiltration, nanofiltration, reversed osmosis)
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TOXIC - EVK1-2001-00182
WP 7 - Alternative TechniquesParticipants: Kiwa, UAL Nanofiltration:
Toxin 72 h
Feed in µg/L
Permeate in µg/L
Rejection in %
MC-RR 7.8 ND > 99
MC-LR 9.0 0.1 99
MC-YR 7.1 ND > 99
MC-LA 1.2 ND > 93
ANT-a 4.8 0.17 96
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TOXIC - EVK1-2001-00182
Final project outcome – published results
Participants: all partners
Providing of an Analytical Manual (ISBN: 951-765-259-3) Providing of a European Best Practice Guidance Manual
for selection, design and operation of treatment plant, raw water monitoring and toxin analysis ([email protected])
Providing of a commercially available software package for treatment process simulation ([email protected])
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TOXIC - EVK1-2001-00182
in 2008:International Guidance Manual for the Management of Toxic Cyanobacteria
• Chapter 1 INTRODUCTION • Chapter 2 RISK ASSESSMENT IN SOURCE WATERS • Chapter 3 MANAGEMENT AND CONTROL OF
CYANOBACTERIA IN SOURCE WATERS• Chapter 4 DEVELOPMENT AND IMPLEMENTATION OF A
MONITORING PROGRAM • Chapter 5 INCIDENT MANAGEMENT PLANS• Chapter 6 TREATMENT OPTIONS• Chapter 7 CASE STUDIES
A paper of the Global Water Research Coalitionwww.globalwaterresearchcoalition.net
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TOXIC - EVK1-2001-00182
Case studies
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TOXIC - EVK1-2001-00182
Case study I: pilote scale
Raw water quality
Treatment Toxin elimination
Microcystis aeruginosa
Anabaena
Cell bound toxins: av. 1.0 µg/L
Dissolved toxins: n.d.
Pre-oxidation with ClO2
Coagulation
Filter I
Filter II (GAC)
0.05 µg/L (cell bound)
0.05 µg/L (diss. = toxin release)
complete
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TOXIC - EVK1-2001-00182
Case study II: pilote scale
Raw water quality
Treatment Toxin elimination
Planktothrix rubescens
Cell bound toxins: av. 1.5 µg/L
Dissolved toxins: av. 0.08 µg/L
Preoxidation with permanganate
Coagulation
Filter
1.0 µg/L (cell bound)
0.41 µg/L (diss. = toxin release)
0.85 µg/L (diss. = toxin release)
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TOXIC - EVK1-2001-00182
Case study III: pilote scale
Raw water quality
Treatment Toxin elimination
Microcystis aeruginosa
Anabaena
Cell bound toxins: av. 2.5 µg/L
Dissolved toxins: av. 0.1 µg/L
Pre-oxidation with ozone
Coagulation
Filter
0.05 µg/L (cell bound)
0.50 µg/L (diss. = toxin release)
n.d (cell bound)
0.91 (diss. = toxin release)
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TOXIC - EVK1-2001-00182
Case study VI: pilote scale
Raw water quality Treatment Toxin elimination
Planktothrix rubescens
Cell bound toxins: till 1.6 µg/L (105 cells /mL)
Dissolved toxins: 0.1 µg/L
UF-mambrane
(dived, dead end)
TMP: - 0.20 till - 0.34 bar
complete (cell bound)
n.d. (dissolved)
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TOXIC - EVK1-2001-00182
Conclusions
• Toxin removal (cell bound and dissolved) with high efficiency is possible !!!
• The non calculable risk is the toxin release – an efficient additional barrier is the use of activated carbon.
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TOXIC - EVK1-2001-00182
• Geoff Codd• Jussi Meriluoto• Tom Hall• Hanne Kaas• Urs von Gunten• Bas Heijman• Maria Rosa• Joanna Mankiewicz• Malgozata Taczynska †• Juan Acero• Jose Meneira• Gayle Newcomb• Bill Harding• Ingrid Chorus
Many thanks