Barriers Against Cyanotoxins in Drinking Water

DVGW-Technology Center Water (TZW) Karlsruhe, Dresden branch

TOXIC - EVK1-2001-00182

TOXIC

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

TOXIC - EVK1-2001-00182

Content

• Introduction

• Results of work packages

• Published results

• Case studies

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 • …..

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

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

TOXIC - EVK1-2001-00182

Structure of TOXIC

Co-ordination and project management

Sub-groups

Raw water quality

Analysis

Treatment

Exploitation

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

TOXIC - EVK1-2001-00182

Work-segments

• Production of standard materials

• Design of evaluated analytical procedures

• Lab scale experiments

• Pilot scale experiments

• Full scale monitoring

TOXIC - EVK1-2001-00182

WP 1 - Co-ordination and Project Management

Participants: TZW

Protocols Reports Public presentations

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

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)

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)

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.

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

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

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

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

TOXIC - EVK1-2001-00182

WP 7 - Alternative Techniques

Participants: Kiwa, UAL

Protocol of optimised membrane filtration procedures (ultrafiltration, nanofiltration, reversed osmosis)

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

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 (tom.hall@wrcplc.co.uk)

Providing of a commercially available software package for treatment process simulation (tom.hall@wrcplc.co.uk)

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

TOXIC - EVK1-2001-00182

Case studies

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

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)

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)

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)

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.

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