Pesticide Degradates
of Concern to the Drinking
Water Community
Project #2938
Subject Area:
High-Quality Water
Web Report
TO:
Awwa Research Foundation Subscribers
RE:
Enclosed report, Pesticide Degradates of Concern to the Drinking Water
Community
The objectives of this project were to develop a priority list of pesticides and their
degradates and adjuvants of potential concern and identify related research priorities. To
meet these objectives, the research team collated data on the occurrence, properties,
persistence and toxicity of pesticide degradates and adjuvants in soils, waters, and
treatment processes; and held a workshop to discuss prioritization approaches and
research needs. The information generated from the literature review and workshop
recommendations has been summarized in the enclosed report and was used to develop a
priority list of pesticide degradates. General research needs in four key areas were also
identified at the workshop and are included in the report.
Due to the technical nature of this project, the results are being made available to both
subscribers and the research community through this electronic version of the report on
AwwaRF’s web site.
©2008 AwwaRF. ALL RIGHTS RESERVED
©2008 AwwaRF. ALL RIGHTS RESERVED
Pesticide Degradates
of Concern to the Drinking
Water Community
©2008 AwwaRF. ALL RIGHTS RESERVED
About the Awwa Research Foundation
The Awwa Research Foundation (AwwaRF) is a member-supported, international, nonprofit organization
that sponsors research to enable water utilities, public health agencies, and other professionals to provide
safe and affordable drinking water to consumers.
The Foundation’s mission is to advance the science of water to improve the quality of life. To achieve
this mission, the Foundation sponsors studies on all aspects of drinking water, including supply and
resources, treatment, monitoring and analysis, distribution, management, and health effects. Funding
for research is provided primarily by subscription payments from approximately 1,000 utilities, consulting
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funding serves as a third source of research dollars.
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The results of research are disseminated through a number of channels, including reports, the Web site,
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has supplied the water community with more than $300 million in applied research.
More information about the Foundation and how to become a subscriber is available on the Web
at www.awwarf.org.
©2008 AwwaRF. ALL RIGHTS RESERVED
Pesticide Degradates
of Concern to the Drinking
Water Community
Prepared by:
Simon A Parsons
School of Water Sciences
Cranfield University, Cranfield, Bedfordshire, MK43 OAL, United Kingdom
and
Alistair Boxall, Chris Sinclair, and Carmel Ramwell
University of York
Central Science Laboratory, Sand Hutton, York, YO41 1LZ, United Kingdom
Sponsored by:
Awwa Research Foundation
6666 West Quincy Avenue, Denver, CO 80235-3098
Published by:
©2008 AwwaRF. ALL RIGHTS RESERVED
DISCLAIMER
This study was funded by the Awwa Research Foundation (AwwaRF). AwwaRF assumes no responsibility
for the content of the research study reported in this publication or for the opinions or statements of fact
expressed in the report. The mention of trade names for commercial products does not represent or imply
the approval or endorsement of AwwaRF. This report is presented solely for informational purposes.
Copyright © 2008
by Awwa Research Foundation
ALL RIGHTS RESERVED.
No part of this publication may be copied, reproduced
or otherwise utilized without permission.
©2008 AwwaRF. ALL RIGHTS RESERVED
CONTENTS
LIST OF TABLES................................................................................................................... ix
LIST OF FIGURES ................................................................................................................. xi
FOREWORD…. .................................................................................................................... xiii
ACKNOWLEDGMENTS .......................................................................................................xv
EXECUTIVE SUMMARY .................................................................................................. xvii
CHAPTER 1: INTRODUCTION AND OBJECTIVES............................................................1
CHAPTER 2: USAGE OF PESTICIDES AND ADJUVANTS ...............................................5
Introduction....................................................................................................................5
Uses of pesticides...........................................................................................................5
Agricultural and horticultural use ......................................................................6
Industry/commercial/government markets ........................................................7
Household usage ................................................................................................8
Pesticides used in or near water .........................................................................9
Adjuvants and co-formulants.........................................................................................9
CHAPTER 3: DEGRADATES IN THE ENVIRONMENT ...................................................13
Introduction..................................................................................................................13
Formation in the environment......................................................................................14
Methods for determining transformation routes ..........................................................19
Experimental methods .....................................................................................19
Predictive approaches ......................................................................................19
Characteristics of degradates of major pestcides .........................................................20
Fate of degradates in the environment .........................................................................24
Degradation in the environment.......................................................................24
Routes into environmental waters....................................................................26
Non-agricultural...........................................................................................................26
Effects of climate and season...........................................................................27
Mobility in the environment ............................................................................27
Occurrence in the environment....................................................................................29
Soil ...................................................................................................................34
Surface water ...................................................................................................34
Groundwater ....................................................................................................35
Occurrence In Drinking water Supplies and Fate during Drinking water treatment ...36
Drinking water standards .............................................................................................38
CHAPTER 4: PRIORITISATION OF DEGRADATES.........................................................39
Introduction..................................................................................................................39
Prioritization approach.................................................................................................39
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©2008 AwwaRF. ALL RIGHTS RESERVED
Data selection...................................................................................................39
Exposure ..........................................................................................................39
Risk characterization and ranking....................................................................40
Calculation of exposure index .........................................................................40
Amount of degradate formed .......................................................................................40
Sorption........................................................................................................................41
Persistence....................................................................................................................41
Effects ..............................................................................................................42
Prioritisation of pesticides in use in the USA and UK.................................................42
USA - Agricultural Pesticides..........................................................................42
USA - Home and Garden Use Pesticides.........................................................45
USA - Industrial/Commercial/Government Use Pesticides.............................45
UK....................................................................................................................47
Sample calculation of the risk index................................................................49
Use and limitations of the prioritization scheme .............................................50
CHAPTER 5: CONCLUSIONS AND FUTURE RESEARCH ..............................................51
Conclusions..................................................................................................................51
Future research.............................................................................................................51
CHAPTER 6: RELEVANCE FOR UTILITIES .....................................................................53
APPENDIX 1: THE EXTENT OF PESTICIDE DEGRADATE FORMATION IN THE
ENVIRONMENT ................................................................................55
APPENDIX 2: THE DEGRADATION RATE OF PESTICIDE DEGRADATES
IN THE ENVIRONMENT ..................................................................71
APPENDIX 3 : DEGRADATE ORGANIC CARBON PARTITION COEFFICIENT
(KOC) ....................................................................................................75
APPENDIX 4: THE OCCURRENCE OF PESTICIDE DEGRADATES IN THE
ENVIRONMENT ................................................................................79
APPENDIX 5: ADI FOR PESTICIDES ...............................................................................89
APPENDIX 6: MAMMALIAN ACUTE, SUBACUTE AND SUBCHRONIC DATA FOR
PESTICIDE DEGRADATES..............................................................91
APPENDIX 7: DEGRADATE ABBREVIATIONS USED IN THE DATA
APPENDICES .....................................................................................93
APPENDIX 8: THE RISK INDEX AND DATA AVAILABILITY FOR DEGRADATES
FROM THE US MOST USED AGRICULTURAL PESTICIDES ....95
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©2008 AwwaRF. ALL RIGHTS RESERVED
APPENDIX 9: THE RISK INDEX AND DATA AVAILABILITY FOR DEGRADATES
FROM THE UK MOST USED AGRICULTURAL PESTICIDES....99
REFERENCES .....................................................................................................................103
LIST OF ABBREVIATIONS................................................................................................117
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©2008 AwwaRF. ALL RIGHTS RESERVED
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LIST OF TABLES
1.1
Workshop Participants List..................................................................................................3
2.1
Most commonly used conventional pesticides in agriculture in the USA in 1999..............7
2.2
Most commonly used pesticides in the industry/commercial/government sector in the
US and approved substance in the UK for amenity use...........................................8
2.3
Most commonly used pesticides in the US households in 1999..........................................8
2.4
Top 10 adjuvants used in the UK (excluding co-formulants)............................................10
3.1
Examples of biodegradation reactions that are relevant to pesticides ...............................15
3.2
Pesticide degradates identified as formed at ≥ 10% of the applied pesticide in one or
more degradation studies .......................................................................................22
3.3
Summary table containing the organic carbon partition coefficient (Koc) for pesticide
degradates ..............................................................................................................29
3.4
A summary of pesticide degradate environmental occurrence data ..................................31
3.5
Drinking water standards set for pesticide degradates.......................................................38
4.1
The risk index for degradates from the US most used agricultural pesticides risk
index is >0.5...........................................................................................................44
4.2
The risk index and data availability for degradates from the US most used home and
garden use pesticides..............................................................................................45
4.3
The risk index and data availability for degradates from the US most used
Industrial/Commercial/Government use pesticides ..............................................47
4.4
The risk index for degradates from the UK most used agricultural pesticides where the
risk index is >0.5 ...................................................................................................48
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©2008 AwwaRF. ALL RIGHTS RESERVED
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©2008 AwwaRF. ALL RIGHTS RESERVED
LIST OF FIGURES
2.1
Usage of different pesticide classes in agricultural and non-agricultural market
sectors (taken from Donaldson et al. 2002). ......................................................6
2.2
Relative areas of crops treated with pesticides annually in the UK (data taken
from Thomas and Wardman 1999) ....................................................................6
3.1
Degradation of the triazine herbicides to DIA and DEA (adapted from
Scribner et al. 2000)........................................................................................15
3.2
The transformation and cleavage degradation pathways of chloroacetamide
(e.g., alachlor) and sulfonylurea (e.g., imazosulfuron) herbicides. .................16
3.3
The oxidative desulphurisation of the insecticide chlorpyrifos ...................................17
3.4
Selected degradation pathways for the insecticide carbaryl (Boxall et al. 2004a). .....18
3.5
Formation of pesticide degradates as a percentage of the parent pesticide
(each degradate is represented by the degradation study where it was
most prevalent)................................................................................................20
3.6
The degradation of pesticide degradates, classified according to the Soil Survey and
Land Research Centre (SSLRC) persistence classification. ............................25
3.7
The comparative persistence of pesticides and their degradates in various
environmental media........................................................................................26
3.8
The comparative sorption of pesticide degradates and their parent pesticides............28
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©2008 AwwaRF. ALL RIGHTS RESERVED
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©2008 AwwaRF. ALL RIGHTS RESERVED
FOREWORD
The Awwa Research Foundation is a nonprofit corporation that is dedicated to the
implementation of a research effort to help utilities respond to regulatory requirements and
traditional high-priority concerns of the industry. The research agenda is developed through a
process of consultation with subscribers and drinking water working professionals. Under the
umbrella of a Strategic Research Plan, the Research Advisory Council prioritizes the suggested
projects based upon current and future needs, applicability, and past work; the recommendations
are forwarded to the Board of Trustees for final selection. The foundation also sponsors research
projects through the unsolicited proposal process; the Collaborative Research, Research
Applications, and Tailored Collaboration programs; and various joint research efforts with
organizations such as the U.S. Environmental Protection Agency, the U.S. Bureau of
Reclamation, and the Association of California Water Agencies.
This publication is a result of one of these sponsored studies, and it is hoped that its
findings will be applied in communities throughout the world. The following report serves not
only as a means of communicating the results of the water industry’s centralized research
program, but also as a tool to enlist the further support of the nonmember utilities and
individuals.
Projects are managed closely from their inception to the final report by the foundation’s
staff and large cadre of volunteers who willingly contribute their time and expertise. The
foundation serves a planning and management function and awards contracts to other institutions
such as water utilities, universities, and engineering firms. The funding for this research effort
comes primarily from the Subscription Program, through which water utilities subscribe to the
research program and make an annual payment proportionate to the volume of water they deliver
and consultants and manufacturers subscribe based on their annual billings. The program offers
a cost-effective and fair method for funding research in the public interest.
A broad spectrum of water supply issues is addressed by the foundation’s research
agenda: resources, treatment and operations, distribution and storage, water quality and analysis,
toxicology, economics, and management. The ultimate purpose of the coordinated effort is to
assist water suppliers to provide the highest possible quality of water economically and reliably.
The true benefits are realized when the results are implemented at the utility level. The
foundation’s trustees are pleased to offer this publication as a contribution toward that end.
David E. Rager
Chair, Board of Trustees
Awwa Research Foundation
Robert C. Renner, P.E.
Executive Director
Awwa Research Foundation
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©2008 AwwaRF. ALL RIGHTS RESERVED
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©2008 AwwaRF. ALL RIGHTS RESERVED
ACKNOWLEDGMENTS
The authors wish to thank Awwa Research Foundation (AwwaRF) for funding this
project and Alice Fulmer for her excellent support as project manager. The authors would like to
thank the following people and organizations for their cooperation, participation and support of
this project.
•
•
•
The technical advisors to the project Dana Kolpin (USGS), Kathrin Fenner
(EAWAG), Steve Maund (Syngenta) and Andrew Craven (Pesticides Safety
Directorate) for their efforts in reviewing the draft prioritization scheme and
helping to run the symposium and workshop.
Noirin Casey, Andrew Spears and Keith Robertson of the International Water
Association for help in organizing the symposium and workshop in Prague.
Michelle Everitt for administrative support and workshop organization.
The authors would also like to thank all the symposium and workshop delegates for their
contribution including the Project Advisory Committee members Dan Binder and Roderick
Dunn, City of Columbus Department of Water, Richard Gullick, American Water, Kathy
Kuivila, USGS and Joel Pedersen, University of Wisconsin-Madison.
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©2008 AwwaRF. ALL RIGHTS RESERVED
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©2008 AwwaRF. ALL RIGHTS RESERVED
EXECUTIVE SUMMARY
BACKGROUND
Recent U.S. and European monitoring data has shown detectable concentrations of
pesticides in more than 95 percent of sampled surface waters and approximately 50 percent of
sampled groundwaters, making them of concern to the drinking water industry. Pesticides can
participate in a variety of transformation processes, resulting in degradation products that may
accumulate in the environment. As the number of degradates and adjuvants is extremely large, a
need was identified for list of pesticides, degradates, and adjuvants that are of potential concern
to the drinking water community and that should be considered in environmental surveillance
monitoring programs.
RESEARCH OBJECTIVES
The objectives of this project were to:
1. Develop a list of pesticides, degradates and adjuvants of potential concern.
2. Collate data on the occurrence, properties, persistence and toxicity of the degradates and
adjuvants in soils, waters and treatment processes; and
3. Develop and run a workshop to discuss approaches to prioritization approaches and
research needs; and
4. Using the information, generated in 1 to 3 and the recommendations from the workshop,
develop a priority list of degradates.
APPROACH
To meet the project objectives, a workshop was convened and attended by 33 experts
from academia, consultancies, government bodies, research associations and water utilities.
The workshop was held in Prague, Czech Republic on June 4-6th, 2004 and included a preworkshop symposium designed to update each participant with current knowledge in analysis,
fate and treatability of pesticides, degradates and adjuvants. The workshop lead to the project
focusing primarily on pesticide degradates.
PESTICIDE USAGE
A literature review provided an overview of the available information on the usage
amount and pattern for pesticide products as these will be key factors in determining the amount
of a substance that will enter the environment. Data are available on the amounts of different
pesticide active ingredients used in the US and the UK and indicates that the greatest use of
pesticides is in agriculture, however large amounts are also used in the
industrial/commercial/government and home and garden areas. The data was used to rank
pesticide and adjuvant products and this indicated that herbicidal products are used in the highest
amounts with the major active substance being atrazine, glyphosate, acetochlor and 2,4-D. The
highest usage insecticides were malathion, chlorpyrifos and tebufos and the highest used
fungicides were chlorothalonil and mancozeb.
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©2008 AwwaRF. ALL RIGHTS RESERVED
DEGRADATES IN THE ENVIRONMENT
Once released into the environment, pesticides are susceptible to degradation by biotic
and abiotic means. Pesticide transformation can produce a diverse range of compounds, and it is
important that degradates are considered when determining the risks to the environment and
human health posed by the application of a pesticide. Here, information from the literature and
industry data have been used to identify the nature and amounts of pesticide degradates, and we
found that 92 pesticide degradates have been detected in the environment with 29 detected in
groundwater and 27 detected in surface waters. Therefore the potential for these compounds to
enter water drinking water sources is high. Information is also presented on the occurrence,
degradation and sorption in the environment and in water treatment works.
PRIORITIZATION SCHEME
The impact of a degradate on drinking water quality will be determined by its potential to
enter drinking water supplies, its treatability and its potential effects on human health. Here a
risk-based prioritization scheme has been developed which considers both exposure and effects.
The scheme uses a range of factors including the amount of parent pesticide used, the way in
which the parent compound is used, the amount of a particular degradate formed, the mobility of
the degradate and its persistence to generate a risk score. The prioritization procedure was
applied to major pesticides in use in the USA and UK in order to illustrate the prioritization
approach and to begin to identify degradates of potential concern to the water industry.
Application of the prioritization approach to the degradates indicated that the degradates of
alachlor, acetochlor, cyanazine, atrazine, dichloropropene, dicamba and 2-4-D as likely to be of
most concern to US water supplies whilst, in the UK, degradates of cyanazine, isoproturon and
flufenacet were ranked highest and should be selected first for monitoring and treatability studies
FUTURE RESEARCH
This project identified future research studies that will benefit drinking water utilities and
in particular four key areas were identified (i) information management, (ii) analysis, (iii)
monitoring and (iv) treatment. Treatment issues included studies into the fate of compounds in
conventional and advanced treatment processes and also the likely transformation of compounds
during treatment.
RECOMMENDATIONS FOR DRINKING WATER UTILITIES
The workshop participants recognized and strongly endorsed the importance of drinking
water utility participation in the development of a usable and robust prioritization scheme. The
identified needs were grouped into six major priorities and will help extend the usefulness of the
prioritization scheme and our overall knowledge on the analysis, occurrence and fate of pesticide
degradates.
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©2008 AwwaRF. ALL RIGHTS RESERVED
CHAPTER 1
INTRODUCTION AND OBJECTIVES
The availability of a reliable supply of water is one of the most important determinants of
our health. Historically improvements in our health have been related to improvements in our
water supply system from source to tap. In both the US and the EU, drinking water from
community and non-community water systems is regulated for the protection of human health.
The quality of water we receive today is achieved through improvements in source protection,
water treatment, operation and maintenance, water quality monitoring, and training and
education.
Recent U.S. and European monitoring data has shown detectable concentrations of
pesticides in more than 95 percent of sampled surface waters and approximately 50 percent of
sampled groundwaters, making them of concern to the drinking water industry. Pesticides can
participate in a variety of transformation processes, resulting in degradation products that may
accumulate in the environment. Moreover, many pesticide products and formulations contain
compounds labeled as inerts by the United States Environmental Protection Agency (USEPA)
that may be of toxicological concern. These inert ingredients, or adjuvants, can also contaminate
water supplies. The general focus of this report is pesticide degradates rather than the parent
compunds or adjuvants. Adjuvants were initially considered in the project but the general
consensus of the expert workshop was to focus on the pesticide degradates.
For regulation purposes pesticides and related products are defined as any organic
insecticide, herbicide, fungicide, nematocide, acaricide, algicide, rodenticide, slimicide and any
product related to any of these including any growth regulator, and their relevant metabolites,
degradation and reaction products. In the US, the EPA has established maximum contaminant
level goals for drinking water resources and maximum contaminant levels for 83 contaminants,
including 24 pesticides. While limits have been set in the US (MCLs range from 500 μg/L for
Picloram down to 0.2 μg/L for Lindane) and in the UK (standards for pesticides and related
products include 0.03 µg/L for aldrin, dieldrin, heptachlor and heptachlor epoxide, 0.10 µg/L for
other pesticides and a total pesticides limit of 0.50 µg/L), little guidance has yet been issued on
pesticide degradates. For example, in the UK, the Drinking Water Inspectorate (DWI) has stated
that there is no evidence at the present time that any pesticide metabolites, degradation or
reaction products represent a risk to health and therefore no additional monitoring is required.
However, the current data are very limited so it would seem wise to begin to consider degradates
and adjuvants in more detail to ensure that they are not posing a risk to human health. As the
number of degradates and adjuvants is extremely large, there is an urgent need to prioritize
substances so that monitoring and research work can focus on substances that are most likely to
be of concern. Thus, there is a need to develop a comprehensive list of pesticides, degradates,
and adjuvants that are of potential concern to the drinking water community and that should be
considered in environmental surveillance monitoring programs.
This report describes the results of a 12-month long AwwaRF funded project, the overall
aim of which was to develop a list of priority substances of potential concern in drinking water
supplies. The objectives were to:
1. Develop a list of pesticides, degradates and adjuvants of potential concern (Chapter 2).
2. Collate data on the occurrence, properties, persistence and toxicity of the degradates and
adjuvants in soils, waters and treatment processes (Chapter 3); and
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©2008 AwwaRF. ALL RIGHTS RESERVED
3. Develop and run a workshop to discuss approaches to prioritization approaches and
research needs; and
4. Using the information, generated in 1 to 3 and the recommendations from the workshop,
develop a priority list of degradates and where possible adjuvants (Chapter 4).
To meet the project objectives, a workshop was convened and attended by 33 experts
from academia, consultants, government bodies, research associations, and water utilities.
Workshop participants were chosen based not only on their expertise and experience but also on
their willingness and availability to participate in the workshop. Based on inputs from the
AwwaRF project manager and recommendations by the project team and technical advisors, a
list of workshop invitees was established. The workshop was held in Prague, Czech Republic on
June 4-6th, 2004 and included a pre-workshop symposium designed to update each participant
with current knowledge in analysis, fate and treatability of pesticides, degradates and adjuvants.
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©2008 AwwaRF. ALL RIGHTS RESERVED
Table 1.1
Workshop Participants List
Name
Craig Adams
Alistair Boxall
Andrew Craven
Kathrin Fenner
Michael Fry
Alice Fulmer
Richard Gullick
Bent Halling-Sorensen
Michelle Hladik
Anthony Johnson
Dana Kolpin
Rai Kookana
Kathy Kuivila
Organization
University of Missouri-Rolla
University of York
Pesticides Safety Directorate
EAWAG
Stratus Consulting
AwwaRF
American Water
Royal Danish School of Pharmacy
John Hopkins University
Lhasa Ltd, University of Leeds
US Geological Survey
CSIRO
US Geological Survey
Jan Linders
Steve Maund
Michael Meyer
Christoph Neumann
Thuy Nguyen
Simon Parsons
Joel Pedersen
Nick Poletika
RIVM
Syngenta
US Geological Survey
Syngenta
US EPA
Cranfield University
University of Wisconsin-Madison
Dow Agroscience LLC
Leo Puijker
Kees Romijn
Hans Siegrist
Geoff Siemering
Chris Sinclair
Shane Snyder
Dennis Tierney
Jack Wang
Derek Wilson
KIWA
Bayer CropScience GmbH
EAWAG
San Francisco Estuary Institute
University of York
Southern Nevada Water Authority
Syngenta Crop Protection Inc.
Louisville Water
Yorkshire Water
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Country
USA
UK
Switzerland
USA
USA
USA
Denmark
USA
UK
USA
Australia
USA
The
Netherlands
Switzerland
USA
Switzerland
USA
UK
USA
USA
The
Netherlands
Germany
Switzerland
USA
UK
USA
USA
USA
UK
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CHAPTER 2
USAGE OF PESTICIDES AND ADJUVANTS
INTRODUCTION
Pesticidal products play an important role in modern agriculture and typically comprise a
formulation containing the active ingredient and co-formulants. Other substances may be added
during the pesticide application process in order to increase the efficacy of the product.
Following release to the environment both the active ingredient and the co-formulants may be
degraded by abiotic and biotic processes resulting in the formation of degradates. The
environment may therefore be exposed to a mixture of the parent compound, degradates and coformulants. In this Chapter we provide an overview of the available information on the use of
pesticides and adjuvants.
USES OF PESTICIDES
The usage amount and pattern for a pesticide product will be a key factor in determining
the amount of a substance that will enter the environment. A product can be used in a number of
ways, including to treat arable crops,
fruit crops, in greenhouses, in amenity areas,
golf courses and in the home. In the UK and US, data are available on the amounts of different
pesticide active ingredients used (Donaldson et al. 2002; Garthwaite et al. 1997). For example,
data from the US indicate that the greatest use of pesticides is in agriculture, however large
amounts are also used in the industrial/commercial/government and home and garden areas
(Figure 2.1). The specific active substances used will vary depending on the usage scenario. In
the following sections we describe the major substances used, based on detailed data for the UK
and the US.
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300000
Amount used (tonnes)
250000
home and garden
industry/commercial/government
agriculture
200000
150000
100000
50000
0
herbicides and insecticides
plant grow th and miticides
regulators
fungicides
nematicide
and fumigant
other
Pesticide type
Figure 2.1 Usage of different pesticide classes in agricultural and non-agricultural market
sectors (taken from Donaldson et al. 2002).
Agricultural and horticultural use
Detailed data are available on the active substances used in agriculture in the UK and the
US (e.g., Donaldson et al. 2002; Garthwaite et al.1997, 1999a and b, 2002). In the UK, the
greatest amounts of pesticides are used in arable farming and treatment of grassland and fodder
(Figure 2.2).
arable
grassland and fodder
vegetables
orchards
other
Figure 2.2 Relative areas of crops treated with pesticides annually in the UK (data taken
from Thomas and Wardman 1999)
In terms of weight of substances applied to arable land in the UK in 2002, herbicides and
desiccants were used in the largest amounts (71%) followed by fungicides (12%), growth
regulators (11%), insecticides and nematicides (2%), molluscicides (1%) and seed treatments
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©2008 AwwaRF. ALL RIGHTS RESERVED
(1%). The most extensively used herbicides were glyphosate, isoproturon, fluroxypyr, mecopropP and diflufenicam. The most used fungicides were epoxiconazole, azoxystrobin, tebuconazole,
kresoxim methyl, fenpropimorph and trifloxystrobin and the most widely used insecticides were
the pyrethroids (cypermethrin, esfenvalerate), orgaophosphates and the carbamates (pirimicarb)
(Garthwaite et al. 2002).
Table 2.1
Most commonly used conventional pesticides in agriculture in the USA in 1999
(taken from Donaldson et al. 2002)
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
Substance
Mass a
Atrazine
Glyphosate
Metam sodium
Acetochlor
Methyl bromide
2,4-D
Malathion
Metolachlor
Trifluralin
Pendimethalin
Dichloropropene
Metolachlor-s
Chlorothalonil
74 - 80
67 - 73
60 - 64
30 - 35
28 - 33
28 - 33
28 - 32
26 - 30
18 - 23
17 - 22
17 - 20
16 - 19
9 - 11
Rank
14
15
16
17
18
19
20
21
22
23
24
25
Substance
Mass a
Chloropicrin
Copper hydroxide
Chlorpyrifos
Alachlor
Propanil
EPTC
Dimethamid
Mancozeb
Dicamba
Terbufos
Ethephon
Cyanazine
8 - 10
8 - 10
8 - 10
7 - 10
7 - 10
7-9
6-8
6-8
6-8
5-7
5-6
4-8
a - ranked by range in millions pounds of active ingredient
Industry/commercial/government markets
Usage in the industry/commercial and government sectors includes the control of weeds
on highways and berms and the treatment of park and amenity areas and open spaces. While the
amount of active substances used in the industrial/commercial and government areas are
significantly lower than those used in agriculture, the use pattern may mean that a
disproportionate amount of these substances will reach water bodies compared to the agricultural
area. For example, pesticides applied to highways and pavements may be washed off from the
hard surface into streams and rivers. The major active substances used in this sector in the US are
2,4-D, glyphosate and pendimethalin (Table 2.2). Data are not available on usage in the UK but a
range of active ingredients are approved (Table 2.2).
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Table 2.2
Most commonly used pesticides in the industry/commercial/government sector in the US
and approved substance in the UK for amenity use
(taken from Donaldson et al. 2002 and Whitehead 2004)
US
Rank Active
substance
Mass a
UK
Approved active
substance
1
2
3
4
5
6
7
8
9
10
17 - 20
11 - 14
5-7
3-5
3-5
2-4
2-4
2-4
1-3
1-3
Dichlorophen
2,4-D
Dicamba
Triclopyr
Diuron
MCPA
Paraquat
Glyphosate
Sodium chlorate
Diquat
2,4-D
Glyphosate
Copper sulphate
Pendimethalin
Chlorpyrifos
MSMA
Chlorothalonil
Diuron
Malathion
Trichlopyr
a - ranked by range in millions pounds of active ingredient
Household usage
Pesticides are commonly used in the home for weed and insect control. While the
amounts used are significantly lower than in the agricultural sector, the substances are typically
used by non-trained operators, there is therefore a high likelihood that the active substance may
be released to water courses (e.g., via pavement drainage systems) or to treatment works due to
improper disposal down the drain. In the US in 1999, 2,4-D was the most commonly used
herbicide in the home and six of the top ten used substances were herbicides (Table 2.3).
Table 2.3
Most commonly used pesticides in the US households in 1999
(taken from Donaldson et al. 2002)
Rank
Substance
Mass a
Rank
Substance
Mass a
1
2
3
4
5
2,4-D
Glyphosate
MCPP
Dicamba
Diazinon
7-9
5-8
3-5
3-5
2-4
6
7
8
9
10
Chlorpyrifos
Carbaryl
Benefin
Malathion
DCPA
2-4
2-4
1-3
1-3
1-3
a - ranked by range in millions pounds of active ingredient
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Pesticides used in or near water
A number of substances are approved for control of weeds in or near water.
Consequently, these substances, even though they may only be used in small amounts, have a
high potential to enter water bodies. Substances currently approved in the UK include 2,4-D,
dichlobenil, diquat, glyphosate, maleic hydrazide and terbutryn. In the US some active
substances are approved for use in aquatic scenarios such as fresh water ponds, lakes reservoirs
and drainage canals to control aquatic vegetation (e.g., glyphosate, 2,4-D, diquat, fluridone and
imazapyr).
ADJUVANTS AND CO-FORMULANTS
An adjuvant is a compound other than water which is used with a pesticide to enhance its
effectiveness. More specifically, a co-formulant is a compound pre-mixed with the technicalgrade active ingredient (a.i.) to create a formulated pesticide product, whereas an adjuvant (or
tank-mix adjuvant) is a product sold as a single entity that can be mixed with formulated
pesticides. Historically, co-formulants have been known as additives or inerts, the latter term
being particularly misleading. In this report, unless otherwise stated, the term adjuvant will be
used to include co-formulants.
Adjuvants can be described as bio-enhancing or utility. Bio-enhancing adjuvants
improve the efficacy of the a.i. These can include stickers, spreaders, penetrants and humectants.
A utility adjuvant modifies the physical characteristics of the spray solution and includes drift
control agents, buffering and acidifying agents, defoamers, colorants and compatibility agents.
However, a single adjuvant can have several modes of action thus it is advantageous to group
adjuvants by their chemistry, namely surfactants, oils (mineral and vegetable), synthetic latex
and inorganic salts. Only limited data are available on the usage of adjuvants, information on the
top ten products in the UK is given in Table 2.4. By far the largest chemical group is surfactants
which can have multiple desired properties enhancing the spreading, sticking and absorption of
pesticides. Within this group non-ionic surfactants are the largest group; others include anionic,
cationic and organosilicone.
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Table 2.4
Top 10 adjuvants contained within products available in the UK (excluding co-formulants data not available) (adapted from Whitehead 2004)
Adjuvant
Number of products
containing adjuvant
Vegetable oil
Alkyl phenol ethoxylate
Fatty amine ethoxylate
Ethoxylate condensates
Paraffinic
Block copolymer
Synthetic latex
Pinolene
Mineral oil
Propionic acid
70
56
48
37
27
20
19
17
15
15
%
18.5
14.8
12.7
9.8
7.1
5.3
5.0
4.5
4.0
4.0
Surfactants are widely used in other industries and agrochemicals account for only 2% of
the global surfactant market compared to detergents and cleaning products (54%) and personal
care (11%) (Agriculture and Agri-food Canada, 2002). Due to the abundant use of surfactants
there are data available on the fate and occurrence of some of the main surfactant groups
including alkyl phenol ethoxylates (APE) (Environment Canada and Health Canada 2000), alkyl
amine ethoxylates (AME) (Madsen et al. 2001), alcohol ethoxylates (AE) (Madsen et al. 2001)
and linear alkylbenzene sulfonates (LAS) (HERA 2004).
When extrapolating the available data on surfactants to the scenario of pesticide use
consideration should be given to the specifics. For example, much of the reported work involves
the fate of surfactants in wastewater treatment plants (WWTPs). Values given for degradation
rates commonly assume a media of sludge or sludge-amended soil which may give rise to a
faster rate than in water or untreated soil with fewer microbes. Likewise, water monitoring data
tend to be focused around rivers and lakes receiving effluent from WWTPs or textile industries
and these concentrations are not necessarily representative of potential surfactant concentrations
arising from pesticide use. Nevertheless, the existing data could allow the pesticide use scenario
to be put into context, particularly given the fact that for tank-mix adjuvants the rates of use are
typically 1% or less volume: volume of pesticide.
A shortcoming of the current literature with regard to surfactants in the environment
arising from pesticide use is the paucity of data on movement to, and concentrations in
groundwater. This is of particular note because a) groundwater receives relatively minimal
treatment prior to distribution to consumers and b) degradation in anaerobic conditions can be
slow, potentially allowing any pollutants to accumulate. Another limitation of the available data
was that reports were not always compound specific but considered a chemical group. For
example, with LAS the alkyl chain length can vary, as can its position on the benzene ring, both
of which can affect the fate and effect of the compound potentially hampering the development
quantitative structure-activity relationships (QSAR) and/or their validation with field data.
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However, in reality, a surfactant will consist of a range of chain lengths thus a generic approach
to considering the fate of chemical groups may be more appropriate.
There is a general move away from the use of mineral oil to that of vegetable oil for
environmental reasons. There is very limited data on the fate of oils used as additives in
pesticides. On the global market, the use of oleochemicals for surfactants is less than half that for
use in soaps (Agriculture and Agri-food Canada, 2002).
Although no figures were found for the use of synthetic latex in pesticides, it is probable
that, like surfactants, agrochemicals account for only a small percentage of the global use of
latex which includes industries such as the automotive industry, information technology and the
household and medical sector. With regard to the use of inorganic salts such as ammonium
sulphate as adjuvants, these salts are also fertilizers and the fate of such compounds is widely
covered under the umbrella of fertiliser use and/or the fate of nitrates.
In addition to the major chemical groups of adjuvants there are numerous other
compounds listed as being used as adjuvants or co-formulants, for example those listed by the
USEPA (www.epa.gov/opprd001/inerts/lists.html)(e.g. hydroquinone, isophorone, nonylphenol
and phthalic acid). Again, many of these compounds have uses in a wide variety of industries,
thus it may be difficult to delineate their occurrence in the environment arising from the
application of pesticides.
To more accurately predict the fate and effects of adjuvants in the environment, data are
required on the composition of co-formulants in pesticide products and the use of tank-mix
adjuvants to enable total usage data to be calculated.
.
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©2008 AwwaRF. ALL RIGHTS RESERVED
CHAPTER 3
DEGRADATES IN THE ENVIRONMENT
INTRODUCTION
Once released into the environment, pesticides are susceptible to degradation by biotic
and abiotic means. This can result in the formation of a range of compounds (Roberts, 1998;
Roberts and Hutson, 1999). The transformation of a pesticide includes all processes where
structural change of the pesticide takes place producing a degradate (Somasundaram and Coats,
1991). Therefore, pesticide transformation can produce a diverse range of compounds and it is
important that degradates are considered when determining the risks to the environment and
human health posed by the application of a pesticide. However, the risks posed by degradates
should not be considered individually but always in conjuction with to those risks posed by their
parental pesticides.
Once pesticides are applied during agricultural practice there is the potential for
degradates to form. These compounds together with the parent pesticide can then, depending on
their physico-chemical properties, move from the soil to other environmental media. These
compounds can volatilize into the air and move large distances in the particulate or gaseous
phase and be deposited by rainfall large distances away from the site of application (Goolsby et
al. 1997); (Majewski et al. 1998); (Thurman and Cromwell, 2000). They can move vertically
through the soil profile to groundwater and then away from the site of application via aquifer
transport (Schiavon, 1988); (Widmer and Spalding, 1995); (Broholm et al. 2001). Additionally,
there is also the potential for these compounds to enter surface waters when they travel laterally
either via overland runoff due to heavy rainfall or via sub-soil tile drains, entering agricultural
ditches and streams and then on to major rivers, reservoirs and ultimately in estuaries and the
marine environment (Aga and Thurman, 2001); (Muir and Baker, 1976); (Phillips et al. 1999).
With pesticide degradates entering major rivers, reservoirs, and groundwater, there is the
potential for these compounds to be present in water abstracted for drinking water treatment
(Heberer and Dünnbier, 1999). Whether these degradates are present in this raw water will
depend on their rate of formation in the environment, the extent of their parental use in the
particular catchment, and the physico-chemical properties and rate of degradation of themselves
and their parents (Boxall et al. 2004c). The movement of these compounds to abstraction
sources is more complex than pesticidal degradation and the subsequent movement through the
environment of the degradates. The movement of the parent pesticide needs to be considered
also because at any point along its ‘journey’ it can degrade and from additional degradates.
Therefore, degradates with low mobility can occur a distance from the site of application
(Brouwer et al. 1990).
If degradates are present in raw water, then, it maybe desirable to remove them during
water treatment. Limited drinking water standards specific to particular degradates have been set
in the USA (aldicarb sulfone and sulfoxide), while in the EU degradate drinking water standards
are covered by the 0.1 µg L-1 for pesticides (and their ‘relevant metabolites’). The term ‘relevant
metabolite’ was introduced in the EU Directive 91/414/EEC (EU, 1994) and its subsequent
amendments. This legislation concerns the placing of plant protection products on the market
and subsequent guidance has been provided on determining the relevance of a degradate (e.g.,
EU, 2003). Water treatment processes designed to remove pesticides may not be as efficient at
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removing the smaller, more polar degradates. An important consideration during drinking water
treatment is the additional formation of degradates from either the pesticides or the
environmental degradates (Zhang and Pehkonen, 1999).
Based on the literature review undertaken during this project, it was identified that the
information available about the monitoring and measurement of degradates in the environment is
dominated by the triazine and chloroacetamide herbicides. A large volume of data was available
concerning the environmental occurrence of the cotton and corn herbicides from studies
undertaken in the USA. Their environmental fate and that of their degradates has been
documented for soil, sediment, surface waters including runoff, streams, rivers, estuaries, lakes
and reservoirs, ground waters, rain and air. A large proportion of the available work focuses on
atrazine, while cyanazine, metolachlor, and alachlor are also studied in detail. The main
degradates under investigation are: deethylatrazine (DEA), hydroxyatrazine (HA) and
deisopropylatrazine (DIA), cyanazine amide and the ethane sulfonic acids (ESA) and oxanilic
acids (OA) of metolachlor and alachlor.
In this Chapter, information from the literature and industry data is used to identify the
nature and amounts of pesticide degradates that are formed in the environment through biotic
degradation (e.g., soil) or abiotic degradation pathways such as surface and aqueous photolysis
or hydrolysis. Information is also presented on their occurrence, degradation and sorption in the
environment.
FORMATION IN THE ENVIRONMENT
Once pesticides are applied in the environment during either normal agricultural practice
or via alternative uses such as domestic, industrial, and amenity, they are susceptible to biotic
and abiotic degradation. The major abiotic processes include hydrolysis, photolysis, and
oxidation/reduction. Hydrolysis is a chemical transformation process in which an organic
molecule reacts with water. Substances that are potentially susceptible to hydrolysis include
alkyl halides, amides, amines, carbamates, epoxides, nitriles, phosphoric acid esters, and
sulphonic acid esters (Samiullah, 1990). Photolytic degradation can occur directly (where the
substance itself absorbs solar radiation) or indirectly (where the energy is transferred from some
other species).
Biodegradation is one of the most important forms of degradation in the environment. It
is generally a significant loss mechanism in soils and aquatic systems and is essential to
wastewater treatment. Although higher organisms can metabolise a substance, it is the microbes
that play the most important role in the degradation of a substance in environmental media. The
majority of biodegradation reactions can be categorized as oxidative, reductive, or conjugative
(Hill, 1978; Table 3.1).
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Table 3.1
Examples of biodegradation reactions that are relevant to pesticides
(Adapted from Hill, 1978)
Type of reaction
Example
ß-oxidation
Oxidative dealkylation; N-dealhylation
O-dealkylation
C-dealkylation
Thioether oxidation
Decarboxylation
Epoxidation
Aromatic hydroxylation
Aromatic, non-heterocyclic ring cleavage
Aromatic, heterocyclic ring cleavage
Hydrolysis
Hydrolytic dehalogenation
Halogen migration
Reductive dehalogenation
Dehydrohalogenation
Nitro-reduction
Phenoxyalkanoate herbicides
Alkyl carbamates, phenylureas, s-traizines
Organophosphorous pesticides, phenoxyalkanoate herbicides
Methoxychlor
Carbophenothio, prometryn, aldicarb
Nicotinic acid
Aldrin, heptachlor
2,4-D, nicotinic acid
Catechols, phenols, phenoxyalkanoate herbicides, carbaryl
Paraquat. Picloram, amitrole
Carbamates, organophosphates, urea and aniline herbicides
TCA, dalapon, chlorobenzoates
Anisoles, 2,4-D
DDT
p,p-DDT, Lindane
parathion
Selected degradates identified in the environment can result from multiple pesticides or
even from non-pesticidal sources. For example, the degradate DIA is a degradate of three
triazine herbicides: atrazine, cyanazine, and simazine; while DEA is a degradate of atrazine,
propazine, and cyprazine (Thurman et al. 1994; Scribner et al. 2000; Muir and Baker, 1976)
(Figure 3.1). The chlorinated phenols, (e.g., 2,4-dichlorophenol, a degradate of the herbicide
2,4-D), can enter the environment either during their manufacture and use or via the degradation
of phenoxycarboxylic acids (Health Canada, 1987). Therefore, when monitoring the occurrence
of degradates in raw water sources such as rivers and groundwater, in some cases it may be
difficult to identify the particular source of a degradate.
Cl
Cl
N
N
H
N
Cl
N
N
H
N
N
N
H
N
H
Cl
s im a z in e
N
N
N
N
H
N
H
N
c y a n a z in e
N
N
Cl
N
N
N
N
H
N
H
N
N
N
H
Cl
N
N
N
N
c y p r a z in e
a tr a z in e
Cl
N
H
N
H
p r o p a z in e
H 2N
NH2
N
N
N
H
DEA
D IA
Figure 3.1 Degradation of the triazine herbicides to DIA and DEA (adapted from (Scribner et al.
2000).
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A pesticide is ‘degraded’ its chemical structure changes, thereby forming a degradate.
These chemical changes can be large structural changes or small alterations of a single structural
moiety. Structural cleavage generally forms two much smaller compounds such as the
hydrolytic cleavage of the sulfonylurea herbicides. The process of pesticide degradation does
not have to be a reduction in structural size. Transformations can also slightly alter the structure
of a pesticide, producing a structurally similar degradate such as the hydrolytic de-chloroination
of the chloroacetamide herbicides (Roberts, 1998) (Figure 3.2).
When a small modification to a pesticide’s structure occurs and the majority of the
pesticide structure is still intact, it is possible for the degradate to maintain the same specific
mode of action of the parent compound. Some pesticides are specifically designed to use a
process such as this to enable greater efficiency. The precursor compound can be more stable or
can enter the target organism more effectively. A transformation then takes place, producing the
more active pesticide. Pesticides that act in this manner are known as pro-pesticides including
the thiophosphate class of organophosphorus (OP) insecticides which undergo oxidative
desulphurisation once in the target organism to the oxon forms, which are much more potent
acetylcholinesterase inhibitors (Drabek and Neumann, 1985) (Figure 3.3). In the environment,
the transformation of the pro-pesticide to the active form can occur. Current legislation in
Europe for placing new pesticides on the market ensures that the environmental risk assessment
process considers the active component of a pesticidal application (EU, 1994).
O
O
HO
Cl
N
N
O
O
N-(2,6-diethylphenyl)-2-hydroxy-N(methoxymethyl)acetamide
alachlor
O
Cl
NH2
S
O
N
N
O
Cl
H
N
H
N
N
O
S
O
N
O
2-chloro-4-hydroimidazolo[1,2-a]
pyridine-3-sulfonamide
N
N
H 2N
O
N
O
N
imazosulfuron
O
4,6-dimethoxypyrimidine-2-ylamine
Figure 3.2 The transformation and cleavage degradation pathways of chloroacetamide
(e.g., alachlor) and sulfonylurea (e.g., imazosulfuron) herbicides.
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S
Cl
Cl
O
P
O
Cl
P
O
O
Cl
N
O
Cl
O
O
chlorpyrifos
N
Cl
chlorpyrifos oxon
Figure 3.3 The oxidative desulphurisation of the insecticide chlorpyrifos
When pesticides are released into the environment a number of different degradates can
be produced. The extent of pesticide degradation and the identity and quantity of degradates
formed depend on the degradation pathways and environmental conditions that are experienced
(Roberts, 1998; Roberts and Hutson, 1999). Pesticide and degradate degradation, and hence,
degradate formation in soil is influenced by soil properties and conditions. These can be inherent
soil properties such as soil texture and pH or transient properties such as organic carbon content,
microbial ecology, water, and oxygen content.
Structurally identical and different degradates can be formed during different degradation
pathways, e.g., when both aerobic and anaerobic soil degradation of carbaryl form 1-napthol
while structurally different naphthoquinone degradates are formed (Figure 3.4). Due to the high
total usage of pesticides in agriculture when compared to other applications (Donaldson, Kiely,
and Grube, 2002), pesticide degradation in soil is one of the most important processes
determining which degradates could be present in potential drinking water sources. Many
factors determine the rate and route of pesticide degradation and hence, degradate formation.
Once a pesticide has undergone a degradation step, additional degradates can then be formed
from this degradate and alternative degradates formed from the pesticide via a different
degradation pathway. Following a single application of atrazine, degradate concentrations
identified in the vadose zone were in the order DEA > didealkylatrazine > DIA > HA. In the
following season when atrazine was not applied, degradate concentrations were in the order
didealkylatrazine > DEA > DIA > HA. This change in degradate concentration ratio is due to
the degradation of the DEA and DIA to didealkylatrazine (Pashin et al. 2000). This branching
degradation of pesticides, influenced by environmental conditions, can therefore produce a wide
range of degradates.
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NH2
O
Anaerobic soil degradation
H
HN
O
Aerobic soil degradation
H
H
Aqueous photolysis
methylamine
OH
4-hydroxyl carbaryl
OH
O
O
O
OH
HN
O
OH
carbaryl
O
1-napthol
salicylic acid
1,4-naphthoquinone
5-hydroxy-1-naphthyl
methylcarbamate
O
O
OH
OH
HN
1-naphthyl-(hydroxymethyl)
carbamate
O
5-hydroxyl carbaryl
O
2-hydroxy-1,4-naphthoquinone
Figure 3.4 Selected degradation pathways for the insecticide carbaryl (Boxall et al. 2004a).
The diversity of the microbial community is very important in the biotic degradation of
pesticides. As an example, the biotic degradation rate of endosulfan is influenced by the
degrading microbes; the fungal species Fusarium ventricosum that degrades endosulfan faster
than the bacterium Pandoraea sp. (Siddique et al. 2003). Moreover, microbial communities can
adapt to degrade compounds, increasing the degradation rate of a compound following its
subsequent application and therefore, degradate formation (Smith and Aubin, 1991). However,
not all pesticides show this increase in degradation rate following repeated application as some
compounds show no change (e.g., chlorpyrifos), while other show a reduction (e.g.,
chlorothalonil) (Singh et al. 2002). Generally, the biotic degradation of compounds decreases
with depth through the soil profile, due to the decrease in microbial biomass and organic carbon
content. However, the degradation of the chlorpyrifos primary degradate, 3,5,6-trichloro-2pyridinol, adheres to this principle while the degradation rate of the parent compound increases
down the soil profile. This increase in the chlorpyrifos degradation rate was due to an increase in
soil pH with depth in this specific soil (Baskaran et al. 2003). Where soil is amended with
organic material such as manure or slurry, pesticide and degradate degradation rate in the top soil
can be increased (Wagner and Zablotowicz, 1997; Benoit and Barriuso, 1997).
The oxygen levels under which degradation occurs can drastically alter the degradation of
pesticides and the formation of degradates. The degradation rate and pathway of a pesticide in
soil, sediment or groundwater can vary depending on whether the environmental compartment is
under aerobic or anaerobic conditions. The degradation rate of alachlor and the formation ratio
of two degradates (alachlor ESA and alachlor OA) differ when under aerobic and anaerobic
conditions (Graham et al. 2000). These two degradates of alachlor are commonly identified in
aerobic environmental compartments (Aga and Thurman, 2001; Kalkhoff et al. 1998). Different
degradates (e.g., acetyl alachlor and diethyl aniline) are identified under methnogenic and
sulphate-reducing conditions (Novak et al. 1997).
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METHODS FOR DETERMINING TRANSFORMATION ROUTES
A number of approaches are available for identifying the degradates of a pesticide
include experimental methods and predictive approaches.
Experimental methods
The pathway of degradation of a substance in soil is typically determined according to
Organisation for Economic Co-operation abd Development (OECD) guidelines (OECD, 2002).
Soil is treated with radiolabelled test substance and incubated in the dark in biometer-type flasks
or in flow-through systems under controlled laboratory conditions (at constant temperature and
soil moisture). The soil used is typically a sandy loam or silty loam or loam or loamy sand with a
pH of 5.5-8.0, an organic carbon content of 0.5-2.5% and a microbial biomass of at least 1% of
the total organic carbon. After appropriate interval times, soil samples are extracted and analyzed
for the parent compound and the degradates. Volatile products are also collected for analysis
using appropriate adsorption devices. The studies are typically performed for up to 120 days.
Following removal from the test system, the substrate is extracted and total radioactivity in the
extracts is determined by liquid scintillation counting (LCS). Extracts can be further investigated
using thin layer chromatography (TLC) and radioscanning, by HPLC with a radiomatic flow
detector, or by fraction collection with LCS. Degradates can be identified by LC-MS, GC-MS
and nuclear magnetic resonance (NMR).
Sediment/water degradation studies are carried out using a similar approach to the soil
degradation studies. Experiments are typically performed on sediments with a high and low
organic matter contents and are carried out in static systems consisting of an anaerobic sediment
and an aerobic water phase. The water/sediment systems are pre-incubated to establish an
anaerobic environment. During pre-incubation pH, oxygen content and redox potential are
carefully monitored. Radiolabelled test substance is added to the water phase and incubated for
up to 14 weeks. CO2 evolution is monitored at regular intervals and both sediment and water
phases are analyzed separately for parent compound, major degradates and bound residue.
Predictive approaches
Degradation route studies are complex and costly, and it is often very difficult to identify
the minor degradates in a system. Information is available for a wide range of pesticides (e.g.,
Roberts, 1998; Roberts and Hutson, 1999), but limited information is available for other
substances. An alternative to experimental testing might be to use structure-biodegradability
relationships (SBR) to predict degradation pathways from the chemical structure of the parent
compound. Predictive techniques such as SBR are commonly known as QSAR (quantitative
structure property activity relationships). A number of systems have been developed for doing
this including BESS (Punch et al., 1996), PPS (Hou et al. 2003) and CATABOL (Jaworska et al.
2002). BESS is a computerized system that simulates the biodegradation of compounds through
sequential application of plausiable biochemical reactions (Punch et al. 1996). PSS is a webbased system that can predict biodegradation of most aliphatic and aromatic organic functional
groups containing C, H, N, O and halogens (Hou et al. 2003). HCATABOL is a probabilistic
approach to modeling biodegradation based on aerobic microbial transformation pathways
generated from MITI-I tests and expert judgement (Jaworska et al. 2002). CATABOL has been
evaluated for determining transformation pathways for pesticides in soil (Sinclair et al. 2003).
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Comparison of predictions with experimental observations indicated that only 24% of
experimentally derived degradates are predicted correctly. Further development of this and other
expert systems is therefore required before they can usefully be used to identify or predict
degradates.
CHARACTERISTICS OF DEGRADATES OF MAJOR PESTCIDES
Data from experimental studies into the transformation of major use pesticides are
summarized in Appendix 1. The data details the extent of formation (i.e., percentage of applied
pesticide) for 215 degradates formed from 62 pesticides. 122 of these degradates were identified
as being formed at ≥ 10% of the applied pesticide in one or more degradation studies (Figure 3.5;
Table 3.2). Therefore, based on the definition in the EU, these compounds can be considered
‘major metabolites’. The extent of degradate formation is presented in Figure 3.5, where each
identified degradate is represented by the extent of its formation in the degradation study where
it is most prevalent. There are a number of degradates (8) with a formation >80% of the applied
pesticide.
Four of these compounds are pesticides that act as a pro-pesticide and their
transformation to the active component can be expected at a high rate, e.g., diclofop-methyl,
fluzifop-p-butyl, fluoroglucofen-ethyl and carbofuran. The data in Figure 3.5 include aerobic
and anaerobic soil degradation, sterile hydrolysis, aquatic and soil photolysis, column and
lysimeter leachate studies and degradation in water/sediment systems. The most common
formation data available in the literature is degradate formation during pesticide degradation in
aerobic soil; ~44% of data points are of this type.
60
Transformation products (n)
50
40
30
20
10
0
0
-<
5
5-
0
<1
10
20
-<
80
70
60
50
40
30
-<
-<
-<
-<
-<
-<
0
0
0
0
0
0
7
6
5
4
3
2
Transformation product formation (% of pesticide)
80
90
-<
90
00
-1
Figure 3.5 Formation of pesticide degradates as a percentage of the parent pesticide (each
degradate is represented by the degradation study where it was most prevalent)
20
©2008 AwwaRF. ALL RIGHTS RESERVED
No conclusions should be drawn about the ratio of major to minor degradates identified
in this review. Degradation studies and the relevant legislation are biased toward identifying
those degradates formed in greater amounts because these that could pose the greatest risk. Due
to restraints on time and money, limitations in analytical capabilities, and the perceived
unimportance of degradates formed in small quantities, these compounds are rarely identified or
quantified during degradation studies undertaken for the purposes of pesticide registration. For
example, when the fate of alachlor is investigated, generally alachlor ESA, alachlor OA, and 2,6diethylaniline are identified in surface water, groundwater, soil and sediment (e.g., Graham et al.
1999 ; Graham et al. 2000 ; Fava et al. 2000 ; Scribner et al. 2000 ; Osano et al. 2003).
However, an extensive investigation into the occurrence of alachlor degradates in groundwater
following agricultural application identified at least twenty different degradates, a number of
which occurred in the ng L-1 range (Potter and Carpenter, 1995). Therefore, a number of
degradates may be formed in quantities two or three orders of magnitude less than the major
degradates of a pesticide. However, the importance of these compounds is probably negligible
when compared to the possible risks posed by either the pesticide itself or its major degradate(s).
21
©2008 AwwaRF. ALL RIGHTS RESERVED
Table 3.2
Summary of pesticide degradates identified as formed at ≥ 10% of the applied pesticide in one or
more degradation studies
Degradate a/b
Parent pesticide
1,2,4-benzenetriol
2,4-dichloroanisole
2,4-dichlorophenol
2-([N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)carbomyl]methylsulfonyl) acetic acid
acetochlor oxanilic acid
N-(2-ethyl-6-methylphenyl)-2-sulfoneacetamide
N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)-2-sulfoneacetamide
2,6-diethyl-N-methoxy-methoxanilic acid
2',6'-diethyl-N-methoxymethyl acetanilide
2,6-diethyl-N-methoxymethyl-2-sulpho-acetanilide
alachlor ethane sulfonic acid
alachlor oxamic acid
2-amino-4,6-dihydroxypyrimidine
2-amino-4,6-dimethoxypyrimidine
HOE 101630
HOE 101632
HOE 101633
HOE 101634
product A (unidentified)
dihydroxy anilazine
monohydroxy anilazine
deethylatrazine
DEHA
deisopropyl deethylatrazine
deisopropylatrazine
hydroxyatrazine
azoxystrobin acid
carbofuran
carbofuran phenol
N-hydroxy-methyl carbofuran
1,2,4-triazole
bitertanol benzoic acid
1-isopropyl-3-phenyl urea
1-tert-butyl-3-isopropyl-5-phenyl-2-biuret
buprofezin sulphoxide
5-amino-4-chloropyridazin-3(2H)-one
3-carbamyl-2,4,5-trichlorobenzoic acid
3,5,6-chloro-2-pyridinol
2-amino-4-methoxy-6-methyl-1,3,5-triazine
2-chlorobenzene sulfonamide
T1S
T2
T2SO
T2SO2
T3
TSO
Ia
Ib
2,4-D
2,4-D
2,4-D
acetochlor
acetochlor
acetochlor
acetochlor
alachlor
alachlor
alachlor
alachlor
alachlor
amidosulfuron
amidosulfuron
amidosulfuron
amidosulfuron
amidosulfuron
amidosulfuron
amidosulfuron
anilazine
anilazine
atrazine
atrazine
atrazine
atrazine
atrazine
azoxystrobin
benfuracarb
benfuracarb
benfuracarb
bitertanol
bitertanol
buprofezin
buprofezin
buprofezin
chloridazon
chlorothalonil
chlorpyrifos
chlorsulfuron
chlorsulfuron
cycloxydim
cycloxydim
cycloxydim
cycloxydim
cycloxydim
cycloxydim
cyhalothrin
cyhalothrin
(continued)
22
©2008 AwwaRF. ALL RIGHTS RESERVED
(continued)
melamine
ethyl-m-hydroxyphenyl carbamate
compound II
pyrimidinol
3,6-dichlorosalicylic acid
4-(2,4-dichlorophenoxy)phenol
diclofop acid
N-demethyldimefuron
O,O-dimethylphosphorothioic acid
O-desmethyldimethoate
DPX M6316 triazine amine
DPX M6316 triazine urea
Cl-Vacid
CONH2-fen
fenoxaprop-ethyl acid
2,2,3,3-tetramethyl cyclopropane carboxylic acid
3-phenoxybenzoic acid
a-(2,2,3,3-tetramethylcyclopropyl)-3-phenoxybenzyl cyanide
a-carbomoyl-3-phenoxybenzyl-2,2,3,3-tetramethyl cyclopropane carboxylate
R0 15-6045
1,3-dimethyl-5-phenoxypyrazole-4-carbonitrile
M3
M4
compound V
compound VII
compound VIII
compound XII
RH-4515
RH-5781
RH-5782
RH-5783
RH-9985
RH-9986
RH-9987
1H-1,2,4-triazole
bis (4-fluorophenyl)methyl silanol
fluzifop acid
fomesafen amine
fomesafen amino acid
3-methyl phosphinico-proprionic acid
HOE 35956
HOE 64619
HOE 64620
HOE 64621
HOE 85355
HOE 72829
HOE 83348
HOE 87607
HOE 88989
1,5-bis(-p-tolyl)-1,4-pentadiene-3-one
cyromazine
desmedipham
diazinon
diazinon
dicamba
diclofop-methyl
diclofop-methyl
dimefuron
dimethoate
dimethoate
DPX M6316
DPX M6316
esfenvalerate
esfenvalerate
fenoxaprop-ethyl
fenpropathrin
fenpropathrin
fenpropathrin
fenpropathrin
fenpropidin
fenpyroximate
fenpyroximate
fenpyroximate
fluazinam
fluazinam
fluazinam
fluazinam
fluoroglycofen-ethyl
fluoroglycofen-ethyl
fluoroglycofen-ethyl
fluoroglycofen-ethyl
fluoroglycofen-ethyl
fluoroglycofen-ethyl
fluoroglycofen-ethyl
flusilazole
flusilazole
fluzifop-P-butyl
fomesafen
fomesafen
glufosinate
ammonium
glufosinate
ammonium
glufosinate
ammonium
glufosinate
ammonium
glufosinate
ammonium
glufosinate
ammonium
HOE 070542
HOE 070542
HOE 070542
HOE 070542
hydramethylnon
(continued)
23
©2008 AwwaRF. ALL RIGHTS RESERVED
(continued)
2H-azolidino[3,4-b]quinoline-1,3-dione
3-imino-2H-azolidino[3,4-b]quinolin-1-one
M1
quinoline-2,3-dicarboxylic acid
quinoline-3-carboxylic acid
1-(6-chloro-pyridine-3-ylmethyl)-2-imino-imidazolidine
2-propenyl butyl-carbamate
propargyl butyl carbamate
acetic acid
formic acid
malonamic acid
malonic acid
N-methyl malonamic acid
RH 886 oxide
kresoxim-methyl acid
malathion dicarboxylic acid
2-N-(2,6-dimethylphenyl)-2-methoxyacetylamino propanoic acid
carbinol
2-(aminosulfonyl) benzoic acid
methyl-2-(aminosulfonyl)benzoate
saccharin
N-(1,1-dimethylacetonyl)-3,5-dichlorobenzamide
imazaquin
imazaquin
imazaquin
imazaquin
imazaquin
Imidacloprid
IPBC
IPBC
kathon 886
kathon 886
kathon 886
kathon 886
kathon 886
kathon 886
kresoxim-methyl
malathion
metalaxyl
metolachlor
metsulfuron-methyl
metsulfuron-methyl
metsulfuron-methyl
propyzamide
a - a full list of degradates and their formation data available in Appendix 1
b - Appendix 7 contains IUPAC names for degradates represented by abbreviations
FATE OF DEGRADATES IN THE ENVIRONMENT
Like all organic substances, once formed in the environment, a degradate may be
degraded by biotic and abiotic processes and may be transported between the different
environmental compartments. A large body of data is available on the persistence and mobility
of pesticide degradates (Appendix 2 and 3).
Degradation in the environment
Available data on the degradation rate of pesticide degradates in different environmental
compartments and under different conditions is provided in Appendix 2. This data comprises
DT50 data and half-life data (t½) DT50 is the time required for one-half the initial quantity or
concentration of a compound to dissipate from a system, whilst half-life is the time taken for the
concentration of a pesticide in a compartment to decline by one half (Holland 1996). The data
are summarized in Figure 3.6 and demonstrate that degradates can be degraded by a range of
processes. Fifteen of the degradates, 55%, are moderately to very persistent in aerobic and
anaerobic soil.
When degradation data for pesticide degradates (Appendix 2) is compared to their
parental compounds (Figure 3.6), 73.6% of the degradates have equal or greater persistence than
the pesticide (Figure 3.6 contains data collected in this review collated with data presented in
Boxall et al. 2004b). When summarizing these data, it is not possible to generalize that
degradates are more persistent than parent pesticide, because the dataset is probably skewed.
Data pertaining to more persistent degradates is probably more likely to be reported during a
24
©2008 AwwaRF. ALL RIGHTS RESERVED
study while data concerning rapidly degrading degradates is unlikely to be reported at all (Boxall
et al. 2004b). Although no generalizations can be made about a pesticide and its degradates
persistence, this dataset includes a number of degradates that are more persistent than the
pesticide. Therefore, these compounds can remain in the environment longer than the parent and
have the potential to contaminate raw water sources.
25
Transformation products (n)
20
sediment
anaerobic soil degradation
water sediment system
sterile hydrolysis
surface water
sewage
aerobic soil degradation
aqueous photolysis
15
10
5
0
<5
5 - 21
22 - 60
> 60
Degradation DT50/t½ (days)
Figure 3.6 The degradation of pesticide degradates, classified according to the Soil Survey
and Land Research Centre (SSLRC) persistence classification.
25
©2008 AwwaRF. ALL RIGHTS RESERVED
Transformation product DT50/t½ (days)
10000
1000
100
10
1
0.1
0.01
0.01
0.1
1
10
100
1000
10000
Pesticide DT50/t½ (days)
Figure 3.7 The comparative persistence of pesticides and their degradates in various
environmental media; aquatic photolysis (○), surface water (●), sterile hydrolysis (□),
aerobic soil (■), anaerobic soil (Δ), sediment (▲) and sediment/water system (×). The
diaganol line represents equal persistence.
Routes into environmental waters
NON-AGRICULTURAL
The monitoring and measurement of pesticides and their degradates is understandably
dominated by the occurrence of agricultural herbicides in agricultural areas. However, pesticides
are also widely used in other areas which could be an important source of degradates in
environmental waters. As discussed in Chapter 2, non-agricultural pesticide market sectors
include industrial, commercial, government and domestic (Donaldson et al. 2002). Due to the
method or site of application, pesticides used in these sectors can have the potential for direct
entry into surface waters. Following herbicidal application to hard surfaces such as asphalt and
concrete, more than half of applied atrazine and diuron can be lost to the highway drainage
system during the first 5 mm of rainfall (Ramwell et al. 2002). In the UK, five herbicides (2,4D, dichlobenil, diquat, glyphosate, terbutryn)and one plant growth regulator (maleic hydrazide)
are approved for use in or near water (Whitehead, 2004). Obviously, this method of application
can provide the pesticides with direct entry route into surface waters where they could degrade
and produce degradates in relatively large quantities. In contrast to agricultural streams, the total
insecticide concentration exceeds that of the total herbicide concentration in urban streams
(Hoffman et al. 2000). However, no insecticidal degradates were detected in urban streams
when sampled during one study, with DEA the only degradate identified (Hoffman et al. 2000).
26
©2008 AwwaRF. ALL RIGHTS RESERVED
Effects of climate and season
One of the dominate factors affecting the occurrence of degradates in environmental
waters (surface and ground) is climatic conditions. Peak concentrations of triazine degradates
(DEA and DIA) reach maximum concentrations following rainfall soon after atrazine application
and a dry summer (Thurman et al. 1994). Following dry summer conditions, the first large
rainfall event can ‘flush’ degradates from the soil resulting in peak concentrations in tile drains.
It is hypothesized that during the summer, degradates quantities increase and are stored in soil
which are then readily transported to tile drains by heavy rainfall. Metolachlor ESA and
metolachlor OA concentrations in tile drain samples peaked in the first tile drain flow in
November following a dry summer. These concentrations quickly declined once the stored
degradates had been flushed out of the soil (Phillips et al. 1999). These large peak
concentrations are observed in subsequent surface waters such as streams and rivers (Clark and
Goolsby, 2000; Boyd, 2000; Albanis and Hela, 1998) .
Mobility in the environment
One of the most important physico-chemical properties of a degradate for determining
whether it will be mobile and enter potential abstraction water is its organic carbon sorption
coefficient (Koc). The data collected during this review is provided in Appendix 3 and
summarized in Table 3.3. This property is a contributing factor to the extent to which a chemical
will adsorb to the soil. Compounds with a high Koc bind to the organic material in soil and
hence, have a low degree of mobility. Boxall et al. (2004b) investigated the relationship between
the sorption of degradates and their pesticidal parents from Koc data collected from numerous
databases. Approximately one third of the degradates had a Koc value of at least an order of
magnitude lower than the corresponding parent compound. During this study, sorption data was
collated from studies where both the parent and the transformation Koc were determined. This
was done so that comparative analysis would not be affected by inter-laboratory variability.
When Koc is determined experimentally, it is usual to use a number of different soils with
varying properties (e.g., pH, clay content and % organic carbon content). This usually provides a
range of Koc values for each compound from the range of soil types used. Therefore, when
comparing the mobility of a pesticide to that of its degradate(s), the minimum Koc value for each
compound derived in a study was considered (Figure 3.8). 10% of the degradates had a Koc at
least an order of magnitude lower than their pesticide. When the mobility of the degradates
(including those without pesticide comparative data) are classified according to the SSLRC
mobility classification (Hollis, 1991), 50% of the degradates are categorized as mobile to very
mobile (Koc <75) with 35.5% categorized as slightly mobile (Koc 75 - 499).
27
©2008 AwwaRF. ALL RIGHTS RESERVED
100000
10000
Transformation product Koc
1000
100
10
1
0.1
0.1
1
10
100
1000
10000
100000
Pesticide Koc
Figure 3.8 The comparative sorption of pesticide degradates and their parent pesticides
The lower sorption coefficients and increased solubility of two atrazine degradates, (DEA
and DIA), indicate that they have a greater potential to move through the soil profile to
groundwater than does the parent compound (Mills and Thurman, 1994). The rate of
degradation and the sorptive behavior of pesticides and their degradates will determine their
persistence in soil and their mobility to surface and ground waters. Degradates of the triazine
herbicides, cyanazine (Reddy et al. 1997) and atrazine (Krutz et al. 2003), show equal or lower
levels of sorption to a range of soil types than the parent compound. This could increase their
mobility and thus, the potential to enter surface and ground waters. Moreover, the sorption of
degradates of the chloroacetamide herbicides alachlor and metolachlor is approximately equal to
or less than that for the parent compounds. However, the rapid rate of degradation (<2.4 days)
for all the degradates of these two herbicides will influence the extent of their persistence and
hence mobility (Fava et al. 2000).
28
©2008 AwwaRF. ALL RIGHTS RESERVED
Table 3.3
Summary table containing the organic carbon partition coefficient (Koc) for pesticide
degradates
Degradate a/b
Parent pesticide
Koc
2,4-dichlorophenol
2-chloro-2',6'-diethylacetanilide
2-hydroxy-2',6'-diethylacetanilide
2,6-diethylaniline
alachlor ethane sulfonic acid
4,6-dihydroxypyrimidin-2-yl-urea
2-amino-4,6-dimethyoxypyrimidine
HOE 101630
dihydroxy anilazine
deethylatrazine
deisopropylatrazine
diaminochlorotriazine
hydroxyatrazine
2-amino-N-isopropyl benzamide
N-methyl bentazone
3,5,6-trichloro-2-pyridinol
3,5,6-trichloro-2-pyridinol
desmethylpropanenitrile cyanazine
hydroxyacid cyanazine
deethylcyanazine
cyanazine amide
chloroacid cyanazine
3,6-dichlorosalicylic acid
diclofop acid
4-chlorophenol
HOE 35956
2,4-D
alachlor
alachlor
alachlor
alachlor
amidosulfuron
amidosulfuron
amidosulfuron
anilazine
atrazine
atrazine
atrazine
atrazine
bentazone
bentazone
chlorpyrifos
chlorpyrifos
cyanazine
cyanazine
cyanazine
cyanazine
cyanazine
dicamba
diclofop-methyl
dichloroprop
glufosinate
ammonium
imidacloprid
imidacloprid
imidacloprid
kresoxim-methyl
MCPA
metolachlor
metalochlor
182.9 - 481.5
148
45
357
182
0.4
89 - 11289
3 - 63
144 - 512
12.2 - 300
31 - 400
31 - 76
103 - 13797
54 - 260
90 - 370
70 - 159
76 - 126
15 - 133
11 - 130
26 - 82
16 - 75
7 - 11
504
191 - 334
95.4 - 227.8
16
imidacloprid-guanidine
imidacloprid-guanidine-olefin
imidacloprid-urea
kresoxim-methyl acid
2-methyl-4-chlorophenol
metolachlor ethane sulfonic acid
2-ethyl-6-methylaniline
189 - 211
2129 - 3805
2314 - 3083
17 - 24
123.8 - 261.1
195
197
a - a full list of degradate data available in Appendix 3
b - Appendix 7 contains IUPAC names for degradates represented by abbreviations
OCCURRENCE IN THE ENVIRONMENT
Whether pesticides are present in environmental waters (surface water and groundwater)
following their agricultural application is determined by a large number of factors including
climatic conditions (e.g., rainfall and temperature), mass transfer processes, chemical properties
(e.g., solubility, degradation and sorption), agricultural practices (e.g., application rate, tillage
practices land use), and specific location properties (e.g., soil properties, hydrological properties,
29
©2008 AwwaRF. ALL RIGHTS RESERVED
topography) (Lerch and Blanchard, 2003). All of these factors are also important in determining
whether degradates are present in surface water and groundwater. However the importance of
these factors in determining the fate of degradates when compared to pesticides will differ. If a
pesticide degrades rapidly in soil, then it is unlikely that this compound will be detected in
environmental waters; however, its degradates could form in relatively large quantities.
Therefore, rapid pesticide degradation is an advantageous property in preventing pesticide
contamination but possibly disadvantageous for preventing its degradates from entering
environmental waters. When the chloroacetamide herbicides are applied at the same rate during
normal agricultural practice, the ESA degradate of alachlor is present at higher concentrations
than metolachlor in soil, 43.5 µg kg-1 and 11.91 µg kg-1 respectively. This difference is due to
the relatively longer half-life of metolachlor (15.5 d) in soil and thus slower formation of
metolachlor ESA when compared to alachlor (8 d) (Aga and Thurman, 2001). However,
pesticide usage will be of greater importance in determining the degree of degradate occurrence
in environmental waters. In 1997, 5.8 - 7.3 million kg of alachlor was used in the agricultural
sector compared to 28.6 - 31.3 million kg of metolachlor (Kiely et al. 2004). Therefore even
though when applied at the same rate, alachlor ESA will be formed in greater amounts in soil,
the higher usage of metolachlor in the agricultural sector will mean that its degradates will be
detected at higher concentration and more frequently. Moreover, during monitoring studies of
surface and ground waters, metalchlor ESA is detected at higher concentrations and more
frequently than the alachlor ESA (Kalkhoff et al. 1998; Kolpin et al. 1998).
Pesticide degradates have been detected in numerous environmental compartments: soil,
soil leachate, tile drains, surface waters including agricultural ditches, streams, rivers, reservoirs,
canals, ponds, lakes and estuaries, groundwater, sediment, air including gaseous, and particulate
phases and rain (Appendix 4). Table 3.4 provides a summary of this occurrence in soil, surface
water, groundwater, raw source water, and finished drinking water. A number of pesticide
degradates have been detected in the environment, with 50 detected in soil, 29 detected in
groundwater and 26 detected in surface waters.
30
©2008 AwwaRF. ALL RIGHTS RESERVED
Table 3.4
A summary of pesticide degradate environmental occurrence date
Environmental
compartment
Soil
Degradate a/b
Parent pesticide
Concentration
3-chlorallyl alcohol
2,4-dichlorophenol
2,6-diethylaniline
2-chloro-2',6'-diethylacetanilide
alachlor ethane sulfonic acid
alachlor ethane sulfonic acid
deethylatrazine
1,3-dichloropropene
2,4-D
alachlor
alachlor
alachlor
alachlor
atrazine
ND
5 - 6 mg kg-1
ND
ND
0.08 - 0.142 mg kg-1
0.0435 - 0.21 mg kg-1
< 0.001 - 0.12 mg kg-1
deethylhydroxyatrazine
deisopropylatrazine
atrazine
atrazine
47 ± 4 - 17 ± 2 μg kg-1
< 0.001 - 0.027 mg kg-1
deisopropylhydroxyatrazine
hydroxyatrazine
atrazine
atrazine
0.021 - 0.074 mg kg-1
< 0.001 - 0.5 mg kg-1
carbofuran
1-(2,4-dichlorophenyl) ethan-1-ol
2,4-dichloroacetophenone
benfuracarb
chlorfenvinphos
chlorfenvinphos
< 1 - 6.3 mg kg-1
ND - 0.3 mg kg-1
0.3 - 0.4 mg kg-1
2,4-dichlorobenzoic acid
chlorfenvinphos
4.7 - 7.9 mg kg-1
2,4-dichlorophenacyl chloride
2,4-dihydroxybenzoic acid
chlorfenvinphos
chlorfenvinphos
0.1 - 4.8 mg kg-1
1.1 - 2.5 mg kg-1
2-hydroxy-4-chlorobenzoic acid
dichlorobenzyl alcohol
chlorfenvinphos
chlorfenvinphos
3.2 - 5.7 mg kg-1
0.5 mg kg-1
trichloroacetophenone
chlorfenvinphos
0.1 mg kg-1
SDS1449
SDS954
(4-amino-6-chloro(1,3,5-triazin-2yl))ethylamine
2-[(4-amino-6-chloro(1,3,5-triazin-2yl))amino]-2-methylpropanenitrile
2-chloro-4-(1-carbonyl-1methylethylamino)-6-amino-1,3,5-triazine
cyanazine acid
chlorthal-dimethyl
chlorthal-dimethyl
cyanazine
ND - 0.11 kg ha-1
ND - 2.09 kg ha-1
0.03 - 0.08 mg kg-1
cyanazine
< 0.01 - 0.02 mg kg-1
cyanazine
< 0.01 - 0.08 mg kg-1
cyanazine
0.72 - 1.66 mg kg-1
cyanazine amide
cyanazine
<0.01 - 1.1 mg kg-1
cyanazine hydroxy acid
3-phenoxybenzaldehyde
3-phenoxybenzoic acid
CCA
melamine
o,p’-DDD
o,p’-DDE
p,p’-DDD
p,p’-DDE
ethyl-m-hydroxyphenyl carbamate
diazoxon
2,5-dihydroxy-3,6-dichlorosalicylic acid
3,6-dichlorosalicylic acid
diclofop acid
2,4-difluoroaniline
3-(trifluoromethyl)phenol
DM2
DM3
DM4
N-demethyldimefuron
RH-6467
RH-9129
cyanazine
cypermethrin
cypermethrin
cypermethrin
cypromazine
DDT
DDT
DDT
DDT
desmedipham
diazinon
dicamba
dicamba
diclofop-methyl
diflufenican
diflufenican
diflufenican
diflufenican
diflufenican
dimefuron
fenbuconazole
fenbuconazole
0.1 - 0.79 mg kg-1
0.001 - 0.01 mg kg-1
0.001 - 0.01 mg kg-1
0.001 - 0.01 mg kg-1
0.05 - 1.4 mg kg-1
16 - 25.8 mg kg-1
> 0.02 mg kg-1
8 - 10 mg kg-1
18.9 mg kg-1
ND - 0.59 mg kg--1
ND
0.03 - 0.1 mg kg-1
0.05 - 1.25 mg kg-1
0.01- 0.28 mg kg-1
ND
ND
ND - 0.021 mg kg-1
ND - 0.027 mg kg-1
ND - 0.024 µg kg-1
0.1 mg kg-1
0.005 - 0.047 mg kg-1
ND - 0.05 mg kg-1
(continued)
31
©2008 AwwaRF. ALL RIGHTS RESERVED
(continued)
Environmental
compartment
Soil continued
Degradate a/b
Parent pesticide
Concentration
RH-9130
fomesafen amine
3-methyl phosphinico-proprionic acid
4-chloro-2-methylphenol
metolachlor ethane sulfonic acid
2-hydroxyquinoxaline
quinoxaline-2-thiol
fenbuconazole
fomesafen
glufosinate-ammonium
MCPA
metolachlor
quinalphos
quinalphos
ND - 0.063 mg kg-1
<0.02 mg kg-1
ND - 0.2 mg kg-1
5 - 6 mg kg-1
0.0036 - 0.128 mg kg-1
ND - 66 µg kg-1
ND - 42 µg kg-1
2,6-diethylaniline
2-chloro-2’,6’-diethylacetanilide
2-hydroxy-2’,6’-diethylacetanilide
alachlor ethane sulfonic acid
deethylatrazine
deisopropylatrazine
didealkylatrazine
hydroxyatrazine
RH-6467
RH-9129
RH-9130
2-ethyl-6-methylaniline
alachlor
alachlor
alachlor
alachlor
atrazine
atrazine
atrazine
atrazine
fenbuconazole
fenbuconazole
fenbuconazole
metolachlor
1 µg L-1
2.2 - 2.7 µg L-1
0.8 µg -1
3 - 73 µg L-1
0.3 - 29 µg L-1
< 0.02 - 15 µg L-1
0.2 - 1.25 µg L-1
0.08 - 0.37 µg L-1
trace
trace
trace
0.6 µg L-1
acetochlor oxanilic acid
alachlor ethane sulfonic acid
alachlor oxanilic acid
deethylatrazine
deisopropylatrazine
metolachlor ethane sulfonic acid
metolachlor oxanilic acid
acetochlor
alachlor
alachlor
atrazine
atrazine
metolachlor
metolachlor
ND - 0.08 µg L-1
ND - 48.84 µg L-1
ND - 0.17 µg L-1
0 - 29 µg L-1
0 - 12.14 µg L-1
ND - 1.26 µg L-1
ND - 0.29 µg L-1
2,4-dichlorophenol
acetochlor ethane sulfonic acid
acetochlor oxanilic acid
2,6-diethylaniline
2-chloro-2’,6’-diethylacetanilide
2-hydroxy-2’,6’-diethylacetanilide
alachlor ethane sulfonic acid
alachlor oxanilic acid
aldicarb sulfone
aldicarb sulfoxide
hydroxyatrazine
deethylatrazine
ND
< 0.2 - 1.6 µg L-1
ND - 1.4 µg L-1
ND - 0.924 µg L-1
ND - 0.35 µg L-1
ND - 0.9 µg L-1
< 0.2 - 27.8 µg L-1
ND - 0.54 µg L-1
ND
ND
< 0.2 - 8.8 µg L-1
ND - 28 µg L-1
8-hydroxy-bentazone
3-hydroxycarbofuran
cyanazine amide
deethylcyanazine
deethylcyanazine amide
p,p’-DDE
p,p’-DDE
2-isoprpyl-6-methyl-4-hydroxypyrimidine
diazioxon
dimethenamid ethane sulfonic acid
dimethenamid oxanilic acid
dichloromethylphenylurea
2,4-D
acetochlor
acetochlor
alachlor
alachlor
alachlor
alachlor
alachlor
aldicarb
aldicarb
atrazine
atrazine, cyprazine and
propazine
atrazine, cyanazine and
simazine
bentazone
carbofuran
cyanazine
cyanazine
cyanazine
DDT
DDT
diazinon
diazinon
dimethenamid
dimethenamid
diuron
ND - 27 µg L-1
ND
ND - 3.3 µg L-1
ND - < 0.05 µg L-1
< 0.05 µg L-1
ND
0.004 µg L-1
ND
ND
0.05 µg L-1
0.05 µg L-1
0.45 µg L-1
dichlorophenylurea
diuron
0.2 µg L-1
Vadose zone and
column leachate
Surface runoff
Surface water
deisopropylatrazine
ND - 15 µg L-1
(continued)
32
©2008 AwwaRF. ALL RIGHTS RESERVED
(continued)
Environmental
compartment
Degradate a/b
Parent pesticide
Concentration
3,4-dichloroaniline
diuron and propanil
0.31 - 0.9 µg L-1
endosulfan sulphate
flufenacet ethane sulfonic acid
flufenacet oxanilic acid
trifluoromethylphenyl urea
alpha-HCH
4-chloro-2-methylphenol
metolachlor oxanilic acid
metolachlor ethane sulfonic acid
metolachlor oxanilic acid
demethylnorflurazon
deisopropylprometryn
endosulfan
flufenacet
flufenacet
fluometuron
gamma-HCH
MCPA
metolachlor
metolachlor
metolachlor
norflurazon
prometryn
0.006 µg L-1v
0.06 µg L-1
0.05 µg L-1
ND
ND
ND
1 - 10 µg L-1
0.1 - > 20 µg L-1
ND - 1.3 µg L-1
0.17 µg L-1
ND
2,4-dichlorophenol
acetochlor ethane sulfonic acid
acetochlor oxanilic acid
2',6'-diethylacetanilide
2,6-diethylanailine
2',6'-diethylformanilide
2'-acetyl-6'-ethylacetanilide
2'-acetyl-6'-ethyl-Nmethoxymethyl)acetanilide
2-chloro-2'-ethyl-6'-ethyl-N(methoxymethyl)acetanilide
2-hydroxy-2',6'-diethyl-Nmethoxymethyl)acetanilide
2-hydroxy-2',6'-diethyl-N-methyl)acetanilide
7-ethylindoline
alachlor ethane sulfonic acid
alachlor oxanilic acid
N-(2,6-diethylphenyl) methylene
N-(2,6-diethylphenyl)-N(methoxymethyl)acetamide
α-N-[(2'-6'-diethylphenyl)amino]ethanol
hydroxyatrazine
deethylatrazine
deisopropylatrazine
cyanazine amide
deethylcyanazine
deethylcyanazine amide
dacthal diacid
dacthal mono acid and dacthal diacid
combined
p,p’-DDE
p,p’-DDE
AMPA
α-HCH
metolachlor ethane sulfonic acid
metolachlor oxanilic acid
2,4-D
acetochlor
acetochlor
alachlor
alachlor
alachlor
alachlor
alachlor
4 µg L-1
ND - 8.6 µg L-1
ND - 11.5 µg L-1
< 0.002 - 0.13 µg L-1
< 0.002 - 0.085 µg L-1
< 0.002 - 0.087 µg L-1
0.028 - 0.12 µg L-1
0.068 - 0.24 µg L-1
alachlor
< 0.002 - 0.31 µg L-1
alachlor
< 0.002 - 0.1 µg L-1
alachlor
alachlor
alachlor
alachlor
alachlor
alachlor
< 0.002 - 0.13 µg L-1
< 0.002 - 0.035 µg L-1
ND - 9.32 µg L-1
ND - 33.4 µg L-1
< 0.002 - 0.01 µg L-1
0.1 - 0.55 µg L-1
alachlor
atrazine
atrazine and propazine
atrazine, cyanazine, simazine
cyanazine
cyanazine
cyanazine
dacthal
dacthal
<0.00 2 - 0.48 µg L-1
ND - 1.3 µg L-1
ND - 5 µg L-1
ND - 1.17 µg L-1
ND - 0.64 µg L-1
ND
ND
2.22 µg L-1
ND - 158.2 µg L-1
DDT
DDT
glyphosate
lindane
metolachlor
metolachlor
0.006 µg L-1
0.03 µg L-1
1.6 µg L-1
0.059 µg L-1
ND - 8.6 µg L-1
ND - 15.3 µg L-1
atrazine
atrazine
atrazine
azinphos-methyl
0.14 - 0.38 µg L-1
0.08 - 0.14 µg L-1
0.8 µg L-1
0.263 µg L-1
Surface water
continued
Groundwater
Raw source water
Reservoir
deethylatrazine
deisopropylatrazine
hydroxyatrazine
azinphos-methyl-oxon
(continued)
33
©2008 AwwaRF. ALL RIGHTS RESERVED
(continued)
Environmental
compartment
Reservoir continued
Degradate a/b
Parent pesticide
Concentration
disulfoton sulfone
disulfoton sulfoxide
fenamiphos sulfone
fenamiphos sulfoxide
malaoxon
disulfoton
disulfoton
fenamiphos
fenamiphos
malathion
0.013 µ g L-1
0.06 µg L-1
0.005 µg L-1
0.021 µg L-1
ND
o-p’-DDA
p-p’-DDA
DDT
DDT
0.28 µg L-1
1.7 µg L-1
azinphos-methyl-oxon
disulfoton sulfone
disulfoton sulfoxide
fenamiphos sulfone
fenamiphos sulfoxide
malaoxon
azinphos-methyl
disulfoton
disulfoton
fenamiphos
fenamiphos
malathion
0.026 µg L-1
ND
ND
0.011 µg L-1
0.022 µg L-1
0.106 µg L-1
Abstraction wells
Finished drinking
water
a - a full list of degradate data available in Appendix 4
b - Appendix 7 contains IUPAC names for degradates represented by abbreviations
Soil
Degradates can be expected to be present in soil following the application of the parent
compound if it is susceptible to biotic or abiotic degradation. The review, identified six
degradates have been detected in soil at concentrations greater than 5 mg kg-1: carbofuran, 2hydroxy-4-chlorobenzoic acid, 2,4-dichlorobenzoic acid, p,p’-DDD, o,p’-DDD, and p,p’-DDE.
The three DDT degradates were detected in soil from a former cattle tick dip site in Australia
(Van Zweiten et al. 2001). Therefore, these concentrations can be considered an exception
rather than the rule as sampling was targeted at a known hotspot. Similarly, the high
concentrations of the chlorfenvinphos degradates, 2-hydroxy-4-chlorobenzoic acid ( 3.2 - 5.7 mg
kg-1) and 2,4-dichlorobenzoic acid (4.7 - 7.9 mg kg-1) in soil were detected following a targeted
sampling strategy (reported in PSD, 1994k). Chlorfenvinphos was applied around the stem of
cauliflower and brussel sprout plants, with subsequent soil samples collected 10 cm around the
base of the plants again targeting the sampling to known hotspots, which may not be
representative of the field as a whole. The final degradate identified was the active component
of the insecticide benfuracarb, carbofuran (6.3 mg kg-1) (PSD, 1998a). This pro-pesticide
utilizes the degradation of benfuracarb to form the potent acetylchloinesterase inhibitor
carbofuran and, in soil, undergoes hydrolysis to carbofuran (Roberts and Hutson, 1999), so high
concentrations can be expected.
Surface water
Whether degradates are present in surface waters at larger or smaller levels than the
parent compound depends on the pesticide and degradates concerned. Seven degradates have
been identified in tile drain water (Appendix 4). Four of these have been observed at peak
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concentrations greater than 3 µg L-1: cyanazine amide, deethylatrazine, metolachlor OA and
metolachlor ESA. Following the agricultural application of atrazine and cyprazine, the peak
concentrations observed in tile drains were larger for the parent compounds for two consecutive
seasons than for their degradate DEA. However, the total loss over the same period is greater for
DEA than for either herbicide. Total losses via tile drains of two cyanazine degradates
(cyanazine amide and DIA) are an order of magnitude greater than the parent compound, loses
of DIA formed solely from atrazine are an order of magnitude less than the parent compound
(Muir and Baker, 1976). Metolachlor degradates (metolachlor ESA and metolachlor OA) were
detected in tile drain samples at concentrations at least two orders of magnitude greater than their
herbicidal parent (Phillips et al. 1999).
A study of streams in the Midwestern USA monitored for triazine and chloroacetamide
herbicides and their degradates (Kalkhoff et al. 2003). The degradates monitored were the ESA
and OA of alachlor, acetochlor, and metolachlor and the triazine degradates cyanazine amide,
DEA, DIA, and HA. The frequency of detection of degradates in 70 streams varied from 23 to
96%, with seven degradates detected in more than 50% of the samples. Multiple degradates
were detected in all samples analyzed (Kalkhoff et al. 2003). In a study of streams and rivers of
Northern Missouri and Southern Iowa, DEA, DIA, HA, atrazine, and cyanazine amide were
detected in > 95% of the samples (Lerch and Blanchard, 2003). In surface water, the two main
metolachlor degradates, ESA and OA, were the major residue of metolachlor present (Phillips et
al. 1999).
When these surface waters will be used for drinking water supply, it is important to
determine in which phase the contaminants are found. In one study no atrazine and alachlor
degradates were detected in suspended sediment in the Mississippi River and its tributaries,
while both parents and their degradates were detected in the dissolved phase (Pereira and Rostad,
1990). This is important in determining which processes will be the most effective in removing
these compounds during water treatment.
Ultimately when degradates are present in rivers and streams, they will be transported to
estuarine and marine environments. The annual load of atrazine discharge to the Gulf of Mexico
in 1993 was estimated at 642 t (Clark et al. 1999). These calculations did not take into account
the discharge of atrazine degradates which could drastically increase the total atrazine residue.
The estimated discharge of DEA into the Greek Amvrakikos Gulf is greater than atrazine, 127.5
g day-1 and 122.7 g day -1, respectively (Albanis and Hela, 1998).
Groundwater
Degradates have been detected in groundwater at higher concentrations (Albanis et al.
1998; Ferrer et al. 2000) and more frequently (Kolpin et al. 2000; Kolpin et al. 2001) than their
parental compounds. Thirty degradates have been identified in groundwater during monitoring
studies (Appendix ). Primarily it is the degradates of the triazines (i.e. atrazine, cyanazine and
simazine) and the chloroacetamides (i.e. alachlor, acetochlor and metolachlor) that have been
detected in groundwater. Twenty-four degradates observed in groundwater originate from these
six herbicides while monitoring data concerning degradates from other from pesticide chemical
groups are limited. The presence of degradates in groundwater depends on the aquifer type, well
depth, surrounding geography, time of sampling (i.e. pre or post application), extent of pesticide
usage, degradate formation, mobility, and concentration in soil during groundwater recharge
(Kolpin et al. 1997; Burkart and Kolpin, 1993; Blanchard and Donald, 1997; Kolpin et al.
1996a). The peak concentration of any degradate identified in this review was 158.2 µg L-1 from
35
©2008 AwwaRF. ALL RIGHTS RESERVED
the combined concentration of dacthal diacid and dacthal monoacid in a groundwater sample
collected from the Malheur River Basin, Oregon (Monohan et al. 1995).
As well as the lateral movement of vadose zone water, the transport of degradates to
groundwater has been attributed to the hydraulic connection to surface waters such as rivers.
The movement of degradates from rivers, through aquifers and into collector wells, driven by the
collection of water has been identified as a means for pesticides and their degradates to enter
drinking waters (Verstraeten et al. 1999). Once degradates have entered groundwater, their
subsequent movement can be more (e.g., DIA) and less (e.g., DEA) retarded when compared to
their parents (e.g., atrazine) (Widmer and Spalding, 1995).
In comprehensive monitoring programs of pesticides and their degradates in
groundwater, degradates are some of the most frequently detected compounds (Kolpin et al.
1996b; Kolpin et al. 1997; Kolpin et al. 1998; Kolpin et al. 2000). Moreover, p,p’-DDE, a
degradate of the insecticide DDT, is still being detected in groundwater decades after a ban on
the use parent compound was imposed (Kolpin et al. 1996b). The detection frequency of
individual herbicides in groundwater is increased considerably when you consider their
degradates (Kolpin et al. 1998). Moreover, for a number of herbicides, the majority of the total
herbicide concentration was in the form of degradates (Kolpin et al. 2000; Kolpin et al. 2001).
Therefore, to fully establish the effect pesticide use has on groundwater, it is necessary to
quantify the degradates present. Generally, when groundwater monitoring for degradates is
undertaken, it is a few primary degradates that are actively sought for each pesticide. However,
a range of additional degradates present in low concentrations will also be present in the
groundwater.
OCCURRENCE IN DRINKING WATER SUPPLIES AND FATE DURING DRINKING
WATER TREATMENT
Pesticide degradates have been regularly identified in groundwater and surface waters
(Appendix 4). Hence, degradates must be present in raw water abstracted from these sources.
There is therefore, the potential for these degradates to be present in finished drinking water if
they are not removed during the treatment process. Five OP insecticide degradates have been
identified in water-supply reservoirs. Azinphos-methyl oxon, the active form of the pesticide
azinphos-methyl has been monitored at a mean concentration of 0.263 µg L-1 in the raw water for
eleven drinking water treatment plants in the USA (Nguyen et al. 2004). Moreover, the three
most commonly identified atrazine degradates, DEA, DIA, and HA have been measured at 0.38,
0.14 and 0.8 µg L-1 in reservoirs (Solomon et al. 1996). DDA is a polar degradate of the
organochlorine insecticide DDT, the use of which has been banned for a number of decades.
However, in Germany, several drinking water wells have been closed to keep the DDA
concentrations below the 0.1 µg L-1 drinking water tolerance level set by the EU (Heberer and
Dünnbier, 1999).
Two areas of importance concerning the fate of pesticide degradates during drinking
water treatment are, their removal from raw water; and their possible transformation during
treatment. Treatment processes such as coagulation, flocculation, sedimentation, and membrane
filtration will assist in the removal of degradates associated with any suspended sediment in the
raw water. Activated carbon adsorption, reverse osmosis, and nanofiltration can assist in the
removal of degradates associated with the aqueous phase (Wang and Song, 2004), there is the
potential for disinfection processes used during water treatment such as oxidation and advanced
36
©2008 AwwaRF. ALL RIGHTS RESERVED
oxidation utilizing chlorine, ozone, hydrogen peroxide, and UV to transform organic compounds
present in the raw water to additional compounds that need to be considered (USEPA, 2001).
It is the presence and transformation of both pesticides and their environmental
degradates to additional water treatment degradates that could pose a risk to human health.
There is very limited data available in the literature identifying which degradation pathways
pesticides and their environmental degradates would undergo during water treatment. There are
a number of processes utilized during water treatment that remove pesticides and their
degradates, however, chemical treatments can transform pesticides and their degradates into
additional compounds (USEPA, 2001).
Data are available on the removal of pesticides from raw water by various water
treatment processes, such as advanced oxidation with ozone and UV radiation (Collivignarelli
and Sorlini, 2004), nanofiltration (Van der Bruggen et al. 2001), and granular activated carbon
(Feleke and Sakakibara, 2001). Generally, pesticide degradates are smaller and more polar than
the parent compounds which could decrease the removal efficiency during treatment processes.
However, only limited data are available on water treatment process removal efficiencies of
pesticide environmental degradates.
The oxidative desulphorisation of OP insecticides occurs during chlorination when the
pesticides are present in raw water. This is where the thiophosphate moiety (P=S) is transformed
to a P=O moiety (Zhang and Pehkonen, 1999). This is an important transformation, especially
for human health, because it is the oxon form that is the active component of the pesticide.
These degradates are very potent acetylcholinesterase inhibitors, a mode of action that can affect
humans (Giesy et al. 1999). During the monitoring of supply reservoirs in the USA, the oxon
degradate of malathion, malaoxon, was not detected in the raw water, while the parent compound
was detected at 0.032µg L-1. Following water treatment, malathion was not detected in the
finished drinking water but maloxon was detected at 0.106 µg L-1 (Nguyen et al, 2004). These
oxon degradates of OP insecticides, such as diazoxon, are stable in water after their formation
even following chlorination. The carbamate insecticide thiobencarb and its degradates formed
following chlorination are degraded completely within 2 hours by the presence of chlorine in the
water (Magara et al. 1994). The chlorination process can therefore both transform insecticides
to stable active degradates and rapidly degrade them and their degradates. The herbicide
isoxaflutole rapidly degrades to a stable phytotoxic degradate, diketonitrile, under environmental
conditions. Chlorination of water containing diketonitrile rapidly degrades this compound to a
nonbiologically active benzoic acid degradate (Lin et al. 2003).
Using ozonation as a disinfection process instead of chlorination can also transform
organic compounds present in the raw water. DEA, DIA, deisopropylatrazine amide, and 2chloro-4,6-diamino-s-triazine have been identified as degradates formed from the major
degradation pathway following the ozonation of water containing atrazine (Adams and Randtke,
1992). When atrazine undergoes advanced oxidation during the water treatment process, two
degradates, not observed during environmental degradation, are formed, 2-chloro-4-ethylimino6-isopropylamino-s-triazine and 6-amino-2-chloro-4-ethylimino-s-triaizne (Acero et al. 2000).
Two degradates of the insecticide aldicarb, aldicarb sulfoxide and aldicarb sulfone, can
be removed during water treatment by reverse osmosis. The efficiency of removal of these
compounds depends on the membrane composition used. However, when these degradates are
present in raw water (groundwater) in the 11-47 µg L-1 concentration range, removal efficiency
is in excess of 90% (Reported in USEPA, 2001).
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©2008 AwwaRF. ALL RIGHTS RESERVED
DRINKING WATER STANDARDS
The USEPA has set maximum contaminate levels (MCL) for three individual pesticide
degradates, heptachlor epoxide, aldicarb sufone and aldicarb sulfoxide (Table 3.5). An MCL of
7 µg L-1 has been set for a combined concentration of aldicarb and its two degradates (USEPA,
2004). Current drinking water standards for pesticides in the EU are governed by the Drinking
Water Directive (98/83/EC). There are no discrete pesticide or pesticide degradate drinking
water quality standards set in the EU, however, concentrations of any pesticide and its “relevant
metabolites” must not exceed 0.1 µg L-1, with a total pesticide concentration not exceeding 0.5
µg L-1 (EU, 1998). In Australia, the maximum acceptable concentration (MAC) for atrazine is
set at 40 µg L-1. This concentration is set on the basis that DEA, DIA, diaminochlorotriazine and
HA may constitute approximately 50% of the total atrazine-derived triazine compounds in
environmental waters (NHMRC, 1996). Currently the health based guidelines for drinking water
set by the World Health Organisation contain drinking water standards for pesticides. There is a
combined pesticide and degradate guideline for DDT of 1µg L-1 (WHO, 2004). UK pesticide
advised daily intake (ADI) data and mammalian toxicity data for pesticide degradates are
provided in Appendix 5 and Appendix 6 respectively.
Table 3.5
Drinking water standards set for pesticide degradates
Region
Compound
Australia
Canada
Canada
Canada
heptachlor and heptachlor epoxide
2,3,4,6-tretrachlorophenol
pentachlorophenol
2,4,6-trichlorophenol
pentachlorophenol
2,4-dichlorophenol
phenoxycarboxylic acid
herbicides
aldicarb, aldicarb sulfone and aldicarb sulfoxide
atrazine and N-dealkylated metabolites
DDT and metabolites
heptachlor and heptachlor epoxide
total lindane
pesticides and their relevant metabolites
total pesticides
aldicarb sulfone
aldicarb
aldicarb sulfoxide
albicarb
aldicarb, aldicarb sulfone and aldicarb sulfoxide
heptachlor epoxide
heptachlor
DDT and metabolites
Canada
Canada
Canada (Ontario)
Canada (Ontario)
Canada (Ontario)
EU
EU
USA
USA
USA
USA
World
Parent pesticide
Standard
(µg L-1)
Source
0.05 b
100 c
5c
900 c
NHMRC, 1996
Health Canada, 1987
Health Canada, 1987
Health Canada, 1987
9c
5c
30
3
4
0.1
0.5
3a
4a
7a
0.2 a
1b
Health Canada, 1995
Health Canada, 1993
Ontario, 2002
Ontario, 2002
Ontario, 2002
EU, 1998
EU, 1998
USEPA, 2004
USEPA, 2004
USEPA, 2004
USEPA, 2004
WHO, 2004
a - maximum contaminate level (MCL)
b - guidance level
c - maximum acceptable concentration (MAC)
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©2008 AwwaRF. ALL RIGHTS RESERVED
CHAPTER 4
PRIORITISATION OF DEGRADATES
INTRODUCTION
It is clear from the data presented in Chapters 2 and 3 that a large number of pesticides
are in use and that these may be transformed into an even greater number of degradates. It will
be impossible to investigate the impacts of all pesticides and all degradates on drinking water
quality. There is therefore, a need to identify those degradates that have the greatest potential to
reach drinking water supplies and those which are of greatest concern in terms of human health.
In this Chapter, a simple prioritization approach to identify degradates of potential concern. The
approach is a risk-based approach is presented that considers the usage of parent substances, the
formation of degradates and their potential to be transported to surface waters and grounds as
well as potential impacts on human health. It is important to recognize that the approach has
been designed for ranking purposes only and a high risk index does not mean that a substance
poses an unacceptable risk to human health. As long as usage data are available, the approach
has can be applied across a range of scales including small catchments, states, and whole
countries. In this project, the prioritization scheme was applied to the major usage pesticides in
the USA and the UK. It is anticipated that the results of the prioritization exercise will be used to
steer future research and monitoring programmes.
PRIORITIZATION APPROACH
The impact of a degradate on drinking water quality will be determined by its potential to
enter drinking water supplies, its treatability and its potential effects on human health. The
prioritization approach is therefore, a risk based approach which considers both exposure and
effects.
Data selection
It is clear from Chapter 3 that a large body of data are available on the formation,
properties, and occurrence of degradates in the environment. While limited data are available on
the effects of degradates on human health, a significant quantity of data is available on the
impacts of the parent compounds. To ensure the integrity of the prioritization results, the
analyses should be based, where possible, on quality assessed data. During the registration
process, industry-generated data is subject to extensive review by regulators and data that have
been reviewed are presented in e.g., EPA and EU summary documents, and thus these
documents can be good data sources and should therefore be used in preference to other
published data.
Exposure
The potential for a degradate to reach drinking water supplies will be determined by a
range of factors, most notably, the amount of parent pesticide used, the way in which the parent
39
©2008 AwwaRF. ALL RIGHTS RESERVED
compound is used, the amount of a particular degradate formed, the mobility of the degradate,
and its persistence. The potential for a degradate to enter drinking water is determined using data
on each of these properties.
Risk characterization and ranking
The proposed has the form of RI, a risk index is derived from a degradate exposure index,
E, and the ADI using Equation 4.1. By ranking the risk indices for each major degradate formed
in a study system it is possible to identify those substances that pose the greatest risk to drinking
water supplies. This information can then be used to steer future monitoring and research.
RI =
Where RI
ADI
=
=
E
ADI
(4.1)
Degradate risk index
Acceptable daily intake (mg kg-1 body weight day-1)
It should be noted that this approach does not consider the formation of additional
degradates created from either pesticides or environmental degradates during water treatment
processes. The data availability was not sufficient to incorporate this component into the current
prioritization approach. There may therefore be a requirement in the future to update this
approach or develop an additional approach to include these ‘water treatment degradates’ when
sufficient data becomes available.
Calculation of exposure index
The exposure index (E) is calculated using Equation 4.2, where E is a unitless value that
reflects the amount of a degradate that could enter drinking water supplies relative to other
degradates formed in the system being investigated.
E = A⋅ F ⋅ P
Where E
A
F
P
=
=
=
=
(4.2)
Degradate exposure index
Degradate amount index
Fraction of degradate in the aqeous phase
Persistence index
AMOUNT OF DEGRADATE FORMED
Information from usage surveys is initially used to identify the pesticides in use in the
area of interest (this could be a country, a state or a catchment). Degradates from each pesticide
parent are then identified from degradation route studies along with information on the amounts
formed. It was recommended during the workshop organized during this study to develop the
approach that only major metabolites (i.e. those performed in concentrations >10% of the parent)
40
©2008 AwwaRF. ALL RIGHTS RESERVED
be considered. An index (A) that reflects the amount of degradate that will be released into the
system being considered is then calculated using Equation 4.3.
A=
Where A
U
Umax
f
=
=
=
=
U
f
U max
(4.3)
Degradate amount index
Amount of parent compound used (Kg yr-1)
Amount of highest usage pesticide used (Kg yr-1)
Fraction of degradate formed
SORPTION
Following release to the environment, the potential for a degradate to enter water bodies
will be determined by its sorption to soils or sediments. The sorption behavior of a compound
can be described by its sorption coefficient (Kd) or organic carbon normalized sorption
coefficient (Koc). Tthe exposure assessment, the fraction of metabolite that is likely to be in the
water component of the environment and which is therefore likely to enter drinking water
supplies is determined using Equation 4.4.
1
Kd + 1
Fraction of degradate in the aqeous phase
Sorption coeffient (cm-3 g-1)
F=
Where F
Kd
=
=
(4.4)
Typically, only Koc values will be available, if this is the case a total organic carbon
content of 2% should be assumed to derive the Kd. The sorption of polar and ionizable
compounds can be to clay minerals and metal oxides present in the soil. Therefore the
prioritization will be conservative for such compounds if Koc data is used as the data input.
PERSISTENCE
The amount of a degradate entering a drinking water supply will also be determined by
the persistence of the substance in the environment. This degradation index is determined using
Equation 4.5. The equation assumes that degradation follows first order kinetics and calculates
the fraction remaining after one year.
ln 2
P = e − DT 50
Where P
=
DT50 =
.365
(4.5)
Persistence index
Degradation half life for the degradate
The half life used in the calculations is determined by the way in which the parent
compound is used. For degradates of pesticides that are applied to soils, the lowest half life from
a degradation in soil study or a degradation in water study is used. For substances applied
41
©2008 AwwaRF. ALL RIGHTS RESERVED
directly to water or to hard surfaces, only the results from aquatic persistence studies should be
used.
Effects
Only limited data are available on the effects of degradates on human health. Therefore
information on the potential health effects of the associated parent compound is used in the
effects component of the prioritization exercise. Parent compounds are generally more toxic than
degradates so the use of parent data is likely to be conservative. The most relevant toxicological
endpoint for drinking water safety is the acceptable daily intake (ADI), ADI values are therefore
used in the prioritization approach.
PRIORITISATION OF PESTICIDES IN USE IN THE USA AND UK
The prioritization procedure was applied to major pesticides in use in the USA and UK in
order to illustrate the prioritization approach and to begin to identify degradates of potential
concern to the water industry. For many degradates, insufficient data were available to fully
prioritize the substance, in these instances conservative default values were assigned in order to
enable an initial prioritization, these defaults were:
Kd DT50 Fraction ADI -
0.02 cm-3 g-1 (i.e. Koc of 1 if soil organic carbon is 2%)
1000 days
1
lowest ADI in prioritization /10
The mobility, persistence and fraction formation default values were selected to represent
the ‘worst-case’ scenario and to ensure that the inclusion of degradates in the approach whose
dataset were incomplete was conservative in nature. A default Kd value of 0.02 (Koc = 1)
classifies a compound, according to the SSLRC mobility classification (Hollis, 1991) as highly
mobile. Similarly a persistence degradation rate of 1000 days would classify a compound as
highly persistent according to the SSLRC persistence classification (Hollis, 1991). A default
fraction value of 1 indicates that all of the applied pesticide would be degraded in the
environment to the degradate, data in appendix 1 indicate that this very rarely happens so this
value again can be considered as a worst-case estimate.
USA - Agricultural Pesticides
Pesticide usage data from the 1999 market estimates were used to prioritize those
degradates that were likely to be formed in the US environment (Donaldson et al. 2002).
Degradates of the 25 most widely used agricultural pesticides in the US were considered (Table
2.1)(Donaldson et al. 2002). For these 25 substances, eight had no environmental degradates
identified. The three highest use pesticides without any relevant degradates data were
metolachlor-s, propanil and chloropicrin. Fifty-six degradates were identified from the
remaining eighteen pesticides. The degradates with a risk index of greater than 0.5 are provided
in (Table 4.1). Appendix 8 provides a full index of all the prioritized degradates together with
42
©2008 AwwaRF. ALL RIGHTS RESERVED
information concerning whether experimental regulatory data or default values were used during
the prioritization. Application of the prioritization approach indicated that degradates of
alachlor, cyanazine, acetochlor and atrazine are likely to be of most concern to US water supplies
(Table 4.1).
43
©2008 AwwaRF. ALL RIGHTS RESERVED
Table 4.1
The risk index for degradates from the US most used agricultural pesticides where the risk
index is >0.5 (degradates were at least one default value was required in the prioritization
are represented in italics)
Pesticide
Degradate a
alachlor
2,6-diethyl-N-methoxymethyl-2-sulpho-acetanilide
47.58
alachlor
alachlor oxanilic acid
42.63
Risk Index
alachlor
2,6-diethyl-N-methoxy-methoxanilic acid
41.87
cyanazine
cyanazine acid
35.95
alachlor
alachlor ethane sulfonic acid
33.33
acetochlor
2-([N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)carbomyl]methylsulfonyl) acetic acid
33.30
acetochlor
acetochlor oxanilic acid
33.30
acetochlor
N-(2-ethyl-6-methylphenyl)-2-sulfoneacetamide
33.30
acetochlor
N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)-2-sulfoneacetamide
33.30
cyanazine
cynazine amide
32.62
alachlor
alachlor DM-oxanilic acid
32.35
alachlor
alachlor sulfinylacetic acid
30.83
alachlor
2',6'-diethyl-2-hydroxy-N-methoxymethylacetanilide
19.41
atrazine
DEHA
13.96
atrazine
deisopropyl atrazine
11.27
atrazine
DIHA
9.90
atrazine
diaminochloroatrazine
7.88
dichloropropene
3-chloroprop-2-enoic acid
7.61
dicamba
3,6-dichlorosalicylic acid
7.24
2,4-D
1,2,4-benzenetriol
6.28
atrazine
hydroxy atrazine
2.51
malathion
malathion dicarboxylic acid
2.43
metolachlor
metolachlor oxanilic acid
2.23
chlorothalonil
3-cyano-2,4,5,6-tetrachlorobenzamide
1.69
trifluralin
a,a,a-trifluoro-2,6-dinitro-N-propyl-p-toluidine
1.34
metolachlor
CGA-37735
1.18
chlorothalonil
3-carbamyl-1,2,4,5-tetrachlorobezoic acid
0.99
trifluralin
2,2'-azoxybis (a,a,a-trifluoro-6-nitro-N-propyl-p-toluidine
0.88
trifluralin
a,a,a-trifluoro-2,6-dinitro-p-cresol
0.79
trifluralin
2-ethyl-7-nitro-5-(trifluoromethyl) benzimidazole
0.76
chlorpyrifos
3,5,6-chloro-2-pyridinol
0.74
ethephon
2-hydroxy ethyl phosphonic acid
0.73
2,4-D
2,4-dichloroanisole
0.69
trifluralin
a,a,a-trifluoro-5-nitro-4-propyl-toluene-3,4-diamine
0.61
0.60
chlorothalonil
3-cyano-6-hydroxy-2,4,5-trichlorobenzamide
chlorothalonil
3-carbamyl-2,4,5-trichlorobenzoic acid
0.60
glyphosate
AMPA
0.52
trifluralin
[2,6-dinitro-4-(trifluoromethyl)phenyl]propylamine
0.50
a - Appendix 7 contains IUPAC names for degradates represented by abbreviations
44
©2008 AwwaRF. ALL RIGHTS RESERVED
USA - Home and Garden Use Pesticides
Pesticide usage data from the 1999 market estimates were used to prioritize those
degradates that were likely to be formed in the US environment (Donaldson et al. 2002).
Degradates of the 10 most used home and garden pesticides in the US were considered (Table
2.3)(Donaldson et al. 2002). For these 25 pesticides, five had no environmental degradates
identified. The three highest use pesticides without any relevant degradates data were MCPP,
dicamba and carbaryl. Thirteen degradates were identified from the remaining five pesticides.
The risk index and information concerning whether experimental regulatory data or default
values were used during the prioritization are provided in (Table 4.2). Application of the
prioritization approach indicated that degradates of diazinon, chlorpyrifos and 2,4-D are likely to
be of most concern to US water supplies. None of the identified degradates had full datasets
available for use during the prioritization.
Table 4.2
The risk index and data availability for degradates from the US most used home and
garden use pesticides (■ = experimental regulatory data available, □ = default value used in
the prioritisation)
Pesticide
Degradates
Formation
Kd
DT50
ADI
RI
diazinon
6-hydroxy-2-isopropyl-4-methylpyrimidine
■
□
□
■
246.98
chlorpyrifos
deethyl chlorpyrifos
□
□
□
■
11.28
2,4-D
1,2,4-benzenetriol
■
□
□
■
4.83
chlorpyrifos
3,5,6-trichloro-2-pyridinol
■
■
□
■
3.81
malathion
■
□
□
■
1.98
■
□
□
■
1.47
malathion
malathion demethyl dicarboxylic acid
O-ethyl O-(3,5,6-trichloro-2-pyridinol)
phosphorothioate
diethyl mercaptosuccinate
■
□
□
■
1.17
malathion
malathion demethyl monocarboxylic acids
■
□
□
■
1.07
malathion
ethyl hydrogen fumarate
■
□
□
■
0.96
malathion
malathion dicarboxylic acid
■
□
■
■
0.69
glyphosate
AMPA
■
■
□
■
0.28
2,4-D
2,4-dichlorophenol
■
■
□
■
0.22
malathion
malathion monocarboxylic acids
■
□
■
■
<0.01
chlorpyrifos
USA - Industrial/Commercial/Government Use Pesticides
Pesticide usage data from the 1999 market estimates were used to prioritize those
degradates that were likely to be formed in the US environment (Donaldson et al. 2002).
Degradates of the 10 most used industrial/commercial/government pesticides in the US were
considered (Table 2.2)(Donaldson et al. 2002). For the 10 pesticides, only one had no
environmental degradates identified (MSMA). Thirty degradates were identified from the
remaining nine pesticides. The risk index and information concerning whether experimental
regulatory data or default values were used during the prioritization are provided in (Table 4.3).
45
©2008 AwwaRF. ALL RIGHTS RESERVED
Application of the prioritization approach indicated that degradates of diuron, triclopyr,
chlorpyrifos and 2,4-D are likely to be of most concern to US water supplies. None of the
identified degradates had full datasets available for use during the prioritization.
46
©2008 AwwaRF. ALL RIGHTS RESERVED
Table 4.3
The risk index and data availability for degradates from the US most used
Industrial/Commercial/Government use pesticides (■ = experimental regulatory data
available, □ = default value used in the prioritisation)
Pesticide
Degradates
Formation
Kd
DT50
ADI
RI
diuron
chlorpyrifos
N'-(3,4-dichlorophenyl)-N-methylurea
5-chloro-3,6-dihydroxy-2-pyridinoloxyacetic
acid
deethyl chlorpyrifos
□
□
□
■
25.37
■
□
□
■
10.96
diuron
N'-(3-chlorophenyl)-N,N-dimethylurea
□
□
□
■
6.34
■
□
□
■
2,4-D
1,2,4-benzenetriol
6.34
■
□
□
■
triclopyr
4.83
3,5,6-trichloro-2-pyridinol
■
■
□
■
3.81
triclopyr
■
□
□
■
3.65
■
□
□
■
2.61
diuron
oxamic acid
5-cyano-4,6,7-tichloro2H-1,2-benzisothiazol-3one
3-chlorophenyl methylurea
■
□
□
■
2.54
diuron
phenyl-1,1-dimethylurea
■
□
□
■
2.54
diuron
N'-(3-chlorophenyl)-N-methyl urea
■
□
□
■
2.54
chlorpyrifos
3,5,6-trichloro-2-pyridinol
■
■
□
■
2.14
chlorothalonil
SDS-67042 sulphoxide
■
□
□
■
1.40
malathion
■
□
□
■
0.89
■
□
□
■
0.85
■
□
□
■
0.85
■
□
□
■
0.82
chlorothalonil
malathion demethyl dicarboxylic acid
2,5,6-trichloro-4-(glutathione-5yl)isophthalonitrile
2,5,6-trichloro-4-(thio)isophthalonitrile
O-ethyl O-(3,5,6-trichloro-2-pyridinol)
phosphorothioate
3-cyano-2,4,5,6-tetrachlorobenzamide
■
□
□
■
0.59
chlorothalonil
4-hydroxy-2,5,6-trichloroisophthalonitrile
■
■
□
■
0.57
malathion
diethyl mercaptosuccinate
■
□
□
■
0.53
malathion
malathion demethyl monocarboxylic acids
■
□
□
■
0.48
malathion
ethyl hydrogen fumarate
■
□
□
■
0.43
chlorothalonil
3-cyano-6-hydroxy-2,4,5-trichlorobenzamide
■
□
□
■
0.34
malathion
malathion dicarboxylic acid
■
□
■
■
0.31
glyphosate
AMPA
■
■
□
■
0.22
2,4-D
2,4-dichlorophenol
■
■
□
■
0.22
pendimethalin
2,6-dinitro-3,4-dimethyl aniline
■
□
□
■
0.14
diuron
3,4-dichloroaniline
■
□
□
■
0.13
chlorothalonil
3-carbamyl-2,4,5-trichlorobenzoic acid
■
■
□
■
0.10
malathion
malathion monocarboxylic acids
■
□
■
■
<0.01
triclopyr
chlorothalonil
chlorothalonil
chlorothalonil
chlorpyrifos
UK
In order to prioritize degradates that are likely to be formed in the UK environment,
pesticide usage data for the UK was generated by combining data presented in the most recent
pesticide usage reports produced by the Central Science Laboratory for various market sectors,
e.g., arable, outdoor vegetables and fodder crops (Garthwaite et al. 1999; Dean et al. 2001;
Garthwaite et al. 2001a; Garthwaite et al. 2001b; Hutson et al. 2001; Garthwaite and Thomas,
47
©2008 AwwaRF. ALL RIGHTS RESERVED
2003a; Garthwaite and Thomas, 2003b; Garthwaite et al. 2003; Stoddart et al. 2003). Fifty-four
pesticides were identified as representing 90% of all pesticide use in the agricultural sector in the
UK, of these, 18 either had no data available to identify their degradation pathway or identify
whether they had environmental degradates. The three highest use pesticides without any
relevant degradates data were chlormequat, MCPP and tri-allate. One hundred and eleven
degradates were identified from the remaining 36 pesticides and these substances were run
through the prioritization system. The degradates with a risk index of greater than 0.5 are
provided in (Table 4.4).
Table 4.4
The risk index for degradates from the UK most used agricultural pesticides where the risk
index is >0.5 (degradates were at least one default value was required in the prioritization
are represented in italics)
Pesticide
Degradate a
cyanazine
cyanazine acid
26.56
cyanazine
cynazine amide
24.11
isoproturon
1-methyl-3-(4-isopropyl phenyl)-urea
7.92
flufenacet
FOE sulfonic acid
4.67
bitertanol/tebuconazole
1,2,4-triazole
4.51
flufenacet
FOE oxalate
3.25
dicamba
3,6-dichlorosalicylic acid
3.15
atrazine/simazine
deisopropylatrazine
2.12
flufenacet
FOE methyl sulfone
2.03
flufenacet
FOE thioglycolate sulfoxide
2.03
flufenacet
thiadone
2.03
metaldehyde
acetaldehyde
1.63
bitertanol
bitertanol benzoic acid
1.59
atrazine
DEHA
1.29
Risk Index
propachlor
propachlor oxanilic acid
1.26
atrazine/simazine
DIHA
1.21
trifluralin
α,α,α-trifluoro-2,6-dinitro-N-propyl-p-toluidine
1.10
isoproturon
3-[4-(2’-hydroxy-2’-propyl)-phenyl]-methyl urea
1.01
bitertanol
4-hydroxybiphenyl
1.00
linuron
demethyl linuron
0.99
atrazine/simazine
diaminochloroatrazine
0.89
dimethoate
O-desmethyl dimethoate
0.81
propachlor
propachlor ethane sulfonic acid
0.72
trifluralin
2,2’-azoxybis (α,α,α-trifluoro-6-nitro-N-propyl-p-toluidine
0.72
2-chloroethylphosphonic acid
ethylene
0.67
trifluralin
α,α,α-trifluoro-2,6-dinitro-p-cresol
0.65
trifluralin
2-ethyl-7-nitro-5-(trifluoromethyl) benzimidazole
0.62
asulam
ionic form of asulam
0.61
chlorothanonil
3-cyano-2,4,5,6-tetrachlorobenzamide
0.61
chlorothanonil
3-carbamyl-2,4,5-trichlorobenzoic acid
0.60
metalaxyl
CGA-62826
0.57
chloridazon
5-amino-4-chloropyridazine-3(2H)-one
0.54
metalaxyl
2-N-(2,6-dimethylphenyl)-2-methoxyacetylamino propanoic acid
0.53
trifluralin
mecoprop-P
α,α,α-trifluoro-5-nitro-4-propyl-toluene-3,4-diamine
0.50
4-chloro-2-methyl phenol
0.50
a – Appendix 7 contains IUPAC names for degradates represented by abbreviations
48
©2008 AwwaRF. ALL RIGHTS RESERVED
Appendix 9 provides a full index of all the prioritized degradates together with information
concerning whether experimental regulatory data or default values where used during the
prioritization. Application of the prioritization approach indicated that degradates of cyanazine,
isoproturon and flufenacet are likely to be of most concern to US water supplies (Table 4.4). A
few degradates were produced by more than one degradate, therefore following the prioritization
of the risk index for these compounds was added so that the degradate has a single entry and the
priority would reflect the overall risk of the compound.
Sample calculation of the risk index
To assist in the use of this prioritization approach a sample calculation of the risk index
for one compound is provided below. Hydroxyatrazine is the highest degradate with no default
data points in both the UK and US prioritization. Therefore this compound was selected for the
sample calculation (using atrazine US usage data):
Available regulatory data for hydroxyatrazine
U
=
36287391 kg yr-1 (atrazine usage)
Umax =
36287391 kg yr-1 (atrazine highest use pesticide in US in 1999)
f
=
0.19
Kd 1.7
DT50 164 days
ADI 0.006 mg kg-1 body weight day-1
Calculation of amount index (A)
A=
36287391
0.19 = 0.19
36287391
Calculation of fraction of degradate in the water column (F)
F=
1
= 0.37
1.7 + 1
Calculation of persistence index (P)
P=e
ln 2
− 164 .365
= 0.21
Caluclation of exposure index (E)
E = 0.19 * 0.37 * 0.21 = 0.015
Calculation of the overall risk index (RI)
0.015
RI =
= 2.5
0.006
49
©2008 AwwaRF. ALL RIGHTS RESERVED
Use and limitations of the prioritization scheme
When undertaking a prioritization for an area of interest, it is the collection and collation
of relevant degradate data that is the most time consuming phase of the whole process. The
staring point to any prioritization is the definition of the system i.e. catchment, watershed,
country etc. The pesticide usage data collected for the system will define the scope of the
prioritization and a data collection phase can then get underway focusing on the pesticides used
within that system. Once a prioritization has been completed for a system it should be regularly
reviewed so that any new data, either pesticide usage or degradate formation and property data,
that has become available since the last prioritization is included. This is important if there is a
dramatic shift in pesticide usage patterns e.g. the banning of one pesticide and the resulting wide
scale use of another. Therefore at a minimum the pesticide usage component of a prioritization
should be updated when new data becomes available, which is generally annually. The first
implementation of a prioritization for a system will be the most labour intensive phase,
subsequent revisions should require significantly less resources. The implementation of a
prioritization will allow resources e.g. monitoring and treatment to be focused towards those
degradates of most concern. However the prioritization approach also has a number of
limitations which include:
•
•
•
•
The prioritization focuses on non-point source pollution from pesticides, point source
pollution e.g. spills, will not be identified;
Any prioritization is only as reliable as the data used to carry it out. Currently there are a
number of pesticides and their degradates without any suitable experimental regulatory
data;
Each prioritization focuses on pesticide usage data from an individual year, the inputs
from persistent pesticides and/or degradates from previous years are not accounted for in
the priority scheme; and
The approach does not provide any characterization of the risks posed by degradates
formed as part of the water treatment process.
50
©2008 AwwaRF. ALL RIGHTS RESERVED
CHAPTER 5
CONCLUSIONS AND FUTURE RESEARCH
CONCLUSIONS
Pesticide degradates are formed in the environment following the biotic and abiotic
degradation of pesticides. To date a number of pesticide degradates have been detected in the
environment, with 50 detected in soil, 29 detected in groundwater and 26 detected in surface
waters. Therefore, the potential for these compounds to enter water sources used for abstraction
is high. The frequency at which these compounds are detected as well as their peak and mean
concentrations vary greatly depending on the water body monitored. Higher concentrations are
often observed at water sources closer to the site of application. The concentration of degradates
can decrease by at least one or two orders of magnitude from surface runoff to the subsequent
streams and rivers (e.g., deethyatrazine). However, sometimes peak concentrations of degradates
detected in surface waters are less than the parent compound, the total loss over the same period
can be greater.
The presence of pesticide degradates in drinking water will depend on numerous factors
including physico-chemical properties, pesticide usage, pesticide application scenario, degradate
formation, degradate and pesticide biotic and abiotic degradation rates and elimination rates,
during water treatment. A number (122) of degradates have been observed in degradation
studies at >10% of the applied parent pesticide while >70% have slower degradation rates than
the parent compound. Therefore, there is the potential for these compounds to remain in the
environment. With 50% of the available sorption data for degradates indicating that their
mobility can be classified as mobile to very mobile, then there is obviously a great deal of
potential for these compounds to enter surface waters and groundwaters at levels that could be of
concern to the water industry.
In this study, the approach has been applied to degradates that are likely to be formed in
the US and UK agricultural environments. Using this approach degradates of alachlor,
acetochlor, cyanazine, atrazine, dichloropropene, dicamba, 2,4-D, chlorpyrifos, chlorothalonil,
flufenacet, isoproturon, simazine and propyzamide have been identified as being the highest
priority. Due to a large number of data gaps, these assessments were based on a significant
number of default values. However, most of the data required will have been developed by
pesticide companies during the registration process. In the near future therefore it would be
beneficial for the water industry and the pesticide manufacturers to work together to fill these
gaps and to develop a final prioritization list. Substances that then appear at the top of the list
should be the focus of any future work in these agricultural systems.
FUTURE RESEARCH
Once the most likely pesticides and degradates to be present in raw water are identified
via a prioritization approach (Chapter 4), further studies will be required. The final session of
the workshop was directed at identifying information and research needs specifically relating to
51
©2008 AwwaRF. ALL RIGHTS RESERVED
drinking water utilities. Four key areas were identified (i) information management, (ii) analysis,
(iii) monitoring and (iv) treatment. Treatment issues included studies into the fate of compounds
in conventional and advanced treatment processes and also the likely transformation of
compounds during treatment.
Identified research priorities:
1. Occurrence study of pesticide degradates was identified as the highest priority. The list
of priority pesticides and degradates produced from the workshop’s prioritization scheme
should be monitored for occurrence (in selected watersheds and treatment works) to
determine their levels in drinking water supplies and ‘test’ the prioritization scheme.
This is particularly true for compounds that are identified for which the USGS and other
agencies have not previously searched. Previous studies, including AWWA’s atrazine
degradate study and USGS monitoring could serve as a starting point.
2. A significant proportion of the workshop discussion focused on availability of
information required to run the prioritization scheme.
It was found that different
agencies possess valuable information for water utilities on toxicological effects,
analytical methods, physical properties, treatment effects, and occurrence levels. Some
information is considered proprietary, while other information is difficult to find. It
would be helpful to initiate a synthesis of available resources as well as a database of
information relevant to pesticides, degradates, and adjuvants beyond the scope of the
aforementioned workshop.
This information would allow future users of the
prioritization scheme to assess implications at a local level and for specific parent
compounds.
3. There is a need for analytical methods to be developed for degradates of interest to help
support occurrence and treatability studies.
4. The fate of parent and degradate compounds in water treatment processes was identified
as a knowledge gap and two approaches to screen compounds were identified. The first
is to use physiochemical information on identified compounds and relate these to
treatment categories. The second approach is laboratory based treatability assessments
on individual compounds or groups of compounds.
For both approaches specific
interest should be paid to the effect of oxidation processes such as chlorine,
chloramination, ozone, and advanced oxidation processes.
5. During the treatment of drinking water, it is possible for additional compounds, “water
treatment degradates”, to be formed from pesticides and their environmental degradates
present in the drinking water especially oxidation and disinfection processes. Therefore
it is important to identity the most likely transformation pathways to occur during water
treatment and identify these additional compounds. The identification of these
compounds was not a component of this study and needs further investigation.
6. Given the relative percentages of adjuvants used in pesticides versus other products, it
makes sense to include all sources in adjuvant studies, not just pesticides. Investigation
of relative source contributions to adjuvant levels in source waters and their fate in
drinking water treatment processes could help shed light on the issue.
52
©2008 AwwaRF. ALL RIGHTS RESERVED
CHAPTER 6
RELEVANCE FOR UTILITIES
One of the major water treatment process improvements in recent years has been the
ability to remove to very low levels a wide variety of pesticides. Monitoring and process
development research has primarily focused on the parent compounds and there is little
information available on the levels or fate of pesticide degradates and as yet there are few
regulatory limits on individual pesticide degradates. This project has shown that a wide range of
pesticide degradates have been detected in both groundwater and surface waters, and hence there
is potential for these compounds to enter water sources used for water supply. This report can be
used a reference source of pesticide usage and reported degradates, but it can also be used to
develop prioritization schemes for utilities interested in monitoring and removing degradates.
The prioritization scheme developed here can be applied across a range of scales from the
catchment scale to the international scale and can be used to produce ranking lists for individual
water treatment works. These ranking lists can then be used to support monitoring programmes
and treatability studies. For example, the prioritization scheme has been used here to identify
those substances that pose the greatest risk to drinking water supplies on a country wide level. It
has identified the degradates of alachlor, acetochlor, cyanazine, atrazine, dichloropropene,
dicamba and 2-4-D as likely to be of most concern to US water supplies whilst, in the UK,
degradates of cyanazine, isoproturon and flufenacet were ranked highest and should be selected
first for monitoring and treatability studies.
Using the prioritization scheme on a state or
catchment level will produce a more focused ranking for identifying monitoring and treatability
needs.
The project and the workshop identified knowledge gaps and resulting research needs,
some of which may be suited for AwwaRF funding but others of which may be more suitable to
organizations such the U.S. Environmental Protection Agency, U.S. Geological Survey and
Global Water Research Coalition (GWRC). The identified needs were grouped into six major
priorities and will help extend the usefulness of the prioritization scheme and our overall
knowledge on the analysis, occurrence and fate of pesticide degradates.
53
©2008 AwwaRF. ALL RIGHTS RESERVED
54
©2008 AwwaRF. ALL RIGHTS RESERVED
APPENDIX 1. THE EXTENT OF PESTICIDE DEGRADATE FORMATION IN THE ENVIRONMENT
Degradate formation
a
Percentage of
b
parent pesticide
Time
acetochlor
acetochlor
3 ± 1%
11%
trace
2-5%
10 ± 1%
2-5%
> 10%
> 10%
acetochlor
Degradate
Parent pesticide
2,4-dichlorophenol
2,4-D
2,4-dichloroanisole
2,4-D
acetochlor oxanilic acid
2-([N-(ethoxymethyl)-N-(2-ethyl-6methylphenyl)carbomyl]methylsulfonyl) acetic
acid
N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)-2sulfoneacetamide
N-(2-ethyl-6-methylphenyl)-2-sulfoneacetamide
2,6-diethyl-N-methoxy-methoxanilic acid
2,6-diethyl-N-methoxymethyl-2-sulphoacetanilide
alachlor ethane sulfonic acid
HOE 101630
c
Country
Reference
8 days
14 days
10 days
16 days
10 days
-
Canada
Canada
-
Smith and Aubin, 1991
Reported in Roberts, 1998
Reported in PSD 68
Reported in PSD 68
Smith and Aubin, 1991
Reported in PSD 68
Reported in Roberts, 1998
Reported in Roberts, 1998
> 10%
-
-
Reported in Roberts, 1998
acetochlor
alachlor
alachlor
> 10%
13 - 22%
15 - 25%
4 - 7 weeks
4 - 7 weeks
-
Reported in Roberts, 1998
Reported in PSD 22
Reported in PSD 22
alachlor
amidosulfuron
20%
7%
5.2%
49.6%
40.4%
21%
30%
19.2%
43%
21%
0.5%
9 - 12%
13.2%
4.6%
6.8% (sterile)
15.7%
7%
19%
0.7%
9 days
3 days
14 days
7 days
49 days
49 days
49 days
72 hours
366 days
46 hours
3 - 112 days
111 days
0 days
28 days
2 days
100 days
95 days
62 days
USA
USA
USA
USA
USA
-
Aga and Thurman, 2001
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994c
Assaf and Turco, 1994
Reported in Solomon et al.
1996
Assaf and Turco, 1994
Reported in Solomon et al.
1996
Assaf and Turco, 1994
aerobic soil
(laboratory)
55
©2008 AwwaRF. ALL RIGHTS RESERVED
2-amino-4,6-dihydroxypyrimidine
dihydroxy anilazine
amidosulfuron
anilazine
dihydroxy anilazine continued
hydroxyatrazine
anilazine
atrazine
deethylatrazine
atrazine
12.4%
4.18%
142 days
244 days
USA
-
deisopropylatrazine
atrazine
10.1%
95 days
USA
Degradate formation
Degradate
Parent pesticide
a
Percentage of
b
parent pesticide
Time
1.61%
c
Country
Reference
244 days
-
Reported in Solomon et al.
1996
Assaf and Turco, 1994
Reported in Solomon et al.
1996
Assaf and Turco, 1994
Assaf and Turco, 1994
Reported in Roberts and
Hutson, 1999
Reported in PSD 5
Reported in Roberts and
Hutson, 1999
Reported in PSD 92
Reported in Roberts and
Hutson, 1999
Reported in PSD 1993i
Reported in PSD 1993i
Reported in PSD 1993i
Reported in PSD 1993i
Reported in PSD 1993i
Reported in Roberts, 1998
Reported in Roberts, 1998
aerobic soil
(laboratory)
56
©2008 AwwaRF. ALL RIGHTS RESERVED
diaminochloroatrazine
atrazine
6.7%
0.7%
95 days
3 days
USA
-
DEHA
DIHA
azoxystrobin acid
atrazine
atrazine
azoxystrobin
11%
7.8%
20%
250 days
250 days
-
USA
USA
-
carbofuran
bitertanol benzoic acid
benfuracarb
bitertanol
73 - 93%
19%
0 days
30 days
-
bitertanol ketone
bitertanol
8.6%
< 2%
29 days
-
-
p-hydroxy buprofezin
buprofezin sulphoxide
buprofezin metabolite 9
1-tert-butyl-3-isopropyl-5-phenyl-2-biuret
1-isopropyl-3-phenyl urea
5-amino-4-chloropyridazin-3(2H)-one
5-amino-4-chloro-2-methyl-2-hydropyridazin-3one
3-carbamyl-2,4,5-trichlorobenzoic acid
buprofezin
buprofezin
buprofezin
buprofezin
buprofezin
chloridazon
chloridazon
< 3%
< 3%
< 3%
< 3%
< 3%
46.6%
1.3%
150 days
150 days
150 days
150 days
150 days
187 days
187 days
-
chlorothalonil
25%
56 days
Brazil
Regitano et al. 2001
4-hydroxy-2,5,6-tetrachloroisophthalonitrile
3-cyano-2,4,5,6-tetrachlorobenzamide
3,5,6-chloro-2-pyridinol
3,5,6-chloro-2-pyridinol
desethyl chlorfenvinphos
2,4-dichlorophenyl)-ethan-1,2-diol
1-(2,4-dichloroheny etha-1-ol
2,4-dichloroacetophenone
2,4-dichlorophenyl chloride
2,4-dichlorophenyloxrane
salts or conjugates desethyl chlorfenvinphos
2-chlorobenzene sulfonamide
T2SO
T2SO2
T2SO
T2SO2
TSO2
T1SO
T1S
CCA
chlorothalonil
chlorothalonil
chlorpyrifos
chlorpyrifos
chorfenvinphos
chorfenvinphos
chorfenvinphos
chorfenvinphos
chorfenvinphos
chorfenvinphos
chorfenvinphos
chlorsulfuron
cycloxydim
cycloxydim
cycloxydim
cycloxydim
cycloxydim
cycloxydim
cycloxydim
cypermethrin
< 10%
< 10%
29%
18.5%
< 7%
< 7%
< 7%
< 7%
< 7%
< 7%
< 7%
50%
39%
3 - 4%
48%
10%
7%
3%
3%
0.2-0.4%
0 - 14 days
0- 14 days
24 months
21 days
4 months
4 months
4 months
4 months
4 months
4 months
4 months
2 months
7 days
21 days
7 days
21 days
43 days
21 days
1 days
-
Brazil
Brazil
Australia
Australia
Germany
Regitano et al. 2001
Regitano et al. 2001
Baskaran et al. 1999
Baskaran et al. 2003
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1991c
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
Class, 1992
Degradate formation
Degradate
Parent pesticide
3-phenoxybenzoic acid
3-phenoxybenzaldehyde
melamine
cypermethrin
cypermethrin
cyromazine
ethyl-m-hydroxyphenyl carbamate
desmedipham
pyrimidinol
diazinon
hydroxyl-pyrimidinol
3,6-dichlorosalicylic acid
3,6-dichlorosalicylic acid
diclofop acid
diazinon
dicamba
dicamba
diclofop-methyl
4-(2,4-dichlorophenoxy)phenol
diclofop-methyl
N-demethyldimefuron
compound B
compound C
compound D
O-desmethyldimethoate
O,O-dimethylphosphorothioic acid
omethoate
3-desmethyl dimethomorph and 4-desmethyl
dimethomorph combined
dintro octyl phenol
desphenyl-fenvalerate
CONH2-fen
dimefuron
dimefuron
dimefuron
dimefuron
dimethoate
dimethoate
dimethoate
dimethomorph
4’-OH-fen
esfenvalerate
3-benzylbenzoic acid
Cl-Vacid
esfenvalerate
esfenvalerate
SD 50365
esfenvalerate
RH-6467
fenbuconazole
a
c
Percentage of
b
parent pesticide
Time
0.2-0.4%
0.2-0.4%
32%
~70%
20 - 44%
41%
16%
4.5%
72.9%
2%
8% (sterile)
1.5%
28%
31%
80 - 87%
77%
90%
0.7 - 3%
trace
1 - 10%
11%
2.5%
16.6 - 29.98%
0.5 - 2.2%
ND - 2.23%
0.32 - 2.8%
2.1%
1%
6%
<0.5%
30 days
2 - 3 weeks
29 weeks
27 weeks
7 days
14 days
14 days
3 weeks
3 weeks
166 days
5 weeks
6 weeks
1 day
8 days
2 days
16 days
14 days
8 days
6 days
93 days
92 days
92 days
92 days
2 weeks
-
5.5%
0.9 - 6.4%
1.5%
32%
1 - 4%
1.3%
3%
1 - 4%
1.4%
3%
1 - 4%
1%
1 - 4%
<10%
30 days
12 weeks
180 days
12 months
30 days
14 days
1 month
30 days
14 days
12 months
30 days
3 months
30 days
-
Country
Reference
Germany
Germany
USA
Switzerland
Germany
Germany
-
Class, 1992
Class, 1992
Reported in PSD 1993l
Reported in PSD 1993l
Reported in PSD 1993l
Reported in PSD 1993l
Reported in PSD 1993f
Reported in PSD 1993f
Reported in PSD 1991b
Reported in PSD 1991b
Reported in PSD 1991b
Reported in PSD 1991b
Smith, 1973
Smith, 1974
Reported in PSD 1991e
Reported in PSD 1991e
Reported in PSD 1991e
Reported in PSD 1991e
Reported in PSD 1991e
Reported in PSD 1991e
Reported in PSD 1991e
Reported in PSD 1991e
Reported in PSD 1993h
Reported in PSD 1993h
Reported in PSD 1993h
Reported in PSD 1993h
Reported in PSD 1993j
Reported in PSD 1993j
Reported in PSD 1993j
Reported in PSD 1994g
aerobic soil
(laboratory)
57
©2008 AwwaRF. ALL RIGHTS RESERVED
dinocap
esfenvalerate
esfenvalerate
Canada
Canada
Canada
Germany
Germany
Japan
Japan
USA
Japan
USA
Japan
USA
USA
-
Reported in PSD 1991a
Reported in PSD 1992b
Reported in PSD 1992b
Reported in PSD 1992b
Reported in PSD 1992b
Reported in PSD 1992b
Reported in PSD 1992b
Reported in PSD 1992b
Reported in PSD 1992b
Reported in PSD 1992b
Reported in PSD 1992b
Reported in PSD 1992b
Reported in PSD 1992b
Reported in PSD 1995c
Degradate formation
a
Percentage of
b
parent pesticide
Time
fenbuconazole
fenbuconazole
fenbuconazole
fenoxaprop-p-ethyl
fenpropathrin
<7.9%
<10%
<4.5%
<3%
14%
fenpropathrin
Degradate
Parent pesticide
RH-6467 continued
RH-9129
RH-9130
4-(6-chloro-2-benzoxazolyloxy)phenol
α-carbomoyl-3-phenoxybenzyl-2,2,3,3tetramethyl cyclopropane carboxylate and αcarboxy-3-phenoxybenzyl-2,2,3,3-tetramethyl
cyclopropane carboxylate combined
α-carboxy-3-phenoxybenzyl-2,2,3,3-tetramethyl
cyclopropane carboxylate
3-phenoxybenzoic acid
fenpropathrin
2,2,3,3-tetramethyl cyclopropane carboxylic acid
fenpropathrin
R0 18-5445
R0 12-7124
M3
fenpropidin
fenpropidin
fenpyroximate
1,3-dimethyl-5-phenoxypyrazole-4-carbonitrile
compound VII
fenpyroximate
fluazinam
compound VIII
fluazinam
compound XII
fluazinam
fluzifop acid
5-trifluoromethyl-2-pyridone and 2-(4hydroxyphenoxy)-5-trifluoromethyl pyridine
combined
RH-5781
RH-9985
RH-5349
bis (4-fluorophenyl)methyl silanol
fomesafen amino acid
fomesafen amine
fomesafen nitro acid
HOE 35956
fluzifop-P-butyl
fluzifop-P-butyl
c
Country
Reference
-
UK
Reported in PSD 1995c
Reported in PSD 1995c
Reported in PSD 1995c
Reported in PSD 1990a
Reported in PSD 1989b
7%
0.3%
8 weeks
26 weeks
-
Reported in PSD 1989b
Reported in PSD 1989b
14%
0.6%
7%
<0.1%
1 – 5%
1 – 5%
2.6 - 10.8%
4.9 - 7.9%
8.2 - 8.8%
2.5%
<2%
1.5%
<2%
11.4%
7%
97%
50%
160 days
8 weeks
60 days
14 - 28 days
16 - 32 days
28 days
90 days
30 days
30 days
2 days
2 - 12 weeks
UK
Japan
Germany
Japan
UK
UK
UK
-
Reported in PSD 1989b
Reported in PSD 1989b
Reported in PSD 1989b
Reported in PSD 1989b
Reported in PSD 1993b
Reported in PSD 1993b
Reported in PSD 1995d
Reported in PSD 1995d
Reported in PSD 1995d
Reported in PSD 1994h
Reported in PSD 1994h
Reported in PSD 1994h
Reported in PSD 1994h
Reported in PSD 1994h
Reported in PSD 1994h
Reported in PSD 1988a
Reported in PSD 1988a
79%
8.1%
6%
4 - 5%
10.2%
20.5%
<1%
25 - 53%
21 days
51 days
52 weeks
88 days
59 days
35 days
UK
UK
UK
Germany
Reported in PSD 1992a
Reported in PSD 1992a
Reported in PSD 1992a
Reported in PSD 1989a
Reported in PSD 1995a
Reported in PSD 1995a
Reported in PSD 1995a
Reported in PSD 1990f
35%
96 days
USA
Reported in PSD 1990f
52%
32%
15 - 47%
31%
95 days
16 days
7 - 14 days
37 days
Germany
USA
Reported in PSD 1990f
Reported in PSD 1990f
Reported in PSD 1990f
Reported in PSD 1990f
aerobic soil
(laboratory)
58
©2008 AwwaRF. ALL RIGHTS RESERVED
3-methyl phosphinico-proprionic acid
fluoroglycofen-ethyl
fluoroglycofen-ethyl
fluoroglycofen-ethyl
flusilazole
fomesafen
fomesafen
fomesafen
glufosinate
ammonium
glufosinate
ammonium
Degradate formation
Degradate
Parent pesticide
HOE 64619
glufosinate
ammonium
a
Percentage of
b
parent pesticide
Time
18%
c
Country
Reference
95 days
-
Reported in PSD 1990f
15%
26%
8%
16 days
14 days
16 days
Germany
-
Reported in PSD 1990f
Reported in PSD 1990f
Reported in PSD 1990f
31 - 38%
8%
21 days
8 days
-
Reported in PSD 1990f
Reported in PSD 1990f
5%
5%
95 days
-
Reported in PSD 1990f
Reported in PSD 1990f
2%
34%
16 days
0 days
Germany
-
Reported in PSD 1990f
Reported in PSD 1990f
8 days
97 days
8 days
8 days
8 days
2 days
8 days
97 days
3 months
12 months
100 days
-
Reported in PSD 1990c
Reported in PSD 1990c
Reported in PSD 1990c
Reported in PSD 1990c
Reported in PSD 1990c
Reported in PSD 1990c
Reported in PSD 1990c
Reported in PSD 1990c
Reported in PSD 1990c
Reported in PSD 1994i
Reported in PSD 1993a
Reported in PSD 1993e
aerobic soil
(laboratory)
HOE 64619
f
3-methyl
phosphinicoproprionic acid
59
©2008 AwwaRF. ALL RIGHTS RESERVED
HOE 65594
glufosinate
ammonium
HOE 86486
glufosinate
ammonium
HOE 85355
HOE 83348
glufosinate
ammonium
HOE 070542
HOE 88988
HOE 88989
HOE 72829
HOE 070542
HOE 070542
HOE 070542
HOE 87606
HOE 87607
HOE 89628
1,5-bis(-p-tolyl)-1,4-pentadiene-3-one
M1
1-(6-chloro-pyridine-3-ylmethyl)-N-nitro-2-imino2,3-dihydro-imidazole and 1-(6-chloro-pyridine3-ylmethyl) imidazolidine-2,4-dione combined
1-(6-chloro-pyridine-3-ylmethyl)-N-nitroso-2imino-imidazolidine
HOE 070542
HOE 070542
HOE 070542
hydramethylnon
imazaquin
imidacloprid
4.5%
20%
1.5%
14.2%
2.1%
36%
1%
11%
7%
25.9%
7.6%
<1.8%
imidacloprid
<1.8%
100 days
-
Reported in PSD 1993e
imidacloprid
<3%
<2%
<1.8%
100 days
-
Reported in PSD 1993e
Reported in PSD 1993e
Reported in PSD 1993e
imidacloprid
4.3%
<2%
<1.8%
100 days
-
Reported in PSD 1993e
Reported in PSD 1993e
Reported in PSD 1993e
<1.8%
<3%
<3%
100 days
-
-
Reported in PSD 1993e
Reported in PSD 1993e
Reported in PSD 1993e
1-(6-chloro-pyridine-3-ylmethyl)-2-iminoimidazolidine
1-(6-chloro-pyridine-3-ylmethyl)-N-nitro
guanidine and 3-(6-chloro-pyridine-3-ylmethyl)
imidazolidine-2,5-dione
6-chloro-nicotinic acid
1-(6-chloro-pyridine-3-ylmethyl)-N-nitro
guanidine
imidacloprid
imidacloprid
Degradate formation
a
Percentage of
b
parent pesticide
Time
imidacloprid
3.4%
<3%
IPBC
kresoxim-methyl
malaoxon
Degradate
Parent pesticide
1-(6-chloro-pyridine-3-ylmethyl)-N-nitro-2-iminoimidazollidine-5-ol
propargyl butyl carbamate
kresoxim-methyl acid
c
Country
Reference
-
-
Reported in PSD 1993e
Reported in PSD 1993e
>90%
43%
6 hours
180 days
-
malathion
1.4%
< 7 days
-
malathion dicarboxylic acid
malathion
62%
7 days
-
4-chloro-2-methyl phenol
2-N-(2,6-dimethylphenyl)-2-methoxyacetylamino
propanoic acid
metloachlor ethane sulfonic acid
carbinol
morpholinone
2-(aminosulfonyl) benzoic acid
mecoprop-P
metalaxyl
2 - 3%
50%
20 days
21 days
-
metolachlor
metolachlor
metolachlor
metsulfuron-methyl
saccharin
metsulfuron-methyl
methyl-2-(aminosulfonyl)benzoate
metsulfuron-methyl
2-(3,5-dichlorophenyl)-4,4-dimethyl-5methyleneoxazoline
N-(1,1-dimethylacetonyl)-3,5-dichlorobenzamide
[2-(3,5-dichlorophenyl)-4,4-dimethyl-1,3oxazolin-5-ylidene]methan-1-ol
(3,5-dichlorophenyl)-N-(3-hydroxy-1,1-dimethyl2-oxopropyl)carboxamide
(3,5-dichlorophenyl)-N-(3-hydroxy-1,1dimethylpropyl)carboxamide
(3,5-dichlorophenyl)-N-(2,3-dihydroxy-1,1dimethylpropyl)carboxamide
3-[(3,5-dichlorophenyl)carbonylamino]-3methylbutanoic acid
2-[(3,5-dichlorophenyl)carbonylamino]-2methylpropanoic acid
3-[(3,5-dichlorophenyl)carbonylamino]-3-methyl2-oxobutanoic acid
deethylterbuthylazine
2,6-dinitro-4-(trifluoromethylphenyl)amine
propyzamide
5%
24.3%
2.9%
16%
19% (sterile)
8 - 29%
32%
4 - 7% (sterile)
16 - 32%
2 - 14%
38 - 51% (sterile)
6 - 9%
9%
14 days
120 days
120 days
24 weeks
8 weeks
16 weeks
2 - 4 weeks
24 weeks
2 weeks
-
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
-
Reported in PSD 1994n
Reported in Roberts and
Hutson, 1999
Reported in Roberts and
Hutson, 1999
Reported in Roberts and
Hutson, 1999
Reported in PSD 1994e
Reported in Roberts and
Hutson, 1999
Aga and Thurman, 2001
Rice et al. 2002
Rice et al. 2002
Reported in PSD 1991d
Reported in PSD 1991d
Reported in PSD 1991d
Reported in PSD 1991d
Reported in PSD 1991d
Reported in PSD 1991d
Reported in PSD 1991d
Reported in PSD 1991d
Reported in PSD 1991d
Reported in Roberts, 1998
propyzamide
propyzamide
77%
0.1 -1.6%
-
-
Reported in Roberts, 1998
Reported in Roberts, 1998
propyzamide
0.1 -1.6%
-
-
Reported in Roberts, 1998
propyzamide
0.1 -1.6%
-
-
Reported in Roberts, 1998
propyzamide
0.1 -1.6%
-
-
Reported in Roberts, 1998
propyzamide
0.1 -1.6%
-
-
Reported in Roberts, 1998
propyzamide
0.1 -1.6%
-
-
Reported in Roberts, 1998
propyzamide
0.1 -1.6%
-
-
Reported in Roberts, 1998
terbuthylazine
trifluralin
< 5%
0.2%
-
-
Reported in Roberts, 1998
Reported in Roberts, 1998
aerobic soil
(laboratory)
60
©2008 AwwaRF. ALL RIGHTS RESERVED
Degradate formation
a
Percentage of
b
parent pesticide
Time
trifluralin
1.7%
atrazine
atrazine
atrazine
azoxystrobin
bitertanol benzoic acid
p-hydroxy bitertanol
2-chlorobenzene sulfonamide
bitertanol
bitertanol
chlorsulfuron
CGA 205374 and CGA 205375 combined
CGA 189138
omethoate
fomesafen amine, fomesafen amino acid and
fomesafen nitro acid combined
terbufos sulfone
Degradate
Parent pesticide
[2,6-dinitro-4(trifluoromethyl)phenyl]propylamine
hydroxyatrazine
deethylatrazine
deisopropylatrazine
azoxystrobin acid
c
Country
Reference
1 year
-
Reported in Roberts, 1998
39.1 ± 9.1%
33 ± 3.8%
8.6 ± 1.9%
< 1%
6 months
16 months
6 months
-
USA
USA
USA
USA
31 days
31 days
3 months
USA
difenoconazole
difenoconazole
dimethoate
fomesafen
21%
1%
30 - 35%
(glasshouse)
18 - 50%
2%
5%
<8%
Sorenson et al. 1993
Sorenson et al. 1993
Sorenson et al. 1993
Reported in Roberts and
Hutson, 1999
Reported in PSD 1994b
Reported in PSD 1994b
Reported in PSD 1991c
-
USA
USA
USA
USA
Reported in PSD 1994j
Reported in PSD 1994j
Reported in PSD 1993j
Reported in PSD 1995a
terbufos
18%
12 weeks
-
42%
104 days
-
α,α,α-trifluoro-p-toluic acid
p-trifluoromethyl cinnamic acid
1,5-bis(α,α,α-p-tolyl)-1,4-pentadien-3-one
saccharin
glufosinate
ammonium
hydramethylnon
hydramethylnon
hydramethylnon
metsulfuron-methyl
Reported in Roberts and
Hutson, 1999
Reported in PSD 1990f
dihydroxy anilazine
anilazine
deethylatrazine
atrazine
<5.1%
<5.1%
<5.1%
17% (glasshouse)
3%
36%
35.7%
2.1%
14 weeks
60 days
60 days
32 days
USA
-
hydroxyatrazine
atrazine
0.4%
94 days
-
deisopropylatrazine
atrazine
0.7%
32 days
-
diaminochlorotriatrazine
atrazine
0.3%
32 days
-
Ia
ethyl-m-hydroxyphenyl carbamate
1,3-diphenyl urea
N-phenyl carbamic acid-ethyl ester
diclofop acid
4-(2,4-dichlorophenoxy)phenol
O-desmethyldimethoate
O,O-dimethylphosphorothioic acid
3-desmethyl dimethomorph and 4-desmethyl
dimethomorph combined
cyhalothrin
desmedipham
desmedipham
desmedipham
diclofop-methyl
diclofop-methyl
dimethoate
dimethoate
dimethomorph
17%
28%
<0.2%
<0.2%
64 - 81%
trace
10%
5%
15%
64 days
60 days
60 days
7 days
Germany
Denmark
Denmark
-
aerobic soil
(laboratory)
61
©2008 AwwaRF. ALL RIGHTS RESERVED
3-methyl phosphinico-proprionic acid
Reported in PSD 1994i
Reported in PSD 1994i
Reported in PSD 1994i
Reported in PSD 1991d
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994c
Reported in Solomon et al.
1996
Reported in Solomon et al.
1996
Reported in Solomon et al.
1996
Reported in Solomon et al.
1996
Reported in PSD 1988b
Reported in PSD 1993f
Reported in PSD 1993f
Reported in PSD 1993f
Reported in PSD 1991e
Reported in PSD 1991e
Reported in PSD 1993j
Reported in PSD 1993j
Reported in PSD 1994g
Degradate formation
a
Percentage of
b
parent pesticide
Time
dimethomorph
~10 - 20%
esfenvalerate
esfenvalerate
esfenvalerate
esfenvalerate
fenpropathrin
fenpropathrin
fluazinam
fluazinam
fluazinam
fluoroglycofen-ethyl
fluoroglycofen-ethyl
fluoroglycofen-ethyl
fluoroglycofen-ethyl
fluoroglycofen-ethyl
glufosinate
ammonium
Degradate
Parent pesticide
3-desmethyl dimethomorph and 4-desmethyl
dimethomorph combined
CONH2-fen
4’-OH-fen
Cl-Vacid
SD 50365
3-phenoxybenzoic acid
2,2,3,3-tetramethyl cyclopropane carboxylic acid
compound VII
compound VIII
compound XII
RH-4515
RH-5781
RH-5349
RH-9985
RH-4514
3-methyl phosphinico-proprionic acid
c
Country
Reference
7 days
-
Reported in PSD 1994g
1%
4%
4%
0.4%
71%
39%
31.2%
12%
7.2%
10.1%
47.7%
5%
2.7%
7.9%
54%
30 days
30 days
30 days
30 days
8 weeks
90 days
30 days
30 days
68 days
2 days
2 days
2 days
68 days
26 days
UK
UK
UK
UK
-
Reported in PSD 1992b
Reported in PSD 1992b
Reported in PSD 1992b
Reported in PSD 1992b
Reported in PSD 1989b
Reported in PSD 1989b
Reported in PSD 1994h
Reported in PSD 1994h
Reported in PSD 1994h
Reported in PSD 1992a
Reported in PSD 1992a
Reported in PSD 1992a
Reported in PSD 1992a
Reported in PSD 1992a
Reported in PSD 1990f
41%
22%
60 days
26 days
USA
-
Reported in PSD 1990f
Reported in PSD 1990f
0.2%
2 months
-
Reported in PSD 1993a
30 days
30 days
20 days
20 days
26 days
45 days
-
Reported in PSD 1994a
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1993i
Reported in PSD 1993i
Reported in PSD 1993l
Reported in PSD 1991b
Reported in PSD 1991b
Reported in PSD 1990b
Reported in PSD 1990b
Reported in PSD 1989b
aerobic soil
(laboratory)
62
©2008 AwwaRF. ALL RIGHTS RESERVED
HOE 64619
M1
glufosinate
ammonium
imazaquin
HOE 101630
dihydroxy anilazine
amidosulfuron
anilazine
monohydroxy anilazine
1-isopropyl-3-phenyl urea
N-(4-hydroxyphenyl)-N-isopropylurea
melamine
pyrimidinol
compound II
benzoxazolone
fenoxaprop-ethyl acid
α-carbomoyl-3-phenoxybenzyl-2,2,3,3tetramethyl cyclopropane carboxylate and
2,2,3,3-tetramethyl cyclopropane carboxylic acid
combined
M3
1,3-dimethyl-5-phenoxypyrazole-4-carbonitrile
1,3-dimethyl-5-phenoxypyrazole-4-carboxylic
acid
fluzifop acid
anilazine
buprofezin
buprofezin
cyromazine
diazinon
diazinon
fenoxaprop-ethyl
fenoxaprop-ethyl
fenoxaprop-ethyl
20%
7%
6 - 10%
1%
trace
trace
29%
7.8 - 9.8%
13.4 - 15.2%
0.2 - 0.6%
0.2%
9.1%
fenpyroximate
fenpyroximate
fenpyroximate
0.3 - 0.6% (soil)
0.2 - 1.7% (soil)
0.1% (soil)
-
-
Reported in PSD 1995b
Reported in PSD 1995b
Reported in PSD 1995b
fluzifop-P-butyl
36 - 47%
-
-
Reported in PSD 1988a
column leachate
(laboratory)
Degradate formation
a
Degradate
Parent pesticide
Percentage of
b
parent pesticide
RH-5781
fluoroglycofen-ethyl
88 - 89% (soil )
f
50 - 60% (soil )
RH-5349
RH-4514
fluoroglycofen-ethyl
fluoroglycofen-ethyl
RH-0265-NH2, RH-5782, RH-670 and
fluoroglycofen-ethyl combined
fomesafen amine
fluoroglycofen-ethyl
fomesafen
fomesafen amino acid
fomesafen
fomesafen nitro acid
fomesafen
saccharin
methyl-2-(aminosulfonyl)benzoate
1-(6-chloro-pyridine-3-ylmethyl)-2-iminoimidazolidine
1-(6-chloro-pyridine-3-ylmethyl)-N-nitro-2-iminoimidazollidine-5-ol
1-(6-chloro-pyridine-3-ylmethyl)-N-nitroso-2imino-imidazolidine
6-chloro-nicotinic acid
1,3-bis[(6-chloro(3-pyridyl))methyl]imidazolidin2-imine
Time
c
Country
Reference
30 days
-
-
Reported in PSD 1992a
Reported in PSD 1992a
3 - 5% (soil )
e
1% (soil )
f
4 - 7% (soil )
f
10% (soil )
30 days
30 days
-
-
Reported in PSD 1992a
Reported in PSD 1992a
Reported in PSD 1992a
Reported in PSD 1992a
82 days
UK
Reported in PSD 1995a
45 days
82 days
UK
UK
Reported in PSD 1995a
Reported in PSD 1995a
45 days
82 days
UK
UK
Reported in PSD 1995a
Reported in PSD 1995a
metsulfuron-methyl
metsulfuron-methyl
34.7 - 47.6%
e
(anaerobic soil )
f
9.1 - 16.9% (soil )
16 - 33.9%
e
(anaerobic soil )
f
5.3 - 5.4% (soil )
0.7 - 0.8%
e
(anaerobic soil )
f
<0.5 - 1.3% (soil )
50 - 85%
5 - 25%
45 days
-
UK
-
Reported in PSD 1995a
Reported in PSD 1991d
Reported in PSD 1991d
imidacloprid
4.2%
-
Germany
Reported in PSD 1993e
imidacloprid
<0.6%
-
Germany
Reported in PSD 1993e
imidacloprid
<0.6%
-
Germany
Reported in PSD 1993e
imidacloprid
imidacloprid
<0.6%
0.2%
-
Germany
Germany
Reported in PSD 1993e
Reported in PSD 1993e
malonic acid
N-methyl malonamic acid
malonamic acid
acetic acid
kathon 886
kathon 886
kathon 886
kathon 886
>20%
>20%
>20%
<20%
-
-
Reported in PSD 1993m
Reported in PSD 1993m
Reported in PSD 1993m
Reported in PSD 1993m
formic acid
RH 886 oxide
kathon 886
kathon 886
<20%
<20%
-
-
Reported in PSD 1993m
Reported in PSD 1993m
2,4-dichlorophenol
2,4-D
0.5%
33 days
-
Reported in PSD 1993c
e
column leachate
(laboratory)
continued
e
63
©2008 AwwaRF. ALL RIGHTS RESERVED
lysimeter studies
sewage sludge
sewage sludge
continued
estuarine sediment
Degradate formation
sediment /water
Time
alachlor
2.7%
alachlor
amdosulfuron
amidosulfuron
anilazine
Parent pesticide
2’,6’-diethyl-N-methoxymethyl-2-methyl
thioacetanilide
2’,6’-diethyl-N-methoxymethyl acetanilide
2-amino-4,6-dihydroxypyrimidine
HOE 101630
dihydroxy anilazine
monohydroxy anilazine
anilazine
monoamino anilazine
anilazine
bitertanol ketone
bitertanol benzoic acid
buprofezin sulphoxide
TSO and T2SO combined
Ia
Ib
ethyl-m-hydroxyphenyl carbamate
bitertanol
bitertanol
buprofezin
cycloxydim
cyhalothrin
cyhalothrin
desmedipham
diclofop acid
diclofop-methyl
4-(2,4-dichlorophenoxy)phenol
diclofop-methyl
210 352
231 761
fenoxaprop-ethyl acid
epoxiconazole
epoxiconazole
fenoxaprop-ethyl
6-chloro-3-dihydrobezoxazol-2-one
fenoxaprop-ethyl acid
6-chloro-3-dihydrobezoxazol-2-one
R0 15-6045
M3
fenoxaprop-ethyl
fenoxaprop-ethyl
fenoxaprop-ethyl
fenpropidin
fenpyroximate
1,3-dimethyl-5-phenoxypyrazole-4-carbonitrile
compound XII
bis (4-fluorophenyl)methyl silanol
1H-1,2,4-triazole
1-(6-chloro-pyridine-3-ylmethyl)-2-iminoimidazolidine
6-chloro-nicotinic acid
N-1-(6-chloro-pyridine-3-ylmethyl)-ethane-1,2diamine
c
Country
Reference
30 days
-
Reported in PSD 1990d
27.7% (anaerobic)
45%
30%
8.5% (water)
0.9% (sediment)
34.3% (water)
1.4% (sediment)
0.6% (water)
0.9% (sediment)
< 1%
< 1%
13%
19 - 82% (pH 9.4)
26.9 - 32%
9 - 15.3%
84% (water)
1.7% (sediment)
70%
40.2% (water)
77.9 % (sediment)
10%
52.4 % (sediment)
0.4 - 1.1%
0.4 - 0.9%
47% (water)
1 week
84 days
61 days
57 days
57 days
7 days
1 day
4 days
4 days
120 days
120 days
56 days
28 days
32 days
32 days
7 days
21 days
7 days
14 days
168 days
7 days
168 days
90 days
90 days
1 day
-
Reported in PSD 1990d
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994b
Reported in PSD 1994b
Reported in PSD 1993i
Reported in PSD 1990e
Reported in PSD 1988b
Reported in PSD 1988b
Reported in PSD 1993f
Reported in PSD 1993f
Reported in PSD 1991e
Reported in PSD 1991e
Reported in PSD 1991e
Reported in PSD 1991e
Reported in PSD 1991e
Reported in PSD 1994l
Reported in PSD 1994l
Reported in PSD 1990b
fenpyroximate
fluazinam
flusilazole
flusilazole
imidacloprid
9.3% (water)
60.4% (sediment)
3.8% (sediment)
15 - 16 %
d
5.8 - 18.3% (water)
4.6 - 16.1%
d
<5% (water)
8%
48 - 60%
12%
8.8 - 12.3%
21 days
29 days
21 days
28 - 84 days
24 hours
90 days
24 hours
0 weeks
52 weeks
52 weeks
Switzerland
Netherlands
-
Reported in PSD 1990b
Reported in PSD 1990b
Reported in PSD 1990b
Reported in PSD 1993b
Reported in PSD 1995d
Reported in PSD 1995d
Reported in PSD 1995d
Reported in PSD 1994h
Reported in PSD 1989a
Reported in PSD 1989a
Reported in PSD 1993e
64% (anaerobic)
0.3 - 4.2%
0.3 - 4.2%
358 days
imidacloprid
imidacloprid
-
Reported in PSD 1993e
Reported in PSD 1993e
Reported in PSD 1993e
e
64
©2008 AwwaRF. ALL RIGHTS RESERVED
sediment /water
continued
a
Percentage of
b
parent pesticide
Degradate
e
Degradate formation
a
Degradate
Parent pesticide
propargyl butyl carbamate
IPBC
2-propenyl butyl-carbamate
IPBC
2-propenyl butyl-carbamate
IPBC
saccharin
metsulfuron-methyl
2-(aminosulfonyl) benzoic acid
metsulfuron-methyl
Percentage of
b
parent pesticide
Time
>97% (water,
anaerobic)
>80% (sterile)
8% (sediment,
anaerobic)
34.7% (water,
anaerobic)
8%
26 - 33% (sterile)
14%
40% (sterile,
anaerobic)
6 - 13% (non-sterile)
c
Reference
1 day
-
Reported in PSD 1994n
29 days
59 days
-
Reported in PSD 1994n
Reported in PSD 1994n
59 days
-
Reported in PSD 1994n
14 days
24 weeks
14 days
5 weeks
-
Reported in PSD 1991d
Reported in PSD 1991d
Reported in PSD 1991d
Reported in PSD 1991d
-
-
Reported in PSD 1991d
Reported in PSD 1994c
Reported in PSD 1994c
Reported in Solomon et al.
1996
Reported in Solomon et al.
1996
Reported in PSD 1992c
Reported in Solomon et al.
1996
Reported in PSD 1991c
Reported in PSD 1991c
Reported in PSD 1988c
Reported in PSD 1988c
Reported in PSD 1990b
Reported in PSD 1990b
Reported in PSD 1993m
Reported in PSD 1993m
Reported in PSD 1993m
aqueous degradation
(non-sterile)
65
©2008 AwwaRF. ALL RIGHTS RESERVED
Country
dihydroxy anilazine
monohydroxy anilazine
deethylatrazine
anilazine
anilazine
atrazine
3%
29%
6.4% (anaerobic)
10 days
10 days
275 days
-
deisopropylatrazine
atrazine
2.6% (anaerobic)
275 days
-
hydroxyatrazine
atrazine
2.7 - 3%
6.6% (anaerobic)
70 days
183 days
-
2-chlorobenzene sulfonamide
2-amino-4-methoxy-6-methyl-1,3,5-triazine
4-fluoro-3-phenoxybenzaldehyde
4-fluoro-3-phenoxybenzoic acid
fenoxaprop-ethyl acid
6-chloro-2,3-dihydroxybenzoxazol-2-one
N-methyl malonamic acid
malonic acid
malonamic acid
chlorsulfuron
chlorsulfuron
cyfluthrin
cyfluthrin
fenoxaprop-ethyl
fenoxaprop-ethyl
kathon 886
kathon 886
kathon 886
9 - 11% (anaerobic)
21 - 25% (anaerobic)
3%
8.5%
44%
2.4%
>20%
<20%
<20%
10 weeks
52 weeks
144 hours
144 hours
192 hours
192 hours
-
-
1,2,4-benzenetriol
dihydroxy anilazine
deethylatrazine
2,4-D
anilazine
atrazine
> 10%
86.9%
2.8%
364 hours
15 days
-
hydroxyatrazine
atrazine
38%
2.6%
7 days
15 days
-
deisopropylatrazine
atrazine
1.2%
6.9 days
-
deisopropyl deethylatrazine
atrazine
4.3%
22%
7 days
7 days
-
aqueous photolysis
Reported in PSD 1993c
Reported in PSD 1994c
Reported in Solomon et al.
1996
Reported in PSD 1992c
Reported in Solomon et al.
1996
Reported in Solomon et al.
1996
Reported in PSD 1992c
Reported in PSD 1992c
Degradate formation
a
Percentage of
b
parent pesticide
Time
atrazine
0.9%
DIHA
atrazine
DEHA
hydroxyatrazine
1,2,4-triazole
Degradate
Parent pesticide
diaminochlorotriatrazine
c
Country
Reference
15 days
-
Reported in Solomon et al.
1996
1.2%
6.9 days
-
Reported in Solomon et al.
1996
atrazine
0.4%
15 days
-
2-amino-4-methoxy-6-methyl-1,3,5-triazine
2-chlorobenzene sulfonamide
2-chlorophenylsulfonyl urea
T1S
atrazine
bitertanol
bitertanol
chlorsulfuron
chlorsulfuron
chlorsulfuron
cycloxydim
T2S
cycloxydim
TSO
TSO2 and T2SO2 combined
TSO and T2SO combined
ethyl-m-hydroxyphenyl carbamate
4-(2,4-dichlorophenoxy)phenol
cycloxydim
cycloxydim
cycloxydim
desmedipham
diclofop-methyl
14.6%
52.5%
12.0%
5 - 44%
4 - 21%
0 - 4%
10 - 45% (pH 5.5)
6 - 43% (pH 9.4)
3 - 9% (pH 5.5)
2 - 7% (pH 9.4)
6 - 11% (pH 5.5)
< 3% (pH 5.5)
2 - 8% (pH 9.4)
5% (pH 3.8)
0 - 33%
-
DPX M6316 triazine amine
DPX M6316 triazine urea
DPX M6316 TP1
Cl-Vacid
fenoxaprop-ethyl acid
4-(6-chloro-2-benzoxazolyloxy)phenol
3-phenoxybenzoic acid
2,2,3,3-tetramethyl cyclopropane carboxylic acid
α-(2,2,3,3-tetramethylcyclopropyl)-3phenoxybenzyl cyanide
α-carbomoyl-3-phenoxybenzyl-2,2,3,3tetramethyl cyclopropane carboxylate
M3 and M4 combined
DPX M6316
DPX M6316
DPX M6316
esfenvalerate
fenoxaprop-ethyl
fenoxaprop-ethyl
fenpropathrin
fenpropathrin
fenpropathrin
11%
14%
7%
17.3%
6.9%
6.4%
11 – 39%
2 – 39%
5 – 13%
7 days
237 - 288
hours
10 days
192 hours
192 hours
6 weeks
6 weeks
6 weeks
Reported in Solomon et al.
1996
Reported in PSD 1992c
Reported in PSD 1994b
Reported in PSD 1994b
Reported in PSD 1991c
Reported in PSD 1991c
Reported in PSD 1991c
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1993f
Reported in PSD 1995e
-
Reported in PSD 1988d
Reported in PSD 1988d
Reported in PSD 1988d
Reported in PSD 1992b
Reported in PSD 1990b
Reported in PSD 1990b
Reported in PSD 1989b
Reported in PSD 1989b
Reported in PSD 1989b
fenpropathrin
4 - 28%
6 weeks
-
Reported in PSD 1989b
fenpyroximate
10%
24 hours
-
Reported in PSD 1995d
1,3-dimethyl-5-phenoxypyrazole-4-carbonitrile
compound V
fenpyroximate
fluazinam
RH-4514
1H-1,2,4-triazole
3-methyl phosphinico-proprionic acid
fluoroglycofen-ethyl
flusilazole
glufosinate
ammonium
47.5 - 58.3%
51% (pH 9)
minor (pH 5)
5.8%
<5%
19% (pH 9)
6 hours
30 days
30 days
30 days
120 hours
-
Reported in PSD 1995d
Reported in PSD 1994h
Reported in PSD 1994h
Reported in PSD 1992a
Reported in PSD 1989a
Reported in PSD 1990f
aqueous photolysis
continued
66
©2008 AwwaRF. ALL RIGHTS RESERVED
aqueous photolysis
continued
Degradate formation
a
Parent pesticide
1,5-bis(α,α,α-p-tolyl)-1,4-pentadien-3-one
TDTP
α,α,α-trifluoro-p-toluic acid
p-trifluoromethyl cinnamic acid
quinoline-3-carboxylic acid
2H-azolidino[3,4-b]quinoline-1,3-dione
3-imino-2H-azolidino[3,4-b]quinolin-1-one
quinoline-2,3-dicarboxylic acid
malonic acid
N-methyl malonamic acid
malonamic acid
acetic acid
formic acid
methyl-2-(aminosulfonyl)benzoate
hydramethylnon
hydramethylnon
hydramethylnon
hydramethylnon
imazaquin
imazaquin
imazaquin
imazaquin
kathon 886
kathon 886
kathon 886
kathon 886
kathon 886
metsulfuron-methyl
saccharin
2-(aminosulfonyl) benzoic acid
metsulfuron-methyl
metsulfuron-methyl
alachlor oxamic acid
alachlor ethane sulfonic acid
2-amino-4,6-dimethoxypyrimidine
alachlor
alachlor
amidosulfuron
product A (unidentified)
monohydroxy anilazine
amidosulfuron
anilazine
monohydroxy anilazine continued
dihydroxy anilazine
anilazine
anilazine
carbofuran
benfuracarb
carbofuran phenol
benfuracarb
N-hydroxy-methyl carbofuran
benfuracarb
1-tert-butyl-3-isopropyl-5-phenyl-2-biuret
1-isopropyl-3-phenyl urea
TSO
buprofezin
buprofezin
cycloxydim
T1S
cycloxydim
Percentage of
b
parent pesticide
Time
<8%
<8%
<8%
<8%
14%
21%
13%
~30%
>20%
>20%
>20%
<20%
<20%
58% (dark)
13%
7%
7%
c
Country
Reference
90 minutes
90 minutes
90 minutes
90 minutes
24 hours
48 hours
48 hours
48 hours
14 days
4 days
14 days
14 days
-
Reported in PSD 1994i
Reported in PSD 1994i
Reported in PSD 1994i
Reported in PSD 1994i
Reported in PSD 1993a
Reported in PSD 1993a
Reported in PSD 1993a
Reported in PSD 1993a
Reported in PSD 1993m
Reported in PSD 1993m
Reported in PSD 1993m
Reported in PSD 1993m
Reported in PSD 1993m
Reported in PSD 1991d
Reported in PSD 1991d
Reported in PSD 1991d
Reported in PSD 1991d
2.2 - 25.1%
0.3 - 5.5%
21% (pH 5)
2% (pH 6)
23%
65.3% (pH 8.9)
52.1% (pH 7)
28 days
28 days
30 days
30 days
30 days
52 hours
23 days
-
Reported in PSD 1990d
Reported in PSD 1990d
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994c
Reported in PSD 1994c
24.1% (pH 5)
0.19% (pH 8.9)
0.97% (pH 7)
52.1% (pH 8.9)
54% (pH 7)
9% (pH 9)
13.6% (pH 7.1)
35% (pH 7)
76% (pH 9)
10.7% (pH 7.1)
24% (pH 7.1)
12 days
48 hours
23 days
18 days
21.5 hours
21.5 hours
21.5 hours
-
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1998a
Reported in PSD 1998a
Reported in PSD 1998a
Reported in PSD 1998a
Reported in PSD 1998a
Reported in PSD 1998a
Reported in PSD 1998a
42% (pH 4)
15% (pH 4)
12 - 16% (pH 7)
19% (pH 3)
7 - 11% (pH 5)
10 - 18% (pH 9)
3 - 6% (pH 7)
11 days
11 days
32 days
0 days
14 days
7 days
32 days
-
Reported in PSD 1993i
Reported in PSD 1993i
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
hydrolysis
(sterile)
67
©2008 AwwaRF. ALL RIGHTS RESERVED
Degradate
Degradate formation
Degradate
Parent pesticide
a
Percentage of
b
parent pesticide
Time
c
Country
Reference
30 minutes
14 days
7 days
32 days
7 days
6 days
6 days
14 days
-
-
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1990e
Reported in PSD 1993f
Reported in PSD 1993h
Reported in PSD 1993h
Reported in PSD 1993h
Reported in PSD 1993h
cycloxydim
T2SO
T2
cycloxydim
cycloxydim
diphenylurea
N-demethyldimefuron
compound D
compound G
[(3-chlorophenyl)amino]-N,Ndimethylcarboxamide
desmedipham
dimefuron
dimefuron
dimefuron
dimefuron
[(3-chloro-4-hydroxyphenyl)amino]-N,Ndimethylcarboxamide
O-desmethyldimethoate
dimefuron
<10%
-
-
Reported in PSD 1993h
dimethoate
O,O-dimethylphosphorothioic acid
dimethoate
Cl-Vacid
M3
1,3-dimethyl-5-phenoxypyrazole-4-carbonitrile
RH-9985
esfenvalerate
fenpyroximate
fenpyroximate
fluoroglycofen-ethyl
RH-5781
fluoroglycofen-ethyl
M1
propargyl butyl carbamate
imazaquin
IPBC
malonic acid
N-methyl malonamic acid
malonamic acid
methyl-2-(aminosulfonyl)benzoate
saccharin
kathon 886
kathon 886
kathon 886
metsulfuron-methyl
metsulfuron-methyl
12% (pH 5)
22% (pH 7)
62% (pH 9)
ND (pH 5)
2% (pH 7)
36% (pH 9)
14.9% (pH 9)
6.7%
10.1%
48.1% (pH 5)
64.7% (pH 7)
21.3% (pH 9)
4% (pH 5)
13.8% (pH 7)
77.7% (pH 9)
10% (pH 9)
12% (pH 7)
1% (pH 5)
<20%
>20%
<20%
26%
37%
30 days
30 days
30 days
30 days
30 days
30 days
28 days
30 days
30 days
30 days
30 days
30 days
30 days
30 days
30 days
30 days
30 days
30 days
30 days
30 days
-
Reported in PSD 1993j
Reported in PSD 1993j
Reported in PSD 1993j
Reported in PSD 1993j
Reported in PSD 1993j
Reported in PSD 1993j
Reported in PSD 1992b
Reported in PSD 1995b
Reported in PSD 1995b
Reported in PSD 1992a
Reported in PSD 1992a
Reported in PSD 1992a
Reported in PSD 1992a
Reported in PSD 1992a
Reported in PSD 1992a
Reported in PSD 1993a
Reported in PSD 1994n
Reported in PSD 1994n
Reported in PSD 1993m
Reported in PSD 1993m
Reported in PSD 1993m
Reported in PSD 1991d
Reported in PSD 1991d
dihydroxy anilazine
deethylatrazine
anilazine
atrazine
75%
19.2%
20 days
3.5 days
-
Reported in PSD 1994c
Reported in Solomon et al.
1996
hydrolysis
(sterile)
continued
68
©2008 AwwaRF. ALL RIGHTS RESERVED
T2S
7% (pH 3)
4 - 7% (pH 5)
4% (pH 9)
3 - 9% (pH 7)
3% (pH 9)
10% (pH 3)
70% (pH 3)
52% (pH 5)
<0.6%
<10%
<10%
<10%
<10%
soil photolysis
Degradate formation
a
Percentage of
b
parent pesticide
Time
atrazine
7.9%
diaminochlorotriatrazine
atrazine
pyrimidinol
diazinon
CONH2-fen
esfenvalerate
COOH-fen
Cl-Vacid
dec-fen
α-carbomoyl-3-phenoxybenzyl-2,2,3,3tetramethyl cyclopropane carboxylate
esfenvalerate
esfenvalerate
esfenvalerate
fenpropathrin
CGA 257 777
RH-5781
RH-9985
3-methyl phosphinico-proprionic acid
fludioxonil
fluoroglycofen-ethyl
fluoroglycofen-ethyl
glufosinate
ammonium
HOE 070542
HOE 070542
HOE 070542
HOE 070542
HOE 070542
imidacloprid
Degradate
Parent pesticide
deisopropylatrazine
c
Country
Reference
7 days
-
Reported in Solomon et al.
1996
6.8%
22 days
-
56 - 62%
56%
48.4%
25%
2%
4.5%
0.9%
6 – 44%
24 hours
24 hours
10 days
5 – 7 days
-
Reported in Solomon et al.
1996
Reported in PSD 1991b
Reported in PSD 1991b
Reported in PSD 1992b
Reported in PSD 1992b
Reported in PSD 1992b
Reported in PSD 1992b
Reported in PSD 1992b
Reported in PSD 1989b
3 – 26% (dark)
8%
5.3%
19%
9.7%
14 days
7 days
13 days
13 days
16 days
-
Reported in PSD 1989b
Reported in PSD 1995b
Reported in PSD 1992a
Reported in PSD 1992a
Reported in PSD 1990f
8.9%
3.6%
1.6%
13%
4.6%
6.3 - 6.5%
45 days
16 days
7 days
3.7 days
16 days
7 - 15 days
-
Reported in PSD 1990c
Reported in PSD 1990c
Reported in PSD 1990c
Reported in PSD 1990c
Reported in PSD 1990c
Reported in PSD 1993e
imidacloprid
<3%
7 - 15 days
-
Reported in PSD 1993e
imidacloprid
imidacloprid
<3%
<3%
7 - 15 days
7 - 15 days
-
Reported in PSD 1993e
Reported in PSD 1993e
metsulfuron-methyl
metsulfuron-methyl
metsulfuron-methyl
10%
8%
<1%
30 days
30 days
-
-
Reported in PSD 1991d
Reported in PSD 1991d
Reported in PSD 1991d
cyfluthrin
cyfluthrin
2%
4%
9 days
9 days
-
Reported in PSD 1988c
Reported in PSD 1988c
soil photolysis
continued
69
©2008 AwwaRF. ALL RIGHTS RESERVED
HOE 83348
HOE 88988
HOE 88989
HOE 72829
HOE 87606
1-(6-chloro-pyridine-3-ylmethyl)-N-nitro-2-iminoimidazollidine-5-ol
1-(6-chloro-pyridine-3-ylmethyl)-N-nitroso-2imino-imidazolidine
6-chloro-nicotinic acid
1-(6-chloro-pyridine-3-ylmethyl)-N-nitro-2-imino2,3-dihydro-imidazole and 1-(6-chloro-pyridine3-ylmethyl)-imazolidine-2-one
saccharin
2-aminosulfonyl) benzoic acid
methyl-2-(aminosulfonyl)benzoate
thin-layer photolysis
(non soil)
abcdef-
4-fluoro-3-phenoxybenzaldehyde
4-fluoro-3-phenoxybenzoic acid
pesticide identified in the reference as the source of the degradate
peak percentage formation of degradate during study
time to peak degradate formation
soil and water system
soil before leaching in column leachate study
soil after leaching in column leachate study
70
©2008 AwwaRF. ALL RIGHTS RESERVED
APPENDIX 2. THE DEGRADATION RATE OF PESTICIDE DEGRADATES IN THE ENVIRONMENT
Test matrix/system
Degradate
Parent pesticide
albendazole sulfoxide
albendazole sulfone
2-aminoalbendazole sulfone
a
Half-life / DT50
Reference
albendazole
albendazole
albendazole
0.034 - 1.05 days
0.014 - 1.77 days
0.163 - 1.94 days
Weerasinghe et al. 1992
Weerasinghe et al. 1992
Weerasinghe et al. 1992
methamidophos
ethyl-m-hydroxyphenyl carbamate
disulfoton sulfoxide
disulfoton sulfone
fenthion sulfoxide
kresoxim-methyl acid
acephate
desmedipham
disulfoton
disulfoton
fenthion
kresoxim-methyl
8.6 - 17.8 days
26 days
10.4 days (estuarine)
8.19 days (estuarine)
6.9 days (estuarine)
337 - 383 days
2,6-di-tert-butyl-4-methylphenyl
carbamate
2,6-di-tert-butyl-4-carboxyphenyl Nmethylcarbamate
2,6-di-tert-butyl-4-carboxyphenyl
carbamate
2,6-di-tert-butyl-4-methylphenol
2,6-di-tert-butyl-4-carboxyphenol
terbutol
47.1 months
Sundaram, 1993
Reported in PSD 1993f
Lacorte et al. 1995
Lacorte et al. 1995
Lacorte et al. 1995
Reported in Roberts and Hutson,
1999
Suzuki et al. 1998
terbutol
63.6 months
Suzuki et al. 1998
terbutol
29.4 months
Suzuki et al. 1998
terbutol
terbutol
42 months
25 months
Suzuki et al. 1998
Suzuki et al. 1998
RH-9985
fluoroglycofen-ethyl
15.1 days (pH 9)
5.3 days (pH 9)
Reported in PSD 1992a
Reported in PSD 1992a
z-3-chloroallyl alcohol
e-3-chloroallyl alcohol
methamidophos
dihydroxy anilazine
2-chloro-2',6'-diethylacetanilide
2-hydroxy-2',6'-diethylacetanilide
2,6-diethylaniline
carbouran
1,3-dichloropropene (z-isomer)
1,3-dichloropropene (e-isomer)
acephate
anilazine
alachlor
alachlor
alachlor
benfuracarb
1-naphthol
3,5,6-trichloro-2-pyridinol
cis-3-chloroallylalcohol
clodinafop-propargyl free acid
melamine
carbaryl
chlorpyrifos
cis-1,3-dichloropropene
clodinafop-propargyl
cyromazine
dacthal mono-acid
dacthal
2.3 - 4.2 days
0.8 - 1.4 days
3.5 - 9.3 days
21 - 45 days
2.4 days
0.8 days
1.3 days
36 - 44 days
30 - 34 days
11 - 23 days
14.93 days
42 - 49 days
1.2 - 1.8 days
5 - 20 days
175 - 186 days (estimated)
150 - 730 days (estimated)
2.8 ± 0.1 days
Leistra et al. 1991
Leistra et al. 1991
Sundaram, 1993
Reported in PSD 1994c
Fava et al. 2000
Fava et al. 2000
Fava et al. 2000
Reported in PSD 1998a
Reported in PSD 1998a
Reported in PSD 1998a
Menon and Gopal, 2003
Baskaran et al. 2003
Dijk, 1974
Reported in Tomlin, 2000
Reported in PSD 1993l
Reported in PSD 1993l
Wettasinghe and Tinsley, 1993
aqueous photolysis
surface water
71
©2008 AwwaRF. ALL RIGHTS RESERVED
hydrolysis (sterile)
aerobic soil
Test matrix/system
Degradate
Parent pesticide
dacthal di-acid
ethyl-m-hydroxyphenyl carbamate
dacthal
desmedipham
diazoxon
diazinon
3,6-dichlorosalicylic acid
dicolfop-methyl and diclofop acid
combined
dicamba
diclofop-methyl
a
Half-life / DT50
Reference
> 300 days
o
21 days (15 C)
o
9 days (25 C)
o
27 days (15 C)
o
21 days (25 C)
88 days
17 hours
> 40 days
21 - 93 days
Wettasinghe and Tinsley, 1993
Reported in PSD 1993f
Reported in PSD 1993f
Reported in PSD 1993f
Reported in PSD 1993f
Reported in Tomlin, 2000
Reported in PSD 1991b
Pearson et al. 1996
Reported in PSD 1991e
Reported in PSD 1991e
Reported in PSD 1991e
Reported in PSD 1991e
Reported in PSD 1991e
Reported in PSD 1991e
Reported in PSD 1991e
Reported in PSD 1990b
Reported in Roberts, 1998
Reported in PSD 1992a
Reported in PSD 1990f
Reported in PSD 1990f
Reported in PSD 1990f
Reported in PSD 1990f
Reported in PSD 1994n
Reported in Roberts and Hutson,
1999
Reported in Roberts and Hutson,
1999
aqueous photolysis
72
©2008 AwwaRF. ALL RIGHTS RESERVED
diclofop acid
diclofop-methyl
fenoxaprop-ethyl acid
fluroxypyr
RH-5781
HOE 35950
3-methyl phosphinico-proprionic
acid
fenoxaprop-ethyl
fluroxpyr-meptyl
fluoroglycofen-ethyl
glufosinate ammonium
glufosinate ammonium
10 - 38 days
21 - 52 days
10 - 30 days
6 - 38 days
63 days
26 - 28.4 days
5 - 14 days
< 7 days
14 - 128 days
4 - 42 days
165 days
propargyl butyl carbamate
kresoxim-methyl acid
IPBC
kresoxim-methyl
7 - 14 days
13 - 22 days
4.3 days
38 -131 days
methyl isothiocyanate
metam sodium
4 - 5 days
2-ethyl-6-methylaniline
paraoxon
2,6-di-tert-butyl-4-methylphenyl
carbamate
2,6-di-tert-butyl-4-carboxyphenyl Nmethylcarbamate
2,6-di-tert-butyl-4-carboxyphenyl
carbamate
tridimenol
trans-3-chloroallylalcohol
3,5,6-trichloro-2-pyridinol
metolachlor
parathion
terbutol
1.7 days
a
4 hours
291 days
Fava et al. 2000
Saffih-Hdadi et al. 2003
Suzuki et al. 2001
terbutol
173 days
Suzuki et al. 2001
terbutol
184 days
Suzuki et al. 2001
triadimefon
trans-1,3-dichloropropene
triclopyr
> 2 years
0.4 - 0.6 days
30 - 90 days
Bromilow et al. 1999
Dijk, 1974
Reported in Tomlin, 2000
diclofop acid
fenoxaprop-ethyl acid
diclofop-methyl
fenoxaprop-ethyl
> 150 days
30 days
Reported in PSD 1991e
Reported in PSD 1990b
anaerobic soil
sediment
Test matrix/system
Degradate
Parent pesticide
ethyl-m-hydroxyphenyl carbamate
a
Half-life / DT50
Reference
desmedipham
43 days
Reported in PSD 1993f
ethyl-m-hydroxyphenyl carbamate
diclofop acid
4-(2,4-dichlorophenoxy)phenol
fluroxypyr
propargyl butyl carbamate
kresoxim-methyl acid
desmedipham
diclofop-methyl
diclofop-methyl
fluroxpyr-meptyl
IPBC
kresoxim-methyl
25 days
27 days
32 days
< 7 days
11.5 days (anaerobic)
464 - 473 days
Reported in PSD 1993f
Reported in PSD 1991e
Reported in PSD 1991e
Reported in Roberts, 1998
Reported in PSD 1994n
Reported in Roberts and Hutson,
1999
O,O-dimethyl phosphorodithioate
dimethoate
1 day
aqueous photolysis
water/sediment system
sewage sludge degradation
73
©2008 AwwaRF. ALL RIGHTS RESERVED
a-
DT100
a
Reported in PSD 1993j
74
©2008 AwwaRF. ALL RIGHTS RESERVED
APPENDIX 3. DEGRADATE ORGANIC CARBON PARTITION COEFFICIENT (KOC)
Parent pesticide
2,4-dichlorophenol
2,4-D
2-chloro-2',6'diethylacetanilide
2-hydroxy-2',6'diethylacetanilide
2,6-diethylaniline
alachlor ethane sulfonic acid
4,6-dihydroxypyrimidin-2-ylurea
2-amino-4,6dimethyoxypyrimidine
a
-3
-1
-3
-1
Details
Kd (cm g )
Koc (cm g )
alachlor
sand
sandy silt loam
sandy loam
clay loam
determined by HPLC
2.64
4.39
2.6
5.02
-
447.5
a
182.9
a
481.5
a
185.9
148
Haberhauer et al.
Haberhauer et al.
Haberhauer et al.
Haberhauer et al.
Fava et al. 2000
alachlor
determined by HPLC
-
45
Fava et al. 2000
alachlor
alachlor
amidosulfuron
determined by HPLC
determined by HPLC
-
357
182
0.4
Fava et al. 2000
Reported in Aga and Thurman, 2001
Reported in PSD 1994a
amidosulfuron
sand
2.47
211
Reported in PSD 1994a
loamy sand
sandy loam
loamy sand
sandy loam
sandy loam
silty clay loam
clay
determined by HPLC
sand
clay
loamy sand
sandy loam
sandy loam
determined by HPLC
sand
sandy loam
silt loam
clay loam
silt loam
sand
sand
loamy sand
loam
clay
sand
sandy loam
silt loam
sand
0.23
8.25
1.06
1.81
4.11
81.28
16.51
0.08
0.43
0.71
0.83
0.51
2.97
0.92
7.39
3.97
0.3
6.5
0.96
0.58
0.24
1.02
0.06
0.36
0.4
8.6
89
625
663
696
395
11289
917
29
51
24
24
63
57
3
512
144
437
310
110
a
300
b
46
b
24
b
25
b
24
36.1
12.2
31.8
130
a
400
b
62
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994a
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994c
Reported in PSD 1994c
Steinheimer and Scoggin, 2001
Mills and Thurman, 1994
Brouwer et al. 1990
Brouwer et al. 1990
Brouwer et al. 1990
Brouwer et al. 1990
Reported in Solomon et al. 1996
Reported in Solomon et al. 1996
Reported in Solomon et al. 1996
Steinheimer and Scoggin, 2001
Mills and Thurman, 1994
Brouwer et al. 1990
75
©2008 AwwaRF. ALL RIGHTS RESERVED
Degradate
HOE 101630
amidosulfuron
dihydroxy anilazine
anilazine
deethylatrazine
atrazine
deethylatrazine continued
atrazine
deisopropylatrazine
atrazine
a
Reference
2000
2000
2000
2000
Degradate
diaminochlorotriazine
hydroxyatrazine
Parent pesticide
atrazine
atrazine
a
-3
-1
-3
-1
76
©2008 AwwaRF. ALL RIGHTS RESERVED
Details
Kd (cm g )
Koc (cm g )
sand
loamy sand
loam
clay
sand
sandy loam
loam
loam
clay
1.2
0.73
0.41
2.73
0.16
0.51
0.27
0.21
1.56
31
b
32
b
41
97
30
45
58
44.9
55
Brouwer et al. 1990
Brouwer et al. 1990
Brouwer et al. 1990
Reported in Solomon et al.
Reported in Solomon et al.
Reported in Solomon et al.
Reported in Solomon et al.
Reported in Solomon et al.
Reported in Solomon et al.
sand
sandy loam
loam
sand
sand
loamy sand
loam
clay
sand
sandy loam
loam
silty clay loam
0.16
0.65
0.36
82
4.1
3.7
1.7
389
1.98
6.52
12.1
-
31
58
76
b
590
b
103
b
161
b
170
13797
374
583
2573
59 ± 5
Reported in Solomon et al.
Reported in Solomon et al.
Reported in Solomon et al.
Brouwer et al. 1990
Brouwer et al. 1990
Brouwer et al. 1990
Brouwer et al. 1990
Reported in Solomon et al.
Reported in Solomon et al.
Reported in Solomon et al.
Reported in Solomon et al.
Gaston et al. 1996
1.62 - 2.86
0.45 - 2.53
1.77 - 2.85
250 ± 10
97 ± 7
350 ± 20
70 - 159
76 - 126
110 - 133
Gaston et al. 1996
Gaston et al. 1996
Gaston et al. 1996
Baskaran et al. 2003
Baskaran et al. 2003
Reddy et al. 1997
b
Reference
2-amino-N-isopropyl
benzamide
bentazone
N-methyl bentazone
bentazone
3,5,6-trichloro-2-pyridinol
3,5,6-trichloro-2-pyridinol
desmethylpropanenitrile
cyanazine
desmethylpropanenitrile
cyanazine continued
chlorpyrifos
chlorpyrifos
cyanazine
clay
silty clay loam
clay
red brown earth
black earth
silt loam
cyanazine
loamy sand
0.18
15
Reddy et al. 1997
hydroxyacid cyanazine
cyanazine
deethylcyanazine
cyanazine
cyanazine amide
cyanazine
chloroacid cyanazine
cyanazine
3,6-dichlorosalicylic acid
diclofop acid
dicamba
diclofop-methyl
silty clay
silt loam
loamy sand
silty clay
silt loam
loamy sand
silty clay
silt loam
loamy sand
silty clay
silt loam
loamy sand
silty clay
silt loam
sandy silt loam
sand
1.69
1.59 - 2.79
0.13
1.17
1.05 - 1.76
0.31
1.44
0.64 - 1.08
0.19
1.43
0.17 - 0.23
0.08
0.21
0.7
1.8
89
99 - 130
11
62
65 - 82
26
76
40 - 50
16
75
10 - 11
7
11
504
191
334
Reddy et al. 1997
Reddy et al. 1997
Reddy et al. 1997
Reddy et al. 1997
Reddy et al. 1997
Reddy et al. 1997
Reddy et al. 1997
Reddy et al. 1997
Reddy et al. 1997
Reddy et al. 1997
Reddy et al. 1997
Reddy et al. 1997
Reddy et al. 1997
Pearson et al. 1996
Reported in PSD 1991e
Reported in PSD 1991e
1996
1996
1996
1996
1996
1996
1996
1996
1996
1996
1996
1996
1996
Parent pesticide
4-chlorophenol
dichloroprop
fluroxypyr
fluroxpyr-meptyl
HOE 35956
imidacloprid-guanidine
glufosinate
ammonium
imidacloprid
imidacloprid-guanidine-olefin
imidacloprid
imidacloprid-urea
imidacloprid
kresoxim-methyl acid
kresoxim-methyl
2-methyl-4-chlorophenol
MCPA
metolachlor ethane sulfonic
acid
2-ethyl-6-methylaniline
ab-
a
-3
-1
-3
-1
Details
Kd (cm g )
Koc (cm g )
Reference
silt loam
sand
sandy silt loam
sandy loam
clay loam
sandy loam
1.7
1.15
2.29
1.23
2.61
1.7
283
a
194.9
a
95.4
a
227.8
a
96.7
-
Reported in PSD 1991e
Haberhauer et al. 2000
Haberhauer et al. 2000
Haberhauer et al. 2000
Haberhauer et al. 2000
Reported in Tomlin, 2000
sand
-
16
Reported in PSD 1990f
clay loam
silt loam
sandy loam
clay loam
silt loam
sandy loam
clay loam
silt loam
sandy loam
-
-
211
189
209
3805
3667
2129
2829
3083
2314
17 - 24
Cox et al. 1997
Cox et al. 1997
Cox et al. 1997
Cox et al. 1997
Cox et al. 1997
Cox et al. 1997
Cox et al. 1997
Cox et al. 1997
Cox et al. 1997
Reported in Tomlin, 2000
metolachlor
sand
sandy silt loam
sandy loam
clay loam
-
1.05
2.97
1.41
3.72
-
178
a
123.8
a
261.1
a
137.8
195
Haberhauer et al. 2000
Haberhauer et al. 2000
Haberhauer et al. 2000
Haberhauer et al. 2000
Reported in Aga and Thurman, 2001
metalochlor
determined by HPLC
-
197
Fava et al. 2000
77
©2008 AwwaRF. ALL RIGHTS RESERVED
Degradate
a
Koc or Kd calculated using % organic carbon data presented in the reference
Kom, organic matter partition coefficient
(Koc is the sorption of a compound to soil normalized for the organic carbon content of that soil, whilst Kom is the sorption of a compound to soil normalized for the organic matter
content of that soil)
78
©2008 AwwaRF. ALL RIGHTS RESERVED
APPENDIX 4. THE OCCURRENCE OF PESTICIDE DEGRADATES IN THE ENVIRONMENT
Environmental
compartment
Degradate
Parent pesticide
3-chlorallyl alcohol
2-chloro-2',6'-diethylacetanilide
2,6-diethylaniline
alachlor ethane sulfonic acid
deethylatrazine
a
Concentration
Limit of detection
Country
Reference
1,3-dichloropropene
alachlor
alachlor
alachlor
atrazine
ND
ND
ND
-1
43.5 - 210 µg kg
-1
< 12 - 60 µg kg
10 µg kg
-1
10 µg g
-1
10 µg g
-
-1
USA
Germany
Germany
USA
USA
Obreza and Ontermaa, 1991
Heyer and Stan, 1995
Heyer and Stan, 1995
Aga and Thurman, 2001
Mills and Thurman, 1994
atrazine
14 ± 2 ppb
-1
< 1 - 15.3 µg kg
-1
0.04 - 0.11 ± 0.01 µg g
-1
< 4 - 27 µg kg
1 - 5 ppb
-
Canada
Canada
USA
USA
Khan and Saidak, 1981
Raju et al. 1993
Winkelmann and Klaine, 1991
Mills and Thurman, 1994
atrazine
< 1 - 10.08 µg kg
0.01 - 0.02
296 ± 27 - 378 ± 30 ppb
1 - 5 ppb
Canada
USA
Canada
Raju et al. 1993
Winkelmann and Klaine, 1991
Khan and Saidak, 1981
1 - 5 ppb
1 - 5 ppb
0.01 ppm
0.01 ppm
-1
2 mg kg
-1
0.02 mg kg
-1
0.02 mg kg
-1
0.02 mg kg
Canada
USA
Canada
Canada
Japan
USA
USA
Belgium
Belgium
Belgium
Belgium
Belgium
Belgium
Belgium
Belgium
Belgium
Belgium
Belgium
Belgium
Belgium
Belgium
Belgium
Belgium
Raju et al. 1993
Winkelmann and Klaine, 1991
Khan and Saidak, 1981
Khan and Saidak, 1981
Reported in PSD 1998a
Niemczyk and Krause, 1994
Niemczyk and Krause, 1994
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Soil
topsoil (0-30 cm)
-1
hydroxyatrazine
-1
79
©2008 AwwaRF. ALL RIGHTS RESERVED
deisopropylatrazine
deethylhydroxyatrazine
deisopropylhydroxyatrazine
carbofuran
SDS1449
SDS954
1-(2,4-dichlorophenyl) ethan-1-ol
atrazine
atrazine
benfuracarb
chlorthal-dimethyl
chlorthal-dimethyl
chlorfenvinphos
2-hydroxy-4-chlorobenzoic acid
chlorfenvinphos
2,4-dichloroacetophenone
chlorfenvinphos
2,4-dichlorophenacyl chloride
chlorfenvinphos
2,4-dichlorobenzoic acid
chlorfenvinphos
< 1 - 52.1 µg kg
-1
0.41 ± 0.08 - 0.5 µg g
47 ± 4 - 17 ± 2 ppb
23 ± 2 - 64 ± 8 ppb
-1
< 1 - 6.3 mg kg
-1
ND - 0.11 kg ha
-1
ND - 2.09 kg ha
ND
-1 c
0.3 mg kg
-1 c
0.3 mg kg
-1
5.6±0.2 mg kg
-1 c
3.2 mg kg
-1 c
4.7 mg kg
-1 c
5.7 mg kg
-1 c
5.0 mg kg
-1 c
0.4 mg kg
-1 c
0.4 mg kg
-1 c
0.3 mg kg
-1
0.1 mg kg
-1
3.5±0.2 mg kg
-1 c
4.8 mg kg
-1 c
4.3 mg kg
-1 c
3.5 mg kg
-1 c
3.3 mg kg
-1
7.3±0.3 mg kg
Environmental
compartment
Degradate
2,4-dihydroxybenzoic acid
Parent pesticide
chlorfenvinphos
a
Concentration
Limit of detection
Country
Reference
-1 c
-1
0.02 mg kg
Belgium
Belgium
Belgium
Belgium
Belgium
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
-1 c
-
Belgium
Belgium
Belgium
Belgium
Belgium
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
Reported in PSD 1994k
-1
-
-
Reported in PSD 1994k
4.7 mg kg
-1 c
4.9 mg kg
-1 c
7.4 mg kg
-1 c
7.9 mg kg
-1
1.5±0.1 mg kg
80
©2008 AwwaRF. ALL RIGHTS RESERVED
2,4-dihydroxybenzoic acid
chlorfenvinphos
dichlorobenzyl alcohol
chlorfenvinphos
1.1 mg kg
-1 c
1.3 mg kg
-1 c
2.5 mg kg
-1 c
2.0 mg kg
-1 c
0.5 mg kg
trichloroacetophenone
chlorfenvinphos
0.1 mg kg
cyanazine amide
cyanazine
<0.01 - 1.1 ppm
-
France and UK
Beynon et al. 1972a
2-chloro-4-(1-carbonyl-1methylethylamino)-6-amino-1,3,5triazine
cyanazine acid
cyanazine
0.41 - 0.9 ppm
< 0.01 - 0.08 ppm
-
UK
France and UK
Beynon et al. 1972b
Beynon et al. 1972a
cyanazine
0.72 - 1.66 ppm
-
UK
Beynon et al. 1972b
cyanazine hydroxy acid
2-[(4-amino-6-chloro(1,3,5-triazin2-yl))amino]-2-methylpropanenitrile
(4-amino-6-chloro(1,3,5-triazin-2yl))ethylamine
CCA
3-phenoxybenzoic acid
3-phenoxybenzaldehyde
melamine
ethyl-m-hydroxyphenyl carbamate
o,p’-DDE
p,p’-DDE
o,p’-DDD
p,p’-DDD
diazoxon
3,6-dichlorosalicylic acid
2,5-dihydroxy-3,6-dichlorosalicylic
acid
diclofop acid
DM2
DM3
DM4
2,4-difluoroaniline
3-(trifluoromethyl)phenol
N-demethyldimefuron
cyanazine
cyanazine
0.1 - 0.79 ppm
< 0.01 - 0.02 ppm
-
UK
UK
Beynon et al. 1972b
Beynon et al. 1972b
cyanazine
0.03 - 0.08 ppm
-
UK
Beynon et al. 1972b
cypermethrin
cypermethrin
cypermethrin
cypromazine
desmedipham
DDT
DDT
DDT
DDT
diazinon
dicamba
dicamba
1-10 ng g
-1
1-10 ng g
-1
1-10 ng g
-1
0.05 - 1.4 mg kg
-1
ND - 0.59 mg kg
-1
> 0.01 ± 0.01 µg g
-1
17.3 ± 1.6 µg g
-1
20.9 ± 4.9 µg g
-1
9.0 ± 1.0 µg g
ND
-1
0.05 - 1.25 µg g
-1
0.03 - 0.1 µg g
ng g range
-1
ng g range
-1
ng g range
-1
0.005 mg kg
0.001 ppm
-1
0.005 µg g
-1
0.005 µg g
Germany
Germany
Germany
Switzerland
USA
Australia
Australia
Australia
Australia
UK
USA
USA
Class, 1992
Class, 1992
Class, 1992
Reported in PSD 1993l
Reported in PSD 1993f
Van Zweiten et al. 2001
Van Zweiten et al. 2001
Van Zweiten et al. 2001
Van Zweiten et al. 2001
Reported in PSD 1991b
Krueger et al. 1991
Krueger et al. 1991
diclofop-methyl
diflufenican
diflufenican
diflufenican
diflufenican
diflufenican
dimefuron
0.01- 0.28 mg kg
-1
ND - 20 ± 1 µg kg
-1
ND - 26 ± 1 µg kg
-1
ND - 23 ± 1 µg kg
ND
ND
-1 b
0.1 mg kg
-1
2 µg kg
-1
2 µg kg
-1
2 µg kg
-1
5 µg kg
-1
5 µg kg
-
USA
Belgium
Belgium
Belgium
Belgium
Belgium
UK
Reported in PSD 1991e
Rouchaud et al. 1991
Rouchaud et al. 1991
Rouchaud et al. 1991
Rouchaud et al. 1991
Rouchaud et al. 1991
Reported in PSD 1993h
-1
-1
-1
Environmental
compartment
a
Parent pesticide
Concentration
Limit of detection
RH-6467
fenbuconazole
RH-9129
fenbuconazole
RH-9130
fenbuconazole
fomesafen amine
3-methyl phosphinico-proprionic
acid
fomesafen
glufosinate ammonium
5 µg kg
-1
0.016 mg kg
-1 b
0.047 mg kg
ND
-1
0.031 mg kg
-1 b
0.05 mg kg
ND
-1
0.01 mg kg
-1 b
0.063 mg kg
-1
<0.02 mg kg
-1
0.03 - 0.2 mg kg
2-hydroxyquinoxaline
quinoxaline-2-thiol
4-chloro-2-methylphenol
metolachlor ethane sulfonic acid
quinalphos
quinalphos
MCPA
metolachlor
ND - 0.03 mg kg
-1
ND - 64 ± 2 µg kg
-1
ND - 35 ± 7 µg kg
-1 b
5 - 6 mg kg
-1
11.91 - 128 µg kg
< 0.05 mg kg
-1
< 1 mg g
-1
< 1 mg g
-1
15 - 45 µg kg
-
3-chlorallyl alcohol
alachlor ethane sulfonic acid
metolachlor ethane sulfonic acid
1,3-dichloropropene
alachlor
metolachlor
ND
-1
80 - 142 µg kg
-1
3.6 - 13.3 µg kg
10 µg kg
-
alachlor ethane sulfonic acid
metolachlor ethane sulfonic acid
alachlor
metolachlor
13.3 - 140 µg kg
-1
18.7 - 122 µg kg
alachlor ethane sulfonic acid
deethylatrazine
alachlor
atrazine
3 - 73 µg L
-1 c
0.3 µg L
atrazine
9 - 19 µg L
-1 b
0.76 - 1.48 µg L
-1 b
15 - 29 µg L
-1 b
4.7 - 22.1 µg L
-1 c
0.6 µg L
didealkylatrazine
hydroxyatrazine
atrazine
atrazine
< 0.5 µg L
-1
0.11 - 0.78 µg L
-1 b
7 - 15 µg L
-1
< 0.02 µg L
-1
0.2 - 1.25 µg L
-1
0.08 - 0.37 µg L
2,6-diethylaniline
2-chloro-2’,6’-diethylacetanilide
2-hydroxy-2’,6’-diethylacetanilide
2-ethyl-6-methylaniline
alachlor
alachlor
alachlor
metolachlor
1 µg L
-1
2.2 - 2.7 µg L
-1
0.8 µg L
-1
0.6 µg L
-1 b
-1
Country
Reference
Germany
USA
USA
Germany
USA
USA
Germany
USA
USA
USA
Reported in PSD 1995c
Reported in PSD 1995c
Reported in PSD 1995c
Reported in PSD 1995c
Reported in PSD 1995c
Reported in PSD 1995c
Reported in PSD 1995c
Reported in PSD 1995c
Reported in PSD 1995c
Reported in PSD 1995a
Reported in PSD 1990f
India
India
Spain
USA
Reported in PSD 1990f
Menon and Gopal, 2003
Menon and Gopal, 2003
Crespin et al. 2001
Aga and Thurman, 2001
USA
USA
USA
Obreza and Ontermaa, 1991
Aga and Thurman, 2001
Aga and Thurman, 2001
USA
USA
Aga and Thurman, 2001
Aga and Thurman, 2001
-1
USA
USA
-1
USA
USA
USA
USA
USA
0.2 µg L
-1
0.03 µg L
-1
0.02 µg L
-1
0.03 µg L
-1
0.04 µg L
-1
USA
USA
USA
USA
USA
USA
Aga and Thurman, 2001
Steinheimer and Scoggin,
2001
Fermanich et al. 1996
Pashin et al. 2000
Mills and Thurman, 1994
Adams and Thurman, 1991
Steinheimer and Scoggin,
2001
Fermanich et al. 1996
Pashin et al. 2000
Mills and Thurman, 1994
Adams and Thurman, 1991
Pashin et al. 2000
Pashin et al. 2000
-
Italy
Italy
Italy
Italy
Fava et al.
Fava et al.
Fava et al.
Fava et al.
-1
0.01 mg kg
-1
0.01 mg kg
-1
0.01 mg kg
-1
0.01 mg kg
-1
0.01 mg kg
-1
0.01 mg kg
-1
0.01 mg kg
-1
0.01 mg kg
-1
0.01 mg kg
-1
0.01 mg kg
-1
subsoil (30 - 60cm)
subsoil (60 - 90cm)
81
©2008 AwwaRF. ALL RIGHTS RESERVED
Degradate
-1
Vadose zone water
deisopropylatrazine
-1
-
-1
0.5 µg L
-1
0.04 µg L
-1 b
0.1 µg L
-1
0.04 µg L
-1
0.02 µg L
-1
0.04 µg L
-1
Leachate
(column study)
-1
2000
2000
2000
2000
Environmental
compartment
Degradate
Parent pesticide
RH-6467
RH-9129
RH-9130
a
Concentration
Limit of detection
Country
Reference
fenbuconazole
fenbuconazole
fenbuconazole
trace
trace
trace
-
-
Reported in PSD 1995c
Reported in PSD 1995c
Reported in PSD 1995c
acetochlor oxanilic acid
alachlor ethane sulfonic acid
alachlor oxanilic acid
deethylatrazine
acetochlor
alachlor
alachlor
atrazine
-1
deisopropylatrazine
metolachlor ethane sulfonic acid
atrazine
metolachlor
metolachlor oxanilic acid
metolachlor
ND - 0.08 µg L
-1
ND - 48.84 µg L
-1
ND - 0.17 µg L
-1 d
0 - 10.33 µg L
-1 b
8 - 29 µg L
-1 c
0.97 µg L
-1 d
0 - 12.14 µg L
-1
ND - 1.26 µg L
-1
0.05 - 0.47 µg L
-1
ND - 0.29 µg L
0.01 µg L
-1
0.5 µg L
-1
0.01 µg L
-1
0.05 µg L
-1
0.02 µg L
-1
0.5 µg L
-1
0.01 µg L
-1
0.01 µg L
USA
USA
USA
France
USA
USA
France
USA
USA
USA
Ferrer et al. 1997
Aga and Thurman, 2001
Ferrer et al. 1997
Patty et al. 1997
Thurman et al. 1994
Blanchard and Donald, 1997
Patty et al. 1997
Aga and Thurman, 2001
Ferrer et al. 1997
Ferrer et al. 1997
deethylatrazine
deisopropylatrazine
cyanazine amide
deisopropylatrazine
deethylatrazine
metolachlor ethane sulfonic acid
metolachlor oxanilic acid
atrazine
atrazine
cyanazine
cyanazine
cyprazine
metolachlor
metolachlor
0.36 - 7.71 µg L
-1
0.01 - 0.78 µg L
-1
< 0.04 - 3.3 µg L
-1
0.02 - 0.62 µg L
-1
0.15 - 3.6 µg L
-1
5 - > 20 µg L
-1
1 - 10 µg L
-1
0.01 µg L
-1
0.01 µg L
-1
0.01 µg L
-1
0.01 µg L
-1
0.01 µg L
-1
0.2 µg L
-1
0.2 µg L
-1
Canada
Canada
Canada
Canada
Canada
USA
USA
Muir and Baker, 1976
Muir and Baker, 1976
Muir and Baker, 1976
Muir and Baker, 1976
Muir and Baker, 1976
Phillips et al. 1999
Phillips et al. 2002
2-isoprpyl-6-methyl-4hydroxypyrimidine
diazioxon
diazinon
ND
1 µg L
Canada
Li et al. 2002
diazinon
ND
Canada
Li et al. 2002
acetochlor ethane sulfonic acid
acetochlor oxanilic acid
2,6-diethylanaline
alachlor ethane sulfonic acid
alachlor ethane sulfonic acid
acetochlor
acetochlor
alachlor
alachlor
alachlor
alachlor oxanilic acid
aldicarb sulfone
aldicarb sulfoxide
deethylatrazine
alachlor
aldicarb
aldicarb
atrazine and propazine
< 0.2 - 1.6 µg L
-1
< 0.02 - 1.4 µg L
ND
-1
< 0.2 - 3.5 µg L
-1 c
0.8 - 5.2 µg L
-1 b
5.2 - 27.8 µg L
-1
< 0.2 - 0.54 µg L
ND
ND
-1
< 0.05 - 0.39 µg L
0.2 µg L
-1
0.2 µg L
-1
0.01 µg L
-1
0.2 µg L
-1
0.1 µg L
-1
0.1 µg L
-1
0.2 µg L
-1
0.05 µg L
-1
0.05 µg L
-1
0.05 µg L
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
Kalkhoff et al. 2003
Kalkhoff et al. 2003
Hoffman et al. 2000
Kalkhoff et al. 2003
Kolpin et al. 1996a
Kolpin et al. 1996a
Kalkhoff et al. 2003
Hoffman et al. 2000
Hoffman et al. 2000
Kalkhoff et al. 2003
deethylatrazine continued
deisopropylatrazine
atrazine and propazine
atrazine, cyanazine and
simazine
-1
USA
USA
Hoffman et al. 2000
Kalkhoff et al. 2003
Surface water
runoff
-1
82
©2008 AwwaRF. ALL RIGHTS RESERVED
tile drain
ditch
-1
0.03 µg L
-1
stream
stream
continued
-1
-1 b
0.04 µg L
-1
< 0.05 - 0.36 µg L
-1
0.01 µg L
-1
0.05 µg L
Environmental
compartment
a
Parent pesticide
hydroxyatrazine
cyanazine amide
3-hydroxycarbofuran
p,p’-DDE
alpha-HCH
metolachlor ethane sulfonic acid
atrazine
cyanazine
carbofuran
DDT
gamma-HCH
metolachlor
metolachlor oxanilic acid
metolachlor
trifluoromethylphenyl urea
deisopropylprometryn
3,4-dichloroaniline
fluometuron
prometryn
propanil
2,4-dichlorophenol
acetochlor oxanilic acid
alachlor ethane sulfonic acid
2,4-D
acetochlor
alachlor
alachlor oxanilic acid
2,6-diethylaniline
2-chloro-2’,6’-diethylacetanilide
2-hydroxy-2’,6’-diethylacetanilide
8-hydroxy-bentazone
cyanazine amide
alachlor
alachlor
alachlor
alachlor
bentazone
cyanazine
deethylcyanazine
cyanazine
deethylcyanazine amide
deethylatrazine
cyanazine
atrazine and propazine
deisopropylatrazine
atrazine, cyanazine and
simazine
Concentration
Limit of detection
-1
-1
< 0.2 - 8.8 µg L
-1
< 0.05 - 1.2 µg L
ND
ND
ND
-1
< 0.2 - 6.7 µg L
-1
< 0.2 - 0.57 µg L
-1
< 0.2 - 1.3 µg L
-1
< 0.2 - > 0.5 µg L
ND
ND
-1
0.9 µg L
0.2 µg L
-1
0.05 µg L
-1
0.05 µg L
-1
0.01µg L
-1
0.01 µg L
-1
0.2 µg L
-1
0.2 µg L
-1
0.2 µg L
-1
0.2 µg L
-1
0.05 µg L
-1
0.05 µg L
-1
0.05 µg L
ND
-1
ND - 0.15 µg L
-1 c
1.55 - 4.75 µg L
-1
2.1 µg L
-1
ND - 0.21 µg L
-1
ND - 0.924 µg L
-1
ND - 0.35 µg L
-1
ND - 0.9 µg L
-1
ND - 27 µg L
-1 c
0.47 - 0.57 µg L
-1 c
0.06 µg L
-1
ND - 222 ng L
-1 c
< 0.05 µg L
ND
-1 c
< 0.05 µg L
-1 c
0.42 - 0.47 µg L
-1 b
0.39 - 4.4 µg L
-1
ND - 0.407 µg L
-1
ND - 0.215 µg L
-1
0.025 - 0.08 µg L
-1
7 - 82 ng L
-1
5 - 855 ng L
L-1 b
150 ng
-1 c
12 - 28 µg L
75 ng L
-1
0.01 µg L
-1
0.1 µg L
-1
0.05 µg L
-1
0.01 µg L
-1
5 ng L
-1
5 ng L
-1
5 ng L
-1
2 ng L
-1
0.05 µg L
-1
0.02 µg L
-1
25 ng L
-1
0.05 µg L
-1
0.05 µg L
-1
0.5 µg L
-1
0.05 µg L
-1
0.05 µg L
-1
0.005 µg L
-1
0.01 µg L
-1
0.3 ng L
-1
5 ng L
-1
5 ng L
-1
1 ng L
-
Country
Reference
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
Kalkhoff et al. 2003
Kalkhoff et al. 2003
Hoffman et al. 2000
Hoffman et al. 2000
Hoffman et al. 2000
Kalkhoff et al. 2003
Phillips et al. 1999
Kalkhoff et al. 2003
Phillips et al. 1999
Coupe et al. 1998
Coupe et al. 1998
Coupe et al. 1998
Italy
USA
USA
USA
USA
USA
USA
USA
Italy
USA
USA
USA
USA
USA
USA
USA
USA
Greece
Greece
USA
USA
USA
USA
USA
river
83
©2008 AwwaRF. ALL RIGHTS RESERVED
Degradate
0.43 - 0.87 µg L
-1 c
< 0.05 - 3.2 µg L
-1 b
-1
0.05 µg L
-1
USA
Lagana et al. 2002
Ferrer et al. 1997
Battaglin and Goolsby, 1999
Verstraeten et al. 1999
Ferrer et al. 1997
Pereira and Rostad, 1990
Pereira and Rostad, 1990
Pereira and Rostad, 1990
Lagana et al. 2002
Battaglin and Goolsby, 1999
Lerch and Blanchard, 2003
Pereira and Hostettler, 1993
Battaglin and Goolsby, 1999
Verstraeten et al. 1999
Battaglin and Goolsby, 1999
Battaglin and Goolsby, 1999
Thurman et al. 1992
Albanis et al. 1998
Albanis and Hela, 1998
Sabik et al. 2003
Pereira and Rostad, 1990
Pereira and Hostettler, 1993
Liu et al. 2002
Reported in Solomon et al.
1996
Battaglin and Goolsby, 1999
0.05 µg L
-1
USA
Thurman et al. 1992
Environmental
compartment
Degradate
Parent pesticide
a
Concentration
0.007 - 0.038 µg L
-1
8 - 45 ng L
-1
ND - 335 ng L
-1 b
64 ng L
-1 c
4.9 - 15 µg L
-1 b
Limit of detection
-1
Reference
0.3 ng L
-1
5 ng L
-1
10 ng L
-1
1.8 ng L
-
USA
-1
USA
USA
USA
USA
USA
Italy
USA
USA
USA
Sabik et al. 2003
Pereira and Rostad, 1990
Pereira and Hostettler, 1993
Liu et al. 2002
Reported in Solomon et al.
1996
Liu et al. 2002
Zimmerman et al. 2002
Zimmerman et al. 2002
Zimmerman et al. 2002
Zimmerman et al. 2002
Lagana et al. 2002
Ferrer et al. 1997
Ferrer et al. 1997
Liu et al. 2002
-1
Greece
Albanis and Hela, 1998
-1
USA
Switzerland
USA
USA
Spalding et al. 1994
Bucheli et al. 1997
Thurman et al. 2000
Spalding et al. 1994
USA
Switzerland
USA
Spalding et al. 1994
Bucheli et al. 1997
Spalding et al. 1994
0.05 µg L
-1
0.2 µg L
-1
0.2 µg L
-1
0.05 µg L
-1
0.2 µg L
-1
0.2 µg L
-1
0.05 µg L
USA
USA
USA
USA
USA
USA
USA
Thurman et al.
Thurman et al.
Thurman et al.
Thurman et al.
Thurman et al.
Thurman et al.
Thurman et al.
-1
0.2 µg L
-1
0.2 µg L
-1
0.1 µg L
-1
0.1 µg L
Denmark
USA
USA
USA
USA
Helweg et al. 2002
Kolpin et al. 2000
Boyd, 2000
Kolpin et al. 1996a
Kolpin et al. 1996a
-1
USA
USA
USA
p,p’-DDE
dimethenamid ethane sulfonic acid
dimethenamid oxanilic acid
flufenacet ethane sulfonic acid
flufenacet oxanilic acid
4-chloro-2-methylphenol
metolachlor oxanilic acid
metolachlor ethane sulfonic acid
endosulfan sulphate
DDT
dimethenamid
dimethenamid
flufenacet
flufenacet
MCPA
metolachlor
metolachlor
endosulfan
4 ng L
-1 c
0.05 µg L
-1 c
0.05 µg L
-1 c
0.06 µg L
-1 c
0.05 µg L
ND
-1
ND - 0.29 µg L
-1
0.33 - 1.82 µg L
-1
6 ng L
0.3 ng L
-1
0.03 µg L
-1
0.02 µg L
-1
0.01 µg L
-1
0.07 µg L
-1
50 ng L
-1
0.01 µg L
-1
0.01 µg L
-1
0.3 ng L
deethylatrazine
atrazine
ND - 0.526
0.01 µg L
deethylatrazine
atrazine
deisopropylatrazine
atrazine
hydroxyatrazine
dichlorophenylurea
dichloromethylphenylurea
3,4-dichloroaniline
metolachlor ethane sulfonic acid
metolachlor oxanilic acid
demethylnorflurazon
atrazine
diuron
diuron
diuron
metolachlor
metolachlor
norflurazon
1.57 µg L
-1 c
92 ng L
-1 c
0.36 µg L
-1 b
0.18 - 1.57 µg L
-1 c
0.1 - 0.54 µg L
-1 b
1.06 µg L
-1 c
26 ng L
-1 b
ND - 1.06 µg L
-1 c
ND - 0.92 µg L
-1 c
0.56 µg L
-1 c
0.2 µg L
-1 c
0.45 µg L
-1 c
0.31 µg L
-1 c
0.1 µg L
-1 c
0.19 µg L
-1 c
0.17 µg L
2,4-dichlorophenol
acetochlor ethane sulfonic acid
2,4-D
acetochlor
acetochlor ethane sulfonic acid
acetochlor
canal
lake
84
©2008 AwwaRF. ALL RIGHTS RESERVED
Country
-1 b
0.05 µg L
-1
2 - 6 ng L
-1
0.05 µg L
-1
0.05 µg L
-1
0.09 µg L
-1
2 - 6 ng L
-1
0.09 µg L
-1
2000
2000
2000
2000
2000
2000
2000
Groundwater
-1 b
4 µg L
-1 b
0.77 µg L
-1
ND - 3.32 µg L
-1 c
0.28 µg L
-1 b
8.6 µg L
Environmental
compartment
a
85
©2008 AwwaRF. ALL RIGHTS RESERVED
Degradate
Parent pesticide
acetochlor oxanilic acid
acetochlor
α-N-[(2'-6'diethylphenylamino]ethanol
2-chloro-2'-ethyl-6'-ethyl-N(methoxymethyl)acetanilide
2'-acetyl-6'-ethylacetanilide
2'-acetyl-6'-ethyl-Nmethoxymethyl)acetanilide
2-hydroxy-2',6'-diethyl-Nmethyl)acetanilide
2-hydroxy-2',6'-diethyl-Nmethoxymethyl)acetanilide
2,6-diethylaniline
alachlor
11.5 µg L
-1
ND - 1.75 µg L
-1
ND - 0.17 µg L
-1
< 2 - 480 ng L
alachlor
< 2 - 310 ng L
alachlor
alachlor
28 - 120 ng L
-1
68 - 240 ng L
alachlor
< 2 - 130 ng L
alachlor
< 2 - 100 ng L
alachlor
2',6'-diethylacetanilide
2',6'-diethylformanilide
7-ethylindoline
alachlor ethane sulfonic acid
alachlor
alachlor
alachlor
alachlor
alachlor oxanilic acid
alachlor
N-(2,6-diethylphenyl) methylene
N-(2,6-diethylphenyl)-N(methoxymethyl)acetamide
deethylatrazine
alachlor
alachlor
atrazine
Concentration
atrazine
Reference
0.2 µg L
-1
0.2 µg L
-1
0.01 µg L
-
USA
USA
USA
USA
Kolpin et al. 2000
Boyd, 2000
Ferrer et al. 1997
Potter and Carpenter, 1995
-
USA
Potter and Carpenter, 1995
-
USA
USA
Potter and Carpenter, 1995
Potter and Carpenter, 1995
-1
-
USA
Potter and Carpenter, 1995
-1
-
USA
Potter and Carpenter, 1995
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
Kolpin et al. 1998
Potter and Carpenter, 1995
Kolpin et al. 1996b
Potter and Carpenter, 1995
Potter and Carpenter, 1995
Potter and Carpenter, 1995
Verstraeten et al. 1999
Kolpin et al. 1996b
Kolpin et al. 2000
Boyd, 2000
Aga et al. 1994
Kolpin et al. 2000
Boyd, 2000
Ferrer et al. 1997
Potter and Carpenter, 1995
Potter and Carpenter, 1995
-1
Greece
USA
-1
USA
Switzerland
USA
USA
USA
USA
USA
USA
Albanis et al. 1998
Steinheimer and Scoggin,
2001
Burkart and Kolpin, 1993
Bucheli et al. 1997
Kolpin et al. 1998
Adams and Thurman, 1991
Kolpin et al. 1996b
Kolpin et al. 2000
Boyd, 2000
Blanchard and Donald, 1997
-1
-1
0.003 µg L
-1
0.02 µg L
-1
0.05 µg L
-1
0.1 µg L
-1
0.2 µg L
-1
0.2 µg L
-1
0.05 µg L
-1
0.2 µg L
-1
0.2 µg L
-1
0.01 µg L
-
-1 b
1 - 5 ng L
-1
0.04 µg L
0.085 µg L
-1
< 2 - 16 ng L
-1 b
0.02 µg L
-1
< 2 - 130 ng L
-1
< 2 - 87 ng L
-1
< 2 - 35 ng L
-1 b
1.2 µg L
-1 b
8.63 µg L
-1 b
8.5 µg L
-1
ND - 2.5 µg L
-1
0.06 - 9.32 µg L
-1 b
33.4 µg L
-1
ND - 0.31 µg L
-1
0.02 - 1.66 µg L
-1
< 2 - 10 ng L
-1
100 - 550 ng L
0.205 µg L
-1 c
0.4 µg L
-1
-1 b
-1 b
deethylatrazine continued
Country
-1 b
Limit of detection
2.32 µg L
-1
7 ng L
-1 b
2.6 µg L
-1
5 µg L
-1 b
2.2 µg L
-1 b
0.59 µg L
-1
ND - 0.44 µg L
-1 b
0.05 - 0.13 µg L
-1
0.05 µg L
-1
0.002 µg L
-1
0.02 µg L
-1
0.05 µg L
-1
0.05 µg L
-1
0.05 µg L
-1
0.02 µg L
Environmental
compartment
Degradate
Parent pesticide
deisopropylatrazine
atrazine
deisopropylatrazine
a
atrazine, cyanazine,
simazine
Concentration
0.6 µg L
Limit of detection
-1 c
1.17 µg L
-1 b
-1
86
©2008 AwwaRF. ALL RIGHTS RESERVED
14 ng L
-1
< 0.02 µg L
-1 b
1.1 µg L
-1
ND - 0.26 µg L
-1 b
1.3 µg L
-1
ND - 0.22 µg L
-1 b
0.55 µg L
-1 b
0.64 µg L
-1
ND - 0.31 µg L
ND
ND
ND
-1 e
ND - 158.2 µg L
-1 b
2.22 µg L
-1 b
0.006 µg L
-1 b
0.03 µg L
-1 b
1.6 µg L
-1 b
0.059 µg L
-1 b
8.6 µg L
-1
ND - 6.84 µg L
-1
0.1 - 1.83 µg L
hydroxyatrazine
atrazine
cyanazine amide
cyanazine
deethylcyanazine
cyanazine
deethylcyanazine amide
dacthal mono acid and diacid
dacthal diacid
p,p’-DDE
cyanazine
dacthal
dacthal
DDT
AMPA
α-HCH
metolachlor ethane sulfonic acid
glyphosate
lindane
metolachlor
metolachlor ethane sulfonic acid
continued
metolachlor oxanilic acid
metolachlor
metolachlor
15.3 µg L
-1
ND - 4.25 µg L
-1
0.03 - 0.91 µg L
deethylatrazine
atrazine
0.14 - 0.24 µg L
-1 b
Country
Reference
Steinheimer and Scoggin,
2001
Kolpin et al. 1996b
0.04 µg L
-1
USA
0.05 µg L
-1
USA
-1
0.02 µg L
-1
0.05 µg L
-1
0.05 µg L
-1
0.2 µg L
-1
0.2 µg L
-1
0.55 µg L
-1
0.05 µg L
-1
0.05 µg L
-1
0.05 µg L
-1
0.05 µg L
-1
0.05 µg L
-1
0.05 µg L
-1
0.01 µg L
-1
0.006 µg L
-1
0.03 µg L
-1
0.002 µg L
-1
0.2 µg L
-1
0.2 µg L
-1
0.01 µg L
Denmark
USA
USA
USA
USA
Bucheli et al. 1997
Adams and Thurman, 1991
Kolpin et al. 2000
Boyd, 2000
Kolpin et al. 2000
Boyd, 2000
Kolpin et al. 1996b
Kolpin et al. 2000
Boyd, 2000
Verstraeten et al. 1999
Kolpin et al. 1996b
Kolpin et al. 1996b
Monohan et al. 1995
Kolpin et al. 1996b
Kolpin et al. 1998
Kolpin et al. 1996b
Helweg et al. 2002
Kolpin et al. 1998
Kolpin et al. 2000
Boyd, 2000
Ferrer et al. 1997
0.2 µg L
-1
0.2 µg L
-1
0.01 µg L
USA
USA
USA
Kolpin et al. 2000
Boyd, 2000
Ferrer et al. 1997
-
USA
-
USA
-
USA
-
USA
Reported in Solomon et al.
1996
Reported in Solomon et al.
1996
Reported in Solomon et al.
1996
Reported in Solomon et al.
1996
Reported in Solomon et al.
1996
Reported in Nguyen et al, 2004
-1
Switzerland
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
Raw source water
reservoir
0.38 µg L
deisopropylatrazine
hydroxyatrazine
azinphos-methyl-oxon
atrazine
atrazine
azinphos-methyl
-1 c
-1 c
0.08 - 0.14 µg L
0.1 µg L
-1 c
0.8 µg L
-1 c
0.263 µg L
-1 c
-1 c
0.031 µg L
USA
-1
USA
Environmental
compartment
a
Degradate
Parent pesticide
Concentration
disulfoton sulfone
disulfoton sulfoxide
fenamiphos sulfone
fenamiphos sulfoxide
malaoxon
disulfoton
disulfoton
fenamiphos
fenamiphos
malathion
0.013 µ g L
-1 c
0.06 µg L
-1 c
0.005 µg L
-1 c
0.021 µg L
ND
o-p’-DDA
DDT
0.28 µg L
p-p’-DDA
DDT
1.7 µg L
-1
azinphos-methyl-oxon
disulfoton sulfone
disulfoton sulfoxide
fenamiphos sulfone
fenamiphos sulfoxide
malaoxon
azinphos-methyl
disulfoton
disulfoton
fenamiphos
fenamiphos
malathion
0.026 µg L
ND
ND
-1 c
0.011 µg L
-1 c
0.022 µg L
-1 c
0.106 µg L
-1 c
Limit of detection
Country
Reference
0.005 µg L
-1
0.016 µg L
-1
0.008 µg L
-1
0.008 µg L
-1
0.005 µg L
USA
USA
USA
USA
USA
Reported in Nguyen et al, 2004
Reported in Nguyen et al, 2004
Reported in Nguyen et al, 2004
Reported in Nguyen et al, 2004
Reported in Nguyen et al, 2004
-
Germany
-
Germany
Reported in Heberer and
Dünnbier, 1999
Reported in Heberer and
Dünnbier, 1999
-1
abstraction wells
-1
Finished drinking water
87
©2008 AwwaRF. ALL RIGHTS RESERVED
a - pesticide identified in the reference as the source of the degradate
b - peak concentration during study
c - median or mean concentration
d - calculated average concentration
e - combined degradate concentration
-1 c
-1
0.031 µg L
-1
0.005 µg L
-1
0.016 µg L
-1
0.008 µg L
-1
0.008 µg L
-1
0.005 µg L
USA
USA
USA
USA
USA
USA
Reported in Nguyen et al, 2004
Reported in Nguyen et al, 2004
Reported in Nguyen et al, 2004
Reported in Nguyen et al, 2004
Reported in Nguyen et al, 2004
Reported in Nguyen et al, 2004
88
©2008 AwwaRF. ALL RIGHTS RESERVED
APPENDIX 5. ADI FOR PESTICIDES
Pesticide
ADI
chlorpropham
cyromazine
desmedipham
diclofop-methyl
difenoconazole
dimefuron
dimethoate
dimethomorph
epoxiconazole
esfenvalerate
fenbuconazole
fenpiclonil
fenpyroximate
fluazinam
fludioxonil
fluoroglycofen-ethyl
fomesafen
imazaquin
imidacloprid
mecoprop
mecoprop-P
0.1 mg kg bw day (temporay)
-1
-1
0.015 mg kg bw day
-1
-1
0.0018 mg kg bw day
-1
-1
0.001 mg kg bw day
-1
-1
0.01 mg kg bw day
-1
-1
0.06 mg kg bw day
-1
-1
0.0008 mg kg bw day
-1
-1
0.05 mg kg bw day
-1
-1
0.01 mg kg bw day
-1
-1
0.003 mg kg bw day
-1
-1
0.01 mg kg bw day
-1
-1
0.23 mg kg bw day
-1
-1
0.01 mg kg bw day
-1
-1
0.006 mg kg bw day
-1
-1
0.01 mg kg bw day
-1
-1
0.0095 mg kg bw day
-1
-1
0.003 mg kg bw day
-1
-1
0.3 mg kg bw day
-1
-1
0.03 mg kg bw day
-1
-1
0.01 mg kg bw day
-1
-1
0.01 mg kg bw day
-1
-1
Region
Source
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
Reported in PSD 1993k
Reported in PSD 1993l
Reported in PSD 1993f
Reported in PSD 1991e
Reported in PSD 1994j
Reported in PSD 1993h
Reported in PSD 1993j
Reported in PSD 1994g
Reported in PSD 1994l
Reported in PSD 1992b
Reported in PSD 1995c
Reported in PSD 1993g
Reported in PSD 1995d
Reported in PSD 1994h
Reported in PSD 1995b
Reported in PSD 1992a
Reported in PSD 1995a
Reported in PSD 1993a
Reported in PSD 1993e
Reported in PSD 1994d
Reported in PSD 1994e
ADI - Acceptable daily intake
89
©2008 AwwaRF. ALL RIGHTS RESERVED
90
©2008 AwwaRF. ALL RIGHTS RESERVED
APPENDIX 6. MAMMALIAN ACUTE, SUBACUTE AND SUBCHRONIC DATA FOR PESTICIDE
DEGRADATES
Parent pesticide
Species
Administration
aldicarb nitrile
aldicarb sulphoxide
aldicarb
aldicarb
aldicarb
aldicarb
rat
rat
rat
rat
rat
rat
rat
mouse
guinea pig
rabbit
rabbit
dog
rat
rat
rat
rat
mouse
guinea pig
rabbit
rabbit
dog
dog
rat
rat
oral
oral
ip
ip
iv
oral
oral
oral
oral
oral
dermal
oral
oral
oral
ip
iv
oral
oral
oral
dermal
oral
oral
inhalation
oral
aldicarb
rat
aldicarb
aldicarb sulfone
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
Reported in PSD 1994m
aldicarb oxime
2-methyl-2-(methyl
sulphinyl) propanol -1
hydroxyl-methyl
aldicarb
aldicarb sulphoxide
oxime
aldicarb sulphone
oxime
aldicarb sulphoxide
nitrile
aldicarb sulphone
nitrile
2-amino-4,6dimethoxypyrimidine
2-amino-4,6dihydroxypyrimidine
HOE 101630
(4,6dihydroxypyrimidin-2-
oral
LD50
42.9
Reported in PSD 1994m
rat
oral
LD50
8060
Reported in PSD 1994m
aldicarb
rat
oral
LD50
1590
Reported in PSD 1994m
aldicarb
rat
oral
LD50
4000
Reported in PSD 1994m
aldicarb
rat
oral
LD50
350
Reported in PSD 1994m
amidosulfuron
rat
oral
LD50
2700
Reported in PSD 1994a
amidosulfuron
rat
oral
LD50
> 5000
Reported in PSD 1994a
amidosulfuron
amidosulfuron
rat
rat
oral
oral
LD50
LD50
> 5000
> 5000
Reported in PSD 1994a
Reported in PSD 1994a
subacute/ sub chronic
subacute/ sub chronic
subacute/ sub chronic
subacute/ sub chronic
subacute/ sub chronic
End-point
Source
LD50
LD50
LD50
LD50
LD50
NOAEL
NOEL
LD50
LD50
LD50
LD50
NOEL
LD50
NOAEL
LD50
LD50
LD50
LD50
LD50
LD50
NOEL
NOAEL
LD50
LD50
aldicarb
Toxicity
a
Concentration
-1
(mg kg body weight)
570
0.49 - 1.13
0.47
0.71
0.47
-1
-1
0.4 mg kg bw day
-1
-1
0.125 mg kg bw day
0.8 - 1.6
0.8 - 1.8
0.4 - 1.8
> 20
-1
-1
0.25 mg kg bw day
20 - 25
-1
-1
2.5 mg kg bw day
21.2
14.9
25
> 50
75
> 20
-1
-1
5.4 mg kg bw day
-1
-1
0.125 mg kg bw day
-1
1.56 mg L
11000
91
©2008 AwwaRF. ALL RIGHTS RESERVED
Degradate
Source
oral
LD50
496 - 2480
rat
rat
oral
oral
LD50
LD50
338 - 2800
> 5050
Reported in PSD 1993d
Reported in PSD 1993d
Reported in PSD 1993d
Reported in PSD 1993d
oral
oral
oral
oral
oral
oral
oral
oral
oral
oral
oral
oral
NTEL
LD50
NTEL
NTEL
LD50
NOEL
NOEL
dinocap
dog
rat
rat
dog
mouse
mouse
mouse
rat
rat
mouse
mouse
rat
NOEL
LD50
LD50
LD50
3.5 mg kg bw day
> 5050
-1
-1
6.3 - 7.35 mg kg bw day
-1
-1
5.8 - 6.2 mg kg bw day
3296 - 7014
-1
-1
1800 mg kg bw day
-1
-1
900 mg kg bw day
3161 - 3828
-1
-1
250 - 300 mg kg bw day
96
122
249
Reported in PSD 1993d
Reported in PSD 1993d
Reported in PSD 1993d
Reported in PSD 1993d
Reported in PSD1993l
Reported in PSD1993l
Reported in PSD1993l
Reported in PSD1993l
Reported in PSD1993l
Reported in PSD1991a
Reported in PSD1991a
Reported in PSD1991a
dinocap
rat
mouse
mouse
mouse
rat
oral
oral
oral
oral
oral
LD50
LD50
LD50
LD50
LD50
211
194
154
> 150
583
Reported in PSD1991a
Reported in PSD1991a
Reported in PSD1991a
Reported in PSD1991a
Reported in PSD1991a
rat
mouse
mouse
rat
rat
oral
oral
oral
percutaneous
oral
LD50
LD50
LD50
LD50
LD50
318
267
271
> 5000
> 5000
Reported in PSD1991a
Reported in PSD1991a
Reported in PSD1991a
Reported in PSD 1988a
Reported in PSD 1988a
rat
oral
LD50
3417 - 3866
Reported in PSD 1988a
rat
rat
oral
oral
LD50
LD50
> 5000
> 2150
Reported in PSD 1989a
Reported in PSD 1994d
Species
Administration
yl
deethylatrazine
atrazine
rat
deisopropylatrazine
deisopropyl
deethylatrazine
atrazine
atrazine
hydroxyatrazine
atrazine
dinitro octyl phenol
cypromazine
b
2,4-dinitro-6-(2-octyl)
phenol
92
©2008 AwwaRF. ALL RIGHTS RESERVED
Concentration
-1
(mg kg body weight)
Parent pesticide
melamine
2,6-dinitro-4-(2-octyl)
phenol
a
End-point
Degradate
dinocap
fluazifop acid
fluazifop-butyl
2-(4-hydroxy
phenoxy) propionic
acid
5-trifluoro-methylpyrid-2-one
triazole acetic acid
flusilazole
mecoprop-hydroxy
mecoprop
a - acute toxicity unless otherwise stated
b - isomer not defined
LC50 - lethal concentration (50%)
LD50 - lethal dose (50%)
LOAEL - lowest observed adverse effect level
MEL - minimum effect level
NOAEC - no observed adverse effect concentration
NOAEL - no observed adverse effect level
NOEC - no observed effect concentration
NOEL - no observed effect level
NTEL - no toxicological effect level
Toxicity
subacute
subacute
subacute
subacute
subacute
subacute
-1
-1
APPENDIX 7. DEGRADATE ABBREVIATIONS USED IN THE DATA
APPENDICES
Where a degradate was not given a chemical name only represented structurally in the
reference, the chemical name (IUPAC) was obtained by drawing the structure in ChemDraw Std.
Ver. 8.0 (CambridgeSoft Corporation, 2003) and naming the compound using the add-on
Nomenclator Ver 6.0 (ChemInnovation Software, 2001).
210 352
231 761
4’-OH-fen
buprofezin metabolite 9
carbinol
CCA
CGA 189138
CGA 205374
CGA 205375
CGA 257 777
Cl-Vacid
compound B
compound C
compound D
compound G
compound V
compound VII
compound VIII
compound XII
CONH2-fen
COOH-fen
cyanazine acid
cyanazine amide
cyanazine hydroxy acid
dec-fen
DEHA
DIHA
DM2
DM3
DM4
DPX M6316 TP1
F0 12-7124
F0 18-5445
[3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiran-2-yl]methan-1-ol
1-(2-chlorophenyl)-2-(4-fluorophenyl)-3-(1,2,4-triazolyl)propane-1,2-diol
(1S)cyano[3-(4-hydroxyphenoxy)phenyl]methyl (2R)-2-(4-chlorophenyl)-3methylbutanoate
3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadiazinone-2,4-dione
N-(2-ethyl-6-methylphenyl)-2-hydroxy-N-(2-methylethyl)-acetamide
2,2-dimethyl-3-(1,1-dichlorovinyl) cyclopropane carboxylic acid
2-chloro-4-(4-chlorophenoxy)benzoic acid
1-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-(1,2,4-triazolyl)ethan-1-one
1-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-(1,2,4-triazolyl)ethan-1-ol
4-(2,2-difluorobenzo[d]1,3-dioxolen-4-yl)pyrrole-3-carboxylic acid
(2R,3R)-2-(4-chlorophenyl)-2,4-dihydroxy-3-methylbutanoic acid
({3-chloro-4-[5-(2-hydroxy-tert-butyl)-2-oxo(1,3,4-oxadiazolin-3yl)]phenyl}amino)-N-methylcarboxamide
({3-chloro-4-[5-(2-hydroxy-tert-butyl)-2-oxo(1,3,4-oxadiazolin-3yl)]phenyl}amino)-N,N-dimethylcarboxamide
amino-N-{4-[5-(tert-butyl)-2-oxo(1,3,4-oxadiazolin-3-yl)]-3chlorophenyl}amide
N-({4-[(N,N-dimethylcarbamoyl)amino]-2-chlorophenyl}amino)-2,2dimethylpropanamide
5-chloro-6-(3-chloro-α,α,α-trifluoro-2,6-dinitro-p-toluidine)-nicotinic acid
2-chloro-6-(3-chlotro-5-trifluoromethyl-2-pyridylamino)-α,α,α-trifluoro-5nitro-m-toluidine
4-chloro-2-(3-chloro-5-trifluoromethyl-2-pyridyl)amino-5-trifluoromethyl-mphenylenediamine
5-(3-chloro-5-trifluoromethyl-2-pyridyl-amino) -α,α,α-trifluoro-4,6-dinitro-ocresol
(1S)carbamoyl(3-phenoxyphenyl)methyl (2R)-2-(4-chlorophenyl)-3methylbutanoate
no structure identified in the reference
2-{[4-chloro-6-(ethylamino)(1,3,5-triazin-2-yl)]amino}-2-methylpropanoic acid
2-chloro-4-(1-carbamoyl-1-methylethylamino)-6-ethylamino-1,3,5-triazine
2-{[6-(ethylamino)-4-hydroxy(1,3,5-triazin-2-yl)]amino}-2-methylpropanoic
acid
no structure identified in the reference
6-hydroxy-N-isopropyl-1,3,5-triazin-2-ylamine
N-ethyl-6-hydroxy-1,3,5-triazin-2-ylamine
2-[3-(trifluoromethyl)phenoxy]pyridine-3-carboxylic acid
N-(2,4-difluorophenyl)(2-hydroxy(3-pyridyl))carboxamide
2-hydroxypyridine-3-carboxylic acid
methyl 2-(4-methoxy-6-methyl-1,3,5-triazin-2-yl-amino)-3-thiophenecarboxylate
(RS)-1-[3-(4-tert-butylphenyl)-2-methylpropyl piperidin-1-oxide
(RS)-1-[3-(4-tert-butylphenyl)-2-methylpropyl piperidin-4-ol
93
©2008 AwwaRF. ALL RIGHTS RESERVED
fomesafen amine
fomesafen amino acid
fomesafen nitro acid
HOE 070542
HOE 101630
HOE 35956
HOE 64619
HOE 65594
HOE 72829
HOE 83348
HOE 85355
HOE 86486
HOE 87606
HOE 88988
HOE 88989
HOE 89628
Ia
Ib
M1
M3
morpholinone
R0 15-6045
RH-0265-NH2
RH-4514
RH-4515
RH-5349
RH-5781
RH-5782
RH-6467
RH-670
RH-9129
RH-9130
RH-9985
SD 53065
SDS 1449
SDS 954
TDTP
{2-amino-5-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl}-N(methylsulfonyl)carboxamide
2-amino-5-[2-chloro-4-(trifluoromethyl)phenoxy]benzoic acid
5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid
ethyl-1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3carboxylate
3-(4-hydroxy-6-methoxypyrimidin-2-yl)-1-(N-methyl-N-methylsulfonylaminosulfonyl)-urea
2-amino-4-(methyl(hydroxyphosphoryl))butanoic acid
2-(methyl(hydroxyphosphoryl))acetic acid
4-(methyl(hydroxyphosphoryl))-2-oxobutanoic acid
1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylic acid
1-(2,4-dichlorophenyl)-(1H)-1,2,4-triazole-3-carboxylic acid
2-(acetylamino)-4-(methyl(hydroxyphosphoryl))butanoic acid
3-(methyl(hydroxyphosphoryl))-3-oxopropanoic acid
ethyl-(2,4-dichlorophenyl)-5-chloromethyl-(1H)-1,2,4-triazole-3-carboxylate
1-(2,4-dichlorophenyl)-5-chloromethyl-(1H)-1,2,4-triazole-3-carboxylic acid
1-(2,4-dichlorophenyl)-5-dichloromethyl-(1H)-1,2,4-triazole-3-carboxylic acid
1-(2,4-dichlorophenyl)-5-hydroxy-(1H)-1,2,4-triazole-3-carboxylic acid
(1RS)-cis-3-(ZE-2 chloro-3,3,3-trifluoroprop-1-enyl)-2,2dimethylcyclopropanecarboxylic acid
(1RS)-trans-3-(ZE-2 chloro-3,3,3-trifluoroprop-1-enyl)-2,2dimethylcyclopropanecarboxylic acid
2-[N-(1-carbamoyl-1,2-dimethylpropyl)carbamoyl]quinoline-3-carboxylic acid
(E)-4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)-methyleneaminooxy-methyl]
benzoic acid
4-(2-ethyl-6-methylphenyl)-5-methyl-3-morpholinone
1-[3-(p-2-hydroxymethylisopropyl)phenyl-2-methylpropyl] piperidine
ethyl 2-{2-amino-5-[2-chloro-4(trifluoromethyl)phenoxy]phenylcarbonyloxy}acetate
2-amino-5-[2-chloro-4-(trifluoromethyl)phenoxy]benzoic acid
2-(acetylamino)-5-[2-chloro-4-(trifluoromethyl)phenoxy]benzoic acid
presented as structurally identical to RH-5781
5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid
methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate
4-(4-chlorophenyl)-4-oxo-2-phenyl-2-(1,2,4-triazolylmethyl)butanenitrile
5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenol
(5S,3R)-5-(4-chlorophenyl)-3-phenyl-3-(1,2,4-triazolylmethyl)-3,4,5trihydrofuran-2-one
(3S,5S)-5-(4-chlorophenyl)-3-phenyl-3-(1,2,4-triazolylmethyl)-3,4,5trihydrofuran-2-one
2-{5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenylcarbonyloxy}acetic
acid
no structure identified in the reference
monomethyltetrachloroterephthalate
tetrachloroterephthalic acid
1,6,7,8-tetrahydro-7,7-dimethyl-3-[p-(trifluoromethyl)-styryl]-4H-pyrimido
[2,1-c]-as-triazo-4-one
94
©2008 AwwaRF. ALL RIGHTS RESERVED
APPENDIX 8. THE RISK INDEX AND DATA AVAILABILITY FOR DEGRADATES FROM THE US
MOST USED AGRICULTURAL PESTICIDES
•
•
degradates where at least one default value was required in the prioritization are represented in italics
■ = experimental regulatory data available, □ = default value used in the prioritisation
Pesticide
Degradate
95
©2008 AwwaRF. ALL RIGHTS RESERVED
Formation
Kd
DT50
ADI
RI
alachlor
2,6-diethyl-N-methoxymethyl-2-sulpho-acetanilide
alachlor
alachlor oxanilic acid
alachlor
2,6-diethyl-N-methoxy-methoxanilic acid
cyanazine acid
cyanazine
alachlor
alachlor ethane sulfonic acid
acetochlor
2-([N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)carbomyl]methylsulfonyl) acetic acid
acetochlor
acetochlor oxanilic acid
acetochlor
N-(2-ethyl-6-methylphenyl)-2-sulfoneacetamide
acetochlor
N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)-2-sulfoneacetamide
cynazine amide
cyanazine
alachlor
alachlor DM-oxanilic acid
alachlor
alachlor sulfinylacetic acid
alachlor
2',6'-diethyl-2-hydroxy-N-methoxymethylacetanilide
DEHA
atrazine
atrazine
deisopropyl atrazine
atrazine
DIHA
atrazine
diaminochloroatrazine
dichloropropene 3-chloroprop-2-enoic acid
dicamba
3,6-dichlorosalicylic acid
2,4-D
1,2,4-benzenetriol
■
■
■
□
■
□
□
□
□
□
■
■
■
■
■
■
■
□
■
□
□
□
□
■
■
□
□
□
□
■
□
□
□
□
■
□
■
□
■
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
47.58
42.63
41.87
35.95
33.33
33.30
33.30
33.30
33.30
32.62
32.35
30.83
19.41
13.96
11.27
9.90
7.88
7.61
7.24
6.28
atrazine
malathion
■
■
■
□
■
■
■
■
2.51
2.43
hydroxy atrazine
malathion dicarboxylic acid
96
©2008 AwwaRF. ALL RIGHTS RESERVED
Pesticide
Degradate
Formation
Kd
DT50
ADI
RI
metolachlor
chlorothalonil
trifluralin
metolachlor
chlorothalonil
trifluralin
trifluralin
trifluralin
chlorpyrifos
ethephon
2,4-D
trifluralin
chlorothalonil
chlorothalonil
glyphosate
trifluralin
trifluralin
chlorothalonil
2,4-D
chlorpyrifos
ethephon
pendimethalin
pendimethalin
pendimethalin
metolachlor
trifluralin
malathion
metolachlor
metolachlor oxanilic acid
3-cyano-2,4,5,6-tetrachlorobenzamide
a,a,a-trifluoro-2,6-dinitro-N-propyl-p-toluidine
CGA-37735
3-carbamyl-1,2,4,5-tetrachlorobezoic acid
2,2'-azoxybis (a,a,a-trifluoro-6-nitro-N-propyl-p-toluidine
a,a,a-trifluoro-2,6-dinitro-p-cresol
2-ethyl-7-nitro-5-(trifluoromethyl) benzimidazole
3,5,6-chloro-2-pyridinol
2-hydroxy ethyl phosphonic acid
2,4-dichloroanisole
a,a,a-trifluoro-5-nitro-4-propyl-toluene-3,4-diamine
3-cyano-6-hydroxy-2,4,5-trichlorobenzamide
3-carbamyl-2,4,5-trichlorobenzoic acid
AMPA
[2,6-dinitro-4-(trifluoromethyl)phenyl]propylamine
2-ethyl-7-nitro-1-propyl-5-(trifluoromethyl) benzimidazole
3-cyano-2,5,6-trichlorobenzamide
2,4-dichlorophenol
3,5,6-trichloro-2-methoxypyridine
ethylene
2,6-dinitro-3,4-xylidine
4-[(1-ethylpropyl)amino]-2-methyl-3,5-dinitro benzyl alcohol
4-[(1-ethylpropyl)amino]-3,5-dinitro-o-toluic acid
CGA-41638
2-ethyl-7-nitro-1-propyl-5-(trifluoromethyl) benzimidazole-3-oxide
malaoxon
CGA-13656
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
□
□
□
□
□
□
□
□
■
□
□
□
□
■
■
□
□
□
■
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
■
□
□
□
□
□
■
□
□
□
□
■
□
□
□
□
□
□
□
□
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
2.23
1.69
1.34
1.18
0.99
0.88
0.79
0.76
0.74
0.73
0.69
0.61
0.60
0.60
0.52
0.50
0.29
0.22
0.20
0.19
0.17
0.17
0.17
0.17
0.16
0.09
0.09
0.08
atrazine
trifluralin
deethylatrazine
2,6-dinitro-4-(trifluoromethylphenyl)amine
■
■
■
□
■
□
■
■
0.07
0.06
Pesticide
Degradate
chlorothalonil 4-hydroxy-2,5,6-trichloroisophthalonitrile
EPTC
EPTC sulfoxide
metam sodium methylisothiocyanate
dichloropropene chloroallyl alcohol
Formation
Kd
DT50
ADI
RI
■
■
■
□
■
□
□
□
■
■
■
■
■
■
■
■
<0.01
<0.01
<0.01
<0.01
97
©2008 AwwaRF. ALL RIGHTS RESERVED
98
©2008 AwwaRF. ALL RIGHTS RESERVED
APPENDIX 9. THE RISK INDEX AND DATA AVAILABILITY FOR DEGRADATES FROM THE UK
MOST USED AGRICULTURAL PESTICIDES
•
•
degradates where at least one default value was required in the prioritization are represented in italics
■ = experimental regulatory data available, □ = default value used in the prioritisation
99
©2008 AwwaRF. ALL RIGHTS RESERVED
Pesticide
Degradate
Formation
Kd
DT50
ADI
RI
cyanazine
cyanazine
isoproturon
flufenacet
bitertanol/tebuconazole
flufenacet
dicamba
atrazine/simazine
flufenacet
flufenacet
flufenacet
metaldehyde
bitertanol
atrazine
propachlor
atrazine/simazine
trifluralin
isoproturon
bitertanol
linuron
atrazine/simazine
dimethoate
cyanazine acid
cynazine amide
1-methyl-3-(4-isopropyl phenyl)-urea
FOE sulfonic acid
1,2,4-triazole
FOE oxalate
3,6-dichlorosalicylic acid
deisopropylatrazine
FOE methyl sulfone
FOE thioglycolate sulfoxide
thiadone
acetaldehyde
bitertanol benzoic acid
DEHA
propachlor oxanilic acid
DIHA
α,α,α-trifluoro-2,6-dinitro-N-propyl-p-toluidine
3-[4-(2’-hydroxy-2’-propyl)-phenyl]-methyl urea
4-hydroxybiphenyl
demethyl linuron
diaminochloroatrazine
O-desmethyl dimethoate
□
□
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
□
□
□
□
■
■
□
□
□
□
□
□
■
□
□
□
□
□
■
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
26.56
24.11
7.92
4.67
4.51
3.25
3.15
2.12
2.03
2.03
2.03
1.63
1.59
1.29
1.26
1.21
1.10
1.01
1.00
0.99
0.89
0.81
propachlor
propachlor ethane sulfonic acid
■
■
□
■
0.72
100
©2008 AwwaRF. ALL RIGHTS RESERVED
Pesticide
Degradate
trifluralin
2-chloroethylphosphonic acid
trifluralin
trifluralin
asulam
chlorothanonil
chlorothanonil
metalaxyl
chloridazon
metalaxyl
trifluralin
mecoprop-P
azoxystrobin
trifluralin
dimethoate
propachlor
chlorothanonil
trifluralin
pendimethalin
pendimethalin
pendimethalin
atrazine
propachlor
cyprodinil
chlorothanonil
linuron
chlorothanonil
2,2’-azoxybis (α,α,α-trifluoro-6-nitro-N-propyl-p-toluidine
ethylene
α,α,α-trifluoro-2,6-dinitro-p-cresol
2-ethyl-7-nitro-5-(trifluoromethyl) benzimidazole
ionic form of asulam
3-cyano-2,4,5,6-tetrachlorobenzamide
3-carbamyl-2,4,5-trichlorobenzoic acid
CGA-62826
5-amino-4-chloropyridazine-3(2H)-one
2-N-(2,6-dimethylphenyl)-2-methoxyacetylamino propanoic acid
α,α,α-trifluoro-5-nitro-4-propyl-toluene-3,4-diamine
4-chloro-2-methyl phenol
azoxystrobin metabolite 2
[2,6-dinitro-4-(trifluoromethyl)phenyl]propylamine
O,O-dimethylphosphorothioic acid
3-isopropyl-2,3-dioxo-5-oxocyclo-penteno-IH-2,1,3-thiadazin4(3H)-one-6-carbonic acid
propachlor sulfinylacetic acid
3-carbamyl-1,2,4,5-tetrachlorobezoic acid
2-ethyl-7-nitro-1-propyl-5-(trifluoromethyl) benzimidazole
2,6-dinitro-3,4-xylidine
4-[(1-ethylpropyl)amino]-2-methyl-3,5-dinitro benzyl alcohol
4-[(1-ethylpropyl)amino]-3,5-dinitro-o-toluic acid
hydroxy atrazine
hydroxypropachlor
CGA 249287
3-cyano-6-hydroxy-2,4,5-trichlorobenzamide
norlinuron
3-cyano-2,5,6-trichlorobenzamide
asulam
conjugated form of asulam
bentazone
Formation
Kd
DT50
ADI
RI
■
■
■
■
■
■
■
■
■
■
■
■
□
■
■
□
□
□
□
□
□
■
□
□
□
□
□
■
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
□
■
■
■
■
■
■
■
■
■
■
■
■
■
■
■
0.72
0.67
0.65
0.62
0.61
0.61
0.60
0.57
0.54
0.53
0.50
0.50
0.42
0.41
0.38
□
□
□
■
0.32
■
■
■
■
■
■
■
■
■
■
■
■
□
□
□
□
□
□
■
□
□
□
□
□
□
□
□
□
□
□
■
□
□
□
□
□
■
■
■
■
■
■
■
■
■
■
■
■
0.26
0.25
0.24
0.23
0.23
0.23
0.23
0.23
0.22
0.22
0.19
0.19
■
□
□
■
0.17
101
©2008 AwwaRF. ALL RIGHTS RESERVED
Pesticide
Degradate
Formation
Kd
DT50
ADI
RI
bitertanol
quinmerac
azoxystrobin
metaldehyde
quinmerac
propachlor
asulam
isoproturon
2,4-D
tebuconazole
tebuconazole
tebuconazole
trifluralin
terbuthylazine
simazine
azoxystrobin
azoxystrobin
azoxystrobin
captan
trifluralin
glyphosate
propachlor
azoxystrobin
quinmerac
quinmerac
azoxystrobin
2,4-D
kresoxim methyl
chloridazon
biteranol ketone
BH518-2
azoxystrobin acid
paraldehyde
BH518-5
propachlor methyl sulfone
sulphanilamide
desmethyl isoproturon
2,4-dichloroanisole
SN 320-1
SN 3678-7/A
SN 3678-7/B
2-ethyl-7-nitro-1-propyl-5-(trifluoromethyl) benzimidazole-3-oxide
deethylterbuthylazine
hydroxysimazine
azoxystrobin metabolite 10
azoxystrobin metabolite 20
azoxystrobin metabolite 3
tetrahydrophthalimide acid
2,6-dinitro-4-(trifluoromethylphenyl)amine
AMPA
norchloropropachlor
azoxystrobin metabolite 30
BH518-1
BH518-4
azoxystrobin metabolite 28
2,4-dichlorophenol
kresoxim-methyl acid
5-amino-4-chloro-2-methyl-2-hydropyridazin-3-one
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0.17
0.16
0.14
0.13
0.13
0.12
0.10
0.09
0.08
0.08
0.08
0.08
0.07
0.07
0.07
0.07
0.07
0.07
0.05
0.05
0.05
0.05
0.05
0.03
0.03
0.02
0.02
0.02
0.02
mepiquat
N-methylpiperidine
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0.01
Pesticide
Degradate
mepiquat
piperidine
(3,5-dichlorophenyl)-N-(2,3-dihydroxy-1,1dimethylpropyl)carboxamide
(3,5-dichlorophenyl)-N-(3-hydroxy-1,1-dimethyl-2oxopropyl)carboxamide
(3,5-dichlorophenyl)-N-(3-hydroxy-1,1dimethylpropyl)carboxamide
[2-(3,5-dichlorophenyl)-4,4-dimethyl-1,3-oxazolin-5ylidene]methan-1-ol
2-[(3,5-dichlorophenyl)carbonylamino]-2-methylpropanoic acid
3-[(3,5-dichlorophenyl)carbonylamino]-3-methyl-2-oxobutanoic
acid
3-[(3,5-dichlorophenyl)carbonylamino]-3-methylbutanoic acid
490M0
4-amino-3,5-dichloro-6-fluoro-methoxypyridine
deethylatrazine
490M4
4-hydroxy-2,5,6-trichloroisophthalonitrile
5-chloro-3-fluoro-2-hydroxy-pyridine
2-(3,5-dichlorophenyl)-4,4-dimethyl-5-methyleneoxazoline
4-amino-3,5-dichloro-6-fluoro-2-pyridinol
omethoate
1,2,3,6-tetrahydrophthalimide
2,4-D
N-(1,1-dimethylacetonyl)-3,5-dichlorobenzamide
n-methylbentazone
di-iodo-4-hydroxybenzamide
3,5-dibromo-4-hydroxy benzamide
di-iodo-4-hydroxybenzoic acid
3,5-dibromo-4-hydroxy benzoic acid
propyzamide
propyzamide
propyzamide
propyzamide
propyzamide
102
©2008 AwwaRF. ALL RIGHTS RESERVED
propyzamide
propyzamide
kresoxim methyl
fluroxypyr
atrazine
kresoxim methyl
chlorothanonil
clodinafop-propargyl
propyzamide
fluroxypyr
dimethoate
captan
2,4-DB
propyzamide
bentazone
ioxynil
bromoxynil
ioxynil
bromoxynil
Formation
Kd
DT50
ADI
RI
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0.01
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0.01
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0.01
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0.01
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0.01
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0.01
0.01
0.01
0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
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LIST OF ABBREVIATIONS
A
a.i.
ADI
AE
AME
APE
AWWA
CO2
DEA
DIA
DT50
DWI
E
ESA
EU
F
GC-MS
GWRC
HA
HPLC
Kd
Koc
LAS
LC-MS
LCS
MCL
NMR
OA
OECD
OP
P
QSAR
RI
SBR
SSLRC
t
t½
UK
US
USEPA
USGS
UV
WWTPs
Degradate amount index
Active ingredient
Acceptable daily amount
alcohol ethoxylates
alkyl amine ethoxylates
alkyl phenol ethoxylates
American Water Works Association
Carbon dioxide
deethylatrazine
deisopropylatrazine,
Degradation half life for the degradate
Drinking Water Inspectorate
Exposure index
ethane sulfonic acids
European Union
Fraction of degradate in the aqeous phase
Liquid chromatography mass spectrometry
Global Water Research Coalition
hydroxyatrazine
High performance liquid chromatography
sorption coefficient
Organic carbon sorption coefficient
linear alkylbenzene sulfonates
Liquid chromatography mass spectrometry
liquid scintillation counting
Maximum concentration limit
Nuclear magnetic resonance
oxanilic acids
Organisation for Economic Co-operation abd Development
organophosphorus insecticides
Persistence index
Quantitative structure-activity relationships
Degradate risk index
Structure-biodegradability relationships
Soil Survey and Land Research Centre
Tonne
Half-life
United Kingdom
United States
United States Environmental Protection Agency
United States Geological Survey
Ultraviolet
Wastewater treatment plants
117
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118
©2008 AwwaRF. ALL RIGHTS RESERVED
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