39
A snapshot of pesticides in South Australian aquatic sediments Environment Protection Authority

A Snapshot of Pesticides in South Australian Aquatic Sediments ·  · 2015-04-24Table 3 Pesticides results in follow -up sediment sampling ... A snapshot of pesticides in South Australian

Embed Size (px)

Citation preview

A snapshot of pesticides in South Australian aquatic sediments

Environment Protection Authority

A snapshot of pesticides in South Australian aquatic sediments

Author: Clive Jenkins

For further information please contact:

Information Officer Environment Protection Authority GPO Box 2607 Adelaide SA 5001

Telephone: (08) 8204 2004 Facsimile: (08) 8124 4670 Free call (country): 1800 623 445

Website: <www.epa.sa.gov.au>

Email: <[email protected]>

ISBN 978-1-921495-32-8

March 2013

© Environment Protection Authority

This document may be reproduced in whole or part for the purpose of study or training, subject to the inclusion of an acknowledgment of the source and to it not being used for commercial purposes or sale. Reproduction for purposes other than those given above requires the prior written permission of the Environment Protection Authority.

Contents Abbreviations ...................................................................................................................................................................... 1

Summary .............................................................................................................................................................................. 3

1 Introduction ................................................................................................................................................................... 5

2 Previous studies of pesticides in South Australia .................................................................................................... 7

3 Methods ......................................................................................................................................................................... 9

4 Results and discussion .............................................................................................................................................. 11

5 Lessons learnt and future developments in pesticide assessment ...................................................................... 17

6 Conclusions ................................................................................................................................................................ 18

7 References................................................................................................................................................................... 20

Appendix 1 Pesticides review – chemistry and environmental fate ...................................................................... 22

Appendix 2 Site numbers, descriptions, GIS coordinates and NRM regions ....................................................... 25

Appendix 3 Pesticides included in the aquatic sediments snapshot.................................................................... 32

List of figures

Figure 1 Locations where sediments (a) contained pesticides and (b) where sediments were sampled but pesticides were not detected ....................................................................................................................... 12

List of tables Table 1 Australian low interim sediment quality trigger values for pesticides ................................................................. 13 Table 2 Pesticide concentrations that were measured in sediment samples ................................................................. 14 Table 3 Pesticides results in follow-up sediment sampling (2009) ................................................................................. 15

A snapshot of pesticides in South Australian aquatic sediments

Abbreviations ANZECC Australia and New Zealand Environment and Conservation Council

DDD dichloro–diphenyl–dichl oroethane

DDE dichloro–diphenyl–dichloroethylene

DDT dichloro–diphenyl–trichloroethane

CSIRO Commonwealth Scientific and Industrial Research Organisation

EPA South Australian Environment Protection Authority

L-ISQG Low level interim sediment quality guideline

PIRSA Department of Primary Industries and Resources South Australia

Kow Octanol–water partition coefficient

MCPA 2-methyl-4-chlorophenoxyacetic acid

PIRI pesticide impact rating index

TOC total organic carbon

u/s upstream

1

A snapshot of pesticides in South Australian aquatic sediments

Summary A snapshot survey of pesticides in aquatic sediments across South Australia was conducted in 2003, with 151 sediment samples collected. These sites represented (a) a cross-section of the state’s inland and estuarine waters and (b) a diversity of catchment landuses.

In general, a range of historically used (de-registered) pesticides were found in sediment samples. These included DDT (and its breakdown products DDE and DDD), dieldrin, aldrin, chlordane, lindane and heptachlor. By far the most common pesticide was DDE (at 15 sites), which is actually a breakdown product from DDT.

The snapshot found some currently used pesticides:

• Insecticides: chlorpyrifos (3 sites) and diazinon (1 site).

• Herbicide: simazine (4 sites).

The main findings were:

• In the 2003 sediment sampling snapshot, 19 out of the 151 sediment sites (ie 13% of sites) were found to contain pesticides.

• The screening level risk assessment of pesticides in sediments was restricted because the Australian sediment quality guidelines are limited in their scope to evaluate pesticide bio-availability.

• A total of 17 sites were re-sampled in 2009 on the basis that the pesticide concentrations were either found above the Australian sediment quality guideline trigger values or sediment quality guidelines were not available.

• In the same follow-up sediment sampling, there was only one site where pesticides were detected (Cox Creek). The pesticides found were DDT, DDE and DDD. The ratio of DDE+DDD to DDT was relatively high, which indicates the presence of long-term contamination and not recent unregistered pesticide use.

• Overall the sampling and analysis of sediments was not found to be an effective method for the assessment of pesticides in South Australian waterways. Sediments are spatially very heterogenous and sediment quality guidelines are poorly established.

Sampling waters via passive sampling devices has been recently emerging as a far more successful strategy for environmental pesticide assessment on the basis that these devices are (a) more likely to detect a wide range of pesticides and (b) they can be used with water quality guidelines which are far more established than sediment quality guidelines. Passive samplers are currently being tested in South Australian waterways for this purpose.

3

A snapshot of pesticides in South Australian aquatic sediments

1 Introduction 1.1 Pesticides in the environment

Pesticides are chemicals designed to control pest plant, fungi and animal species that can reduce agricultural productivity, cause human health impacts and property damage. There are currently about 2,000 pesticide chemicals registered in Australia. These chemicals have become commonplace in Australian agriculture and households. In 2002, the total annual market value of pesticides was estimated at $1.6 billion (Radcliffe 2002). Croplife Australia1 suggests that pesticides increase Australian crop yields by about 40% as well as increasing the value of our food production by $13 billion each year.

Pesticides are categorised according to their target organisms, insecticides (insects), herbicides (plants) and fungicides (fungi). Within each of these categories, pesticides are grouped more specifically according to their chemical structure. For instance, insecticides include organochlorines, organophosphates, carbamates, pyrethroids and various miscellaneous chemical groups.

While pesticides are important in modern agriculture, they can have negative effects on non-target organisms in the surrounding environment. In some cases, pesticides have been banned because the risks to the environment are considered too high (eg DDT, aldrin, dieldrin and chlordane). On the other hand, many modern pesticides decompose to harmless substances relatively quickly and if they are applied correctly, environmental impacts are expected to be minimal.

With respect to the management of pesticide use, there are initiatives in place at the Commonwealth and State Government levels to improve pesticide application practices to minimise environmental risks. In this context, the EPA has released the EPA Guidelines for responsible pesticide use in South Australia (2005). The document is intended to guide the general public and agricultural industries in maximising the effectiveness of pesticides while minimising the environmental harm that may be caused.

Although pesticides are usually applied to crops on the land, they can be washed into aquatic ecosystems. In waterways, pesticides can cause ecological impacts due to their acute and chronic toxicity as well as endocrine disruption. These effects may occur despite being at very low concentrations in the aquatic environment. Moreover, some pesticides are very persistent in the environment, which means these effects can potentially occur over extended periods. Some are also fat soluble, and because of this, they can bio-accumulate and sometimes magnify through the food chain.

Since pesticides usually have low solubility in water, they often become bound to sediments (especially the fine, silty particles), which also provide important habitat for many organisms in aquatic ecosystems. A summary of pesticide chemistry and environmental fate is provided in Appendix 1.

1.2 Purpose of the snapshot

The main purpose of this snapshot was to broadly identify the distribution of pesticides in South Australian aquatic sediments.

The snapshot represents the largest single monitoring study for pesticides in South Australia and provides an important information source for future environmental risk assessments and management.

1.3 Sediments

The sediments in a water body are useful for monitoring pesticides in the environment because these substances tend to adhere to sediment particles and settle out, rather than remain dissolved in the water.

1 CropLife Australia is the peak industry organisation representing the agricultural chemical and biotechnology (plant science) sector in Australia <www.croplifeaustralia.org.au>

5

A snapshot of pesticides in South Australian aquatic sediments

However, the limitation with collecting sediment samples for monitoring purposes is that sediment characteristics are highly variable. Even within a few square metres, their composition can change from sandy to rocky and silty material. Pesticides are not evenly spread throughout these different components. Instead they will mainly be found in the organic silty components.

The sediment sampling protocol was designed to maximise the likelihood of finding pesticides by employing the following principles, consistent with the recommendations in Mudroch and Azcue (1995):

• a total of 6 samples were collected at each site and these samples were amalgamated (ie composited) into a single sample. The composite sample was then sub-sampled for laboratory analyses.

• The sampling targeted the silty, high organic content sediments.

1.4 Waters

Pesticides are typically at extremely low concentrations in waters, often too low to be detected by traditional ‘grab sampling’ and laboratory analyses. Normal water sampling is therefore not considered very useful for monitoring pesticides in the environment.

However, there have been significant advances in the area of ’passive sampling devices‘ for flowing water environments covering a wide range of persistent organic pollutants such as pesticides. These were not used in the snapshot but the EPA is actively exploring their potential application and this is discussed later in the report.

6

A snapshot of pesticides in South Australian aquatic sediments

2 Previous studies of pesticides in South Australia 2.1 Mount Lofty Ranges Watershed

The EPA’s Watershed Protection Office (closed since 2008) conducted a sampling program of subcatchments in the Mount Lofty Ranges (MLR) watershed during winter–spring 2002 for pesticides and other pollutants (Holmes 2003). Subcatchments were selected on the basis of representing a high risk of pesticide transport in the Torrens catchment (Millers, Cox and Footes Creeks).

Grab water samples were collected during the rising limb2 of significant storm events and a total of 41 pesticides were analysed, representing a range of historical and currently used insecticides, herbicides and fungicides. The summary results from this work indicated the detection of pesticides at the following locations:

• Millers Creek (dieldrin, picloram)

• Cox Creek (dieldrin, MCPA)

• Footes Creek (picloram, trichlopyr).

ANZECC and ARMCANZ (2000) water quality guidelines were not available for the herbicides picloram, trichlopyr or MCPA or the historically used insecticide dieldrin.

2.2 Port River and Barker Inlet Estuary

The EPA surveyed sediments at eight locations in the Port River and Barker Inlet during 1995 and 1996 (EPA 1997). Several historically used insecticides were measured as well as the herbicide, atrazine.

Only chlordane was detected in sediments (220 µg/kg) and this was only at one site in the Port River. The chlordane was found in the inner harbour and while the source of the contamination could not be confirmed, this location was also where high metal concentrations were observed and it was very close to the previous Port Adelaide wastewater treatment plant outfall.

When the EPA report was released in 1997, there were no sediment quality guidelines available for chlordane. If the ANZECC and ARMCANZ (2000) sediment quality guidelines3 were retrospectively applied to the EPA study, the chlordane concentration would be regarded as highly contaminated.

2.3 Onkaparinga Catchment

A study of pesticide contamination in sediments within the Onkaparinga catchment (Kumar et al 2001) was conducted by CSIRO and the University of South Australia during 2000. Twelve sites were chosen, from Lenswood Creek, Cox Creek, Pedler Creek, Field River, Onkaparinga River and Mackreath Creek weres included as a reference (native vegetation). The study was conducted during November, which was coincident with the main spraying season in the catchment.

Sediment samples were screened for 37 pesticides, comprising a variety of insecticides and herbicides that were possibly used in the area. Only organochlorines were detected, including endosulfan, dieldrin, DDT DDD, DDE and lindane. Of these, only endosulfan was registered for use and the other pesticides had been phased out by 1994. These results highlighted the fact that many of the previously used organochlorines are highly persistent in the environment. No pesticides were detected at the reference site.

The Onkaparinga study also found that several organochlorine insecticides and chlorpyrifos (an organophosphate insecticide) had bio-accumulated in yabbies (Cherax destructor).

2 The early part of a stormwater hydrograph, leading up to the maximum discharge. 3 Section 2.4

7

A snapshot of pesticides in South Australian aquatic sediments

Cox Creek, followed closely by Lenswood Creek were the most significantly impacted subcatchments, both in terms of sediment and yabbie concentrations.

2.4 South East aquifers

A monitoring program of 129 groundwater bores in the South East was conducted during the mid-1990s by the then Department of Environment and Natural Resources (Schmidt et al 1996). A survey of the local community indicated that 96 pesticides were used in the area. Of this list, 17 pesticides were targeted for analyses in groundwater samples after a risk-based selection process. Dieldrin, lindane, alachlor and chlorpyrifos were detected.

2.5 Riverland

Vinclozolin is a widely used fungicide that is commonly applied to viticulture to control downy mildew. A study of vinclozolin in the Riverland (Ueoka et al 1997) found that although it was regarded as quite soluble and readily moved through the soil profile, its degradation was very quick, with almost 100% broken down within 10 days.

8

A snapshot of pesticides in South Australian aquatic sediments

3 Methods 3.1 Site selection

The scope of this survey was to cover a wide range of the state’s surface waters, including marine, estuarine, rivers and streams and lakes.

Sampling sites were selected to represent a variety of catchment landuses across the state. Sediment sampling, emphasis was given to locations where pesticides were likely to be deposited in waterbodies. This tended to be near the bottom of catchments, where sedimentation was most likely to occur.

A total of 151 sediment sampling sites across the state were selected. The sites were representative of broad landuse categories including:

• urban

• intensive agriculture (market gardening, fruit orchards, vines)

• forestry

• broadacre copping and grazing.

There were also four ‘reference’ sites representative of catchments where pesticides have not been used, representing the ‘background’ sediment condition:

• Rocky River (Flinders Chase National Park)

• First Creek (Cleland Conservation Park)

• Bunyeroo Creek (Flinders Ranges)

• Murtho Forest (adjacent the River Murray).

The sites that were sampled (site names, site numbers, GIS coordinates and NRM regions) are listed in Appendix 2.

3.2 Time period

Sediment sampling for the pesticides snapshot was conducted during July 2003.

3.3 How sediments were collected

Sediment samples were collected in a manner consistent with AS/NZS 5667.12.1999: Water quality–Sampling Part 12: Guidance on sampling of bottom sediments (Standards Australia 1999). Sediment sampling involved the collection of the upper 2 cm of fine-grained sediments (silty and rich in organic matter). Six sub-samples were collected and combined to create one sample per site (approximately 1.5 kg wet sediment).

Sediment sampling quality control

The sediment sampling equipment was cleaned between collecting samples and the water used to rinse the equipment was collected and analysed to confirm that no cross contamination occurred.

Pesticides analysed

The list of pesticides for inclusion in the survey was initially based on those that were considered most likely to cause environmental harm as well as most likely to be present because of the land uses in each catchment (after consultation with various state government authorities).

The most environmentally harmful pesticides are those that are toxic and persistent in the environment, have low water solubility and tend to accumulate in the food chain. These pesticides also tend to adhere to sediment particles (especially the natural organic matter in sediments) and settle to the bottom of a water body.

9

A snapshot of pesticides in South Australian aquatic sediments

This initial list of pesticides was then reduced because some analytical methods were not yet available in NATA accredited laboratories.

The result of these considerations lead to the final selection of 82 pesticides in the sediment sampling program (Appendix 3).

3.4 Screening level risk assessment

A screening level risk assessment approach was used to evaluate the sediment pesticides data. The purpose of a screening level risk assessment was to (a) identify where environmental impacts are not likely and (b) to assess the need to conduct a follow-up assessment at particular sites (Chapman et al 1999).

The screening assessment was not designed to provide definitive estimates of actual risk, nor was it based upon site-specific assumptions. It should also not be used in isolation to inform any sediment quality rehabilitation agenda.

The assessment was performed according to the decision tree in the sediment quality guidelines (ANZECC and ARMCANZ 2000). This process separates the sampling sites into two categories:

• Sites that are considered low risk and require no further action.

• Sites that contain concentrations that warrant follow-up sampling/further investigation.

10

A snapshot of pesticides in South Australian aquatic sediments

4 Results and discussion 4.1 Main findings

Pesticides were detected in freshwater and estuarine sediments. The sites where pesticides were detected in sediment samples are shown on Figure 1 and listed in Table 2.

The main findings were:

• Pesticides were detected at 19 out of the 151 sites (ie 13% of sites).

• There were 10 pesticides detected in sediments.

• Historically used pesticides were found at several sites. The most common was DDE (14 sites), which is a breakdown product of DDT. The other historical pesticides found were aldrin (3 sites), chlordane (2 sites), dieldrin (3 sites), lindane (1 site), DDT (1 site) and DDD (2 sites).

• Currently used pesticides found in sediments included chlorpyrifos (3 sites), simazine (4 sites) and diazinon (1 site).

4.2 Screening level risk assessment

Background sediment concentrations

No pesticides were detected in the sediments at the four reference sites (see page 9). Therefore the ‘background concentrations’ of pesticides in South Australian sediments are considered to be undetectable using the sampling and analytical methods in this study.

Pesticides with sediment quality trigger values (guidelines)

The Australian and New Zealand Guidelines for Fresh and Marine Water Quality (ANZECC and ARMCANZ 2000) include a shortlist of sediment quality guidelines for pesticides. These include DDT, DDD, DDE, chlordane, dieldrin, endrin and lindane (Table 1). These guidelines are also called sediment quality trigger values that are supposed to be used to indicate when sediments are either at low risk of contamination or in need of further investigation. This is an important point to emphasise—trigger values are used as a protective guide and they should not be used to indicate where environmental impacts are likely to occur.

ANZECC and ARMCANZ (2000) also includes a decision tree that sets out the preferred approach for comparing contaminant concentrations with trigger values and deciding under what circumstances further investigations are appropriate. Sediment quality trigger values were exceeded at some locations:

• There were four pesticides that were found at levels above the low interim sediment quality guidelines (L-ISQG) or sediment quality trigger values. These were chlordane, DDD, DDE, total DDT4 and dieldrin.

• There were 13 sites where pesticide concentrations exceeded these trigger values and hence categorised as requiring further investigation (Table 2).

4 There is no Australian sediment quality guideline specifically for DDT. The relevant trigger value is for total DDT (ie the sum of DDT, DDD and DDE).

11

A snapshot of pesticides in South Australian aquatic sediments

Figure 1 Locations where (a) sedimentscontained pesticides and (b) where sediments were sampled but pesticides were not detected

12

A snapshot of pesticides in South Australian aquatic sediments

Table 1 Australian low interim sediment quality trigger values for pesticides (in µg/kg for sediments containing 1% organic carbon)

Pesticide L-ISQG ‘trigger values’

Total DDT (DDT, DDD and DDE) 1.6

DDE 2.2

DDD 2

Chlordane 0.5

Lindane 0.32

Endrin 0.02

Dieldrin 0.02

Based on the work by Long et al (1995)

Pesticides without sediment quality guidelines

There were five pesticides found in sediments that do not have sediment quality guidelines (aldrin, delta-HCH, chlorpyrifos, diazinon, and simazine). Note that delta–HCH (hexachlorocycolxexane) is an isomer5 of lindane.

For pesticides without sediment quality guidelines, the approach recommended by ANZECC and ARMCANZ (2000, section 3.5.4.3) is to:

… derive a value on the basis of natural background (reference) concentration multiplied by an appropriate factor. A factor of two is recommended, although in some highly disturbed ecosystems a slightly larger factor may be more appropriate, but no larger than three.

Since the background concentrations for all pesticides were undetectable in this snapshot, the detection of any pesticides that do not have sediment quality trigger values automatically warrants further investigation.

5 An isomer is a close ‘relative’ to another chemical. It has the same chemical formula but has a different structural arrangement and often very different biological impacts. Delta–HCH is an isomer of gamma–HCH (ie lindane) for which there is a sediment quality trigger value.

13

A snapshot of pesticides in South Australian aquatic sediments

Table 2 Pesticide concentrations that were measured in sediment samples (µg/kg or parts per billion).

Refer to Appendix 3 for locations. Pesticides with an asterix (*) have sediment quality trigger values (Table 1). Shaded results highlight where sediment quality trigger values were exceeded.

Historical pesticides Currently used pesticides

NRM Region Sampling sites (site number)

Ald

rin

Chl

orda

ne *

DD

D *

DD

E *

Tota

l-DD

T *

Die

ldrin

*

Del

ta-H

CH

Chl

orpy

rifos

Dia

zino

n

Sim

azin

e

Adelaide and Mt Lofty Ranges

River Torrens, Lake Weir (72) 6.6

River Torrens outfall (9) 4.4 15

River Torrens, Holbrooks Weir (128) 4.7

Greenfields Wetland (67) 2.7

Barker Inlet Wetland (66) 45

Onkaparinga River (116) 1.5 23 18

Lenswood Creek (103) 4.1

Cox Creek (38) 2.8 35 4.1 40

Virginia Drainage Lines (40) 15

Patawalonga Weir (117) 5.5 4.6 16.6 4.6 27.6 61

South East

Cuppa Cup Swamp, Tatiara Creek (56) 9.8

Drain C, Coonawarra (35) 1.9

SA Murray– Darling Basin

Coorong (16) 2.4 3.6 2.2

Lake Albert (151) 0.6

Finniss River (96) 20

Northern and Yorke

Broughton River (51) 4.8

Hill River (98) 3.1

Kangaroo Island

Cygnet River Estuary (28) 9.0 1.1 2.3 3.3

Middle River (110) 9.0

Further investigation level 1: bio-availability

Regarding the pesticides that exceeded trigger values, the first level of further investigation was to consider contaminant bio-availability (ANZECC and ARMCANZ 2000). This addresses the extent to which the pesticide contaminants are accessible to living organisms in the waterway—as opposed to being chemically immobilised in sediment particles. ANZECC and ARMCANZ (2000) suggests that the naturally occurring organic carbon (OC) is the key to pesticide bio-availability because pesticides can bind very strongly to this sediment component.

ANZECC and ARMCANZ (section 3.5.5) recommends that the ‘bio-available’ pesticide concentration be compared with the sediment quality trigger value. Unfortunately however, there is no reliable or standardised method to measure the bio-available pesticide concentration (S Simpson pers. comm 2012), so this avenue of further investigation is not actually viable.

14

A snapshot of pesticides in South Australian aquatic sediments

Further investigation level 2: follow-up sampling for pesticides in sediments

Since the bio-available pesticide concentrations could not be analysed for some pesticides that did not actually have any trigger values, sediments were re-sampled at locations meeting either of the following criteria:

• pesticides were detected and were present at concentrations above the sediment quality trigger value

• pesticides were detected but do not have sediment quality trigger values.

There were 17 sites where sediments were re-sampled in April 2009—six years after the initial samples were collected. This time delay meant that the initial sediments were likely to have been buried or transported downstream from the sampling location. The follow-up sampling therefore represented freshly deposited material and was reflective of recent catchment runoff and deposition.

Table 3 Pesticides results in follow-up sediment sampling (2009)

Site description (site number) Pesticides detected

River Torrens, Lake Weir (72) No pesticides detected

River Torrens outfall (9) No pesticides detected

River Torrens, Holbrooks Weir (128) No pesticides detected

Greenfields Wetland (67) No pesticides detected

Barker Inlet Wetland (66) No pesticides detected

Onkaparinga River (116) No pesticides detected

Lenswood Creek (103) No pesticides detected

Cox Creek (38) DDD (6.8 µg/kg); DDE (61 µg/kg); DDT (15 µg/kg)

Virginia Drainage Lines (40) No pesticides detected

Patawalonga Weir (117) No pesticides detected

Cuppa Cup Swamp, Tatiara Creek (56) No pesticides detected

Coorong (16) No pesticides detected

Finniss River (96) No pesticides detected

Broughton River (51) No pesticides detected

Hill River (98) No pesticides detected

Middle River (110) No pesticides detected

Cygnet River Estuary (28) No pesticides detected

The results (Table 3) indicated that only one site had detectable pesticides: Cox Creek in the Adelaide Mount Lofty Ranges. This site contained appreciable quantities of DDT and its degradation products DDE and DDD.

The previous study by Kumar et al (2001) also highlighted that sediments in Cox Creek contained elevated concentrations of DDT (16 µg/kg), DDE (28 µg/kg) and DDD (7 µg/kg), although that sampling location was not the same as the Cox Creek (site 38) in this snapshot.

15

A snapshot of pesticides in South Australian aquatic sediments

The concentrations of DDD, DDE and DDT at Cox Creek in the 2009 follow-up sampling were slightly higher than those in 2003 (Table 2). This does not mean these products have been recently used in the Cox Creek catchment. Aside from the fact that DDT has not been registered for use in South Australia since 1985, the ratios of its degradation products (DDD and DDE) to the parent compound (DDT) were relatively high, which provides good evidence that DDT itself has not been applied to the landscape for many years. Instead, the high concentrations observed in the follow-up samples relative to the 2003 samples and also the Kumar et al (2001) samples—were most likely due to variability in sediment characteristics within these creeks.

16

A snapshot of pesticides in South Australian aquatic sediments

5 Lessons learnt and future developments in pesticide assessment

5.1 Pesticides in the environment

The pesticide snapshot has shown that organochlorine pesticides (insecticides) can still be found in South Australian waterways (despite being deregistered 10 to 30 years ago) and these may represent a risk to aquatic ecosystems. The finding is consistent with interstate and overseas studies of aquatic sediments (Ding et al 2010; Yang, Zhang et al 2012).

In the 1996 Port River Estuary sediments monitoring (EPA 1997), chlordane was detected at 220 µg/kg (Port River site 1), although chlordane was undetectable at the same location in 2003; this dramatic variation in a very persistent pesticide is not easily explained, although sediment heterogeneity was probably a significant factor. The Port Adelaide wastewater treatment plant closed in 2004, so the most likely source of the 1996 contamination was still present at the time of sampling.

The fact that a small number of modern pesticides were found in sediments is of some concern, although it is very difficult to use these observations in a risk analysis because there is a lack of pesticide-sediment ecotoxiciology. Also, the follow-up sampling of sediments in 2009 where these modern pesticides were found suggests the risk of extensive contamination of the South Australian aquatic environment is quite low.

Overall, the pesticide concentrations that have been observed in this snapshot are also within the expected range for sediments in urbanised and agricultural catchments (Warren et al 2003). The levels of pesticide occurrence in South Australian aquatic sediments is about what would be found in most developed countries.

Another consideration to note is that South Australian aquatic environments are often under stress due to modified flow dynamics, salinity variations, excessive sedimentation and eutrophication (nitrogen, phosphorus inputs)6. These issues are likely to be far more significant causes of environmental degradation than localised pesticide effects.

5.2 Value of sediment sampling in environmental pesticide assessments

While finding pesticides in aquatic sediments, and frequently the historically used pesticides, is to be expected in urbanised and relatively intense agricultural catchments, their occurrence is patchy and occasionally confounding. Aquatic sediments are notoriously variable in their natural composition in terms of their particle size distribution, mineral content, organic content, living organisms, water/solids ratio, etc. Even though many pesticides are known the bind to the fine particles (and especially the natural organic material in those fine particles), the spatial patterns of pesticides in a waterbody can be difficult to predict and measure. To overcome this spatial heterogeneity, sediment sampling programs need to be very elaborate and expensive.

There are very few risk-based sediment quality guidelines for assessing pesticides in sediments, which is expected to continue because sediment ecotoxicology (which should be used to derive guidelines) is much more complicated than the water-only ecotoxicology (Di Toro 2012, Burgess et al 2012 ). Hence there are far more water quality guidelines than for sediment quality. There is also very limited guidance in terms of pesticide–sediment bio-availability for the same reason.

While pesticides are known to generally bind to sediments, sampling requirements are substantial and the application of meaningful risk analysis is very problematic.

6 Refer to the EPA aquatic ecosystem condition reports for more information <www.epa.sa.gov.au/environmental_info/water_quality/aquatic_ecosystem_monitoring_evaluation_and_reporting>

17

A snapshot of pesticides in South Australian aquatic sediments

5.3 Passive sampling for pesticides in surface waters

The future of pesticide assessment in aquatic environments is moving to the use of ’passive sampling devices‘ in water to overcome some of the problems with sediment assessments. This has been an emerging technology in recent years and is now being demonstrated as a viable approach in Queensland and New South Wales.

The idea of passive sampling is to deploy a device in a waterbody (by attaching it to a rigid structure). This device remains submerged in the water for approximately four weeks, whereupon it is retrieved and sent to a laboratory for preparation and analysis. There are different devices although the principle is that pesticides in the water become preferentially bound to the material in the passive sampler and the ‘uptake rate‘ for each pesticide is well established through extensive laboratory testing.

The passive sampling devices can, in effect, soak up significant concentrations of pesticides because they are sitting in the water for an extended period. This means they can be used to detect pesticides at concentrations much lower than could be achieved by the conventional water grab sampling approach.

The data provided by these sampling devices are ’time averaged concentrations‘, which can be related to the relatively extensive (and always growing) list of water quality guidelines for pesticides. Hence, this approach is very conducive to risk-based assessments of pesticides in the environment.

There are several publications that have recently demonstrated the efficacy of this approach (Alvarez 2008, Cranor et al 2008, Hale 2004, Pablo et al 2004, Hyne 2010, Martin et al 2010).

During 2013, the EPA will be testing passive sampling devices developed by the University of Queensland for pesticide monitoring in South Australia.

18

A snapshot of pesticides in South Australian aquatic sediments

6 Conclusions A snapshot survey of pesticides in aquatic sediments across South Australia was conducted in 2003, with 151 sediment samples collected. These sites represented (a) a cross-section of the state’s inland and estuarine waters and (b) a diversity of catchment landuses.

In general, a range of historically used (de-registered) pesticides were found in sediment samples. These included DDT (and its breakdown products DDE and DDD), dieldrin, aldrin, chlordane, lindane and heptachlor. By far the most common pesticide was DDE (at 15 sites), which is actually a breakdown product from DDT.

The fact that DDT was only found at one site (Patawalonga Weir, site 117) and its breakdown products were often observed is good justification to suggest that while the DDT legacy still exists, this historically used pesticide is gradually declining in the environment, consistent with other sediment studies (Connell et al 2002).

The snapshot found some currently used pesticides:

• Insecticides: chlorpyrifos (3 sites) and diazinon (1 site).

• Herbicide: simazine (4 sites).

In summary, the main findings from the snapshot were:

• In the 2003 sediment sampling snapshot, 19 out of the 151 sediment sites (ie 13% of sites) were found to contain pesticides.

• The screening level risk assessment of pesticides in sediments was restricted because the Australian sediment quality guidelines are limited in their scope to evaluate pesticide bio-availability.

• A total of 17 sites were re-sampled in 2009 on the basis that the pesticide concentrations were either found above the Australian sediment quality guideline trigger values or sediment quality guidelines were not available.

• In the same follow-up sediment sampling, there was only one site where pesticides were detected (Cox Creek). The pesticides found were DDT, DDE and DDD. The ratio of DDE+DDD to DDT was relatively high, which indicates the presence of long term contamination and not recent unregistered pesticide use.

• Overall the sampling and analysis of sediments was not found to be an effective method for the assessment of pesticides in South Australian waterways. Sediments are spatially very heterogenous and sediment quality guidelines are poorly established.

Further pesticide assessment work in South Australia

Sampling waters via passive sampling devices has been recently emerging as a far more successful strategy for environmental pesticide assessment on the basis that these devices are (a) more likely to detect a wide range of pesticides and (b) they can be used with water quality guidelines which are far more established than for sediment quality guidelines. Passive samplers are currently being tested in South Australian waterways for this purpose.

Aside from the need to consolidate the technical aspects of pesticide assessments in South Australian waterways, there is also a need to develop a consultative, integrated and risk-based approach to pesticide monitoring program design.

19

A snapshot of pesticides in South Australian aquatic sediments

7 References Journals

Alvarez DA, Petty JD and JN Huckins 2004, ‘Development of a passive, in situ, integrative sampler for hydrophilic organic contaminants in aquatic environments’, Environmental Toxicology and Chemistry 23(7):1640–48.

Alvarez DA, Cranor WL, Perkins SD, Clark RC and SB Smith 2008, ‘Chemical and toxicology assessment of organic contaminants in surface water using passive samplers’, Journal of Environmental Quality 7(3):1024–33.

Burgess RM and WJ Berry 2012, ‘Mechanistic sediment quality guidelines based on contaminant bio-availability: Equilibrium partitioning sediment benchmarks’, Environmental Toxicology and Chemistry, in press.

Chapman PM, Wang F, Adams WJ and A Green 1999, ‘Appropriate applications of sediment quality values for metals and metalloids‘, Environmental Science & Technology 33(22):3937–41.

Chen W and P Hertl 2002, ‘A pesticide surface water mobility index and its relationship with concentrations in agriculutural drainage watersheds‘, Environmental Toxicology and Chemistry 21(2):298–308.

Connell D, Miller G and S Anderson 2002, ‘Chlorohydrocarbon pesticides in the Australian marine environment after banning in the period from the 1970s to 1980s‘, Marine Pollution Bulletin 45:78–83.

Ding Y, Harwood, AD, Foslund HM and MJ Lydy 2010, ‘Distribution and toxicity of sediment-associated pesticides in urban and agricultural waterways from Illinois, USA’, Environmental Toxicology and Chemistry 29(1):149–157.

Di Toro DM 2012, ‘The interplay of environmental toxicology and chemistry in the development of sediment quality criteria’, Environmental Toxicology and Chemistry, in press.

Hale SE, Martin TJ, Goss KU, Arp HPH and D Werner 2010, ‘Partitioning of organochlorine pesticides from water to polyethylene passive samplers’, Environmental Pollution 158(7):2511–17.

Hyne RV, Pablo F, Aistrope M, Leonard AW and N Ahmad 2004, ‘Comparison of time-integrated pesticide concentrations determined from field-deployed passive samplers with daily river-water extractions’, Environmental Toxicology and Chemistry 23 (9):2090–98.

Kookana R, Baskaran S and R Naidu 1998, ‘Pesticide fate and behaviour in Australian soils in relation to contamination and management of soil and water: a review’, Australian Journal of Soil Research 36:715–764.

Long ER, MacDonald DD, Smith SL and ED Calder 1995, ‘Incidence of adverse biological effects within ranges of chemical concentrations in marine and estuarine sediments’, Environment Management 19:81–97.

Ueoka M, Allinson G, Kelsell Y, Graymore M and F Stagnitti 1997, ‘Environmental fate of pesticides used in Australian viticulture–behaviour of dithianon andand vinclozolin in the soils of the South Australian Riverland’, Chemosphere 35(12):2915–24.

Warren N, Allan IJ, Carter JE, House WA and A Parker, 2003, ‘Pesticides and other micro-organic contaminants in freshwater sedimentary environments–a review’, Applied Geochemistry 18(2):159–194.

Yang L, Li X, Zhang P, Melcer ME, Wu Y and U Jans 2012, ‘Concentrations of DDTs and dieldrin in Long Island Sound sediment‘, Journal of Environmental Monitoring 14 (3):878–885.

20

A snapshot of pesticides in South Australian aquatic sediments

Reports and books

ANZECC and ARMCANZ 2000, Australian and New Zealand Guidelines for Fresh and Marine Water Quality, Australian and New Zealand Environment and Conservation Council and the Agriculture and the Resource Management Council of Australia and New Zealand, Canberra.

AS/NZS 1999, AS/NZS 5667.12.1999: Water quality–Sampling Part 12: Guidance on sampling of bottom sediments, Standards Australia and Standards New Zealand, Sydney & Wellington.

Damstra T, Barlow S, Bergman A, Kavlock R and G Van Der Kraak (eds) 2002, Global sssessment of the state-of-the-science of endocrine disruptors, World Health Organization, International Labour Organization, and the United National Environment Programme, Geneva, viewed 5 March 2013, <www.who.int/ipcs/publications/new_issues/endocrine_disruptors/en/>.

EPA 1997, Sediment quality monitoring of the Port River Estuary: Report No. 1, South Australian Environment Protection Authority, Adelaide, viewed 5 March 2013, <www.epa.sa.gov.au/xstd_files/Water/Report/wqm_portsediment.pdf>.

Holmes, B 2003, The pollutant trace sampling, source detection and remediation program: status report, Watershed Protection Office, South Australian Environment Protection Authority, Adelaide, viewed 5 March 2013, <www.epa.sa.gov.au/xstd_files/Water/Report/pollutant.pdf>.

Kamrin MA 1997, Pesticide profiles: toxicity, environmental impact, and fate, CRC Press, Boca Raton.

Kumar A, Sarneckis K, Gorrie J, Megharaj M and R Kookana 2001, Monitoring the effects of bioaccumulation of pesticides within the Onkaparinga catchment and pesticide residues on sediments and their ecotoxicity in the Onkaparinga catchment, Final Report, CSIRO Land and Water and the University of South Australia, Adelaide.

Mudroch A and JM Azcue 1995, Manual of aquatic sediment sampling, ISBN 1566700299 CRC Press

Radcliffe J 2002, Pesticide use in Australia, Australian Academy of Technological Sciences and Engineering, Parkville, Victoria.

Schmidt L, Telfer A and M Waters 1996, Pesticides and nitrate in groundwater in relation to landuse in the South East of South Australia, Department of Environment and Natural Resources, Adelaide.

Shelton L and P Capel 1994, Guidelines for collecting and processing samples of stream bed sediment for analysis of trace elements and organic contaminants for the national water-quality assessment program, US Geological Survey. Sacremento, California.

US EPA 2001, Methods for collection, storage and manipulation of sediments for chemical and toxicological analyses: technical manual, US Environment Protection Agency, Office of Water, Washington DC, EPA 823–B–01–002.

Personal communication

Simpson S, CSIRO Senior Principal Research Scientist and Team Leader, Aquatic Chemistry and Ecotoxicology, email correspondence (September 2012).

21

A snapshot of pesticides in South Australian aquatic sediments

Appendix 1 Pesticides review – chemistry and environmental fate

It has been suggested by the CSIRO that appropriate use of pesticides based on recommendations is generally expected to cause little adverse impact on the environment (Kookana et al 1998) However, there is some concern that if pesticides become entrained in surface water runoff and enter aquatic ecosystems, there may be short, medium and long-term environmental impacts. In order to prioritise which pesticides should be targeted for monitoring and control, the CSIRO developed a pesticide risk-based screening tool—the pesticide impact rating index (PIRI).

The extremely wide variability in pesticide physico-chemistry makes it difficult to generalise the fate and effects of these substances in the environment. However, as a rule, those pesticides that are persistent (ie resistant to degradation) and lipid (ie fat) soluble are most likely to cause long-term ecological problems due to accumulation in the food web.

On the other hand, there are many short lived and highly water soluble pesticides that may cause serious short term (acute) effects. Overall, if short-lived pesticides are applied correctly, the probability of their exposure to non-target species is minimal, while persistent pesticides are more likely to be transported significant distances over long periods, thereby allowing for increased exposure to non-target species.

Pesticides have the greatest impact when they are dissolved in surface waters, although most have very low water solubility because they have a strong tendency to bind to soil and sediment particles. The natural organic matter within sediments usually provides the most effective pesticide binding sites and this adsorption process can render most pesticides as biologically unavailable.

Various studies on pesticide fate in the Australian environment have tended to confirm the overseas experience. The phase-out of many organochlorine (OC) pesticides during the 1970s and 1980s (eg DDT, dieldrin, hexachlorocyclohexane–several isomers) has resulted in lower concentrations in being found in waters, sediments and fish although these compounds are still detected in the environment (Connell et al 2002, Radcliffe 2002). Some of these persistent pesticides also have degradation products with similar toxicity than their parent compounds. For instance, DDT breaks down to DDE and DDD, and the ratio of these pesticides can sometimes be used to indicate when the original pesticide was applied. Similarly, aldrin breaks down to form dieldrin, while dieldrin itself has also been used as a pesticide.

In assessing the possible environmental effects of pesticides, a number of factors need consideration, such as their persistence, tendency to bio-accumulate, toxicity and tendency to adsorb to particulate matter. These properties can be used in a general sense to describe how pesticides behave in the environment, although detailed predictions are not possible because of the inherent spatial and temporal complexity within ecosystems themselves (Kamrin 1997).

Generally speaking, there is a paucity of data on pesticide concentrations in Australian waters, soils and sediments, and the behaviour of pesticides under Australian conditions remains poorly understood (Kookana et al 1998).

The Australian Water Quality Guidelines for Pesticides was developed by the National Water Quality Management Strategy. Sediment quality guidelines for pesticides are less advanced although duly recognised by the NWQMS (ANZECC 2000)

Water solubility

The solubility of a pesticide in water is its maximum concentration at a given temperature (usually standardised at 20ºC or 25ºC). The explanation for why the solubility of pesticides is variable relates to the concept of polarity, which has to do with the partial charge within a molecule. Water molecules have the property of being polar, meaning they have a fairly high degree of partial charge formation (with positive hydrogen atoms and a negative oxygen atom). On the other hand, many pesticide molecules are classified as non-polar because they have very little partial charge. The upshot is that ’like dissolves like‘. In other words, relatively polar compounds such as glucose dissolve in water very easily, while non-polar molecules such as chloroform only slightly dissolve in water.

22

A snapshot of pesticides in South Australian aquatic sediments

Persistence

The persistence of a pesticide in the environment is defined in terms of its half-life, T1/2 (ie the time it takes for half the initial amount to degrade). T1/2 values depend on factors such as potential to undergo chemical hydrolysis, microbial breakdown (anaerobic and aerobic) and photo-oxidation. A generally accepted three-tier classification is as follows:

• T1/2 <30 days low persistence

• T1/2 30-100 days moderate persistence

• T1/2 >100 days high persistence.

Octanol–water partition coefficient

As mentioned, many pesticides are characterised as non-polar or hydrophobic, so they have low water solubility. It also means they are soluble in fats and lipids and, general speaking, the more lipid-soluble pesticides are more likely to bio-accumulate in the food web.

Octanol, CH3(CH2)7OH, is used as a reference substance to quantify a pesticide’s lipid-solubility. The octanol–water partition coefficient (Kow) for a pesticide is defined as the ratio of equlibrium concentrations of the pesticide in the octanol–water two phase system:

Since values for pesticide Kow span several orders of magnitude, they are usually quoted as LogKow to enable convenient comparison. Kow data have proved useful for predicting soil adsorption, biological uptake and biomagnification, so they are frequently cited in pesticide risk assessments.

Soil adsorption coefficient

The soil adsorption coefficient is conceptually similar to the octanol–water partition coefficient in that is quantifies the extent that a pesticide is distributed between two distinct phases. In this case, they are soil solid particles and water. There tends to be a large variability in the soil adsorption coefficient for a given pesticide because of the variability in soil characteristics. Probably the greatest factor that controls soil adsorption coefficients is the amount of natural organic matter in the soil, since this is the component that provides the most abundant pesticide binding sites.

The Australian sediment quality guidelines, which are part of the guidelines for marine and freshwater quality, considers total organic carbon (TOC) in the sediment as a source of pesticide bio-availability amelioration, although the guidelines do not specify how to evaluate bio-availability.

Environmental mobility

By design, all pesticides are obviously toxic to some forms of life. The extent to which pesticides impact on non-target species varies widely, although physico-chemical properties such as persistence and LogKow values can be used as a guide.

The physico-chemical properties of pesticides strongly influence their environmental fate. The relative probability for pesticides to be detected in waters given equivalent usage and application times may be estimated by a mobility index. This index is based on two environmental variables: the soil half-life (a measure of pesticide degradation) and the organic carbon normalised soil/water partition coefficient (a measure of the extent to which pesticides bind to soil particles).

A useful ranking tool for the likelihood of detecting pesticides in the aquatic environment is a mobility index that incorporates relevant physico-chemical properties. Pesticide mobility has been defined elsewhere in terms of groundwater contamination risk7 and surface water contamination (Chen et al 2002). Both approaches make use of the same environmental variables, namely the soil half-life (in days) and the organic carbon normalised soil adsorption coefficient (Koc in L/kg).

7 <http://npic.orst.edu/ppdmove.htm>

23

A snapshot of pesticides in South Australian aquatic sediments

The groundwater ubiquity score (GUS) is the alternative mobility index, designed to rank pesticides according to their potential for groundwater contamination,

GUS = log10 (soil half-life) x [4 – log10 (Koc)]

Mobility is qualitatively rated as extremely low to very high potential for groundwater contamination. Pesticides with a GUS less than 1 have extremely low potential, values 1–2 are low, 2–3 are moderate, 3–4 are high, and values greater than 4 have a very high potential to move toward groundwater.

A PIRI has also been developed by the CSIRO. This tool can estimate the likelihood that specific pesticides will be transported from an agricultural landscape to a surface water receiving environment8.

8 Refer to <www.clw.csiro.au/staff/kookanar/Environ_Impact_Pesticides_Sept2002.pdf> for further information on PIRI.

24

A snapshot of pesticides in South Australian aquatic sediments

Appendix 2 Site numbers, descriptions, GIS coordinates and NRM regions9

Site names, site numbers, GIS coordinates and NRM Regions

Site number

Site description NRM Region

Zone Easting Northing

1 Broughton River Estuary NY 54 204035 6315746

2 Wakefield River Site 1 NY 54 237670 6214598

3 Light River Estuary AMLR 54 261617 6172916

4 Gawler River Site 1 AMLR 54 265755 6160564

5 Barker Inlet - Site 1 AMLR 54 273801 6151038

6 Barker Inlet - Site 2 AMLR 54 274438 6149693

7 Barker Inlet - Site 3 AMLR 54 275993 6146693

8 Port River Site 1 AMLR 54 271138 6140715

9 Torrens River Site 1 AMLR 54 271739 6131361

10 Onkaparinga Estuary Site - 1 AMLR 54 269809 6107134

11 Onkaparinga Estuary Site - 2 AMLR 54 272160 6106646

12 Inman River Estuary AMLR 54 283356 6061994

13 Hindmarsh River Estuary AMLR 54 283700 6062842

14 Pelican Lagoon Kangaroo Is KI 53 747923 6033624

15 Coorong - Site 1 SAMDB 54 321305 6058889

16 Coorong - Site 2 SAMDB 54 325813 6055901

17 Coorong - Site 3 SAMDB 54 333741 6048290

9 AMLR - Adelaide and Mt Lofty Ranges

EP - Eyre Peninsula

KI – Kangaroo Island

NY – Northern and Yorke

SAAL – South Australian Arid lands

SAMDB – South Australian Murray Darling Basin

SE – South East

25

A snapshot of pesticides in South Australian aquatic sediments

Site number

Site description NRM Region

Zone Easting Northing

18 Coorong - Site 4 SAMDB 54 342960 6049332

19 Coorong - Site 5 SAMDB 54 348002 6037348

20 Coorong - Site 6 SE 54 354884 6029446

21 Coorong - Site 7 SE 54 355257 6025779

22 Coorong - Site 8 SE 54 363715 6021952

23 Coorong - Site 9 SE 54 363780 6021969

24 Coorong - Site 10 SE 54 371014 6012630

25 Coorong - Site 11 SE 54 374008 6006381

26 Coorong - Site 12 SE 54 377074 5999308

27 Cygnet River Estuary Site 1 KI 53 733655 6047770

28 Cygnet River Estuary Site 2 KI 53 733700 6048250

29 Tanunda Ck Bethany AMLR 54 313545 6176461

30 North Para River - Flaxman Valley AMLR 54 323996 6173505

31 McCormick Creek AMLR 54 311121 6144330

33 River Murray - Renmark Drainage Channel SAMDB 54 475000 6217044

34 Mclaren Vale Site 1 AMLR 54 277267 6100258

35 Coonawarra Site 1 SE 54 485238 5875284

36 Stanley Flat Clare NY 54 277070 6259018

37 Cox Creek Site 1 AMLR 54 297063 6121969

38 Cox Creek Site 2 AMLR 54 293599 6127899

39 Virginia Drainage Lines - Site 1 AMLR 54 280841 6160788

40 Virginia Drainage Lines - Site 2 AMLR 54 273800 6158029

41 Cobdogla Irrigation Drainage Basin SAMDB 54 444700 6208491

42 Ramco Irrigation Drainage Basin SAMDB 54 400278 6219845

26

A snapshot of pesticides in South Australian aquatic sediments

Site number

Site description NRM Region

Zone Easting Northing

43 South East Site 1 SE 54 451290 5833481

44 South East Site 2 SE 54 477668 5838468

45 South East Site 3 SE 54 496902 5818385

46 Kuitpo Forest Site 1 AMLR 54 271094 6099848

47 Mt Crawford Forest Site 1 AMLR 54 315751 6157741

48 Wirrabarra Forest Site 1 NY 54 234134 6344168

49 Second Valley Site 1 AMLR 54 252729 6060865

50 Mid North Site 1 NY 54 251139 6218183

51 Mid North Site 2 NY 54 224144 6308529

52 Mid North Site 3 AMLR 54 268515 6177404

53 Eyre Peninsula Site 1 EP 53 572885 6233207

54 Eyre Peninsula Epa Site 2 EP 53 657840 6288722

56 Cuppa Cup Swamp (Tatiara Creek) SE 54 471155 5982498

57 Cock Ck (Lenswood) Sub-catchment AMLR 54 302573 6128010

58 Upper Cock Ck Sub-catchment AMLR 54 300495 6133877

59 Upper Sixth Ck Subcatchment AMLR 54 294836 6130834

60 Rocky River KI 53 653100 6019500

61 First Creek Waterfall Gully AMLR 54 288480 6127599

62 Bunyeroo Creek - East Car Park SAAL 54 268987 6521120

64 Warwilla/Murtho SAMDB 54 482600 6230000

65 Pike River/Lyrup Heights SAMDB 54 470532 6209016

66 Barker Inlet Wetland AMLR 54 277660 6142853

67 Greenfields Wetland AMLR 54 279508 6148360

68 Gilman Wetlands AMLR 54 273505 6143089

27

A snapshot of pesticides in South Australian aquatic sediments

Site number

Site description NRM Region

Zone Easting Northing

69 Breakout Creek Wetlands AMLR 54 272476 6131336

70 Aldinga Washpool AMLR 54 268377 6088543

71 Patawalonga River Basin AMLR 54 273019 6126903

72 River Torrens Lake Weir AMLR 54 279534 6133452

73 Warraparinga Wetlands AMLR 54 277345 6122152

74 Whyalla Wetlands EP 53 739044 6341457

75 Murray Bridge Wetlands SAMDB 54 343900 6111950

76 Angas R - D/S Strathalbyn, Hamburg Rd SAMDB 54 310287 6095144

77 Angas R - Lake Plains Road SAMDB 54 323139 6083629

78 Arkaroola Ck - Arkaroola Waterhole SAAL 54 339700 6648634

80 Blackford Drain SE 54 401822 5927201

81 Bremer R - Lake Plains Road SAMDB 54 318375 6081214

82 Bremer R - Wanstead Road SAMDB 54 317121 6099064

83 Bremer River: Near Hartley SAMDB 54 319898 6106533

84 Broughton River- Cockeys Crossing NY 54 226367 6307676

85 Cooper Creek: Cullyamurra Waterhole SAAL 54 483847 6935844

86 Cygnet River - Bark Hut Rd KI 53 700301 6043273

87 Cygnet River - Stokes Bay Rd KI 53 691050 6040625

88 Deep Creek - Access Track Culvert AMLR 54 249655 6054130

89 Diamantina - Clifton Hills SAAL 54 272880 6997361

90 Drain K - Reedy Creek Old Robe Rd SE 54 422273 5897521

91 Drain M - Beachport Robe Rd SE 54 415345 5855100

92 Dry Creek - Conway Cres AMLR 54 287352 6142326

28

A snapshot of pesticides in South Australian aquatic sediments

Site number

Site description NRM Region

Zone Easting Northing

93 Dutton River EP 53 611975 6233200

94 Eight Mile Ck SE 54 482375 5789189

95 Finniss River - Winery Road SAMDB 54 302600 6080800

96 Finniss River: 4km East Of Yundi SAMDB 54 288057 6088822

97 Gawler River AMLR 54 274623 6164154

98 Hill River Near Andrews G NY 54 280260 6278168

99 Hindmarsh River - Victor Harbour AMLR 54 283650 6069900

100 Hindmarsh River Hindmarsh Weir AMLR 54 280636 6072687

101 Inman R - Swains Crossing AMLR 54 282591 6064111

102 Kanyaka Creek - Old Kanyaka Ruins NY 54 244393 6445837

103 Lenswood AMLR 54 301505 6133706

104 Light - 4km U/S Mouth AMLR 54 266485 6174167

105 Light River Mingays Waterhole AMLR 54 313661 6196361

106 Little Para - Outfall AMLR 54 278878 6147096

107 Margaret Ck - S Oodnadatta Track SAAL 53 697760 6735966

108 Marne R SAMDB 54 365197 6158904

109 Marne River Upstream Cambrai SAMDB 54 339909 6161400

110 Middle River - Western River Rd KI 53 678354 6039914

111 Mosquito Creek Struan SE 54 481215 5894838

112 Myponga River - Upstream Of Dam AMLR 54 271213 6082117

113 Neales - Algebuckina Waterhole SAAL 53 580162 6913608

114 North Para R - Turretfield AMLR 54 302471 6173150

115 North Para River Penrice AMLR 54 321667 6184771

116 Onkaparinga R AMLR 54 272518 6104132

29

A snapshot of pesticides in South Australian aquatic sediments

Site number

Site description NRM Region

Zone Easting Northing

117 Patawalonga - Final Weir AMLR 54 272955 6128445

118 Pekina Creek - Ford Near 'Raevale' NY 54 271605 6366745

119 River Murray Loxton SAMDB 54 458464 6187542

120 River Murray Murtho Park SAMDB 54 484705 6232053

122 River Murray Pelican Point S/Morgan SAMDB 54 378314 6222702

123 River Murray Swan Reach SAMDB 54 371395 6174297

124 River Murray U/S Berri SAMDB 54 475616 6212727

125 River Murray U/S Murray Bridge SAMDB 54 343147 6114213

126 River Murray U/S Tailem Bend SAMDB 54 358652 6098296

127 River Murray Pellaring Flat SAMDB 54 352853 6140822

128 Torrens River - Holbrooks Rd AMLR 54 275940 6133767

129 Scotts Creek At Scotts Bottom AMLR 54 287939 6113328

130 Sixth Ck - Castambul AMLR 54 294849 6138631

131 Skillogallee - Hoyleton Rd NY 54 280723 6234818

132 South Para - Mount Rd U/S Warren Res AMLR 54 313048 6158400

133 Tod R At Koppio EP 53 579849 6189822

134 Tod R White Flat EP 53 576949 6179826

136 Torrens River At Mt Pleasant Gs504512 AMLR 54 319636 6148800

137 Wakefield R NY 54 243553 6218868

138 Wakefield R - Rocks NY 54 271053 6216700

139 Willochra - S Of Partacoona NY 54 230101 6447985

140 Willson River Ki KI 53 766814 6031517

141 Yardaparinna Ck - Macumba H/Stead SAAL 53 564332 6985990

30

A snapshot of pesticides in South Australian aquatic sediments

Site number

Site description NRM Region

Zone Easting Northing

142 Big Swamp Eyre Peninsula EP 53 564178 6166754

143 Little Swamp Eyre Peninsula EP 53 572308 6160862

144 Torrens Lake AMLR 54 279698 6133463

145 Lake Bonney SE Site 1 SE 54 446809 5811358

146 Lake Bonney SE Site 2 SE 54 443359 5823804

147 Lake George SE Site 1 SE 54 413598 5861142

148 Lake George SE Site 2 SE 54 414613 5854045

149 Reedy Creek Wetlands SAMDB 54 338802 6132623

150 Lake Bonney Berri SAMDB 54 450270 6210117

151 Lake Albert - Meningie SAMDB 54 349886 6050209

152 Lake Albert - Albert Passage SAMDB 54 335475 6068456

153 Lake Alexandrina: Milang SAMDB 54 316351 6080031

154 Lake Alexandrina - Pt Mcleay SAMDB 54 330521 6069374

155 Lake Alexandrina - Poltalloch Plains SAMDB 54 351408 6077200

156 Finniss River Wetlands SAMDB 54 302943 6080421

157 Currency Creek Wetlands SAMDB 54 297760 6074167

31

A snapshot of pesticides in South Australian aquatic sediments

Appendix 3 Pesticides included in the aquatic sediments snapshot

Pesticide categories were obtained from <www.alanwood.net/pesticides/index.html>.

Pesticide Category

Aldicarb Carbamate insecticide

Aldrin Organochlorine insecticide

Ametryn Methylthiotriazine herbicide

Atrazine Chlorotriazine herbicide

Azinphos-methyl Organophosphate insecticide

Bendiocarb Carbamate insecticide

alpha–Hexachlorocyclohexane (α–HCH) Organochlorine insecticide

beta–Hexachlorocyclohexane (β–HCH) Organochlorine insecticide

delta–Hexachlorocyclohexane (χ–HCH) Organochlorine insecticide

Lindane (gamma–Hexachlorocyclohexane (δ–HCH))

Organochlorine insecticide

Bifenthrin Pyrethroid insecticide

Bromophos–ethyl Organophosphate insecticide

Carbaryl Carbamate insecticide

Carbofuran Carbamate insecticide

3-Hydroxy Carbofuran Carbamate insecticide

Carbophenothion Organophosphate insecticide

Chlordane – cis Organochlorine insecticide

Chlordane – tran Organochlorine insecticide

Chlordane – trans Organochlorine insecticide

Chlordane a Organochlorine insecticide

Chlordane g Organochlorine insecticide

Chlorfenvinphos E Organophosphate insecticide

Chlorfenvinphos Z Organophosphate insecticide

Chlorsulfuron Triazinylsulfonylurea herbicide

Chlorpyrifos Organophosphate insecticide

Chlorpyrifos–methyl Organophosphate insecticide

32

A snapshot of pesticides in South Australian aquatic sediments

Pesticide Category

Chlorthal-dimethyl (DCPA) Phthalic acid herbicide

Chlorothalonil Aromatic fungicide

Cyfluthrin Pyrethroid insecticide

Cyhalothrin Pyrethroid insecticide

Cypermethrin Pyrethroid insecticide

DDD Organochlorine insecticide

DDE Organochlorine insecticide

DDT Organochlorine insecticide

Deltamenthrin Pyrethroid insecticide

Demeton-S-methyl Organophosphate insecticide

Desethyl Atrazine Chlorotriazine herbicide

Desisopropyl Atrazine Chlorotriazine herbicide

Diazinon Organophosphate insecticide

Dichlorvos Organophosphate insecticide

Dieldrin Organochlorine insecticide

Dimethoate Organophosphate insecticide

Diuron Urea herbicide

Endosulfan 1 Organochlorine insecticide

Endosulfan 2 Organochlorine insecticide

Endosulfan sulfate Organochlorine insecticide

Endrin Organochlorine insecticide

Endrin aldehyde Organochlorine insecticide

Endrin ketone Organochlorine insecticide

Ethion Organophosphate insecticide

Fenamiphos Organophosphate insecticide

Fenitrothion Organophosphate insecticide

Fenthion Organophosphate insecticide

Fenvalerate Pyrethroid insecticide

Fipronil Pyrazole acaricide

Fluvalinate Pyrethroid insecticide

33

A snapshot of pesticides in South Australian aquatic sediments

Pesticide Category

Hexachlorobenzene (HCB) Organochlorine insecticide

Heptachlor Organochlorine insecticide

Heptachlor Epoxide Organochlorine insecticide

Imidacloprid Pyridylmethylamine insecticide

Malathion Organophosphate insecticide

Methiocarb Carbamate insecticide

Methomyl Carbamate insecticide

Methoxychlor Organochlorine insecticide

Metsulfuron Sulfonylurea herbicide

Monocrotophos Organophosphate insecticide

Oxamyl Carbamate insecticide

Parathion Organophosphate insecticide

Parathion-Methyl Organophosphate insecticide

Permethrin Pyrethroid insecticide

Phenothrin Organophosphate insecticide

Piperonyl Butoxide Synergist

Pirimphos-ethyl Pyrimidine organothiophosphate insecticide

Prometryn Methylthiotriazine herbicide

Prothiofos Organophosphate insecticide

Simazine Chlorotriazine herbicide

Tetramethrin Pyrethroid insecticide

Thiodicarb Carbamate insecticide

Transfluthrin Pyrethroid insecticide

Triasulfuron Triazinylsulfonylurea herbicide

Trifluralin Dinitroaniline herbicide

Vinclozolin Dichlorophenyl dicarboximide fungicide; oxazole fungicide

34

A snapshot of pesticides in South Australian aquatic sediments

35