Samples of water and sediments were collected from 24 urban wetlands in Melbourne, Australia, in April 2010, and tested for more than 90 pesticides using a range of gas chromatographic (GC) and liquid chromatographic (LC) techniques, sample 'hormonal' activity using yeast-based recombinant receptor-reporter gene bioassays, and trace metals using spectroscopic techniques. At the time of sampling, there was almost no estrogenic activity in the water column. Twenty-three different pesticide residues were observed in one or more water samples from the 24 wetlands; chemicals observed at more than 40% of sites were simazine (100%), atrazine (79%), and metalaxyl and terbutryn (46%). Using the toxicity unit (TU) concept, less than 15% of the detected pesticides were considered to pose an individual, short-term risk to fish or zooplankton in the ponds and wetlands. However, one pesticide (fenvalerate) may have posed a possible short-term risk to fish (log10TUf > -3), and three pesticides (azoxystrobin, fenamiphos and fenvalerate) may have posed a risk to zooplankton (logTUzp between -2 and -3); all the photosystem II (PSII) inhibiting herbicides may have posed a risk to primary producers in the ponds and wetlands (log10TUap and/or log10TUalg > -3). The wetland sediments were contaminated with 16 different pesticides; no chemicals were observed at more than one third of sites, but based on frequency of detection and concentrations, bifenthrin (33%, maximum 59 μg/kg) is the priority insecticide of concern for the sediments studied. Five sites returned a TU greater than the possible effect threshold (i.e. log10TU > 1) as a result of bifenthrin contamination of their sediments. Most sediments did not exceed Australian sediment quality guideline levels for trace metals. However, more than half of the sites had threshold effect concentration quotients (TECQ) values >1 for Cu (58%), Pb (50%), Ni (67%) and Zn (63%), and 75% of sites had mean probable effect concentration quotients (PECQ) >0.2, suggesting that the collected sediments may have been having some impact on sediment-dwelling organisms.
Herbicides are regularly applied in horticultural production systems and may migrate off-site, potentially posing an ecological risk to surface waterways. However, few studies have investigated the levels and potential ecotoxicological impact of herbicides in horticultural catchments in southern Australia. This study investigated the presence of 10 herbicides at 18 sites during a 5-month period in horticulturally important areas of the Yarra Valley in southeastern Australia. Seven of the 10 herbicides were detected in the streams, in 39 % of spot water samples, in 25 % of surface sediment samples, and in>70 % of the passive sampler systems deployed. Few samples contained residues of ≥2 herbicides. Simazine was the herbicide most frequently detected in water, sediment, and passive sampler samples and had the highest concentrations in water (0.67 μg/L) and sediment (260 μg/kg dry weight). Generally the concentrations of the herbicides detected were several orders of magnitude lower than reported ecotoxicological effect values, including those for aquatic plants and algae, suggesting that concentrations of individual chemicals in the catchment were unlikely to pose an ecological risk. However, little is known about the combined effects of simultaneous, low-level exposure of multiple herbicides of the same mode of action on Australian aquatic organisms nor their contribution when found in mixtures with other pesticides. Further research is required to adequately assess the risk of pesticides in Victorian aquatic environments.
Water and sediment samples were collected from up to 17 sites in waterways entering the Corner Inlet Marine National Park monthly between November 2009 and April 2010, with the Chemcatcher passive sampler system deployed at these sites in November 2009 and March 2010. Trace metal concentrations were low, with none occurring at concentrations with the potential for adverse ecological effects. The agrochemical residues data showed the presence of a small number of pesticides at very low concentration (ng/L) in the surface waters of streams entering the Corner Inlet, and as widespread, but still limited contamination of sediments. Concentrations of pesticides detected were relatively low and several orders of magnitude below reported ecotoxicological effect and hazardous concentration values. The low levels of pesticides detected in this study indicate that agricultural industries were responsible agrochemical users. This research project is a rarity in aligning both agrochemical usage data obtained from chemical resellers in the target catchment with residue analysis of environmental samples. Based on frequency of detection and concentrations, prometryn is the priority chemical of concern for both the water and sediments studied, but this chemical was not listed in reseller data. Consequently, the risks may be greater than the field data would suggest, and priorities for monitoring different since some commonly used herbicides (such as glyphosate, phenoxy acid herbicides, and sulfonyl urea herbicides) were not screened. Therefore, researchers, academia, industry, and government need to identify ways to achieve a more coordinated land use approach for obtaining information on the use of chemicals in a catchment, their presence in waterways, and the longer term performance of chemicals, particularly where they are used multiple times in a year.
Urban stormwater samples were collected from five aquatic systems in Melbourne, Australia, on six occasions between October 2011 and March 2012 and tested for 30 herbicides and 14 trace metals. Nineteen different herbicides were observed in one or more water samples from the five sites; chemicals observed at more than 40% of sites were simazine (100%), MCPA (83%), diuron (63%) and atrazine (53%). Using the toxicity unit (TU) concept to assess potential risk to aquatic ecosystems, none of the detected herbicides were considered to pose an individual, group or collective short-term risk to fish or zooplankton in the waters studied. However, 13 herbicides had TU values suggesting they might have posed an individual risk to primary producers at the time of sampling. Water quality guideline levels were exceeded on many occasions for Cd, Cu, Cr, Pb and Zn. Similarly, RQ and RQ exceeded 1 for Cd, Cr, Cu, Mn, Ni, Pb, V and Zn. Almost all the metals screened exceeded a logTU of -3 for every trophic level, suggesting that there may have been some impact on aquatic organisms in the studied waterbodies. Our data indicate that Melbourne's urban aquatic environments may be being impacted by approved domestic, industrial and sporting application of herbicides and that stormwater quality needs to be carefully assessed prior to reuse. Further research is required to understand the performance of different urban stormwater wetland designs in removing pesticides and trace metals. Applying the precautionary principle to herbicide regulation is important to ensure there is more research and assessment of the long-term 'performance' standard of all herbicides and throughout their 'life cycle'. Implementing such an approach will also ensure government, regulators, decision makers, researchers, policy makers and industry have the best possible information available to improve the management of chemicals, from manufacture to use.
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