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Land application of composted municipal solid waste (C-MSW) can divert waste from landfill but can also be a route of entry into the environment for contaminants. This study presents a preliminary human health and ecological risk assessment for organic contaminants in C-MSW generated in New South Wales, Australia, to identify and prioritise contaminants of concern. Following an initial screening assessment, terrestrial and aquatic risks were assessed by predicted soil and water concentrations, respectively. The assessment ranked contaminants as very high, high, medium or low priority. A qualitative review was then used to identify contaminants of concern, which included polybrominated diphenyl ethers, phthalates, bisphenol A and dibutyltin. Phenol was initially categorised as very high priority but due to its rapid degradation in soil, this is likely to be overly-conservative. The herbicides dicamba and MCPA were categorised as medium priority or higher but due to uncertainties in the data, these categories are also likely to be overly-conservative. A range of contaminants had concentrations below the screening criteria and were therefore considered low risk. Many contaminants were below the limit of reporting in all samples and were therefore not considered to be sufficiently distributed in the material to pose a risk. Some contaminants were detected in the material but could not be assessed as no criteria were available. The information from this study can be used by regulators when managing land application of C-MSW to ensure that the risks to human health and the environment are managed appropriately.

Bicarbonate is often a major ionic constituent associated with produced waters from methane gas extraction and coal mining, yet few studies have determined its specific toxicity. Currently, the environmental risk of bicarbonate anion in water discharges is assessed based on the toxicity of sodium chloride or artificial seawater and is regulated via electrical conductivity. Increased NaHCO3 added to Ceriodaphnia dubia in synthetic or natural water gave similar 48-h 10% effective concentration (EC10) values of 1750 ± 125 mg NaHCO3/L (mean ± standard error) and 1670 ± 180 mg NaHCO3/L, respectively. Bicarbonate was toxic to C. dubia in both waters with conductivities above 1900 µS/cm. In contrast, when conductivity was elevated with NaCl, toxicity to C. dubia was observed only above 2800 µS/cm. Bicarbonate also impaired C. dubia reproduction with an EC10 of 340 mg NaHCO3/L. Major ion composition also influenced Zn bioavailability, a common co-occurring metal contaminant in coal mine waters, with sublethal concentrations of NaHCO3 and elevated pH increasing Zn toxicity. Higher pH was the dominant parameter determining a 10-fold increase in the 48-h 50% effective concentration (EC50) for Zn toxicity to C. dubia at pH 8.6 of 34 µg Zn/L (95% confidence limit = 32–37 µg Zn/L) compared with the Zn toxicity at approximately circumneutral pH. Exposure of the freshwater shrimp Paratya australiensis (Atyidae) in natural water to increasing bicarbonate gave a mean 10-d 10% lethal concentration (LC10) of 850 ± 115 mg NaHCO3/L, associated with a mean conductivity EC10 of 1145 µS/cm, which is considerably lower than toxicity of NaCl and artificial seawater to this species reported elsewhere. Because toxicity was influenced by salt composition, specific ions should be regulated rather than conductivity alone in mine wastewater discharges. Environ Toxicol Chem 2014;33:1179–1186. © 2014 SETAC

A model mesocosm system was used to simulate the effect of endosulfan entering a waterway from episodic events such as accidental overspray or in runoff water containing contaminated sediment following storm events. The fate of technical endosulfan applied to a 24-stream mesocosm was compared in experiments where the pesticide was applied either directly as water contamination or after being pre-bound to sediment. The flow of water through the streams was discontinued for a 10-12 h period following the pesticide application. Following the water application, only approximately 3% of endosulfan remained in the streams after 4 days and then was not detectable after 7 days. In contrast, after application pre-bound to sediment, approximately 33% of the endosulfan remained in the streams after 4 days and 14% after 7 days. Additionally, with the sediment-bound application, the proportion of endosulfan was higher in the substrate (11%) after 7 days than in the overlying water (3%), and approximately 1% was oxidised to the sulphate form. The dissipation of endosulfan in the water column of both experiments followed a two-parameter exponential decay model characterised by a relatively fast first-order single-phase process. In sediment of both experiments and the gravel of the sediment-dosing experiment, the dissipation of endosulfan followed more closely a four-parameter bi-exponential decay model characterised by first-order kinetics of two fractions: the first fraction dissipates quickly, and in the longer term the second fraction dominates the overall dissipation with a slower rate. In the gravel section of the water-dosing experiment, endosulfan dissipation was characterised by relatively very slow two-parameter exponential decay. The overall dissipation rates of the alpha- and beta-endosulfan isomers were significantly higher in the water-dosing than in the sediment-dosing experiment, except in the gravel section of the mesocosm. The uptake of the endosulfan into passive samplers constructed from polyethylene membrane bags containing trimethylpentane solvent (TRIMPS) placed in the overlying water was linear. In contrast, TRIMPS buried in sediment failed to uptake endosulfan from the sediment substrate, indicating that short-term deployment of passive samplers can only be used to determine time-weighted average concentrations of bioavailable chemicals in the water column. A 34-h LC50 of 2.8 microg/l [95% confidence interval (CI) 1.5-4.2 microg/l] for juveniles of the native fish Macquaria ambigua was obtained when exposed during the water-dosing experiment. This study demonstrated that the pulse entry of sediment contaminated with endosulfan into a receiving waterway was more persistent compared with direct aqueous contamination and the endosulfan would be bioavailable to pelagic organisms following a gradual partitioning to the water column.

Cigarette butts are the most numerically frequent form of litter in the world. In Australia alone, 24-32 billion cigarette butts are littered annually. Despite this littering, few studies have been undertaken to explore the toxicity of cigarette butts in aquatic ecosystems. The acute toxicity of 19 filtered cigarette types to Ceriodaphnia cf. dubia (48-hr EC50 (immobilization)) and Vibrio fischeri (30-min EC50 (bioluminescence)) was determined using leachates from artificially smoked cigarette butts. There was a 2.9- and 8-fold difference in toxicity between the least and most toxic cigarette butts to C. cf. dubia and V. fischeri, respectively. Overall, C. cf. dubia was more inherently sensitive than V. fischeri by a factor of approximately 15.4, and the interspecies relationship between C. cf. dubia and V. fischeri was poor (R(2) = 0.07). This poor relationship indicates that toxicity data for cigarette butts for one species could not predict or model the toxicity of cigarette butts to the other species. However, the order of the toxicity of leachates can be predicted. It was determined that organic compounds caused the majority of toxicity in the cigarette butt leachates. Of the 14 organic compounds identified, nicotine and ethylphenol were suspected to be the main causative toxicants. There was a strong relationship between toxicity and tar content and between toxicity and nicotine content for two of the three brands of cigarettes (R(2 )0.70) for C. cf. dubia and one brand for V. fischeri. However, when the cigarettes were pooled, the relationship was weak (R(2)0.40) for both test species. Brand affected the toxicity to both species but more so for V. fischeri.

A laboratory continuous-flow system delivering known aqueous concentrations of pesticides to passive samplers was used to examine the kinetics of pesticide uptake and release. The passive samplers were constructed of low-density polyethylene membrane bags containing 2,2,4-trimethylpentane solvent (TRIMPS). Both uptake and release experiments were run in triplicate. Each experiment involved four treatments, including a control and three fivefold dilutions of a pesticide mixture that included the usual range of these pesticides as measured in the riverine environment of cotton-growing regions of Australia. The results indicated that for nonpolar pesticides with a log K o w > 3.5, uptake was linear over the 42-d exposure time and was independent of the treatment concentration. The half-lives for release of these pesticides from the TRIMPS varied from 26 to 130 d in clean water. The relatively polar pesticides with a log K o w < 3.5 had lower uptake rates into the TRIMPS because of their affinity for water. Release of trimethylpentane from the TRIMPS placed in 0.85-mm mesh nylon bags in river water was used as an indicator for chemical diffusion across the aqueous boundary to examine the effect of environmental factors. Most variability in solvent release in the field-deployed TRIMPS across all sites was explained by time of deployment and was not significantly influenced by river flow or water temperature. This suggests that river flow and water temperature may not be important in influencing uptake rates of pesticides into TRIMPS when employed in the field.

The toxicity of the organochlorine pesticide endosulfan to macroinvertebrate communities was tested using a system of 24 artificial streams. Macroinvertebrate communities in the streams were exposed to a range of endosulfan concentrations for a 12-h period and then monitored for 96 h. Endosulfan was prebound to fine river sediment and applied to the streams as a contaminated sediment slurry. This did not cause changes in the structure of benthic communities; however, significant changes (P

Bicarbonate is often a major ionic constituent associated with produced waters from methane gas extraction and coal mining, yet few studies have determined its specific toxicity. Currently, the environmental risk of bicarbonate anion in water discharges is assessed based on the toxicity of sodium chloride or artificial seawater and is regulated via electrical conductivity. Increased NaHCO(3) added to Ceriodaphnia dubia in synthetic or natural water gave similar 48-h 10% effective concentration (EC10) values of 1750 ± 125 mg NaHCO(3)/L (mean ± standard error) and 1670 ± 180 mg NaHCO(3)/L, respectively. Bicarbonate was toxic to C. dubia in both waters with conductivities above 1900 µS/cm. In contrast, when conductivity was elevated with NaCl, toxicity to C. dubia was observed only above 2800 µS/cm. Bicarbonate also impaired C. dubia reproduction with an EC10 of 340 mg NaHCO(3)/L. Major ion composition also influenced Zn bioavailability, a common co-occurring metal contaminant in coal mine waters, with sublethal concentrations of NaHCO(3) and elevated pH increasing Zn toxicity. Higher pH was the dominant parameter determining a 10-fold increase in the 48-h 50% effective concentration (EC50) for Zn toxicity to C. dubia at pH 8.6 of 34 µg Zn/L (95% confidence limit = 32-37 µg Zn/L) compared with the Zn toxicity at approximately circumneutral pH. Exposure of the freshwater shrimp Paratya australiensis (Atyidae) in natural water to increasing bicarbonate gave a mean 10-d 10% lethal concentration (LC10) of 850 ± 115 mg NaHCO(3)/L, associated with a mean conductivity EC10 of 1145 µS/cm, which is considerably lower than toxicity of NaCl and artificial seawater to this species reported elsewhere. Because toxicity was influenced by salt composition, specific ions should be regulated rather than conductivity alone in mine wastewater discharges.

The widespread use of chlorpyrifos for pest control in urban and rural environments poses a risk of contamination to aquatic environments via runoff, spray drift or spillage. The aim of this study was to assess the fate of chlorpyrifos and its toxicity to common freshwater invertebrates in the laboratory and in stream mesocosms. Chlorpyrifos was rapidly lost from the test systems but the rates of loss varied considerably, such that losses in the mesocosms could not be reliably predicted from the static laboratory studies. This was likely due to the mass transport of chlorpyrifos from the mesocosm via stream flow. Chlorpyrifos was acutely toxic to all invertebrates tested with the cladoceran species (laboratory 48 h LC50 values 0.07–0.10 μg L−1) being most sensitive. Despite the differences in the dynamics of chlorpyrifos in the laboratory and mesocosm systems, the sensitivities of the mayfly Atalophlebia australis and the cladoceran Simocephalus vetulus were similar in the 2 systems.

An artificial neural network (ANN) was employed to model the chromatographic response surface for the linear gradient separation of 10 herbicides that are commonly detected in storm run-off water in agricultural catchments. The herbicides (dicamba, simazine, 2,4-D, MCPA, triclopyr, atrazine, diuron, clomazone, bensulfuron-methyl and metolachlor) were separated using reverse phase high performance liquid chromatography and detected with a photodiode array detector. The ANN was trained using the pH of the mobile phase and the slope of the acetonitrile/water gradient as input variables. A total of nine experiments were required to generate sufficient data to train the ANN to accurately describe the retention times of each of the herbicides within a defined experimental space of mobile phase pH range 3.0-4.8 and linear gradient slope 1-4% acetonitrile/min. The modelled chromatographic response surface was then used to determine the optimum separation within the experimental space. This approach allowed the rapid determination of experimental conditions for baseline resolution of all 10 herbicides. Illustrative examples of determination of these components in Milli-Q water, Sydney mains water and natural water samples spiked at 0.5-1mug/L are shown. Recoveries were over 70% for solid-phase extraction using Waters Oasis((R)) HLB 6cm(3) cartridges.

The toxicity of the organochlorine pesticide endosulfan to macroinvertebrate assemblages was tested using a system of 24 artificial streams. In separate experiments, the effects of 12- and 48-h exposure to aqueous endosulfan were assessed. No-observed-effect concentrations (NOEC) for endosulfan on macroinvertebrate assemblages were 8.69 and 1.00μg/L for the 12- and 48-h exposure studies, respectively. In both studies, changes were driven by reduced abundances of the mayfly, Jappa kutera. Algal blooms occurred in the 48-h exposure experiment in streams that received the 6.87 or 30.70μg/L treatments. These effects occurred at concentrations that might occur as a result of episodic events such as accidental overspray or rainstorms. By establishing a causal link between endosulfan and changes to macroinvertebrate assemblages, this study adds further weight to the hypothesis that endosulfan is a major contributor to changes observed in rivers of the cotton-growing region of New South Wales, Australia during the pesticide spray season. © 2003 Elsevier Science (USA). All rights reserved.

Recent investigations into the level of heavy metal enrichment in the sediments of Lake Macquarie have indicated that significant contamination has occurred over the past 100 years, with elevated levels of lead, zinc, cadmium, copper, and selenium being observed in most parts of the lake. Pore water extracted from sediments showing the greatest contamination by these metals exhibited toxicity to the larval development of the sea urchin Heliocidaris tuberculata. However, an analysis of pore water metal concentrations revealed that the concentrations of these metals were too low to cause toxicity. Rather, pore water toxicity was highly correlated with manganese for the majority of sites sampled; subsequent spiking experiments confirmed manganese as a cause of toxicity. Current levels of manganese in the sediments of Lake Macquarie have arisen from natural sources and are not the result of anthropogenic activities. These results reiterate the importance of identifying the causes of toxicity in assessments of sediment contamination, particularly when testing sediment pore waters using sensitive early life stages.

Population densities of six dominant macroinvertebrate taxa (mayfly nymphs Jappa kutera, Atalophlebia sp., Tasma-nocoenis sp., Baetis sp. and the caddisfly larvae Cheumatopsyche sp. and Ecnomus sp.) were negatively correlated to total endosulfan concentrations in the Namoi River (New South Wales, Australia) in the 1995/96 and 1997/98 cotton growing seasons (November-March). Total endosulfan concentrations measured in solvent-filled polyethylene bags (passive samplers) at the exposed sites correlated with rainfall, suggesting that endosulfan entered the riverine environment in runoff from land. At the start of both surveys, in November 1995 and November 1997, there was no significant difference (p < 0.05) between the reference and exposed sites for both total endosulfan concentrations and mean population densities of the combined study taxa. This indicates distance downstream, which was negatively correlated with exposure, was not an important variable in explaining the significantly higher population densities in other months at the reference sites compared with those at sites subsequently exposed to increased (10–25-fold) total endosulfan concentrations. The multivariate analysis of the 1997/98 data with the principal response curves (PRC) method indicated that endosulfan explained a significant proportion (25%) of the variation in the total macroinvertebrate community. Principal components analysis (PCA) indicated other covariables were involved, including river discharge. River discharge was positively correlated to increased densities of the mayfly taxa at the reference sites in the 1995/96 survey, but these correlations were reduced to near zero, except for Baetis sp., in the 1997/98 survey.

Environmental Context.A rapid Chelex resin method is shown to be a valuable speciation screening tool for use in a tiered risk assessment of copper toxicity in fresh waters. It is a more conservative measure than toxicity testing with sensitive biota, but a better indicator of toxicity than a dissolved copper measurement. Abstract.Twelve natural fresh waters with similar pH and hardness, but varying dissolved organic carbon (DOC) and copper concentrations, were assessed for (a) toxicity to an alga (Chlorella sp. 12), a cladoceran (Ceriodaphnia cf. dubia) and a bacterium (Erwinnia sp.), and (b) copper speciation using a rapid Chelex extraction method, diffusive gradients in thin films (DGT) and anodic stripping voltammetry (ASV). In synthetic fresh water with no added DOC, at pH 7.0 and low hardness, the toxic responses (EC/IC50) of all three organisms to copper were similar. However, in the toxicity of copper added to natural water samples exhibited a negative linear relationship to DOC (r2 = 0.82–0.83), with respective slopes for algae, cladocerans and bacteria decreasing in the ratio 7.4 : 3.5 : 1. The marked difference in responses in the presence of natural dissolved organic matter indicated that not all of the organisms conformed to the free ion activity model (FIAM). This was confirmed by copper ion selective electrode measurement of copper ion activity. Copper toxicity to algae in the presence of DOC was overestimated by free ion activity possibly due to surface binding of DOC. Copper toxicity to the bacteria was greater than predicted and was shown to be a result of bioavailability of some copper complexes formed with organic matter. Cladocerans appear to more closely follow FIAM predictions. These findings have important implications for attempts to extend predictive models of metal toxicity beyond fish to more sensitive freshwater species. The measured labile copper concentrations of copper-spiked natural waters varied from 0 to 70% of total copper concentrations. There was no clear relationship between the three measurement techniques. Good correlations were obtained between both algal and bacterial growth inhibitions measured on copper-spiked natural waters and the corresponding Chelex-labile copper concentrations. A single natural water sample was manipulated to different pH and hardness values, spiked with copper, and tested using the above three organisms with the Chelex method. Toxicity test results generally agreed with studies performed in synthetic fresh waters, showing that the relationships between toxicity, pH and hardness were organism-specific. Chelex-labile copper was always over-predictive of toxicity but significantly better (P ≤ 0.05) than dissolved copper concentrations, as it only detects the fraction of total copper that is reactive over biologically-relevant timescales. Colloidally-bound copper and copper associated with strong ligands are not detected. The Chelex method is therefore useful as a measure where speciation is accepted in water quality regulations.

This study determined the influence of key water chemistry parameters (pH, alkalinity, dissolved organic carbon [DOC], and hardness) on the aqueous speciation of copper and zinc and its relationship to the acute toxicity of these metals to the cladoceran Ceriodaphnia cf dubia. Immobilization tests were performed for 48-h in synthetic or natural waters buffered at various pH values from 5.5 to 8.4 (other chemical parameters held constant). The toxicity of copper to C. cf dubia decreased fivefold with increasing pH, whereas the toxicity of zinc increased fivefold with increasing pH. The effect of DOC on copper and zinc toxicity to C. cf dubia was determined using natural fulvic acid in the synthetic water. Increasing DOC was found to decrease linearly the toxicity of copper, with the mean effect concentration of copper that immobilized 50% of the cladocerans (EC50) value 45 times higher at 10 mg/L, relative to 0.1 mg/L DOC at pH 6.5. In contrast, the addition of 10 mg/L DOC only resulted in a very small (1.3-fold) reduction in the toxicity of zinc to C. cf dubia. Copper toxicity to C. cf dubia generally did not vary as a function of hardness, whereas zinc toxicity was reduced by a factor of only two, with an increase in water hardness from 44 to 374 mg CaCO3/L. Increasing bicarbonate alkalinity of synthetic waters (30-125 mg/L as CaCO3) decreased the toxicity of copper up to fivefold, which mainly could be attributed to the formation of copper-carbonate complexes, in addition to a pH effect. The toxicity of copper added to a range of natural waters with varying DOC content, pH, and hardness was consistent with the toxicity predicted using the data obtained from the synthetic waters.

The rate of release of three performance reference compounds (PRCs) from passive samplers when deployed in rivers with variable flow and temperature were compared with their release from passive samplers in a laboratory continuous-flow system. The passive samplers used in the current study were constructed from low-density polyethylene bags containing trimethylpentane solvent (TRIMPS). The half-lives for release from the TRIMPS of the PRCs tributylphosphate, endosulfan sulfate, and chlorpyrifos-ethyl were 7.3, 20.8, and >75 d, respectively, when deployed in rivers, compared with half-lives of 10.4, 26.5, and approximately 73 d in a laboratory flow system. The mean pesticide concentrations taken up by TRIMPS deployed for periods from 7 to 22 d in rivers adjacent to cotton fields were determined during two studies in the austral summer of 2000/2001 and 2001/2002. During the studies, mean total endosulfan and chlorpyrifos-ethyl concentrations were also determined from daily river-water extractions. Regression equations established in previous laboratory studies related the concentration factors into TRIMPS to the time of deployment for a number of pesticides, including endosulfan and chlorpyrifos-ethyl. The laboratory-derived calibration factors were used to determine the mean pesticide concentrations for each deployment period, and these were compared with the cumulative mean concentrations calculated from the daily extractions. The pesticide concentrations determined using the TRIMPS were within twofold of the cumulated mean of the daily river-water extractions of endosulfan and chlorpyrifos-ethyl for deployment periods of 7 to 22 d when the mean river-water concentrations were >0.005 microg/L.