Exposures of Limnodynastes tasmaniensis tadpoles to atrazine (0.1, 1, 3 and 30microgL(-1)), metol... more Exposures of Limnodynastes tasmaniensis tadpoles to atrazine (0.1, 1, 3 and 30microgL(-1)), metolachlor (0.1, 1 and 10microgL(-1)) and thiobencarb (90, 180 and 360microgL(-1)) from Gosner stage 28 to 42 under controlled laboratory conditions gave no significant effects on tadpole growth, development and sex ratios. A binary mixture of atrazine and thiobencarb as well as a ternary mixture of all three herbicides also had no significant effects on the developing larvae to show no evidence of interactive toxicity. Abnormal gonad morphology was observed on two occasions; both from 0.1microgL(-1) atrazine treatments with one tadpole observed with testicular ovarian follicles. The low frequencies of abnormal gonadal morphology and testicular ovarian follicles did not indicate a concentration associated response to herbicide exposure. No significantly unbalanced sex ratios were observed to suggest any evidence of chemically induced feminisation. These observations suggest that environmenta...
An artificial neural network (ANN) was employed to model the chromatographic response surface for... more 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 ...
nymphs and one species of caddisfly larvae (Leonard et al., 1999) were less than the highest conc... more nymphs and one species of caddisfly larvae (Leonard et al., 1999) were less than the highest concentrations Endosulfan (6,7,8,9,10,10,-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9measured in river water following storm events methano-2,4,3-benzodioxathiepine-3-oxide) sorption (standardized to 1% total organic carbon and dry weight) was significantly (P Ͻ 0.05) . Changes in taxon densities, which inmore concentrated on the large (Ͼ63 m) particle fraction compared cluded epibenthic species, had weaker correlations to with smaller size fractions (Ͻ5 m and 5-24 m) of bottom sediments total endosulfan concentrations measured in the bottom from the Namoi River, Australia. Following completion of the particle sediment (Leonard et al., 1999). This may have been size fractionation (6 to 12 wk) and a sediment toxicity assessment due to the more precise data obtained by using passive (2 wk), the sediments showed large decreases in concentrations of samplers, although the differences may also have been ␣-endosulfan that coincided with an increase in endosulfan sulfate due to a reduced toxicity of sediment-bound endosulfan.
Integrated Environmental Assessment and Management, 2011
A comparison of environmental risks of pesticides between tropical and nontropical regions has be... more A comparison of environmental risks of pesticides between tropical and nontropical regions has been performed, using data from the literature and modeling outputs based on the physicochemical properties of the compounds. With a few exceptions, the level of risk of exposure for most pesticides in tropical agriculture is similar to that in other climatic regions of the world. Generally, dissipation of pesticides increases under the warm and wet conditions of the tropics, with most of the dissipation occurring through hydrolysis in water and biological degradation in water and soil. High temperatures in the tropics also foster volatilization rates, whereas high precipitation and poor soils tend to increase losses into runoff and, for certain chemicals, affects their leaching behavior. The environmental risk is determined by a balance of soil types, soil organic carbon, pH, and the rates of degradation in the various environmental compartments. Integr Environ Assess Manag 2011;7:577-586. ß 2011 SETAC
Bicarbonate is often a major ionic constituent associated with produced waters from methane gas e... more 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.
An underlying assumption of laboratory-based toxicity tests is that the sensitivity and exposure ... more An underlying assumption of laboratory-based toxicity tests is that the sensitivity and exposure of organisms in the laboratory is comparable to that in the field. We sought to make a comparison between field-based and laboratory-based sediment toxicity tests using a recently developed rapid amphipod reproduction test that encompasses gametogenesis, fertilization, and embryo development before hatching. The test species, Melita plumulosa, is an epibenthic, detritivorous amphipod native to Eastern Australia. Test sediments were sourced from Lake Macquarie, a large saltwater lagoon located 100 km north of Sydney (New South Wales, Australia) that has received heavy-metal pollution over many decades, primarily from a Pb/Zn smelter but also from collieries, coal-fired power stations, and urban areas. This has led to a north-south trace-metal concentration gradient, including Pb, Zn, Cd and Cu, in the sediments of Lake Macquarie. Sediments from these northern bays were demonstrated to reduce amphipod fecundity in laboratory-based tests. For the current study, the amphipod reproduction test has been modified for use in situ. In situ test chambers were deployed at the mouth of Cockle Creek, Lake Macquarie. Sediments that were demonstrated to reduce fecundity of M. plumulosa in the laboratory reproduction test were not similarly toxic when amphipods were exposed to the same sediments in situ. Factors related to the regular tidal renewal of overlying water likely altered exposure profiles in situ, including the provision of additional or alternative nutrition that obviated the need for amphipods to interact with the contaminated sediments, and a washout effect that prevented the accretion of dissolved zinc in the overlying water. Environ. Environ. Toxicol. Chem. 2010;29:256629: -257429: . # 2010
The influence of various diets on the survival, fecundity, and the polyunsaturated fatty acid (PU... more The influence of various diets on the survival, fecundity, and the polyunsaturated fatty acid (PUFA) composition of the benthic estuarine amphipod Melita plumulosa (Zeidler) in laboratory cultures were determined. Apart from a natural silty sediment, six commercial food supplements were examined: an omega-6 PUFA enriched Spirulina-based dry powder, Sera micron; a shrimpbased pellet food; an omega-3 PUFA enriched algal paste, Rotiselco-ALG; an omega-6 PUFA enriched algal dry powder, AlgaMac-ARA (arachidonic acid); flaxseed meal; and an omega-3 PUFA enriched dry powder, Frippak. We have previously established that M. plumulosa cultures perform poorly and eventually decline if provided with silty sediment alone, but will thrive if supplemented with Sera micron. Conversely, if the amphipods are cultured on a nutrient-depleted sand substrate, Sera micron alone does not constitute an adequate feed. The major difference in the fatty acid composition of M. plumulosa cultured on silty sediment compared to amphipods cultured on a sand substrate and both fed Sera micron was an increase in the ratio of omega-3 to omega-6 PUFAs, indicating that the silty sediment provides additional food sources rich in omega-3 PUFAs. Furthermore, amphipods cultured in sand and fed any of the three algal-based foods or the Frippak powder as the sole food source had poor survival rates, although Sera micron maintained the best survival-this was attributed to it containing high amounts of -carotene and terpenoids. Melita plumulosa fed a mixture of Sera micron in conjunction with the omega-3 PUFA enriched Rotiselco-ALG and cultured on a silty substrate were found to have good fecundity with low variability.
The rate of release of three performance reference compounds (PRCs) from passive samplers when de... more 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 chlorpyrifosethyl were 7.3, 20.8, and Ͼ75 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 Ͼ0.005 g/L.
A series of single-species toxicity tests was conducted in the laboratory and in outdoor stream m... more A series of single-species toxicity tests was conducted in the laboratory and in outdoor stream mesocosms. The mayfly nymphs of Atalophlebia spp. (A. av2 and A. av6) were exposed to the organochlorine pesticide endosulfan for either 12- or 48-h periods, with mortality recorded after 96 h. For both exposure periods, the lethal concentration (LC50 and LC 10) values were not significantly different between laboratory and mesocosm single-species tests, suggesting that the absence of natural environmental conditions and biological interactions in laboratory single-species tests did not influence the toxicity of technical endosulfan to Atalophlebia spp. Interpolation of toxicity test data indicates that peak endosulfan concentrations recorded in the rivers during storm events are likely to cause only minimal impact on Atalophlebia spp. populations. This suggests that changes in the abundance of populations observed in the field, if due to total endosulfan alone, are the result of chronic rather than acute exposure.
Laboratory survival tests were conducted with an indigenous infaunal amphipod, Corophium colo, on... more Laboratory survival tests were conducted with an indigenous infaunal amphipod, Corophium colo, on 103 sediment samples from Sydney Harbor (NSW, Australia) and vicinity, containing a wide range of chemicals and concentrations. The present study describes the sensitivity of C. colo to the sediments and compares the results to data for North American amphipods (Rhepoxynius abronius and Ampelisca abdita) previously used to establish and validate sediment-quality guidelines (SQGs). The incidence of toxicity increased with increasing contamination, as indicated by increasing numbers of SQGs exceeded and increasing mean SQG quotients. The incidence of highly toxic results (p Ͻ 0.05 and mean amphipod survival of Ͻ80% that of controls) for highly contaminated samples was approximately half (28-40%) that of a large U.S. database (74%). The incidence of highly toxic responses for samples with intermediate levels of contamination also was lower in the present study (5-13%) compared to the results in large U.S. studies (ϳ30-50%). Corophium colo reburial tests showed greater sensitivity compared to survival tests, with a maximum incidence of statistically significant responses in moderately contaminated sediments of 70%. The present study showed that adult Corophium organisms are suitable for testing lethal responses in highly contaminated sediments (i.e., with mean effects range-median quotients of Ͼ1.5). Reburial results provide additional sensitivity.
This study determined the influence of key water chemistry parameters (pH, alkalinity, dissolved ... more 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 CaCO 3 /L. Increasing bicarbonate alkalinity of synthetic waters (30-125 mg/L as CaCO 3 ) 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.
Two types of solid-phase materials, a styrenedivinylbenzene copolymer sorbent (embedded in a SDB-... more Two types of solid-phase materials, a styrenedivinylbenzene copolymer sorbent (embedded in a SDB-XC Empore disk) and a styrenedivinylbenzene copolymer sorbent modified with sulfonic acid functional groups (embedded in a SDB-RPS Empore disk), were compared as a receiving phase in a passive sampling device for monitoring polar pesticides. The SDB-XC Empore disk was selected for further evaluation, overlayed with either a polysulfone or a polyethersulfone diffusion membrane. The target herbicides included five nonionized herbicides (simazine, atrazine, diuron, clomazone, and metolachlor) and four phenoxy acid herbicides (dicamba, (2,4-dichlorophenoxy)acetic acid [2,4-D], (4-chloro-2-methylphenoxy)acetic acid [MCPA], and triclopyr) with log octanol/water partition coefficient (log K OW ) values of less than three in water. Uptake of these herbicides generally was higher into a device constructed of a SDB-XC Empore disk as a receiving phase covered with a polyethersulfone membrane compared to a similar device covered with a polysulfone membrane. Using the device with a SDB-XC Empore disk covered with a polyethersulfone membrane, linear uptake of simazine, atrazine, diuron, clomazone, and metolachlor was observed for up to 21 d, and daily sampling rates of the herbicides from water in a laboratory flow-through system were determined. The uptake rate of each nonionized herbicide by the Empore disk-based passive sampler was linearly proportional to its concentration in the water, and the sampling rate was independent of the water concentrations over the 21-d period. Uptake of the phenoxy acid herbicides (2,4-D, MCPA, and triclopyr) obeyed first-order kinetics and rapidly reached equilibrium in the passive sampler after approximately 12 d of exposure. The Empore disk-based passive sampler displayed isotropic kinetics, with a release half-life for triclopyr of approximately 6 d.
A laboratory continuous-flow system delivering known aqueous concentrations of pesticides to pass... more 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 ow Ͼ 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 ow Ͻ 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.
Population densities of six dominant macroinvertebrate taxa (mayfly nymphs Jappa kutera, Atalophl... more Population densities of six dominant macroinvertebrate taxa (mayfly nymphs Jappa kutera, Atalophlebia sp., Tasmanocoenis 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 Ͻ 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.
Agricultural landscapes, although often highly altered in nature, provide habitat for many specie... more Agricultural landscapes, although often highly altered in nature, provide habitat for many species of amphibian. However, the persistence and health of amphibian populations are likely to be compromised by the escalating use of pesticides and other agricultural chemicals. This review examines some of the issues relating to exposure of amphibian populations to these chemicals and places emphasis on mechanisms of toxicity. Several mechanisms are highlighted, including those that may disrupt thyroid activity, retinoid pathways, and sexual differentiation. Special emphasis is also placed on the various interactions that may occur between different agro-chemicals and between chemicals and other environmental factors. We also examine the indirect effects on amphibian populations that occur when their surrounding pond communities are altered by chemicals.
The toxicity of leachate water from acid-sulfate soil to the early embryonic development of the S... more The toxicity of leachate water from acid-sulfate soil to the early embryonic development of the Sydney Rock oyster, Saccostrea commercialis, was assessed. Concentrations of acid-sulfate soil leachate water as low as 3.3% in seawater were found to decrease the normal development of oyster embryos after 48 hr exposure, and this effect could not be attributed to any significant change in pH or salinity. An EC 50 value for the acid-sulfate soil leachate water of 2.5 to 2.9% in seawater was obtained, and the no observed effect concentration was determined at a concentration of 2% in seawater. In tests conducted with aluminum added to seawater, a significant decrease in the percentage of embryos developed to the D-veliger stage occurred at concentrations of 150 µg/liter and greater, with no effects at 100 µg/liter. An EC 50 of 225 µg/liter for the effect of added aluminum on embryo survival was obtained and all embryos showed developmental abnormalities at concentrations of 400 µg/liter and greater. A significant decrease in the embryonic development occurred when the fertilized eggs were incubated in pH-adjusted seawater at pH values р6.75, but no significant effects were found at pH 7.0 or above. Since aluminum was present in high concentrations in the acid-sulfate soil leachate water, it was concluded that aluminum was the main toxicant in the acid-sulfate water that disrupted the oyster embryonic development.
A rapid Chelex resin method is shown to be a valuable speciation screening tool for use in a tier... more 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.
Melita plumulosa is an epibenthic, detritivorous amphipod found in estuaries along the eastern co... more Melita plumulosa is an epibenthic, detritivorous amphipod found in estuaries along the eastern coast of Australia. It has been utilized as a test organism in rapid ten to thirteen days reproduction toxicity tests for sediment quality assessment. The fecundity of females in the toxicity test has been found to be inhibited by exposure of the amphipods to contaminated sediments enriched with zinc and other metals. This study investigated the proposal that interference in vitellogenesis is the cause of reproductive toxicity of metals in crustaceans. Inspection of the ovaries from amphipods on day 6 of the test either from control or Zn/Pb/Cd/Cu-spiked sediment, that were nearing completion of vitellogenesis, showed that the females in all treatments were producing similar numbers of oocytes undergoing secondary vitellogenesis. The distribution of the Zn, Cu and Pb in the oocytes and ventral caeca of females was examined by X-ray fluorescence microscopy. Elemental mapping revealed a dense accumulation of Zn in primary oocytes and a uniform distribution of Zn and Cu in the secondary oocytes in all treatments. Zn and Cu were also observed to be uniformly distributed in the ventral caeca. Pb was not detected in either of these tissues. The apparent normal morphology and the typical number of oocytes undergoing secondary vitellogenesis suggest that vitellogenesis was not being disrupted by Pb displacing Zn in the metal-binding domain of vitellogenin in amphipods exposed to the contaminated sediment during the test. Alternative mechanisms for the reproductive toxicity of amphipods exposed for six days to metalcontaminated sediment are discussed.
The toxicity of the organochlorine pesticide endosulfan to macroinvertebrate assemblages was test... more 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 1.00 microg/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 30.70 microg/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.
Exposures of Limnodynastes tasmaniensis tadpoles to atrazine (0.1, 1, 3 and 30microgL(-1)), metol... more Exposures of Limnodynastes tasmaniensis tadpoles to atrazine (0.1, 1, 3 and 30microgL(-1)), metolachlor (0.1, 1 and 10microgL(-1)) and thiobencarb (90, 180 and 360microgL(-1)) from Gosner stage 28 to 42 under controlled laboratory conditions gave no significant effects on tadpole growth, development and sex ratios. A binary mixture of atrazine and thiobencarb as well as a ternary mixture of all three herbicides also had no significant effects on the developing larvae to show no evidence of interactive toxicity. Abnormal gonad morphology was observed on two occasions; both from 0.1microgL(-1) atrazine treatments with one tadpole observed with testicular ovarian follicles. The low frequencies of abnormal gonadal morphology and testicular ovarian follicles did not indicate a concentration associated response to herbicide exposure. No significantly unbalanced sex ratios were observed to suggest any evidence of chemically induced feminisation. These observations suggest that environmenta...
An artificial neural network (ANN) was employed to model the chromatographic response surface for... more 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 ...
nymphs and one species of caddisfly larvae (Leonard et al., 1999) were less than the highest conc... more nymphs and one species of caddisfly larvae (Leonard et al., 1999) were less than the highest concentrations Endosulfan (6,7,8,9,10,10,-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9measured in river water following storm events methano-2,4,3-benzodioxathiepine-3-oxide) sorption (standardized to 1% total organic carbon and dry weight) was significantly (P Ͻ 0.05) . Changes in taxon densities, which inmore concentrated on the large (Ͼ63 m) particle fraction compared cluded epibenthic species, had weaker correlations to with smaller size fractions (Ͻ5 m and 5-24 m) of bottom sediments total endosulfan concentrations measured in the bottom from the Namoi River, Australia. Following completion of the particle sediment (Leonard et al., 1999). This may have been size fractionation (6 to 12 wk) and a sediment toxicity assessment due to the more precise data obtained by using passive (2 wk), the sediments showed large decreases in concentrations of samplers, although the differences may also have been ␣-endosulfan that coincided with an increase in endosulfan sulfate due to a reduced toxicity of sediment-bound endosulfan.
Integrated Environmental Assessment and Management, 2011
A comparison of environmental risks of pesticides between tropical and nontropical regions has be... more A comparison of environmental risks of pesticides between tropical and nontropical regions has been performed, using data from the literature and modeling outputs based on the physicochemical properties of the compounds. With a few exceptions, the level of risk of exposure for most pesticides in tropical agriculture is similar to that in other climatic regions of the world. Generally, dissipation of pesticides increases under the warm and wet conditions of the tropics, with most of the dissipation occurring through hydrolysis in water and biological degradation in water and soil. High temperatures in the tropics also foster volatilization rates, whereas high precipitation and poor soils tend to increase losses into runoff and, for certain chemicals, affects their leaching behavior. The environmental risk is determined by a balance of soil types, soil organic carbon, pH, and the rates of degradation in the various environmental compartments. Integr Environ Assess Manag 2011;7:577-586. ß 2011 SETAC
Bicarbonate is often a major ionic constituent associated with produced waters from methane gas e... more 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.
An underlying assumption of laboratory-based toxicity tests is that the sensitivity and exposure ... more An underlying assumption of laboratory-based toxicity tests is that the sensitivity and exposure of organisms in the laboratory is comparable to that in the field. We sought to make a comparison between field-based and laboratory-based sediment toxicity tests using a recently developed rapid amphipod reproduction test that encompasses gametogenesis, fertilization, and embryo development before hatching. The test species, Melita plumulosa, is an epibenthic, detritivorous amphipod native to Eastern Australia. Test sediments were sourced from Lake Macquarie, a large saltwater lagoon located 100 km north of Sydney (New South Wales, Australia) that has received heavy-metal pollution over many decades, primarily from a Pb/Zn smelter but also from collieries, coal-fired power stations, and urban areas. This has led to a north-south trace-metal concentration gradient, including Pb, Zn, Cd and Cu, in the sediments of Lake Macquarie. Sediments from these northern bays were demonstrated to reduce amphipod fecundity in laboratory-based tests. For the current study, the amphipod reproduction test has been modified for use in situ. In situ test chambers were deployed at the mouth of Cockle Creek, Lake Macquarie. Sediments that were demonstrated to reduce fecundity of M. plumulosa in the laboratory reproduction test were not similarly toxic when amphipods were exposed to the same sediments in situ. Factors related to the regular tidal renewal of overlying water likely altered exposure profiles in situ, including the provision of additional or alternative nutrition that obviated the need for amphipods to interact with the contaminated sediments, and a washout effect that prevented the accretion of dissolved zinc in the overlying water. Environ. Environ. Toxicol. Chem. 2010;29:256629: -257429: . # 2010
The influence of various diets on the survival, fecundity, and the polyunsaturated fatty acid (PU... more The influence of various diets on the survival, fecundity, and the polyunsaturated fatty acid (PUFA) composition of the benthic estuarine amphipod Melita plumulosa (Zeidler) in laboratory cultures were determined. Apart from a natural silty sediment, six commercial food supplements were examined: an omega-6 PUFA enriched Spirulina-based dry powder, Sera micron; a shrimpbased pellet food; an omega-3 PUFA enriched algal paste, Rotiselco-ALG; an omega-6 PUFA enriched algal dry powder, AlgaMac-ARA (arachidonic acid); flaxseed meal; and an omega-3 PUFA enriched dry powder, Frippak. We have previously established that M. plumulosa cultures perform poorly and eventually decline if provided with silty sediment alone, but will thrive if supplemented with Sera micron. Conversely, if the amphipods are cultured on a nutrient-depleted sand substrate, Sera micron alone does not constitute an adequate feed. The major difference in the fatty acid composition of M. plumulosa cultured on silty sediment compared to amphipods cultured on a sand substrate and both fed Sera micron was an increase in the ratio of omega-3 to omega-6 PUFAs, indicating that the silty sediment provides additional food sources rich in omega-3 PUFAs. Furthermore, amphipods cultured in sand and fed any of the three algal-based foods or the Frippak powder as the sole food source had poor survival rates, although Sera micron maintained the best survival-this was attributed to it containing high amounts of -carotene and terpenoids. Melita plumulosa fed a mixture of Sera micron in conjunction with the omega-3 PUFA enriched Rotiselco-ALG and cultured on a silty substrate were found to have good fecundity with low variability.
The rate of release of three performance reference compounds (PRCs) from passive samplers when de... more 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 chlorpyrifosethyl were 7.3, 20.8, and Ͼ75 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 Ͼ0.005 g/L.
A series of single-species toxicity tests was conducted in the laboratory and in outdoor stream m... more A series of single-species toxicity tests was conducted in the laboratory and in outdoor stream mesocosms. The mayfly nymphs of Atalophlebia spp. (A. av2 and A. av6) were exposed to the organochlorine pesticide endosulfan for either 12- or 48-h periods, with mortality recorded after 96 h. For both exposure periods, the lethal concentration (LC50 and LC 10) values were not significantly different between laboratory and mesocosm single-species tests, suggesting that the absence of natural environmental conditions and biological interactions in laboratory single-species tests did not influence the toxicity of technical endosulfan to Atalophlebia spp. Interpolation of toxicity test data indicates that peak endosulfan concentrations recorded in the rivers during storm events are likely to cause only minimal impact on Atalophlebia spp. populations. This suggests that changes in the abundance of populations observed in the field, if due to total endosulfan alone, are the result of chronic rather than acute exposure.
Laboratory survival tests were conducted with an indigenous infaunal amphipod, Corophium colo, on... more Laboratory survival tests were conducted with an indigenous infaunal amphipod, Corophium colo, on 103 sediment samples from Sydney Harbor (NSW, Australia) and vicinity, containing a wide range of chemicals and concentrations. The present study describes the sensitivity of C. colo to the sediments and compares the results to data for North American amphipods (Rhepoxynius abronius and Ampelisca abdita) previously used to establish and validate sediment-quality guidelines (SQGs). The incidence of toxicity increased with increasing contamination, as indicated by increasing numbers of SQGs exceeded and increasing mean SQG quotients. The incidence of highly toxic results (p Ͻ 0.05 and mean amphipod survival of Ͻ80% that of controls) for highly contaminated samples was approximately half (28-40%) that of a large U.S. database (74%). The incidence of highly toxic responses for samples with intermediate levels of contamination also was lower in the present study (5-13%) compared to the results in large U.S. studies (ϳ30-50%). Corophium colo reburial tests showed greater sensitivity compared to survival tests, with a maximum incidence of statistically significant responses in moderately contaminated sediments of 70%. The present study showed that adult Corophium organisms are suitable for testing lethal responses in highly contaminated sediments (i.e., with mean effects range-median quotients of Ͼ1.5). Reburial results provide additional sensitivity.
This study determined the influence of key water chemistry parameters (pH, alkalinity, dissolved ... more 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 CaCO 3 /L. Increasing bicarbonate alkalinity of synthetic waters (30-125 mg/L as CaCO 3 ) 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.
Two types of solid-phase materials, a styrenedivinylbenzene copolymer sorbent (embedded in a SDB-... more Two types of solid-phase materials, a styrenedivinylbenzene copolymer sorbent (embedded in a SDB-XC Empore disk) and a styrenedivinylbenzene copolymer sorbent modified with sulfonic acid functional groups (embedded in a SDB-RPS Empore disk), were compared as a receiving phase in a passive sampling device for monitoring polar pesticides. The SDB-XC Empore disk was selected for further evaluation, overlayed with either a polysulfone or a polyethersulfone diffusion membrane. The target herbicides included five nonionized herbicides (simazine, atrazine, diuron, clomazone, and metolachlor) and four phenoxy acid herbicides (dicamba, (2,4-dichlorophenoxy)acetic acid [2,4-D], (4-chloro-2-methylphenoxy)acetic acid [MCPA], and triclopyr) with log octanol/water partition coefficient (log K OW ) values of less than three in water. Uptake of these herbicides generally was higher into a device constructed of a SDB-XC Empore disk as a receiving phase covered with a polyethersulfone membrane compared to a similar device covered with a polysulfone membrane. Using the device with a SDB-XC Empore disk covered with a polyethersulfone membrane, linear uptake of simazine, atrazine, diuron, clomazone, and metolachlor was observed for up to 21 d, and daily sampling rates of the herbicides from water in a laboratory flow-through system were determined. The uptake rate of each nonionized herbicide by the Empore disk-based passive sampler was linearly proportional to its concentration in the water, and the sampling rate was independent of the water concentrations over the 21-d period. Uptake of the phenoxy acid herbicides (2,4-D, MCPA, and triclopyr) obeyed first-order kinetics and rapidly reached equilibrium in the passive sampler after approximately 12 d of exposure. The Empore disk-based passive sampler displayed isotropic kinetics, with a release half-life for triclopyr of approximately 6 d.
A laboratory continuous-flow system delivering known aqueous concentrations of pesticides to pass... more 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 ow Ͼ 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 ow Ͻ 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.
Population densities of six dominant macroinvertebrate taxa (mayfly nymphs Jappa kutera, Atalophl... more Population densities of six dominant macroinvertebrate taxa (mayfly nymphs Jappa kutera, Atalophlebia sp., Tasmanocoenis 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 Ͻ 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.
Agricultural landscapes, although often highly altered in nature, provide habitat for many specie... more Agricultural landscapes, although often highly altered in nature, provide habitat for many species of amphibian. However, the persistence and health of amphibian populations are likely to be compromised by the escalating use of pesticides and other agricultural chemicals. This review examines some of the issues relating to exposure of amphibian populations to these chemicals and places emphasis on mechanisms of toxicity. Several mechanisms are highlighted, including those that may disrupt thyroid activity, retinoid pathways, and sexual differentiation. Special emphasis is also placed on the various interactions that may occur between different agro-chemicals and between chemicals and other environmental factors. We also examine the indirect effects on amphibian populations that occur when their surrounding pond communities are altered by chemicals.
The toxicity of leachate water from acid-sulfate soil to the early embryonic development of the S... more The toxicity of leachate water from acid-sulfate soil to the early embryonic development of the Sydney Rock oyster, Saccostrea commercialis, was assessed. Concentrations of acid-sulfate soil leachate water as low as 3.3% in seawater were found to decrease the normal development of oyster embryos after 48 hr exposure, and this effect could not be attributed to any significant change in pH or salinity. An EC 50 value for the acid-sulfate soil leachate water of 2.5 to 2.9% in seawater was obtained, and the no observed effect concentration was determined at a concentration of 2% in seawater. In tests conducted with aluminum added to seawater, a significant decrease in the percentage of embryos developed to the D-veliger stage occurred at concentrations of 150 µg/liter and greater, with no effects at 100 µg/liter. An EC 50 of 225 µg/liter for the effect of added aluminum on embryo survival was obtained and all embryos showed developmental abnormalities at concentrations of 400 µg/liter and greater. A significant decrease in the embryonic development occurred when the fertilized eggs were incubated in pH-adjusted seawater at pH values р6.75, but no significant effects were found at pH 7.0 or above. Since aluminum was present in high concentrations in the acid-sulfate soil leachate water, it was concluded that aluminum was the main toxicant in the acid-sulfate water that disrupted the oyster embryonic development.
A rapid Chelex resin method is shown to be a valuable speciation screening tool for use in a tier... more 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.
Melita plumulosa is an epibenthic, detritivorous amphipod found in estuaries along the eastern co... more Melita plumulosa is an epibenthic, detritivorous amphipod found in estuaries along the eastern coast of Australia. It has been utilized as a test organism in rapid ten to thirteen days reproduction toxicity tests for sediment quality assessment. The fecundity of females in the toxicity test has been found to be inhibited by exposure of the amphipods to contaminated sediments enriched with zinc and other metals. This study investigated the proposal that interference in vitellogenesis is the cause of reproductive toxicity of metals in crustaceans. Inspection of the ovaries from amphipods on day 6 of the test either from control or Zn/Pb/Cd/Cu-spiked sediment, that were nearing completion of vitellogenesis, showed that the females in all treatments were producing similar numbers of oocytes undergoing secondary vitellogenesis. The distribution of the Zn, Cu and Pb in the oocytes and ventral caeca of females was examined by X-ray fluorescence microscopy. Elemental mapping revealed a dense accumulation of Zn in primary oocytes and a uniform distribution of Zn and Cu in the secondary oocytes in all treatments. Zn and Cu were also observed to be uniformly distributed in the ventral caeca. Pb was not detected in either of these tissues. The apparent normal morphology and the typical number of oocytes undergoing secondary vitellogenesis suggest that vitellogenesis was not being disrupted by Pb displacing Zn in the metal-binding domain of vitellogenin in amphipods exposed to the contaminated sediment during the test. Alternative mechanisms for the reproductive toxicity of amphipods exposed for six days to metalcontaminated sediment are discussed.
The toxicity of the organochlorine pesticide endosulfan to macroinvertebrate assemblages was test... more 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 1.00 microg/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 30.70 microg/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.
Uploads
Papers by Ross Hyne