Fleur Pablo

Influence of water chemistry on the acute toxicity of copper and zinc to the cladoceran Ceriodaphnia cf dubia.

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.

Optimisation of the separation of herbicides by linear gradient high performance liquid chromatography utilising artificial neural networks.

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.

A Comparison of Copper Speciation Measurements with the Toxic Responses of Three Sensitive Freshwater Organisms

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 (Ceriodaph- nia 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 (r 2 = 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 concentra- tions 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.

Comparison of the fate and toxicity of chlorpyrifos—Laboratory versus a coastal mesocosm system

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 48h LC(50) values 0.07-0.10 microg 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.

Short-term exposure to aqueous endosulfan affects macroinvertebrate assemblages

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.