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.

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.

Abstract-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 (NovemberMarch). 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.

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.

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.