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The protective effect of reactive sulfide against AgNO3 toxicity to Daphnia magna neonates was studied. Acute (48-h) toxicity tests were performed in the absence (<5 nM) and presence of low (approximately 25 nM) and high (approximately 250 nM) concentrations of zinc sulfide clusters under oxic conditions. In both the presence and the absence of sulfide, lower mean lethal concentration (LC50) values were observed when measured as opposed to nominal silver concentrations were used in calculations. This reflected the fact that measured total silver concentrations were lower than nominal concentrations due to losses of silver from solution observed during the experiment. High concentration (approximately 250 nM) of sulfide completely protected against toxicity up to the highest silver concentration tested (2 microg/L [19 nM]) with measured silver data. In the presence of environmentally realistic levels of sulfide (approximately 25 nM) in receiving waters, acute silver toxicity was reduced by about 5.5-fold. However, when filtered (0.45 microm) silver concentrations alone were considered, toxicity (48-h LC50) was similar in the absence (0.22 microg/L) and presence (0.28 microg/L) of sulfide. The difference between measured total and filtered silver was attributed to chemisorption of the metal sulfide onto the membrane filter and provides evidence that the toxic fraction of silver is that which is unbound to sulfide. Accumulation of silver was greater in daphnids exposed to silver in the presence of sulfide than in its absence, even though a toxic effect was not observed under these conditions. In this case, silver appears to be incorporated by daphnids rather than merely adsorbed on the surface. Our results point out the need to incorporate sulfide into the acute biotic ligand model and to assess its potentially large role in preventing chronic toxicity.

The bioaccumulation of mercury in the food webs incorporating the major piscivorous fish species of Lake Murray, Papua New Guinea, has been characterised. Methylmercury concentrations increased with trophic level and the proportion of total mercury present as methylmercury increased from <1% in plants to 94% in piscivorous fish. Methylmercury bioaccumulation factors (BAFs) were similar to those found in temperate environments, with a typical increase of 1 log unit between planktivore and piscivore trophic levels. The greatest bioaccumulation of methylmercury occurred between seston and the water column (log BAF of 5.36). The bioaccumulation of mercury to levels of regulatory concern by the lake's piscivores was attributable to the biomagnification power of the plankton-based food chain comprising four trophic levels (phytoplankton, zooplankton, planktivore, piscivore) rather than any elevated concentrations of mercury in waters or sediments. The methylmercury concentrations of individual piscivores were positively correlated with both trophic position, as indicated by δ15N measurements, and fish size. Stable-isotope measurements were used to identify fish species where dietary changes occurring with age significantly augmented age-related bioaccumulation of mercury.

Experiments were designed to assess the potential protective effect of the presence of sulfide against the acute (48-h) toxicity of silver(I) to Daphnia magna. Tests were conducted in borosilicate glass beakers (250 ml) in moderately hard synthetic water. Toxicity solutions were replaced after 24 h by static renewal method. This paper describes the chemical system, and the acute toxicity results are presented in a companion paper. Sulfide was below detection limit (<5 nM) in controls with no sulfide added. Sulfide, added as zinc sulfide clusters at approximately 35- or approximately 350-nM concentration, dropped in concentration to approximately 25 and 250 nM, respectively, over the 24-h period of measurements. Silver also decreased in concentration during the experiment (up to 59%), and the rate of loss was greater in the absence of sulfide compared with the presence of sulfide. A filtration experiment indicated a 1:1 binding ratio of silver to sulfide and a conditional stability constant for the Ag(I)-zinc sulfide complex of log K' = 8.9. The losses of sulfide and silver during the experiments highlighted the need for regular monitoring of the important chemical components of the system, even during short (48-h) toxicity tests.

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