This study examines the effect on aquatic copper toxicity of the chemical fractionation of fulvic acid (FA) that results from its association with iron and aluminum oxyhydroxide precipitates. Fractionated and unfractionated FAs obtained from streamwater and suspended sediment were utilized in acute Cu toxicity tests on Ceriodaphnia dubia. Toxicity test results with equal FA concentrations (6 mg FA/L) show that the fractionated dissolved FA was 3 times less effective at reducing Cu toxicity (EC50 13 ± 0.6 μg Cu/L) than were the unfractionated dissolved FAs (EC50 39 ± 0.4 and 41 ± 1.2 μg Cu/L). The fractionation is a consequence of preferential sorption of molecules having strong metal-binding (more aromatic) moieties to precipitating Fe- and Al-rich oxyhydroxides, causing the remaining dissolved FA to be depleted in these functional groups. As a result, there is more bioavailable dissolved Cu in the water and hence greater potential for Cu toxicity to aquatic organisms. In predicting Cu toxicity, biotic ligand models (BLMs) take into account dissolved organic carbon (DOC) concentration; however, unless DOC characteristics are accounted for, model predictions can underestimate acute Cu toxicity for water containing fractionated dissolved FA. This may have implications for water-quality criteria in systems containing Fe- and Al-rich sediment, and in mined and mineralized areas in particular. Optical measurements, such as specific ultraviolet absorbance at 254 nm (SUVA254), show promise for use as spectral indicators of DOC chemical fractionation and inferred increased Cu toxicity.
A series of toxicity tests were conducted to investigate the role of chronological age on zinc tolerance in juvenile brown trout (Salmo trutta). Four different incubation temperatures were used to control the maturation of the juveniles before zinc exposures. These 96-h exposures used flow-through conditions and four chronological ages of fish with weights ranging from 0.148 to 1.432 g. Time-to-death (TTD) data were collected throughout the exposure along with the final mortality. The results indicate that chronological age does not play a predictable role in zinc tolerance for juvenile brown trout. However, a relationship between zinc tolerance and fish size was observed in all chronological age populations, which prompted us to conduct additional exploratory data analysis to quantify how much of an effect size had during this stage of development. The smallest fish (0.148-0.423 g) were shown to be less sensitive than the largest fish (0.639-1.432 g) with LC50 values of 868 and 354 µg Zn/L, respectively. The Kaplan-Meier product estimation method was used to determine survival functions from the TTD data and supports the LC50 results with a greater median TTD for smaller fish than larger juvenile fish. These results indicate that fish size or a related characteristic may be a significant determinant of susceptibility and should be considered in acute zinc toxicity tests with specific attention paid to the expected exposure scenario in the field.
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