Influence of contact duration on sediment-associated copper fractionation and bioavailability
Introduction
Copper formulations are applied to aquatic systems for algal control in situations where nuisance algal species have disrupted water uses. The applied copper subsequently partitions to the sediments (Haughey et al., 2000; Mastin et al., 2002; Murray-Gulde et al., 2002). Due to its affinity to bind to particles, the copper that partitions to sediments after an application or treatment is rendered less bioavailable after a relatively short period of time (McIntosh, 1975; Button et al., 1977; Huggett et al., 1999; Murray-Gulde et al., 2005). Accumulation of applied copper in sediments is a residual concern to reservoir managers due to potential bioavailability to non-target species such as benthic invertebrates and fish (Miller et al., 1997). Both the amount of copper accumulated in sediments and the form or ligands with which the copper is associated can influence bioavailability to biota and potential for dissolution. The distribution or fractionation of sediment-associated metals, such as copper, among various sediment fractions regulates both mobility and bioavailability (Ankley et al., 1993). If the binding capacity of the sediment for copper is exceeded or the copper is weakly bound, adverse effects on benthic biota might be expected. With repeated use of copper-containing algaecides, the effects on benthic biota may be anticipated to become more acute if the applied copper is not strongly bound in sediment or the sediment-binding capacity is exceeded. Comparing changes in copper fractionation and distributions over time, often referred to as aging, with synoptic toxicity data could further elucidate temporal changes in copper bioavailability in contaminated sediments.
Recent research has illustrated that various sediment components can bind copper in reservoirs and render the copper less bioavailable (Huggett et al., 1999; Deaver and Rodgers, 1996; Suedel et al., 1996). The fraction of copper in sediments that is bioavailable is related to the physical and chemical characteristics and mineral constituents of the sediments (Deaver and Rodgers, 1996; Chapman et al., 1998; Simpson et al., 2004). Attributes frequently cited as influencing the bioavailability of copper in sediments include organic matter (OM) content and type (Besser et al., 2003; Milani et al., 2003), organic carbon (Mahony et al., 1996), acid-volatile sulfides (Allen et al., 1993), pH (Burton, 1991), particle size distribution (Hoss et al., 1997) and cation exchange capacity (CEC) (Chapman et al., 1998). Emerging notions are that the composition of sediments can vary spatially at a relatively small scale as well as temporally (Suedel and Rodgers, 1991) and that multiple attributes control the bioavailability of copper in sediments (Ankley et al., 1993).
Several studies suggest distributions of contaminants, such as copper, among operationally defined sediment fractions may be influenced by the duration of contact between copper and sediment (Han et al., 2001; Huggett et al., 2001). Han et al. (2001) used a sequential extraction procedure to measure accumulation and fractionation of copper in sediments of aquaculture ponds following application of copper algaecides. In that study, sequential extraction results indicated that 31.6% of the recently applied copper was associated with carbonate phases and 31.1% was associated with oxidizable sediment fractions. The same study also found that up to 70% of the extracted copper in sediments was associated with reducible and oxidizable phases in ponds which had not received copper applications. Huggett et al. (2001) found that carbonate phases accounted for up to 70% of copper applied to aquaculture ponds and suggested the potential for transition of some of the applied copper to alternate sediment fractions (reducible and oxidizable) for long-term binding. These results suggest that copper has the potential to redistribute in sediments over time and copper bound to oxidizable phases was relatively stable under the conditions studied. To further our understanding of transfers and transformations of copper in sediments, information regarding the relative binding strengths and the influence of contact duration may be useful (Ianni et al., 2001; Kim et al., 2001).
The objectives of this research were: (1) to measure distributions of amended copper over time in three reservoir sediments with divergent characteristics using sequential extraction, (2) to estimate partition coefficients for copper in the three reservoir sediments, (3) to measure differences in bioavailability of amended copper over time in three reservoir sediment samples with divergent characteristics using responses of Hyalella azteca, and (4) to discern relationships between measured distributions of the applied copper as indicated by sequential extractions and responses of H. azteca to sediment exposures.
Section snippets
Sediment collection and characterization
Three sediments with divergent characteristics (Table 1) were collected from Lay Lake and Lake Jordan, Alabama. Each of the field-collected sediments (identified as Sediments A, B, and C) was transferred into separate 10-L plastic containers, and mixed thoroughly to promote homogeneity (Suedel et al., 1996; Deaver and Rodgers, 1996). Sediments A and B were collected from sites receiving periodic copper-based algaecide applications for over a decade. Sediment C was collected from a designated
Characteristics and distributions of copper in reservoir sediments
The characteristics of Sediments A, B, and C differed with regards to particle size distribution and OM content (Table 1). The particle size distribution for Sediment A was approximately 2% sand, 48% silt, and 50% clay. Sediment B was approximately 60% sand, 33% silt, and 7% clay. The particle size distribution of Sediment C was intermediate relative to those of Sediments A and B, with 32% sand, 44% silt, and 24% clay. OM content was lowest in Sediment A (7%). Sediment B had the highest OM
Distributions of copper in sediments
In the current study, copper had a tendency to redistribute from the exchangeable and carbonate fractions to the reducible and oxidizable fractions over the 60 d period following amendments. This was in contrast to relatively even distributions of copper between the exchangeable, carbonate, and oxidizable fractions after 2 d contact duration.
Studies have reported copper associated with most sediment fractions depending upon prior conditions and the specific situation. Han et al. (2001) and
Conclusions
Results of this study indicate that duration-of-contact between recently applied copper and sediments along with overlying water and sediment characteristics can greatly influence copper partitioning in sediments and the bioavailability of the applied copper. Since binding characteristics and bioavailability depend on the form of copper in sediments, changes in sediment copper fractionation and responses of organisms exposed to those sediments would indicate the transfers and transformations of
Acknowledgments
Funding sources: This research was funded in part by Alabama Power Company and Applied Biochemists, Inc. All research involving experimental animals was conducted in accordance with national and institutional guidelines for animal welfare.
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