Copper Contamination Affects the Biogeochemical Cycling of Nitrogen in Freshwater Sediment Mesocosms

Trace elements can have a wide variety of effects on microbial populations and their function in the aquatic environment. However, specific impacts on chemical and biological processes are often difficult to unravel, due to the wide variety of chemical species involved and interactions between different elemental cycles. A replicated mesocosm experiment was used to test the effect of increasing copper concentrations, i.e., from 6 mg kg(-1) to 30 and 120 mg kg(-1), on nitrogen cycling in a freshwater sediment under laboratory conditions. Nitrous oxide emissions from the treated sediments were measured over three consecutive 24 h periods. This was followed by measurements of iron, manganese, copper and mineral nitrogen species (nitrate and ammonium) mobilisation in the sediments using the diffusive gradients in thin films (DGT) and diffusive equilibria in thin films (DET) techniques and sequential extractions. Increasing copper concentrations are shown to have resulted in significantly reduced nitrate formation near the sediment-water interface and increased nitrous oxide emissions from the sediment overall. The concomitant mobilisation and sequestration of iron with ammonium in the sediment with the highest Cu treatment strongly imply links between the biogeochemical cycles of the two elements. Modest Cu contamination was shown to affect the nitrogen cycle in the tested freshwater sediment, which suggests that even relatively small loads of the metal in fresh watercourses can exert an influence on nutrient loads and greenhouse gas emissions from these environments.