Copper toxicity and organic matter: Resiliency of watersheds in the Duluth Complex, Minnesota, USA

We estimated copper (Cu) toxicity in surface water with high dissolved organic matter (DOM) for unmined mineralized watersheds of the Duluth Complex using the Biotic Ligand Model (BLM), which evaluates the effect of DOM, cation competition for biologic binding sites, and metal speciation. A sediment-based BLM was used to estimate stream-sediment toxicity; this approach factors in the cumulative effects of multiple metals, incorporation of metals into less bioavailable sulfides, and complexation of metals with organic carbon.

For surface water, the formation of Cu-DOM complexes significantly reduces the amount of Cu available to aquatic organisms. The protective effects of cations, such as calcium (Ca) and magnesium (Mg), competing with Cu to complex with the biotic ligand is likely not as important as DOM in water with high DOM and low hardness. Standard hardness-based water quality criteria (WQC) are probably inadequate for describing Cu toxicity in such waters and a BLM approach may yield more accurate results. Nevertheless, assumptions about relative proportions of humic acid (HA) and fulvic acid (FA) in DOM significantly influence BLM results; the higher the HA fraction, the higher calculated resiliency of the water to Cu toxicity. Another important factor is seasonal variation in water chemistry, with greater resiliency to Cu toxicity during low flow compared to high flow.

Based on generally low total organic carbon and sulfur content, and equivalent metal ratios from total and weak partial extractions, much of the total metal concentration in clastic streambedsediments may be in bioavailable forms, sorbed on clays or hydroxide phases. However, organicrich fine-grained sediment in the numerous wetlands may sequester significant amount of metals, limiting their bioavailability. A high proportion of organic matter in waters and some sediments will play a key role in the resiliency of these watersheds to potential additional metal loads associated with future mining operations.