Concentration-discharge relations and transient metal loads reveal spatiotemporal variability in solute-generation mechanisms in a mine-affected watershed

Concentration-discharge (CQ) relations are commonly used to understand geochemical and hydrologic controls on the generation of solutes in watersheds. Despite the widespread application of CQ relations, this technique has been infrequently applied to acid mine drainage (AMD) sites, but the CQ framework may allow mechanistic understanding of remedial outcomes such as impoundment of water within underground mines. Results of CQ analyses and changes in metal loads in an AMD affected watershed in Colorado, USA indicate that dissolved loads increased at many individual locations following water impoundment within mine workings. Although increased loads were observed at most individual locations, these increases were offset by a large decrease in loading from the largest mine. A loading analysis that included data from an instream monitoring location showed a statistically significant decrease in Fe and Zn after bulkhead emplacement, indicating a net positive effect of bulkheads. Streams generally displayed dilution CQ patterns whereas mines and springs showed either flushing or chemostatic patterns prior to bulkheading, which transitioned to chemostatic patterns following bulkheading, indicating a transition from dynamic to equilibrium geochemical processes. Saturation indices for sulfide and secondary minerals indicated that mines and springs were near equilibrium for phases including schwertmannite, fluorite, and gypsum. Saturation indices vary through time for mines suggesting progressive leaching of sulfide minerals as the mass of available minerals in the mine workings decreases. Together, these diverse analyses provide an integrated understanding of the variability in solute generating processes in this watershed and may inform remediation plans for similarly affected sites by indicating the nature of mineralogic controls on water quality.