Effects of acid mine drainage on dissolved inorganic carbon and stable carbon isotopes in receiving streams

Abstract

Dissolved inorganic carbon (DIC) constitutes a significant fraction of a stream’s carbon budget, yet the role of acid mine drainage (AMD) in DIC dynamics in receiving streams remains poorly understood. The objective of this study was to evaluate spatial and temporal effects of AMD and its chemical evolution on DIC and stable isotope ratio of DIC ( δ 13 C DIC ) in receiving streams. We examined spatial and seasonal variations in physical and chemical parameters, DIC, and δ 13 C DIC in a stream receiving AMD. In addition, we mixed different proportions of AMD and tap water in a laboratory experiment to investigate AMD dilution and variable bicarbonate concentrations to simulate downstream and seasonal hydrologic conditions in the stream. Field and laboratory samples showed variable pH, overall decreases in Fe 2+ , alkalinity, and DIC, and variable increase in δ 13 C DIC . We attribute the decrease in alkalinity, DIC loss, and enrichment of 13 C of DIC in stream water to protons produced from oxidation of Fe 2+ followed by Fe 3+ hydrolysis and precipitation of Fe(OH) 3(s) . The extent of DIC decrease and 13 C enrichment of DIC was related to the amount of HCO 3 - dehydrated by protons. The laboratory experiment showed that lower 13 C enrichment occurred in unmixed AMD (2.7‰) when the amount of protons produced was in excess of HCO 3 - or in tap water (3.2‰) where no protons were produced from Fe 3+ hydrolysis for HCO 3 - dehydration. The 13 C enrichment increased and was highest for AMD-tap water mixture (8.0‰) where Fe 2+ was proportional to HCO 3 - concentration. Thus, the variable downstream and seasonal 13 C enrichment in stream water was due in part to: (1) variations in the volume of stream water initially mixed with AMD and (2) to HCO 3 - input from groundwater and seepage in the downstream direction. Protons produced during the chemical evolution of AMD caused seasonal losses of 50 to >98% of stream water DIC. This loss of DIC in AMD impacted streams may have implications for CO 2 transfer to the atmosphere and watershed DIC export.