Processes affecting δ34S and δ18O values of dissolved sulfate in alluvium along the Canadian River, central Oklahoma, USA

The delta S-34 and delta O-18 values for dissolved sulfate in groundwater are commonly used in aquifer studies to identify sulfate reservoirs and describe biogeochemical processes. The utility of these data, however, often is compromised by mixing of sulfate sources within reservoirs and isotope fractionation during sulfur redox cycling. Our study shows that, after all potential sulfate sources are identified and isotopically characterized, the delta S-34(SO4) and delta O-18(SO4) values differentiate processes such as sulfate-source mixing, sulfide oxidation, barite dissolution, and organosulfur decomposition. During bacterial reduction of sulfate, the values reflect kinetic sulfur isotope fractionation and exchange of oxygen isotopes between sulfate and water. Detailed analysis of the chemistry (Cl and SO4 concentrations) and isotopic composition (delta H-2(H2O) and delta O-18(H2O)) of groundwater in an alluvial aquifer in Central Oklahoma, USA allowed the identification of five distinct end members that supply water to the aquifer (regional groundwater flowing into the study area, river water, leachate from a closed landfill that operated within the site, rain, and surface runoff). The delta S-34(SO4) and delta O-18(SO4) values in each end member differentiated three sources of sulfate: sulfate dissolved from Early to Late Permian rocks within the drainage basin (delta S-34(SO4) = 8-12 parts per thousand and delta O-18(SO4) = 10 parts per thousand), iron sulfides oxidized by molecular oxygen during low water-table levels (delta S-34(SO4) = -16 parts per thousand and delta O-18(SO4) = 10 parts per thousand), and organosulfur compounds (predominately ester sulfates) from decomposition of vegetation on the surface and from landfill trash buried in the alluvium (delta S-34(SO4) = 8 parts per thousand and delta O-18(SO4) = 6 parts per thousand). During bacterial reduction of these sulfate sources, similar isotope fractionation processes are recorded in the parallel trends of increasing delta S-34(SO4) and delta O-18(SO4) values. When extensive reduction occurs, the kinetic sulfur isotope fractionation (estimated by epsilon(H2S-SO4) = -23 parts per thousand) results in the steady increase of delta S-34(SO4) values to greater than 70 parts per thousand. Equilibrium isotope fractionation during exchange of sulfate oxygen and water oxygen, a process not commonly observed in field-based studies, is documented in delta O-18(SO4) values asymptotically approaching 21 parts per thousand, the value predicted for conditions at the study site (epsilon(SO4-H2O) = 27 parts per thousand). These results show that recognition of all potential sulfate sources is a critical first step to resolving complexities in delta S-34(SO4) and delta O-18(SO4) data. The approach taken in this study can be used in other aquifer systems where the identification of multiple sulfate sources and sulfur redox cycling is important to understanding natural processes and anthropogenic influences. Published by Elsevier B.V.