Nickel Isotope Fractionation As an Indicator of Ni Sulfide Precipitation Associated with Microbially Mediated Sulfate Reduction.

Microbially mediated sulfate reduction is a promising cost-effective and sustainable process utilized in permeable reactive barriers (PRB) and constructed wetlands to treat mine wastewater. Laboratory batch experiments were performed to evaluate nickel (Ni) isotope fractionation associated with precipitation of Ni-sulfides in the presence of the sulfate-reducing bacterium (SRB) Desulfovibrio desulfuricansT (DSM-642). Precipitates were collected anaerobically and characterized by synchrotron powder X-ray diffraction (PXRD), scanning electron microscopy combined with energy-dispersive X-ray spectroscopy (SEM-EDS), and transmission electron microscopy (TEM). Solid-phase analyses showed that the precipitates associated with bacteria attached to the serum bottle walls were characterized by enhanced size and crystallinity. Lighter Ni isotopes were preferentially concentrated in the solid phase, whereas the solution was enriched in heavier Ni isotopes compared to the input solution. This fractionation pattern was consistent with closed-system equilibrium isotope fractionation, yielding a fractionation factor of Δ60Nisolid-aq = -1.99‰. The Ni isotope fractionation measured in this study indicates multiple Ni reaction mechanisms occurring in the complex SRB-Ni system. The results from this study offer insights into Ni isotope fractionation during interaction with SRB and provide a foundation for the characterization and development of Ni stable isotopes as tracers in environmental applications.

Mechanisms of Ni removal from contaminated groundwater by calcite using X-ray absorption spectroscopy and Ni isotope measurements.

A flow-through cell (FTC) experiment was conducted to identify mechanisms of Ni removal by calcite through study of changes in Ni speciation and Ni isotope signature during the treatment of simulated Ni-contaminated groundwater. Synthetic Ni-contaminated groundwater was pumped through a FTC packed with crushed natural calcite. Effluent samples were collected to determine concentrations of anions, cations, and for Ni isotope-ratio measurement. X-ray absorption spectroscopy (XAS) was performed on chosen spots of the solid phase along the FTC length. Isotope data indicated multiple mechanisms affected Ni removal in the FTC system. Ni adsorption to and coprecipitation with calcite dominated the early part of the experiment yielding a fractionation factor of ε = -0.5 ‰. Subsequently, Ni precipitation as a Ni-hydroxide phase became the major process controlling Ni removal, resulting in a fractionation factor ε = -0.4 ‰. XAS analysis confirmed the presence of both Ni(OH)2 and (Ni, Ca)CO3 types of Ni local structural environments. Results from this study highlight the potential of Ni isotopes as auxiliary tools to determine the processes involved in Ni attenuation from the environment. The characterization of mechanisms involved in Ni removal from solution is necessary to evaluate potential impacts to the environment and to develop effective remediation strategies.