The objective of this work was to investigate the reaction stoichiometry, kinetics, and mechanism for Cr(VI) reduction by hydrogen sulfide in the aqueous phase. Batch experiments with excess [Cr(VI)] over [H2S]T indicated that the molar amount of sulfide required for the reduction of 1 M Cr(VI) was 1.5, suggesting the following stoichiometry: 2CrO4(2-) + 3H2S + 4H+-->2Cr(OH)3(s) + 3S(s) + 2H2O. Further study with transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS) confirmed that chromium hydroxide and elemental sulfur were the stable products. The kinetics of Cr(VI) reduction by hydrogen sulfide was measured under various initial concentrations of Cr(VI) and sulfide as well as pH values controlled by HEPES, phosphate, and borate buffers. Results showed that the overall reaction was second-order, i.e., first-order with respect to Cr(VI) and first-order to sulfide. The reaction rate increased as pH was decreased, and the pH dependence correlated well with the fraction of fully protonated sulfide (H2S) in the pH range of 6.5-10. The nature of buffers did not influence the reaction rate significantly in the homogeneous system. The reaction kinetics could be interpreted by a three-step mechanism: formation of an inner-sphere chromate-sulfide intermediate complex ((H2O4CrVIS)2-), intramolecular electron transfer to form Cr(IV) species, and subsequent fast reactions leading to Cr(III).

Twenty sediment samples were collected at depths ranging from 5 to 100 feet beneath a chromate-contaminated plating-waste site and analyzed for Cr(VI), total chromium, and related constituents. Three of the samples were selected for treatment with dilute hydrogen sulfide (H2S) gas to evaluate this approach as a possible in-situ remediation technique. Gas treatment was performed in soil-packed columns using 100 ppm (μL L-1) H2S mixtures, and treatment progress was assessed by monitoring the breakthrough of H2S. Evaluation of treatment efficacy included (1) water-leaching of the treated and untreated columns for 10 days, (2) repetitive extraction of treated and untreated subsamples by water, 0.01 M phosphate (pH 7) or 6 M HCl solutions, and (3) Cr K-edge X-ray absorption near-edge structure (XANES) spectroscopy of treated and untreated subsamples. Results of the water-leaching studies showed that the H2S treatment decreased Cr(VI) levels in the column effluent by 90% to nearly 100%. Repetitive extractions by water and phosphate solutions echoed these results, and the extraction by HCl released only 35−40% as much Cr in the treated as in the untreated samples. Analysis by XANES spectroscopy showed that a substantial portion of the Cr in the samples remained as Cr(VI) after treatment, even though it was not available to the water and phosphate extracting solutions. These results indicate that the residual Cr(VI) was sequestered in unreacted grain interiors under impermeable coatings formed during H2S treatment. However, this fraction is immobile and thus unavailable to the environment.

To rigorously assess treatment technologies and establish regulatory framework for chromatecontaminated site remediation, it is useful to know the exact chromium speciation in soil matrices. In an earlier study, Thornton, E. C., & Amonette, J. E. (1999). Hydrogen sulfide gas treatment of Cr(VI)-contaminated sediment samples from a plating-waste disposal siteimplications for in-situ remediation. Environmental Science & Technology, 33, 4096-4101, reported that some chromate in the bulk particles was not accessible to gaseous reductants or solution-phase extractants, based on XANES studies. We hypothesized that part of this non-extractable chromate may reside in the structure of minerals such as calcium carbonate. To test this hypothesis, a number of calcium carbonate precipitates were prepared in the presence of various concentrations of chromate during the precipitation, which could coprecipitate chromate, or by adding chromate after the precipitation was completed. Hydrochloric acid was used to dissolve calcium carbonate and therefore extract the coprecipitated and surface attached chromate. The results showed that the coprecipitated chromate was non-extractable by hot alkaline solution or phosphate buffer, but could be solubilized by HCl in proportional to the amount of calcium carbonate dissolved. The X-ray diffraction experiments revealed that the coprecipitation of chromate with calcium carbonate had an influence on its crystal structure: The higher the chromate concentration, the greater the ratio of vaterite to calcite.