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Title: Effects of common groundwater ions on chromate removal by magnetite: Importance of chromate adsorption

Reductive precipitation of hexavalent chromium (Cr(VI)) with magnetite is a well-known Cr(VI) remediation method to improve water quality. The rapid (< a few hr) reduction of soluble Cr(VI) to insoluble Cr(III) species by Fe(II) in magnetite has been the primary focus of the Cr(VI) removal process in the past. However, the contribution of simultaneous Cr(VI) adsorption processes in aged magnetite has been largely ignored, leaving uncertainties in evaluating the application of in situ Cr remediation technologies for aqueous systems. In this study, effects of common groundwater ions (i.e., nitrate and sulfate) on Cr(VI) sorption to magnetite were investigated using batch geochemical experiments in conjunction with X-ray absorption spectroscopy. As a result, in both nitrate and sulfate electrolytes, batch sorption experiments showed that Cr(VI) sorption decreases with increasing pH from 4 to 8. In this pH range, Cr(VI) sorption decreased with increasing ionic strength of sulfate from 0.01 to 0.1 M whereas nitrate concentrations did not alter the Cr(VI) sorption behavior. This indicates the background electrolyte specific Cr(VI) sorption process in magnetite. Under the same ionic strength, Cr(VI) removal in sulfate containing solutions was greater than that in nitrate solutions. This is because the oxidation of Fe(II) by nitrate is moremore » thermodynamically favorable than by sulfate, leaving less reduction capacity of magnetite to reduce Cr(VI) in the nitrate media. X-ray absorption spectroscopy analysis supports the macroscopic evidence that more than 75 % of total Cr on the magnetite surfaces was adsorbed Cr(VI) species after 48 h. In conclusion, this experimental geochemical study showed that the adsorption process of Cr(VI) anions was as important as the reductive precipitation of Cr(III) in describing the removal of Cr(VI) by magnetite, and these interfacial adsorption processes could be impacted by common groundwater ions like sulfate and nitrate. The results of this study highlight new information about the large quantity of adsorbed Cr(VI) surface complexes at the magnetite-water interface. It has implications for predicting the long-term stability of Cr at the magnetite-water interface.« less
 [1] ;  [2]
  1. Clemson Univ., Clemson, SC (United States). School of Agricultural, Forest and Environmental Sciences
  2. Univ. of Illinois, Urbana, IL (United States). Dept. of Natural Resources and Environmental Sciences
Publication Date:
OSTI Identifier:
Grant/Contract Number:
AC09-08SR22470; AC02-76SF00515
Accepted Manuscript
Journal Name:
Geochemical Transactions
Additional Journal Information:
Journal Volume: 17; Journal Issue: 1; Journal ID: ISSN 1467-4866
American Chemical Society, Geochemistry Div.
Research Org:
Univ. of Illinois at Urbana-Champaign, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
54 ENVIRONMENTAL SCIENCES; chromate; Cr; groundwater ions; magnetite; adsorption; surface speciation; reduction; sulfate; nitrate; X-ray absorption spectroscopy; x-ray-absorption; pressure-jump relaxation; oxide water interface; retention mechanisms; hexavalent chromium; cr(vi) reduction; aqueous cr(vi); zero charge; surface