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Title: Effects of citrate on hexavalent chromium reduction by structural Fe(II) in nontronite

Abstract

Previous studies have shown that organic ligands could influence Cr(VI) reduction by aqueous Fe 2+ and pyrite. In this study, the effects of citrate on Cr(VI) reduction by structural Fe(II) in nontronite (NAu-2) were investigated at pH 6. Our results showed that the presence of citrate decreased the rate but increased the amount of Cr(VI) reduction. The decreased rate was likely due to competitive sorption of citrate and anionic dichromate (Cr 2O 7–) to NAu-2 surface sites, because sorption of dichromate appeared to be the first step for subsequent Cr(VI) reduction. The increased amount of Cr(VI) reduction was likely because citrate served as an additional electron donor to reduce Cr(VI) through ligand-metal electron transfer in the presence of soluble Fe 3+, which was possibly derived from dissolution of reduced NAu-2. Soluble Cr(III)-citrate complex was a possible form of reduced Cr(VI) when citrate was present. Without citrate, nanometer-sized Cr 2O 3 particles were the product of Cr(VI) reduction. In conclusion, our study highlights the importance of citrate on Cr(VI) reduction and immobilization when iron-rich smectite is applied to treat Cr(VI) contaminant in organic carbon rich environments.

Authors:
 [1];  [2];  [1];  [3];  [1];  [1]
  1. China Univ. of Geosciences, Beijing (China)
  2. China Univ. of Geosciences, Beijing (China); Miami Univ., Oxford, OH (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1395357
Grant/Contract Number:
AC05-76RL01830; 41630103
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Hazardous Materials
Additional Journal Information:
Journal Volume: 343; Journal Issue: C; Journal ID: ISSN 0304-3894
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 54 ENVIRONMENTAL SCIENCES; Citrate; Cr(III)-citrate complex; Cr2O3; Cr(VI) reduction; Nontronite

Citation Formats

Liu, Xiaolei, Dong, Hailiang, Yang, Xuewei, Kovarik, Libor, Chen, Yu, and Zeng, Qiang. Effects of citrate on hexavalent chromium reduction by structural Fe(II) in nontronite. United States: N. p., 2017. Web. doi:10.1016/J.JHAZMAT.2017.09.038.
Liu, Xiaolei, Dong, Hailiang, Yang, Xuewei, Kovarik, Libor, Chen, Yu, & Zeng, Qiang. Effects of citrate on hexavalent chromium reduction by structural Fe(II) in nontronite. United States. doi:10.1016/J.JHAZMAT.2017.09.038.
Liu, Xiaolei, Dong, Hailiang, Yang, Xuewei, Kovarik, Libor, Chen, Yu, and Zeng, Qiang. 2017. "Effects of citrate on hexavalent chromium reduction by structural Fe(II) in nontronite". United States. doi:10.1016/J.JHAZMAT.2017.09.038.
@article{osti_1395357,
title = {Effects of citrate on hexavalent chromium reduction by structural Fe(II) in nontronite},
author = {Liu, Xiaolei and Dong, Hailiang and Yang, Xuewei and Kovarik, Libor and Chen, Yu and Zeng, Qiang},
abstractNote = {Previous studies have shown that organic ligands could influence Cr(VI) reduction by aqueous Fe2+ and pyrite. In this study, the effects of citrate on Cr(VI) reduction by structural Fe(II) in nontronite (NAu-2) were investigated at pH 6. Our results showed that the presence of citrate decreased the rate but increased the amount of Cr(VI) reduction. The decreased rate was likely due to competitive sorption of citrate and anionic dichromate (Cr2O7–) to NAu-2 surface sites, because sorption of dichromate appeared to be the first step for subsequent Cr(VI) reduction. The increased amount of Cr(VI) reduction was likely because citrate served as an additional electron donor to reduce Cr(VI) through ligand-metal electron transfer in the presence of soluble Fe3+, which was possibly derived from dissolution of reduced NAu-2. Soluble Cr(III)-citrate complex was a possible form of reduced Cr(VI) when citrate was present. Without citrate, nanometer-sized Cr2O3 particles were the product of Cr(VI) reduction. In conclusion, our study highlights the importance of citrate on Cr(VI) reduction and immobilization when iron-rich smectite is applied to treat Cr(VI) contaminant in organic carbon rich environments.},
doi = {10.1016/J.JHAZMAT.2017.09.038},
journal = {Journal of Hazardous Materials},
number = C,
volume = 343,
place = {United States},
year = 2017,
month = 9
}

Journal Article:
Free Publicly Available Full Text
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  • Iron-bearing clay minerals and organic matter are two important components in natural environments that influence hexavalent chromium (Cr(VI)) reduction. Previous studies have shown that organic ligands could influence Cr(VI) reduction by aqueous Fe2+ and pyrite. However, the effects of organic ligands on Cr(VI) reduction by structural Fe(II) in clays are not well understood. In this study, the effects of citrate on Cr(VI) reduction by nontronite (NAu-2) were investigated under near neutral pH condition (pH=6). Our results showed that the presence of citrate decreased the rate but increased the amount of Cr(VI) reduction by structural Fe(II) in NAu-2. The decreased reactionmore » rate was likely due to competitive sorption of citrate and polyanionic dichromate (Cr2O7- ), because sorption of dichromate appeared to be the first step for subsequent Cr(VI) reduction. The increased amount of Cr(VI) reduction in the presence of citrate was likely because citrate provided additional reducing power through ligand-metal electron transfer in the presence of soluble Fe 3+ derived from dissolution of reduced NAu-2. Soluble Cr(III)-citrate complex was the possible form of reduced chromium when citrate was present. In contrast, nanometer-sized Cr2O3 particles were the product of Cr(VI) reduction by reduced NAu-2 without citrate. Our study highlights the importance of organic ligands on Cr(VI) reduction and immobilization when iron-bearing clay minerals are applied to treat Cr(VI) contaminant in organic matter rich environments.« less
  • The reduction of structural Fe in smectite may be mediated either abiotically by reaction with chemical reducing agents or biotically by reaction with various bacterial species. The effects of abiotic reduction on clay surface chemistry are much better known than the effects of biotic reduction, and differences between them are still in need of investigation. The purpose of the present study was to compare the effects of dithionite (abiotic) and bacteria (biotic) reduction of structural Fe in nontronite on the clay structure as observed by variable-temperature Mössbauer spectroscopy. Biotic reduction was accomplished by incubating Na-saturated Garfield nontronite (sample API 33a)more » with« less
  • Desulfovibrio vulgaris Hildenborough is a well-studiedsulfate reducer that can reduce heavy metals and radionuclides [e.g.,Cr(VI) and U(VI)]. Cultures grown in a defined medium had a lag period ofapproximately 30 h when exposed to 0.05 mM Cr(VI). Substrate analysesrevealed that although Cr(VI) was reduced within the first 5 h, growthwas not observed for an additional 20 h. The growth lag could beexplained by a decline in cell viability; however, during this time smallamounts of lactate were still utilized without sulfate reduction oracetate formation. Approximately 40 h after Cr exposure (0.05 mM),sulfate reduction occurred concurrently with the accumulation of acetate.Similar amounts ofmore » hydrogen were produced by Cr-exposed cells compared tocontrol cells, and lactate was not converted to glycogen duringnon-growth conditions. D. vulgaris cells treated with a reducing agentand then exposed to Cr(VI) still experienced a growth lag, but theaddition of ascorbate at the time of Cr(VI) addition prevented the lagperiod. In addition, cells grown on pyruvate displayed more tolerance toCr(VI) compared to lactate-grown cells. These results indicated that D.vulgaris utilized lactate during Cr(VI) exposure without the reduction ofsulfate or production of acetate, and that ascorbate and pyruvate couldprotect D. vulgaris cells from Cr(VI)/Cr(III) toxicity.« less
  • In situ technetium-99 (99Tc) immobilization by Fe(II) associated with clay minerals has been studied and is a potential cost-effective method for Tc remediation at the United States Department of Energy (DOE) sites. Fe redox cycling are common in sedimentary environments, however their effect on Tc reduction and immobilization has not yet been investigated. The objective of this project was therefore to study how multiple cycles of reduction-reoxidation of Fe-rich clay mineral, nontronite, affected its reactivity toward Tc (VII) reduction. Iron-rich nontronite NAu-2 was used as a model clay mineral. NAu-2 suspension was first bioreduced by Shewanella putrefaciens CN32, which consequentlymore » was re-oxidized by air. Three cycles of reduction-oxidation were conducted and bioreduced NAu-2 samples from all three cycles were collected and used for Tc(VII) reduction experiments. Each redox cycle resulted in a small fraction of dissolution of small size and/or poorly crystalline NAu-2. The released Fe(II) from the dissolution was likely adsorbed onto NAu-2 surface/edge sites with a high reactivity. Upon exposure to O2, this reactive Fe(II) fraction was oxidized more rapidly than structural Fe(II) and may have accounted for a two-step reoxidation kinetics of NAu-2 associated Fe(II): rapid oxidation over first few hours followed by slow oxidation. Progressive increase of this reactive fraction of Fe(II), from increased dissolution, accounted for the successively higher rate of bioreduction and reoxidation with increased redox cycles. The same Fe redistribution accounted for two-step Tc(VII) reduction kinetics as well. Rapid Tc(VII) reduction in the first few hours may be attributed to a small fraction of highly reactive Fe(II) at the NAu-2 surface/edge sites, and more steady Tc(VII) reduction over longer time may be carried out by structural Fe(II). Similar to the increased rates of Fe(III) reduction and Fe(II) oxidation, the Tc(VII) reduction rate also increased with redox cycles and could be explained by progressive increase of the reactive Fe(II) on NAu-2 surface/edges. These results suggest that iron-rich clay minerals undergo important changes after redox cycles, but eventually reach a steady state with continued reactivity toward heavy metals.« less