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

Abstract

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

Authors:
;
Publication Date:
Research Org.:
Univ. of Illinois at Urbana-Champaign, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1619397
Alternate Identifier(s):
OSTI ID: 1288268
Grant/Contract Number:  
AC02-76SF00515; AC09-08SR22470
Resource Type:
Published Article
Journal Name:
Geochemical Transactions
Additional Journal Information:
Journal Name: Geochemical Transactions Journal Volume: 17 Journal Issue: 1; Journal ID: ISSN 1467-4866
Publisher:
Springer Science + Business Media
Country of Publication:
United Kingdom
Language:
English
Subject:
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

Citation Formats

Meena, Amanda H., and Arai, Yuji. Effects of common groundwater ions on chromate removal by magnetite: importance of chromate adsorption. United Kingdom: N. p., 2016. Web. doi:10.1186/s12932-016-0033-9.
Meena, Amanda H., & Arai, Yuji. Effects of common groundwater ions on chromate removal by magnetite: importance of chromate adsorption. United Kingdom. https://doi.org/10.1186/s12932-016-0033-9
Meena, Amanda H., and Arai, Yuji. Fri . "Effects of common groundwater ions on chromate removal by magnetite: importance of chromate adsorption". United Kingdom. https://doi.org/10.1186/s12932-016-0033-9.
@article{osti_1619397,
title = {Effects of common groundwater ions on chromate removal by magnetite: importance of chromate adsorption},
author = {Meena, Amanda H. and Arai, Yuji},
abstractNote = {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 more 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.},
doi = {10.1186/s12932-016-0033-9},
journal = {Geochemical Transactions},
number = 1,
volume = 17,
place = {United Kingdom},
year = {Fri Apr 29 00:00:00 EDT 2016},
month = {Fri Apr 29 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
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https://doi.org/10.1186/s12932-016-0033-9

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Works referenced in this record:

Sorption of cesium, barium and europium on magnetite
journal, December 1998


An in Situ ATR-FTIR Investigation of Sulfate Bonding Mechanisms on Goethite
journal, October 1999

  • Peak, Derek; Ford, Robert G.; Sparks, Donald L.
  • Journal of Colloid and Interface Science, Vol. 218, Issue 1
  • DOI: 10.1006/jcis.1999.6405

Sorption of Cr(III) and Cr(VI) to high and low pressure synthetic nano-magnetite (Fe3O4)particles
journal, October 2014

  • Parsons, Jason G.; Hernandez, Jeffrey; Gonzalez, Christina M.
  • Chemical Engineering Journal, Vol. 254
  • DOI: 10.1016/j.cej.2014.05.112

Characterization and surface reactivity of natural and synthetic magnetites
journal, June 2013


Cr(VI) Reduction and Immobilization by Magnetite under Alkaline pH Conditions:  The Role of Passivation
journal, June 2005

  • He, Y. Thomas; Traina, Samuel J.
  • Environmental Science & Technology, Vol. 39, Issue 12
  • DOI: 10.1021/es0483692

The pH-dependent surface charging and points of zero charge
journal, January 2011


Surface complexation models: An evaluation of model parameter estimation using FITEQL and oxide mineral titration data
journal, March 1991


Arsenate and Chromate Retention Mechanisms on Goethite. 2. Kinetic Evaluation Using a Pressure-Jump Relaxation Technique
journal, February 1997

  • Grossl, Paul R.; Eick, Matthew; Sparks, Donald L.
  • Environmental Science & Technology, Vol. 31, Issue 2
  • DOI: 10.1021/es950654l

Biotechnological Treatment of Sulfate-Rich Wastewaters
journal, January 1998

  • Lens, P. N. L.; Visser, A.; Janssen, A. J. H.
  • Critical Reviews in Environmental Science and Technology, Vol. 28, Issue 1
  • DOI: 10.1080/10643389891254160

Systematics of the spinel structure type
journal, January 1979

  • Hill, Roderick J.; Craig, James R.; Gibbs, G. V.
  • Physics and Chemistry of Minerals, Vol. 4, Issue 4
  • DOI: 10.1007/BF00307535

Chromium(III) hydrolysis constants and solubility of chromium(III) hydroxide
journal, February 1987

  • Rai, Dhanpat; Sass, Bruce M.; Moore, Dean A.
  • Inorganic Chemistry, Vol. 26, Issue 3
  • DOI: 10.1021/ic00250a002

Arsenic and chromium removal by mixed magnetite–maghemite nanoparticles and the effect of phosphate on removal
journal, November 2010


Solubility of amorphous chromium(III)-iron(III) hydroxide solid solutions
journal, July 1987


Kinetics and Mechanisms of Sulfate Adsorption/Desorption on Goethite Using Pressure-Jump Relaxation
journal, September 1990


Underassessed phosphorus fixation mechanisms in soil sand fraction
journal, January 2013


Activated carbons and low cost adsorbents for remediation of tri- and hexavalent chromium from water
journal, September 2006


Removal of chromium (VI) from water streams: a thermodynamic study
journal, November 2007


Reduction of aqueous transition metal species on the surfaces of Fe(II) -containing oxides
journal, October 1996


Chromium Diffusion and Reduction in Soil Aggregates
journal, August 2001

  • Tokunaga, Tetsu K.; Wan, Jiamin; Firestone, Mary K.
  • Environmental Science & Technology, Vol. 35, Issue 15
  • DOI: 10.1021/es010523m

X-ray absorption spectroscopic study of the sorption of Cr(III) at the oxide-water interface
journal, February 1992


Spectroscopic study of the reaction of aqueous Cr(VI) with Fe3O4 (111) surfaces
journal, December 2000


Spectroscopic investigation of magnetite surface for the reduction of hexavalent chromium
journal, August 2007


Arsenate and Chromate Retention Mechanisms on Goethite. 1. Surface Structure
journal, February 1997

  • Fendorf, Scott; Eick, Matthew J.; Grossl, Paul
  • Environmental Science & Technology, Vol. 31, Issue 2
  • DOI: 10.1021/es950653t

Behavior of Chromium in Soils: III. Oxidation
journal, January 1979


Compilation of PZC and IEP of sparingly soluble metal oxides and hydroxides from literature
journal, November 2009


Potentiometric Titrations as a Tool for Surface Charge Determination
journal, January 2012

  • Lützenkirchen, Johannes; Preočanin, Tajana; Kovačević, Davor
  • Croatica Chemica Acta, Vol. 85, Issue 4
  • DOI: 10.5562/cca2062

X-ray absorption and photoemission study of the adsorption of aqueous Cr(VI) on single crystal hematite and magnetite surfaces
journal, April 1999


Aging Effects in the Electrokinetics of Colloidal Iron Oxides
journal, January 2002

  • Plaza, R. C.; Arias, J. L.; Espín, M.
  • Journal of Colloid and Interface Science, Vol. 245, Issue 1
  • DOI: 10.1006/jcis.2001.7964

Metal Oxide Surfaces and Their Interactions with Aqueous Solutions and Microbial Organisms
journal, January 1999

  • Brown, Gordon E.; Henrich, Victor E.; Casey, William H.
  • Chemical Reviews, Vol. 99, Issue 1
  • DOI: 10.1021/cr980011z

Interfacial properties of zirconium dioxide and magnetite in water
journal, February 1983

  • Regazzoni, Alberto E.; Blesa, Miguel A.; Maroto, Alberto J. G.
  • Journal of Colloid and Interface Science, Vol. 91, Issue 2
  • DOI: 10.1016/0021-9797(83)90370-3

X-ray absorption spectroscopic study of the sorption of Cr(III) at the oxide-water interface
journal, February 1992


Direct XAFS evidence for heterogeneous redox reaction at the aqueous chromium/magnetite interface
journal, February 1996

  • Peterson, Maria L.; Brown, Gordon E.; Parks, George A.
  • Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 107
  • DOI: 10.1016/0927-7757(95)03345-9

Differential redox and sorption of Cr (III/VI) on natural silicate and oxide minerals: EXAFS and XANES results
journal, August 1997


Vibrational Spectroscopy Study of Selenate and Sulfate Adsorption Mechanisms on Fe and Al (Hydr)oxide Surfaces
journal, September 2000

  • Wijnja, Hotze; Schulthess, Cristian P.
  • Journal of Colloid and Interface Science, Vol. 229, Issue 1
  • DOI: 10.1006/jcis.2000.6960

Works referencing / citing this record:

Structure and Properties of Nanosized Composites Based on Fe3O4 and Humic Acids
journal, January 2018

  • Kokorin, A. I.; Kulyabko, L. S.; Degtyarev, E. N.
  • Russian Journal of Physical Chemistry B, Vol. 12, Issue 1
  • DOI: 10.1134/s1990793118010207