DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Retention mechanisms of citric acid in ternary kaolinite-Fe(III)-citrate acid systems using Fe K-edge EXAFS and L3,2-edge XANES spectroscopy

Abstract

Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L-3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorption and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤ 0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. In conclusion, these findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropicalmore » soils.« less

Authors:
 [1];  [2];  [3];  [2];  [2];  [4];  [5];  [3]
  1. Univ. of Delaware, Newark, DE (United States). Dept. of Plant and Soil Sciences
  2. Univ. of Saskatchewan, Saskatoon (Canada). Canadian Light Source Inc.
  3. Univ. of Delaware, Newark (United States). Delaware Environmental Inst., Dept. of Plant and Soil Sciences
  4. Inst. of Ecology and Environment Paris, Thiverval-Grignon (France). CNRS, IEES, UMR (CNRS-INRA-UPMC-UPEC-IRD)
  5. Univ. of Newcastle, (Australia). Global Centre for Environmental Remediation (GCER); Univ. of South Australia, Mawson Lakes (Australia). Centre for Environmental Risk Assessment and Remediation (CERAR)
Publication Date:
Research Org.:
Univ. of Delaware, Newark, DE (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1282972
Grant/Contract Number:  
AC02-98CH10886
Resource Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 6; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; x-ray-absorption; tetrahedrally coordinated fe(iii); differential orbital covalency; soil solution concentrations; dissolved organic-matter; forest soils; surface complexes; carboxylic-acids; iron; sorption

Citation Formats

Yang, Jianjun, Wang, Jian, Pan, Weinan, Regier, Tom, Hu, Yongfeng, Rumpel, Cornelia, Bolan, Nanthi, and Sparks, Donald. Retention mechanisms of citric acid in ternary kaolinite-Fe(III)-citrate acid systems using Fe K-edge EXAFS and L3,2-edge XANES spectroscopy. United States: N. p., 2016. Web. doi:10.1038/srep26127.
Yang, Jianjun, Wang, Jian, Pan, Weinan, Regier, Tom, Hu, Yongfeng, Rumpel, Cornelia, Bolan, Nanthi, & Sparks, Donald. Retention mechanisms of citric acid in ternary kaolinite-Fe(III)-citrate acid systems using Fe K-edge EXAFS and L3,2-edge XANES spectroscopy. United States. https://doi.org/10.1038/srep26127
Yang, Jianjun, Wang, Jian, Pan, Weinan, Regier, Tom, Hu, Yongfeng, Rumpel, Cornelia, Bolan, Nanthi, and Sparks, Donald. Mon . "Retention mechanisms of citric acid in ternary kaolinite-Fe(III)-citrate acid systems using Fe K-edge EXAFS and L3,2-edge XANES spectroscopy". United States. https://doi.org/10.1038/srep26127. https://www.osti.gov/servlets/purl/1282972.
@article{osti_1282972,
title = {Retention mechanisms of citric acid in ternary kaolinite-Fe(III)-citrate acid systems using Fe K-edge EXAFS and L3,2-edge XANES spectroscopy},
author = {Yang, Jianjun and Wang, Jian and Pan, Weinan and Regier, Tom and Hu, Yongfeng and Rumpel, Cornelia and Bolan, Nanthi and Sparks, Donald},
abstractNote = {Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L-3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorption and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤ 0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. In conclusion, these findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils.},
doi = {10.1038/srep26127},
journal = {Scientific Reports},
number = ,
volume = 6,
place = {United States},
year = {Mon May 23 00:00:00 EDT 2016},
month = {Mon May 23 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 24 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Low molecular weight organic acid adsorption in forest soils: effects on soil solution concentrations and biodegradation rates
journal, August 2003


The carbon we do not see—the impact of low molecular weight compounds on carbon dynamics and respiration in forest soils: a review
journal, January 2005


Influence of sorption on the biological utilization of two simple carbon substrates
journal, December 1998


Organic acid behavior in soils – misconceptions and knowledge gaps
journal, January 2003


Citrate sorption and biodegradation in acid soils with implications for aluminum rhizotoxicity
journal, December 2007


Carbon Pools and Flux of Global Forest Ecosystems
journal, January 1994


Interactive effects of pH and substrate quality on the fungal-to-bacterial ratio and qCO2 of microbial communities in forest soils
journal, September 1998


Variation in pH Optima of Hydrolytic Enzyme Activities in Tropical Rain Forest Soils
journal, August 2010

  • Turner, Benjamin L.
  • Applied and Environmental Microbiology, Vol. 76, Issue 19
  • DOI: 10.1128/AEM.00560-10

Sorption of organic carbon compounds to the fine fraction of surface and subsurface soils
journal, January 2014


Pasture degradation impacts soil phosphorus storage via changes to aggregate-associated soil organic matter in highly weathered tropical soils
journal, January 2014


Development of buffer methods and evaluation of pedotransfer functions to estimate pH buffer capacity of highly weathered soils
journal, January 2013

  • Wong, M. T. F.; Webb, M. J.; Wittwer, K.
  • Soil Use and Management, Vol. 29, Issue 1
  • DOI: 10.1111/sum.12022

Rates of Dissolved Organic Matter Release and Sorption in Forest Soils
journal, January 1998


Functional Characterization of Colloidal Phosphorus Species in the Soil Solution of Sandy Soils
journal, February 2001

  • Hens, Maarten; Merckx, Roel
  • Environmental Science & Technology, Vol. 35, Issue 3
  • DOI: 10.1021/es0013576

Organic complexation of Al and Fe in acidic soil solutions
journal, November 2003

  • Jansen, Boris; Mulder, Jan; Verstraten, Jacobus M.
  • Analytica Chimica Acta, Vol. 498, Issue 1-2
  • DOI: 10.1016/j.aca.2003.08.054

Tree Species Effects on Soil Organic Matter Dynamics: The Role of Soil Cation Composition
journal, July 2007


Formation of Ternary Metal-Oxalate Surface Complexes on α-FeOOH Particles
journal, October 2011

  • Simanova, Anna A.; Loring, John S.; Persson, Per
  • The Journal of Physical Chemistry C, Vol. 115, Issue 43
  • DOI: 10.1021/jp2058707

Influence of mineral characteristics on the retention of low molecular weight organic compounds: A batch sorption–desorption and ATR-FTIR study
journal, October 2014

  • Yeasmin, Sabina; Singh, Balwant; Kookana, Rai S.
  • Journal of Colloid and Interface Science, Vol. 432
  • DOI: 10.1016/j.jcis.2014.06.036

Attenuated total reflectance Fourier-transform infrared spectroscopy of carboxylic acids adsorbed onto mineral surfaces
journal, September 1999


Some Aspects of Clay-Humus Complexation: Effect of Exchangeable Cations and Lattice Charge
journal, January 1991


Characterization of the chemical composition of soil humic acids using Fourier transform ion cyclotron resonance mass spectrometry
journal, March 2015

  • Ikeya, Kosuke; Sleighter, Rachel L.; Hatcher, Patrick G.
  • Geochimica et Cosmochimica Acta, Vol. 153
  • DOI: 10.1016/j.gca.2015.01.002

Selective stabilization of aliphatic organic carbon by iron oxide
journal, June 2015

  • Adhikari, Dinesh; Yang, Yu
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep11214

Organo-mineral associations in temperate soils: Integrating biology, mineralogy, and organic matter chemistry
journal, February 2008

  • Kögel-Knabner, Ingrid; Guggenberger, Georg; Kleber, Markus
  • Journal of Plant Nutrition and Soil Science, Vol. 171, Issue 1
  • DOI: 10.1002/jpln.200700048

X-ray Microspectroscopy and Chemical Reactions in Soil Microsites
journal, January 2011

  • Hesterberg, Dean; Duff, Martine C.; Dixon, Joe B.
  • Journal of Environment Quality, Vol. 40, Issue 3
  • DOI: 10.2134/jeq2010.0140

Characterization of iron in floating surface films of some natural waters using EXAFS
journal, October 2012


Binding of Iron(III) to Organic Soils:  EXAFS Spectroscopy and Chemical Equilibrium Modeling
journal, February 2007

  • Gustafsson, Jon Petter; Persson, Ingmar; Kleja, Dan Berggren
  • Environmental Science & Technology, Vol. 41, Issue 4
  • DOI: 10.1021/es0615730

EXAFS Study on the Reactions between Iron and Fulvic Acid in Acid Aqueous Solutions
journal, April 2008

  • van Schaik, Joris W. J.; Persson, Ingmar; Kleja, Dan Berggren
  • Environmental Science & Technology, Vol. 42, Issue 7
  • DOI: 10.1021/es072092z

Iron speciation in soft-water lakes and soils as determined by EXAFS spectroscopy and geochemical modelling
journal, March 2013

  • Sjöstedt, Carin; Persson, Ingmar; Hesterberg, Dean
  • Geochimica et Cosmochimica Acta, Vol. 105
  • DOI: 10.1016/j.gca.2012.11.035

X-ray absorption spectroscopy study on the effect of hydroxybenzoic acids on the formation and structure of ferrihydrite
journal, September 2011


L-edge X-ray Absorption Spectroscopy of Non-Heme Iron Sites:  Experimental Determination of Differential Orbital Covalency
journal, October 2003

  • Wasinger, Erik C.; de Groot, Frank M. F.; Hedman, Britt
  • Journal of the American Chemical Society, Vol. 125, Issue 42
  • DOI: 10.1021/ja034634s

Direct Observation of Tetrahedrally Coordinated Fe(III) in Ferrihydrite
journal, March 2012

  • Peak, Derek; Regier, Tom
  • Environmental Science & Technology, Vol. 46, Issue 6
  • DOI: 10.1021/es203816x

New opportunities in XAFS investigation in the 1–2 keV region
journal, November 1994


Organic acids in the rhizosphere – a critical review
journal, August 1998


Fate of low molecular weight organic substances in an arable soil: From microbial uptake to utilisation and stabilisation
journal, October 2014


Equilibrium models of aluminium and iron complexation with different organic acids in soil solution
journal, February 2000


Integrated investigations on the adsorption mechanisms of fulvic and humic acids on three clay minerals
journal, July 2012

  • Zhang, Lichao; Luo, Lei; Zhang, Shuzhen
  • Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 406
  • DOI: 10.1016/j.colsurfa.2012.05.003

Effect of citrate on the local Fe coordination in ferrihydrite, arsenate binding, and ternary arsenate complex formation
journal, October 2010

  • Mikutta, Christian; Frommer, Jakob; Voegelin, Andreas
  • Geochimica et Cosmochimica Acta, Vol. 74, Issue 19
  • DOI: 10.1016/j.gca.2010.06.024

Atomic Force Microscopy and Surface Characteristics of Iron Oxides Formed in Citrate Solutions
journal, January 1999


Ferrihydrite: Surface Structure and its Effects on Phase Transformation
journal, January 1994


New insight into the structure of nanocrystalline ferrihydrite: EXAFS evidence for tetrahedrally coordinated iron(III)
journal, May 2011

  • Maillot, Fabien; Morin, Guillaume; Wang, Yuheng
  • Geochimica et Cosmochimica Acta, Vol. 75, Issue 10
  • DOI: 10.1016/j.gca.2011.03.011

Characterization of Iron(III) in Organic Soils Using Extended X-ray Absorption Fine Structure Spectroscopy
journal, August 2008

  • Karlsson, Torbjörn; Persson, Per; Skyllberg, Ulf
  • Environmental Science & Technology, Vol. 42, Issue 15
  • DOI: 10.1021/es800322j

Coordination chemistry and hydrolysis of Fe(III) in a peat humic acid studied by X-ray absorption spectroscopy
journal, January 2010


Structure of aluminum, iron, and other heteroatoms in zeolites by X-ray absorption spectroscopy
journal, October 2014


Ligand and metal X-ray absorption in transition metal complexes
journal, March 2008


Fe L-Edge X-ray Absorption Spectroscopy Determination of Differential Orbital Covalency of Siderophore Model Compounds: Electronic Structure Contributions to High Stability Constants
journal, March 2010

  • Hocking, Rosalie K.; DeBeer George, Serena; Raymond, Kenneth N.
  • Journal of the American Chemical Society, Vol. 132, Issue 11
  • DOI: 10.1021/ja9090098

Response to Comment on “Direct Observation of Tetrahedrally Coordinated Fe(III) in Ferrihydrite”
journal, October 2012

  • Peak, Derek; Regier, Tom Z.
  • Environmental Science & Technology, Vol. 46, Issue 20
  • DOI: 10.1021/es303399u

Five coordination in 3d metal complexes
journal, January 1968


Properties of Fe-Organic Matter Associations via Coprecipitation versus Adsorption
journal, November 2014

  • Chen, Chunmei; Dynes, James J.; Wang, Jian
  • Environmental Science & Technology, Vol. 48, Issue 23
  • DOI: 10.1021/es503669u

Fractionation of Organic Matter Due to Reaction with Ferrihydrite: Coprecipitation versus Adsorption
journal, January 2011

  • Eusterhues, Karin; Rennert, Thilo; Knicker, Heike
  • Environmental Science & Technology, Vol. 45, Issue 2
  • DOI: 10.1021/es1023898

Sorption of dissolved organic carbon in soils: effects of soil sample storage, soil-to-solution ratio, and temperature
journal, February 2001


ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


Speciation and distribution of copper in a mining soil using multiple synchrotron-based bulk and microscopic techniques
journal, October 2013

  • Yang, Jianjun; Liu, Jin; Dynes, James J.
  • Environmental Science and Pollution Research, Vol. 21, Issue 4
  • DOI: 10.1007/s11356-013-2214-8

Soft X-ray Induced Photoreduction of Organic Cu(II) Compounds Probed by X-ray Absorption Near-Edge (XANES) Spectroscopy
journal, October 2011

  • Yang, Jianjun; Regier, Tom; Dynes, James J.
  • Analytical Chemistry, Vol. 83, Issue 20
  • DOI: 10.1021/ac201622g

Influence of mineral characteristics on the retention of low molecular weight organic compounds: A batch sorption–desorption and ATR-FTIR study
journal, October 2014

  • Yeasmin, Sabina; Singh, Balwant; Kookana, Rai S.
  • Journal of Colloid and Interface Science, Vol. 432
  • DOI: 10.1016/j.jcis.2014.06.036

Modeling the adsorption of citric acid onto Muloorina illite and related clay minerals
journal, November 2003

  • Lackovic, Kurt; Johnson, Bruce B.; Angove, Michael J.
  • Journal of Colloid and Interface Science, Vol. 267, Issue 1
  • DOI: 10.1016/s0021-9797(03)00693-3

Soft X-ray Induced Photoreduction of Organic Cu(II) Compounds Probed by X-ray Absorption Near-Edge (XANES) Spectroscopy
journal, October 2011

  • Yang, Jianjun; Regier, Tom; Dynes, James J.
  • Analytical Chemistry, Vol. 83, Issue 20
  • DOI: 10.1021/ac201622g

Functional Characterization of Colloidal Phosphorus Species in the Soil Solution of Sandy Soils
journal, February 2001

  • Hens, Maarten; Merckx, Roel
  • Environmental Science & Technology, Vol. 35, Issue 3
  • DOI: 10.1021/es0013576

Binding of Iron(III) to Organic Soils:  EXAFS Spectroscopy and Chemical Equilibrium Modeling
journal, February 2007

  • Gustafsson, Jon Petter; Persson, Ingmar; Kleja, Dan Berggren
  • Environmental Science & Technology, Vol. 41, Issue 4
  • DOI: 10.1021/es0615730

EXAFS Study on the Reactions between Iron and Fulvic Acid in Acid Aqueous Solutions
journal, April 2008

  • van Schaik, Joris W. J.; Persson, Ingmar; Kleja, Dan Berggren
  • Environmental Science & Technology, Vol. 42, Issue 7
  • DOI: 10.1021/es072092z

Fractionation of Organic Matter Due to Reaction with Ferrihydrite: Coprecipitation versus Adsorption
journal, January 2011

  • Eusterhues, Karin; Rennert, Thilo; Knicker, Heike
  • Environmental Science & Technology, Vol. 45, Issue 2
  • DOI: 10.1021/es1023898

Properties of Fe-Organic Matter Associations via Coprecipitation versus Adsorption
journal, November 2014

  • Chen, Chunmei; Dynes, James J.; Wang, Jian
  • Environmental Science & Technology, Vol. 48, Issue 23
  • DOI: 10.1021/es503669u

Characterization of Iron(III) in Organic Soils Using Extended X-ray Absorption Fine Structure Spectroscopy
journal, August 2008

  • Karlsson, Torbjörn; Persson, Per; Skyllberg, Ulf
  • Environmental Science & Technology, Vol. 42, Issue 15
  • DOI: 10.1021/es800322j

L-edge X-ray Absorption Spectroscopy of Non-Heme Iron Sites:  Experimental Determination of Differential Orbital Covalency
journal, October 2003

  • Wasinger, Erik C.; de Groot, Frank M. F.; Hedman, Britt
  • Journal of the American Chemical Society, Vol. 125, Issue 42
  • DOI: 10.1021/ja034634s

Soil clay–humus complexes. II. Bridging cations and DTA studies
journal, January 2002

  • Ahmed, Nayan; Varadachari, Chandrika; Ghosh, Kunal
  • Soil Research, Vol. 40, Issue 4
  • DOI: 10.1071/sr01046

Chemically and Geographically Distinct Solid-Phase Iron Pools in the Southern Ocean
journal, November 2012

  • von der Heyden, B. P.; Roychoudhury, A. N.; Mtshali, T. N.
  • Science, Vol. 338, Issue 6111
  • DOI: 10.1126/science.1227504

Carbon Pools and Flux of Global Forest Ecosystems
journal, January 1994


Five coordination in 3d metal complexes
journal, January 1968


X-ray Microspectroscopy and Chemical Reactions in Soil Microsites
journal, January 2011

  • Hesterberg, Dean; Duff, Martine C.; Dixon, Joe B.
  • Journal of Environment Quality, Vol. 40, Issue 3
  • DOI: 10.2134/jeq2010.0140

Works referencing / citing this record:

Role of microorganisms in bioleaching of rare earth elements from primary and secondary resources
journal, November 2018

  • Fathollahzadeh, Homayoun; Eksteen, Jacques J.; Kaksonen, Anna H.
  • Applied Microbiology and Biotechnology, Vol. 103, Issue 3
  • DOI: 10.1007/s00253-018-9526-z

Advances in Scanning Transmission X-Ray Microscopy for Elucidating Soil Biogeochemical Processes at the Submicron Scale
journal, November 2017

  • Stuckey, Jason W.; Yang, Jianjun; Wang, Jian
  • Journal of Environmental Quality, Vol. 46, Issue 6
  • DOI: 10.2134/jeq2016.10.0399