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Title: Bio-reduction of ferrihydrite-montmorillonite-organic matter complexes: Effect of montmorillonite and fate of organic matter

Abstract

Organic matter (OM) is often associated with Fe (hydr)oxides such as ferrihydrite (Fh) in soils and sediments, forming binary Fh-OM complexes. Microbial reduction of Fh results in destabilization of the complexes and mineral/OM transformation. However, little is known about the role of clay minerals in such processes, despite their common co-existence with Fh and OM in natural environments. Here Fh-OM complexes were synthesized in the presence of montmorillonite (SWy-2), forming ternary Fh-(SWy-2)-OM complexes. A metal-reducing bacterium Geobacter sulfurreducens was used to reduce Fh in the complexes under circumneutral pH and anoxic conditions with or without H2 as extra electron donor. Various spectroscopy and mass spectrometry methods were used to monitor the progress of Fh bio-reduction and mineral/OM transformation. Results showed that G. sulfurreducens utilized mineral-bound OM as electron donor and/or carbon source to couple with Fh reduction. Relative to Fh-OM complex, Addition of SWy-2 to Fh-OM complex enhanced the bio-reduction extent of Fh by increasing the proportion of bioavailable OM that was weakly bound to SWy-2. However, its effect on the bio-reduction rate was variable. SWy-2 initially decreased the rate, because it spatially separated OM (electron donor) from Fh (electron acceptor). During later incubation, SWy-2 increased the reduction rate bymore » sorbing biogenic Fe2+ that would otherwise passivate the Fh and cell surfaces. Bio-reduction transformed mineral-bound OM to microbial products (e.g. necromass, extracellular polymeric substances), but organic compounds with aromatic structures, carboxyl groups and large molecular weight were more resistant to desorption and oxidation. The persistence of these compounds against bio-reduction induced transformation is likely due to their stronger binding with minerals and/or lower nominal oxidation states of carbon relative to other compounds. Our results provide new insights into the role of clay minerals in regulating biogeochemical cycling of solid-phase Fe and transformation of mineral-associated OM in anoxic soil environments.« less

Authors:
 [1];  [2];  [1]; ORCiD logo [3];  [4]; ORCiD logo [4];  [2];  [5]; ORCiD logo [1];  [6]
  1. China Univ. of Geosciences, Beijing (China)
  2. China Univ. of Geosciences, Wuhan (China); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  4. China Univ. of Petroleum, Beijing (China)
  5. China Univ. of Geosciences, Beijing (China); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  6. China Univ. of Geosciences, Beijing (China); Miami Univ., Oxford, OH (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER); National Natural Science Foundation; National Key Research and Development Program of China
OSTI Identifier:
1616566
Report Number(s):
PNNL-SA-152385
Journal ID: ISSN 0016-7037
Grant/Contract Number:  
AC05-76RL01830; NSFC-41572328; 2018YFC0310603
Resource Type:
Accepted Manuscript
Journal Name:
Geochimica et Cosmochimica Acta
Additional Journal Information:
Journal Volume: 276; Journal Issue: C; Journal ID: ISSN 0016-7037
Publisher:
Elsevier; The Geochemical Society; The Meteoritical Society
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; 58 GEOSCIENCES; Ferrihydrite; Montmorillonite; Organic matter; Bio-reduction; Desorption; Transformation

Citation Formats

Zeng, Qiang, Huang, Liuqin, Ma, Jingyu, Zhu, Zihua, He, Chen, Shi, Quan, Liu, Wen, Wang, Xi, Xia, Qingyin, and Dong, Hailiang. Bio-reduction of ferrihydrite-montmorillonite-organic matter complexes: Effect of montmorillonite and fate of organic matter. United States: N. p., 2020. Web. doi:10.1016/j.gca.2020.03.011.
Zeng, Qiang, Huang, Liuqin, Ma, Jingyu, Zhu, Zihua, He, Chen, Shi, Quan, Liu, Wen, Wang, Xi, Xia, Qingyin, & Dong, Hailiang. Bio-reduction of ferrihydrite-montmorillonite-organic matter complexes: Effect of montmorillonite and fate of organic matter. United States. https://doi.org/10.1016/j.gca.2020.03.011
Zeng, Qiang, Huang, Liuqin, Ma, Jingyu, Zhu, Zihua, He, Chen, Shi, Quan, Liu, Wen, Wang, Xi, Xia, Qingyin, and Dong, Hailiang. Wed . "Bio-reduction of ferrihydrite-montmorillonite-organic matter complexes: Effect of montmorillonite and fate of organic matter". United States. https://doi.org/10.1016/j.gca.2020.03.011. https://www.osti.gov/servlets/purl/1616566.
@article{osti_1616566,
title = {Bio-reduction of ferrihydrite-montmorillonite-organic matter complexes: Effect of montmorillonite and fate of organic matter},
author = {Zeng, Qiang and Huang, Liuqin and Ma, Jingyu and Zhu, Zihua and He, Chen and Shi, Quan and Liu, Wen and Wang, Xi and Xia, Qingyin and Dong, Hailiang},
abstractNote = {Organic matter (OM) is often associated with Fe (hydr)oxides such as ferrihydrite (Fh) in soils and sediments, forming binary Fh-OM complexes. Microbial reduction of Fh results in destabilization of the complexes and mineral/OM transformation. However, little is known about the role of clay minerals in such processes, despite their common co-existence with Fh and OM in natural environments. Here Fh-OM complexes were synthesized in the presence of montmorillonite (SWy-2), forming ternary Fh-(SWy-2)-OM complexes. A metal-reducing bacterium Geobacter sulfurreducens was used to reduce Fh in the complexes under circumneutral pH and anoxic conditions with or without H2 as extra electron donor. Various spectroscopy and mass spectrometry methods were used to monitor the progress of Fh bio-reduction and mineral/OM transformation. Results showed that G. sulfurreducens utilized mineral-bound OM as electron donor and/or carbon source to couple with Fh reduction. Relative to Fh-OM complex, Addition of SWy-2 to Fh-OM complex enhanced the bio-reduction extent of Fh by increasing the proportion of bioavailable OM that was weakly bound to SWy-2. However, its effect on the bio-reduction rate was variable. SWy-2 initially decreased the rate, because it spatially separated OM (electron donor) from Fh (electron acceptor). During later incubation, SWy-2 increased the reduction rate by sorbing biogenic Fe2+ that would otherwise passivate the Fh and cell surfaces. Bio-reduction transformed mineral-bound OM to microbial products (e.g. necromass, extracellular polymeric substances), but organic compounds with aromatic structures, carboxyl groups and large molecular weight were more resistant to desorption and oxidation. The persistence of these compounds against bio-reduction induced transformation is likely due to their stronger binding with minerals and/or lower nominal oxidation states of carbon relative to other compounds. Our results provide new insights into the role of clay minerals in regulating biogeochemical cycling of solid-phase Fe and transformation of mineral-associated OM in anoxic soil environments.},
doi = {10.1016/j.gca.2020.03.011},
journal = {Geochimica et Cosmochimica Acta},
number = C,
volume = 276,
place = {United States},
year = {Wed Mar 18 00:00:00 EDT 2020},
month = {Wed Mar 18 00:00:00 EDT 2020}
}

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