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Title: Environmental Mercury Chemistry – In Silico

Abstract

Mercury (Hg) is a global environmental contaminant. Major anthropogenic sources of Hg emission include gold mining and the burning of fossil fuels. Once deposited in aquatic environments, Hg can undergo redox reactions, form complexes with ligands, and adsorb onto particles. It can also be methylated by microorganisms. Mercury, especially its methylated form methylmercury, can be taken up by organisms, where it bioaccumulates and biomagnifies in the food chain, leading to detrimental effects on ecosystem and human health. In support of the recently enforced Minamata Convention on Mercury, a legally binding international convention aimed at reducing the anthropogenic emission of—and human exposure to—Hg, its global biogeochemical cycle must be understood. Thus, a detailed understanding of the molecular-level interactions of Hg is crucial.The ongoing rapid development of hardware and methods has brought computational chemistry to a point that it can usefully inform environmental science. This is particularly true for Hg, which is difficult to handle experimentally due to its ultratrace concentrations in the environment and its toxicity. The current account provides a synopsis of the application of computational chemistry to filling several major knowledge gaps in environmental Hg chemistry that have not been adequately addressed experimentally.Environmental Hg chemistry requires defining the factorsmore » that determine the relative affinities of different ligands for Hg species, as they are critical for understanding its speciation, transformation and bioaccumulation in the environment. Formation constants and the nature of bonding have been determined computationally for environmentally relevant Hg(II) complexes such as chlorides, hydroxides, sulfides and selenides, in various physical phases. Quantum chemistry has been used to determine the driving forces behind the speciation of Hg with hydrochalcogenide and halide ligands. Of particular importance is the detailed characterization of solvation effects. Indeed, the aqueous phase reverses trends in affinities found computationally in the gas phase. Computation has also been used to investigate complexes of methylmercury with (seleno)amino acids, providing a molecular-level understanding of the toxicological antagonism between Hg and selenium (Se). Furthermore, evidence is emerging that ice surfaces play an important role in Hg transport and transformation in polar and alpine regions. Therefore, the diffusion of Hg and its ions through an idealized ice surface has been characterized.Microorganisms are major players in environmental mercury cycling. Some methylate inorganic Hg species, whereas others demethylate methylmercury. Quantum chemistry has been used to investigate catalytic mechanisms of enzymatic Hg methylation and demethylation. The complex interplay between the myriad chemical reactions and transport properties both in and outside microbial cells determines net biogeochemical cycling. In conclusion, prospects for scaling up molecular work to obtain a mechanistic understanding of Hg cycling with comprehensive multiscale biogeochemical modeling are also discussed.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [5]; ORCiD logo [2]; ORCiD logo [5]
  1. Univ. of Manitoba, Winnipeg, MB (Canada); Penn State Harrisburg, Middletown, PA (United States)
  2. Univ. of Tennessee/Oak Ridge National Lab. Center for Molecular Biophysics, Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  3. Univ. of Manitoba, Winnipeg, MB (Canada); Al-Balqa Applied Univ., Al-Salt (Jordan)
  4. Univ. of Tennessee, Knoxville, TN (United States)
  5. Univ. of Manitoba, Winnipeg, MB (Canada)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1504023
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Accounts of Chemical Research
Additional Journal Information:
Journal Volume: 52; Journal Issue: 2; Journal ID: ISSN 0001-4842
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Asaduzzaman, Abu, Riccardi, Demian, Afaneh, Akef T., Cooper, Sarah J., Smith, Jeremy C., Wang, Feiyue, Parks, Jerry M., and Schreckenbach, Georg. Environmental Mercury Chemistry – In Silico. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.accounts.8b00454.
Asaduzzaman, Abu, Riccardi, Demian, Afaneh, Akef T., Cooper, Sarah J., Smith, Jeremy C., Wang, Feiyue, Parks, Jerry M., & Schreckenbach, Georg. Environmental Mercury Chemistry – In Silico. United States. https://doi.org/10.1021/acs.accounts.8b00454
Asaduzzaman, Abu, Riccardi, Demian, Afaneh, Akef T., Cooper, Sarah J., Smith, Jeremy C., Wang, Feiyue, Parks, Jerry M., and Schreckenbach, Georg. Mon . "Environmental Mercury Chemistry – In Silico". United States. https://doi.org/10.1021/acs.accounts.8b00454. https://www.osti.gov/servlets/purl/1504023.
@article{osti_1504023,
title = {Environmental Mercury Chemistry – In Silico},
author = {Asaduzzaman, Abu and Riccardi, Demian and Afaneh, Akef T. and Cooper, Sarah J. and Smith, Jeremy C. and Wang, Feiyue and Parks, Jerry M. and Schreckenbach, Georg},
abstractNote = {Mercury (Hg) is a global environmental contaminant. Major anthropogenic sources of Hg emission include gold mining and the burning of fossil fuels. Once deposited in aquatic environments, Hg can undergo redox reactions, form complexes with ligands, and adsorb onto particles. It can also be methylated by microorganisms. Mercury, especially its methylated form methylmercury, can be taken up by organisms, where it bioaccumulates and biomagnifies in the food chain, leading to detrimental effects on ecosystem and human health. In support of the recently enforced Minamata Convention on Mercury, a legally binding international convention aimed at reducing the anthropogenic emission of—and human exposure to—Hg, its global biogeochemical cycle must be understood. Thus, a detailed understanding of the molecular-level interactions of Hg is crucial.The ongoing rapid development of hardware and methods has brought computational chemistry to a point that it can usefully inform environmental science. This is particularly true for Hg, which is difficult to handle experimentally due to its ultratrace concentrations in the environment and its toxicity. The current account provides a synopsis of the application of computational chemistry to filling several major knowledge gaps in environmental Hg chemistry that have not been adequately addressed experimentally.Environmental Hg chemistry requires defining the factors that determine the relative affinities of different ligands for Hg species, as they are critical for understanding its speciation, transformation and bioaccumulation in the environment. Formation constants and the nature of bonding have been determined computationally for environmentally relevant Hg(II) complexes such as chlorides, hydroxides, sulfides and selenides, in various physical phases. Quantum chemistry has been used to determine the driving forces behind the speciation of Hg with hydrochalcogenide and halide ligands. Of particular importance is the detailed characterization of solvation effects. Indeed, the aqueous phase reverses trends in affinities found computationally in the gas phase. Computation has also been used to investigate complexes of methylmercury with (seleno)amino acids, providing a molecular-level understanding of the toxicological antagonism between Hg and selenium (Se). Furthermore, evidence is emerging that ice surfaces play an important role in Hg transport and transformation in polar and alpine regions. Therefore, the diffusion of Hg and its ions through an idealized ice surface has been characterized.Microorganisms are major players in environmental mercury cycling. Some methylate inorganic Hg species, whereas others demethylate methylmercury. Quantum chemistry has been used to investigate catalytic mechanisms of enzymatic Hg methylation and demethylation. The complex interplay between the myriad chemical reactions and transport properties both in and outside microbial cells determines net biogeochemical cycling. In conclusion, prospects for scaling up molecular work to obtain a mechanistic understanding of Hg cycling with comprehensive multiscale biogeochemical modeling are also discussed.},
doi = {10.1021/acs.accounts.8b00454},
journal = {Accounts of Chemical Research},
number = 2,
volume = 52,
place = {United States},
year = {2019},
month = {1}
}

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    Works referencing / citing this record:

    Endophytic bacteria mitigate mercury toxicity to host plants
    journal, September 2019


    Hg–C bond protonolysis by a functional model of bacterial enzyme organomercurial lyase MerB
    journal, January 2020

    • Karri, Ramesh; Das, Ranajit; Rai, Rakesh Kumar
    • Chemical Communications
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