Mercury in Sediments

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Mercury (Hg) is released into the environment typically in the inorganic form. Industrial and natural emissions of gaseous elemental mercury, Hg(0), can travel long distances in the atmosphere before being oxidized and deposited on land and in water as inorganic Hg(II). Direct exposure to Hg(II) and Hg(0) can be a human health risk at heavily contaminated sites. However, the organic form of Hg, methylmercury (MeHg), is a neurotoxin that can bioaccumulate and is the form of Hg that poses the greatest human and ecological health risk. As a chemical element, Hg cannot be destroyed, so the goal of Hg-remediation is immobilization and prevention of food web bioaccumulation.

Related Article(s):

Contributor(s): Dr. Grace Schwartz

Key Resource(s):

  • Challenges and opportunities for managing aquatic mercury pollution in altered landscapes[1]
  • The assessment and remediation of mercury contaminated sites: A review of current approaches[2]
  • Bioaccumulation and Biomagnification of Mercury through Food Webs[3]

Introduction

Figure 1. Conceptual model of mercury speciation in the environment[4]

Mercury (Hg) is released into the environment typically in the inorganic form. Natural emissions of Hg(0) come mainly from volcanoes and the ocean. Anthropogenic emissions are mainly from artisanal and small-scale gold mining, coal combustion, and various industrial processes that use Hg ( see the UN Global mercury assessment). Industrial and natural emissions of gaseous elemental mercury, Hg(0), can travel long distances in the atmosphere before being oxidized and deposited on land and in water as inorganic Hg(II). The long range transport and atmospheric deposition of Hg results in widespread low-level Hg contamination of soils at concentrations of 0.01 to 0.3 mg/kg[2].

Hg-contaminated sites are most commonly contaminated with Hg(II) from industrial discharge and have soil concentrations in the range of 100s to 1000s of mg/kg[2]. Direct exposure to Hg(II) and Hg(0) can be a human health risk at heavily contaminated sites. However, the organic form of Hg, methylmercury (MeHg or CH3Hg+) is typically the greater concern. MeHg is a neurotoxin that is particularly harmful to developing fetuses and young children. Direct contamination of the environment with MeHg is not common, but has occurred, most notably in Minamata Bay, Japan (see also Minamata disease). More commonly, MeHg is formed in the environment from Hg(II) in oxygen-limited conditions in a processes mediated by anaerobic microorganisms. Because MeHg biomagnifies in the aquatic food web, MeHg concentrations in fish can be elevated in areas that have relatively low levels of Hg contamination. The MeHg production depends heavily on site geochemistry, and high total Hg sediment concentrations do not always correlate with MeHg production potential.

Biogeochemistry/Mobility of Hg in soils

In the environment, Hg mobility is largely controlled by chelation with various ligands or adsorption to particles[1]. Hg(II) is most strongly attracted to the sulfur functional groups in dissolved organic matter (DOM) and to sulfur ligands. Over time, newly released Hg(II) “ages” and becomes less reactive to ligands and is less likely to be found in the dissolved phase. Legacy Hg(II) found in sediments and soils is more likely to be strongly adsorbed to the soil matrix and not very bioavailable compared to newly released Hg(II)[1]. MeHg has mobility tendencies similar to Hg, with DOM and sulfur ligands competing with each other to form complexes with MeHg[5]. However, unlike Hg-S complexes, MeHg-S does not have limited solubility.

The bioavailability of Hg(II) is one of the factors controlling MeHg production in the environment. MeHg production occurs in anoxic environments and is affected by: (1) the bioavailability of Hg(II) complexes to Hg- methylating microorganisms, (2) the activity of Hg-methylating microorganisms, and (3) the rate of biotic and abiotic demethylation. MeHg is produced by anaerobic microorganisms that contain the hgcAB gene[6]. These microorganisms are a diverse group and include, sulfate-reducing bacteria, iron-reducing bacteria, and methanogenic bacteria. Site geochemistry has a significant effect on MeHg production. Methylating microorganisms are sensitive to oxygen, and MeHg production occurs in oxygen-depleted or anaerobic zones in the environment, such as anoxic aquatic sediments, saturated soils, and biofilms with anoxic microenvironments[7]. The activity of methylating microorganisms can be impacted by redox conditions, the concentrations of organic carbon, and different electron acceptors (e.g. sulfate vs iron)[7]. Overall, MeHg concentrations and production are impacted by demethylation as well. Demethylation can occur both abiotically and biotically and occurs at a much faster rate than methylation. The main routes of abiotic demethylation are photochemical reactions and demethylation catalyzed by reduced sulfur surfaces[8][9]. Methylmercury can be degraded biotically by aerobic bacteria containing the mercury detoxification, mer operon and through oxidative demethylation by anaerobic microorganisms[8].

Bioaccumulation and Toxicology

Regulatory criteria are most often based on total Hg concentrations, however, MeHg is the form of Hg that can bioaccumulate in wildlife and is the greatest human and ecological health risk[10]. MeHg represents over 95% of the Hg found in fish[11]. Hg and MeHg can be taken up directly from contaminated water into organisms, with the identity of the Hg-ligand complexes determining how readily the Hg is taken up into the organism[12]. Direct bioconcentration from water is the major uptake route at the base of the food web. Hg and MeHg can also enter the food web when benthic organisms ingest contaminated sediments[13]. Further up the food web organisms are exposed to Hg and MeHg both through exposure to contaminated water and through their diet. The higher up the trophic level, the more important dietary exposure becomes. Fish obtain more than 90% of Hg from their diet[12].

Humans are mainly exposed to Hg in the forms of MeHg and Hg(0). Hg(0) exposure comes from dental amalgams and industrial/contaminated site exposures. Hg(0) readily crosses the blood/brain barrier and mainly effects the nervous system and the kidneys[14]. MeHg exposure comes from the consumption of contaminated fish. In the human body, MeHg is readily absorbed through the gastrointestinal tract into the bloodstream and crosses the blood/brain barrier, affecting the central nervous system. MeHg can also pass through the placenta to the fetus and is particularly harmful to the developing nervous system of the fetus.

MeHg and Hg toxicity in the body occurs through multiple pathways and may be linked to the affinity of Hg for sulfur groups. Hg and MeHg bind to S-containing groups, which can block normal bodily functions[15].

Regulatory Framework for Mercury

In the United States, mercury is regulated by several different environmental laws including: the Mercury Export Ban Act of 2008, the Mercury-Containing and Rechargeable Battery Management Act of 1996, the Clean Air Act, the Clean Water Act, the Emergency Planning and Community Right-to-Know Act, the Resource Conservation and Recovery Act, and the Safe Drinking Water Act[16].

In 2013, the United States signed the international Minamata Convention on Mercury. The Minamata Convention on Mercury seeks to address and reduce human activities that are contributing to widespread mercury pollution. Worldwide, 128 countries have signed the Convention.

Remediation Technologies

As a chemical element, Hg cannot be destroyed, so the goal of Hg-remediation is immobilization and prevention of food web bioaccumulation. At very highly contaminated sites (>100s ppm), sediments are often removed and landfilled[2]. In situ capping is also a common remediation approach. Both dredging and capping can be costly and ecologically destructive, and the development of less invasive, less costly remediation technologies for Hg and MeHg contaminated sediments is an active research field. Eckley et al.[2]and Wang et al.[17] give thorough reviews of standard and emerging technologies.

Recently application of in situ sorbents has garnered interest as a remediation solution for Hg[2]. Many different materials, including biochar and various formulations of activated carbon, are successful in lowering porewater concentrations of Hg and MeHg in contaminated sediments[18]. More research is needed to determine whether Hg and MeHg sorbed to these materials are available for uptake into organisms. Site biogeochemistry can also impact the efficacy of sorbent materials, with dissolved organic matter and sulfide concentrations impacting Hg and MeHg sorption. Overall, knowing site biogeochemical characteristics is important for predicting Hg mobility and MeHg production risks as well as for designing a remediation strategy that will be effective.

References

  1. ^ 1.0 1.1 1.2 Hsu-Kim, H., Eckley, C.S., Achá, D., Feng, X., Gilmour, C.C., Jonsson, S., Mitchell, C.P.J., 2018. Challenges and opportunities for managing aquatic mercury pollution in altered landscapes. Ambio, 47, pp. 141-169. DOI: 10.1007/s13280-017-1006-7   Free access article   Report.pdf
  2. ^ 2.0 2.1 2.2 2.3 2.4 2.5 Eckley, C.S., Gilmour, C.C., Janssen, S., Luxton, T.P., Randall, P.M., Whalin, L., Austin, C., 2020. The assessment and remediation of mercury contaminated sites: A review of current approaches. Science of the Total Environment, 707, Article 136031. DOI: 10.1016/j.scitotenv.2019.136031   Free download from: ResearchGate
  3. ^ Kidd, K., Clayden, M., Jardine, T., 2012. Bioaccumulation and Biomagnification of Mercury through Food Webs. Environmental Chemistry and Toxicology of Mercury, pp. 453-499. Liu, G., Yong, C. O’Driscoll, N., Eds. John Wiley and Sons, Inc. Hoboken, NJ. DOI: 10.1002/9781118146644.ch14
  4. ^ European Commission's Joint Research Centre, 2017. A new CRM to make mercury measurements in food more reliable. Website
  5. ^ Loux, N.T., 2007. An assessment of thermodynamic reaction constants for simulating aqueous environmental monomethylmercury speciation. Chemical Speciation and Bioavailability, 19(4), pp.183-196. DOI: 10.3184/095422907X255947   Free access article   Report.pdf
  6. ^ Parks, J.M., Johs, A., Podar, M., Bridou, R. Hurt, R.A., Smith, S.D., Tomanicek, S.J., Qian, Y., Brown, S.D., Brandt, C.C., Palumbo, A.V., Smith, J.C., Wall, J.D., Elias, D.A., Liang, L., 2013. The Genetic Basis for Bacterial Mercury Methylation. Science, 339(6125), pp. 1332-1335. DOI: 10.1126/science.1230667
  7. ^ 7.0 7.1 Bravo, A.G., Cosio, C., 2020. Biotic formation of methylmercury: A bio–physico–chemical conundrum. Limnology and Oceanography, 65(5), pp. 1010-1027. DOI: 10.1002/lno.11366   Free Access Article   Report.pdf
  8. ^ 8.0 8.1 Du, H. Ma, M., Igarashi, Y., Wang, D., 2019. Biotic and Abiotic Degradation of Methylmercury in Aquatic Ecosystems: A Review. Bulletin of Environmental Contamination and Toxicology, 102 pp. 605-611. DOI: 10.1007/s00128-018-2530-2
  9. ^ Jonsson, S., Mazrui, N.M., Mason, R.P., 2016. Dimethylmercury Formation Mediated by Inorganic and Organic Reduced Sulfur Surfaces. Scientific Reports, 6, Article 27958. DOI: 10.1038/srep27958   Free access article   Report.pdf
  10. ^ Agency for Toxic Substances and Disease Registry (ATSDR), 1999. Toxicological Profile for Mercury. Free download   Report.pdf
  11. ^ Bloom, N.S., 1992. On the Chemical Form of Mercury in Edible Fish and Marine Invertebrate Tissue. Canadian Journal of Fisheries and Aquatic Sciences 49(5), pp. 1010-117. DOI: 10.1139/f92-113
  12. ^ 12.0 12.1 Kidd, K., Clayden, M., Jardine, T., 2012. Bioaccumulation and Biomagnification of Mercury through Food Webs. Environmental Chemistry and Toxicology of Mercury, pp. 453-499. Liu, G., Yong, C. O’Driscoll, N., Eds. John Wiley and Sons, Inc. Hoboken, NJ. DOI: 10.1002/9781118146644.ch14
  13. ^ Mason, R.P., 2001. The Bioaccumulation of Mercury, Methylmercury and Other Toxic Elements into Pelagic and Benthic Organisms. Coastal and Estuarine Risk Assessment, pp. 127-149. Newman, M., Roberts, M., and Hale, R.C., Ed.s. CRC Press. ISBN: 978-1-4200-3245-1 Free download from: ResearchGate
  14. ^ Clarkson, T.W., Magos, L., Myers, G.J., 2003. The Toxicology of Mercury — Current Exposures and Clinical Manifestations. New England Journal of Medicine, 349, pp. 1731-1737. DOI: 10.1056/NEJMra022471
  15. ^ Bjørklund, G., Dadar, M., Mutter, J. and Aaseth, J., 2017. The toxicology of mercury: Current research and emerging trends. Environmental Research, 159, pp.545-554. DOI: 10.1016/j.envres.2017.08.051
  16. ^ US EPA, 2021. Environmental Laws that Apply to Mercury. US EPA Website
  17. ^ Wang, L., Hou, D., Cao, Y., Ok, Y.S., Tack, F., Rinklebe, J., O’Connor, D., 2020. Remediation of mercury contaminated soil, water, and air: A review of emerging materials and innovative technologies. Environmental International, 134, 105281. DOI: 10.1016/j.envint.2019.105281   Free access article
  18. ^ Gilmour, C.C., Riedel, G.S., Riedel, G., Kwon, S., Landis, R., Brown, S.S., Menzie, C.A., Ghosh, U., 2013. Activated Carbon Mitigates Mercury and Methylmercury Bioavailability in Contaminated Sediments. Environmental Science and Technology, 47(22), pp. 13001-13010. DOI: 10.1021/es4021074   Free download from: ResearchGate

See Also