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Here, we demonstrate that extracellular polymeric substances (EPS), the main components of biofilm matrices, significantly interfere with mercury sulfide precipitation and lead to the formation of nanoparticulate metacinnabar available for microbial methylation, a natural process predominantly responsible for the environmental occurrence of methylmercury. EPS derived from mercury methylating bacteria, particularly Desulfovibrio desulfuricans ND132, substantially increase the methylation potential of nanoparticulate mercury. This is likely due to the abundant aromatic biomolecules in EPS that strongly interact with mercury sulfide via inner-sphere complexation and consequently enhance the short-range structural disorder while mitigating the aggregation of nanoparticulate mercury. The EPS-elevated bioavailability of nanoparticulate mercury to D. desulfuricans ND132 is not induced by dissolution of these nanoparticles in aqueous phase, and may be dictated by cell\u2013nanoparticle interfacial reactions. Our discovery is the first step of mechanistically understanding methylmercury production in biofilms. These new mechanistic insights will help incorporate microbial EPS and particulate-phase mercury into mercury methylation models, and may facilitate the assessment of biogeochemical cycling of other nutrient or toxic elements driven by EPS-producing microorganisms that are prevalent in nature.<\/jats:p>","DOI":"10.1021\/acs.est.0c01456","type":"journal-article","created":{"date-parts":[[2020,6,8]],"date-time":"2020-06-08T18:56:51Z","timestamp":1591642611000},"page":"8061-8071","source":"Crossref","is-referenced-by-count":53,"title":["Effects\nof Extracellular Polymeric Substances on the\nFormation and Methylation of Mercury Sulfide Nanoparticles"],"prefix":"10.1021","volume":"54","author":[{"given":"Zhanhua","family":"Zhang","sequence":"first","affiliation":[{"name":"Nankai University , , ,","place":["Tianjin, P. R. China, 300350"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rui","family":"Si","sequence":"additional","affiliation":[{"name":"Shanghai Institute of Applied Physics, Chinese Academy of Sciences , , ,","place":["Shanghai, P. R. China, 201204"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5664-0029","authenticated-orcid":true,"given":"Jitao","family":"Lv","sequence":"additional","affiliation":[{"name":"Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences , , ,","place":["Beijing, P. R. China, 100085"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yunyun","family":"Ji","sequence":"additional","affiliation":[{"name":"Nankai University , , ,","place":["Tianjin, P. R. China, 300350"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wenshan","family":"Chen","sequence":"additional","affiliation":[{"name":"Nankai University , , ,","place":["Tianjin, P. R. China, 300350"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wenyu","family":"Guan","sequence":"additional","affiliation":[{"name":"Nankai University , , ,","place":["Tianjin, P. R. China, 300350"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuxiao","family":"Cui","sequence":"additional","affiliation":[{"name":"Nankai University , , ,","place":["Tianjin, P. R. China, 300350"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8151-3697","authenticated-orcid":true,"given":"Tong","family":"Zhang","sequence":"additional","affiliation":[{"name":"Nankai University , , ,","place":["Tianjin, P. R. China, 300350"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2020,6,8]]},"reference":[{"issue":"10","key":"2026081417175562000_cit1","doi-asserted-by":"publisher","first-page":"4967","DOI":"10.1021\/es305071v","article-title":"Mercury as\na global pollutant: Sources, pathways, and effects","volume":"47","author":"Driscoll","year":"2013","journal-title":"Environ. Sci. 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Microbiol."},{"key":"2026081417175562000_cit5","doi-asserted-by":"publisher","first-page":"136827","DOI":"10.1016\/j.scitotenv.2020.136827","article-title":"Understanding\nmercury methylation in the changing environment: Recent advances in\nassessing microbial methylators and mercury bioavailability","volume":"714","author":"Tang","year":"2020","journal-title":"Sci. Total Environ."},{"issue":"4","key":"2026081417175562000_cit6","doi-asserted-by":"publisher","first-page":"247","DOI":"10.1038\/s41579-019-0158-9","article-title":"Bacteria and archaea on Earth and their abundance in\nbiofilms","volume":"17","author":"Flemming","year":"2019","journal-title":"Nat. Rev. Microbiol."},{"issue":"9","key":"2026081417175562000_cit7","doi-asserted-by":"publisher","first-page":"563","DOI":"10.1038\/nrmicro.2016.94","article-title":"Biofilms:\nAn emergent form of bacterial\nlife","volume":"14","author":"Flemming","year":"2016","journal-title":"Nat. Rev. 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Microbiol."},{"key":"2026081417175562000_cit37","volume-title":"Method 1631, Revision D: Mercury in Water by Oxidation,\nPurge and\nTrap, and Cold Vapor Atomic Fluorescence Spectroscopy","year":"2001"},{"key":"2026081417175562000_cit38","volume-title":"Method 1630: Methyl Mercury in water by Distillation, Aqueous Ethylation,\nPurge and Trap, and CVAFS","year":"2001"},{"issue":"16","key":"2026081417175562000_cit39","doi-asserted-by":"publisher","first-page":"4693","DOI":"10.1016\/j.gca.2010.05.012","article-title":"Rate of\nformation and dissolution of mercury sulfide nanoparticles: The dual\nrole of natural organic matter","volume":"74","author":"Slowey","year":"2010","journal-title":"Geochim. 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