Silver (Ag) production in Hispanic America between the 16th and 19th centuries is thought to be one of the largest sources of anthropogenic mercury (Hg) emissions in history. Recent reviews of the chemistry behind the patio process, which used Hg amalgamation to extract Ag from ore, reveal that a large amount of the Hg may not have been immediately released to the atmosphere; instead, it may have been captured in the form of calomel (HgCl, in which Hg exists as monovalent Hg) and remained in the local environment. Here we show that Hg used in the patio process centuries ago in the Guanajuato Mining District of Mexico continues to elevate present-day concentrations of gaseous elemental mercury (GEM) throughout the region. In the ground-level air, GEM ranged from 8 to 454 ng m, exceeding the Northern Hemispheric average (~1.4 ng m) by up to two orders of magnitude. Much higher concentrations, up to 44,700 ng m, were found in the interstitial air of reprocessed mineral wastes, sediment, and soil. These highly elevated present-day GEM values are due, at least in part, to the disproportionation of legacy calomel, as supported by the presence of Hg in the reprocessed wastes and by the GEM release pattern from calomel disproportionation. Our results imply that the contribution of historical Ag refining to atmospheric Hg emissions must be re-evaluated to account for calomel and its subsequent disproportionation and releases of GEM to the present-day.

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http://dx.doi.org/10.1016/j.scitotenv.2022.157093DOI Listing

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