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Photoreduction of gaseous oxidized mercury changes global atmospheric mercury speciation, transport and deposition.

ABSTRACT: Anthropogenic mercury (Hg(0)) emissions oxidize to gaseous Hg(II) compounds, before deposition to Earth surface ecosystems. Atmospheric reduction of Hg(II) competes with deposition, thereby modifying the magnitude and pattern of Hg deposition. Global Hg models have postulated that Hg(II) reduction in the atmosphere occurs through aqueous-phase photoreduction that may take place in clouds. Here we report that experimental rainfall Hg(II) photoreduction rates are much slower than modelled rates. We compute absorption cross sections of Hg(II) compounds and show that fast gas-phase Hg(II) photolysis can dominate atmospheric mercury reduction and lead to a substantial increase in the modelled, global atmospheric Hg lifetime by a factor two. Models with Hg(II) photolysis show enhanced Hg(0) deposition to land, which may prolong recovery of aquatic ecosystems long after Hg emissions are lowered, due to the longer residence time of Hg in soils compared with the ocean. Fast Hg(II) photolysis substantially changes atmospheric Hg dynamics and requires further assessment at regional and local scales.

SUBMITTER: Saiz-Lopez A

PROVIDER: S-EPMC6237998 | biostudies-literature | 2018 Nov

REPOSITORIES: biostudies-literature

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Photoreduction of gaseous oxidized mercury changes global atmospheric mercury speciation, transport and deposition.

Saiz-Lopez Alfonso A Sitkiewicz Sebastian P SP Roca-Sanjuán Daniel D Oliva-Enrich Josep M JM Dávalos Juan Z JZ Notario Rafael R Jiskra Martin M Xu Yang Y Wang Feiyue F Thackray Colin P CP Sunderland Elsie M EM Jacob Daniel J DJ Travnikov Oleg O Cuevas Carlos A CA Acuña A Ulises AU Rivero Daniel D Plane John M C JMC Kinnison Douglas E DE Sonke Jeroen E JE

Nature communications 20181115 1

Anthropogenic mercury (Hg(0)) emissions oxidize to gaseous Hg(II) compounds, before deposition to Earth surface ecosystems. Atmospheric reduction of Hg(II) competes with deposition, thereby modifying the magnitude and pattern of Hg deposition. Global Hg models have postulated that Hg(II) reduction in the atmosphere occurs through aqueous-phase photoreduction that may take place in clouds. Here we report that experimental rainfall Hg(II) photoreduction rates are much slower than modelled rates. W ...[more]

PMID: 30442890

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Project description:Gaseous oxidized mercury (GOM) dry deposition measurements using surrogate surface passive samplers were collected at six sites in the Four Corners area, U.S.A., for the two-year period August, 2017-August, 2019, after the implementation of large power plant mercury emission reductions across the U.S.A. Two-year baseline GOM dry deposition measurements at the same six sites in the Four Corners area, taken before the implementation of U.S.A. power plant mercury control regulations, were conducted earlier from August, 2009-August, 2011. The GOM dry deposition rate estimate decreased at the Four Corners area high elevation remote mountain site of Molas Pass, Colorado (3249 m asl) from 0.4 ng/m2h for August, 2009-August, 2011 to 0.3 ng/m2h for August, 2017-August, 2019. In contrast, GOM dry deposition rate estimates for the remaining five sites increased for August, 2017-August, 2019, ranging from 0.8-1.3 ng/m2h, up from the August, 2009-August, 2011 range of 0.6-1.0 ng/m2h. Comparisons of median GOM dry deposition values showed a statistically significant decrease of 17 ng/m2 at the Molas Pass site between August, 2009-August, 2011 and August, 2017-August, 2019, and a statistically significant increase of 66 ng/m2 and 64 ng/m2, respectively, at the Mesa Verde National Park and Farmington Substation sites between August, 2009-August, 2011 and August, 2017-August, 2019. For the four years of GOM dry deposition data collected in the Four Corners area annual GOM dry deposition levels ranged from 2237 ng/m2yr (at the Molas Pass high elevation remote mountain site) to 11542 ng/m2yr (at the Mesa Verde National Park site), and the estimates were generally higher in magnitude in the spring and summer compared to the fall and winter. In light of the unexpected increases in GOM dry deposition rates at the non-remote sites, it is suggested that large regional wildfires and local anthropogenic mercury emission sources from cities and oil/gas production areas are possible notable contributors to the GOM dry deposition measurements collected in the Four Corners area.

Project description:Understanding atmospheric mercury chemistry is the key for explaining the biogeochemical cycle of mercury and for improving the predictive capability of computational models. Increased efforts are being made to ensure comparable Hg speciation measurements in the air through establishing metrological traceability. While traceability for elemental mercury has been recently set, this is by no means the case for gaseous oxidized mercury (GOM). Since a calibration unit suitable for traceable GOM calibrations based on evaporation of HgCl2 solution was recently developed, the purpose of our work was to extensively evaluate its performance. A highly specific and sensitive 197Hg radiotracer was used for validation over a wide range of concentrations. By comparing experimental and calculated values, we obtained recoveries for the calibration unit. The average recoveries ranged from 88.5% for 1178 ng m-3 HgCl2 gas concentration to 39.4% for 5.90 ng m-3 HgCl2 gas concentration. The losses were due to the adsorption of oxidized Hg on the inner walls of the calibrator and tubing. An adsorption isotherm was applied to estimate adsorption enthalpy (ΔHads); a ΔHads value of -12.33 kJ mol-1 was obtained, suggesting exothermal adsorption. The results of the calibrator performance evaluation suggest that a newly developed calibration unit is only suitable for concentrations of HgCl2 higher than 1 µg m-3. The concentration dependence of recoveries prevents the system from being used for calibration of instruments for ambient GOM measurements. Moreover, the previously assessed uncertainty of this unit at µg m-3 level (2.0%, k = 2) was re-evaluated by including uncertainty related to recovery and was found to be 4.1%, k = 2. Calibrator performance was also evaluated for HgBr2 gas calibration; the recoveries were much lower for HgBr2 gas than for HgCl2 gas even at a high HgBr2 gas concentration (>1 µg m-3). As HgBr2 is often used as a proxy for various atmospheric HgBr species, the suitability of the unit for such calibration must be further developed.

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Photoreduction of gaseous oxidized mercury changes global atmospheric mercury speciation, transport and deposition.

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Photoreduction of gaseous oxidized mercury changes global atmospheric mercury speciation, transport and deposition.

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