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1. Reactive mercury flux measurements using cation exchange membranes https://amt.copernicus.org/preprints/amt-2018-360/

   https://doi.org/10.5194/amt-2018-360  

   Miller, M; Edwards, G; Gustin, M (November 2018, Atmospheric measurement techniques)

   null (Ed.)

   A method was developed to measure gaseous oxidized mercury (GOM) air-surface exchange using 2 replicated dynamic flux chambers (DFCs) in conjunction with cation exchange membrane (CEM) filters. The experimental design and method was developed and tested in a laboratory setting, using materials collected from industrial scale open pit gold mines in central Nevada, USA. Materials used included waste rock, heap leach ore, and tailings, with substrate concentrations ranging from 100 to 40000 ng g-1 total mercury (THg). CEM filters were used to capture GOM from the DFC sample lines while a Tekran® 2537A analyzer measured GEM concurrently. Previous and ongoing work has demonstrated that CEM do not collect GEM and efficiently collect multiple compounds of GOM. GOM emission rates up to 4000 pg m- 2 h-1 were measured from tailings materials with high Hg substrate concentrations, and this has significant implication with respect to air-Hg surface exchange. GOM flux was variable for lower Hg concentration substrates, with both emission and deposition observed, and this was affected by ambient air GOM concentrations. For substrates that experienced GOM deposition, deposition velocities were in the range 0.01 – 0.07 cm s-1. 

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2. Mercury source changes and food web shifts alter contamination signatures of predatory fish from Lake Michigan

   https://doi.org/10.1073/pnas.1907484116  

   Lepak, Ryan F.; Hoffman, Joel C.; Janssen, Sarah E.; Krabbenhoft, David P.; Ogorek, Jacob M.; DeWild, John F.; Tate, Michael T.; Babiarz, Christopher L.; Yin, Runsheng; Murphy, Elizabeth W.; et al (November 2019, Proceedings of the National Academy of Sciences)

   To understand the impact reduced mercury (Hg) loading and invasive species have had on methylmercury bioaccumulation in predator fish of Lake Michigan, we reconstructed bioaccumulation trends from a fish archive (1978 to 2012). By measuring fish Hg stable isotope ratios, we related temporal changes in Hg concentrations to varying Hg sources. Additionally, dietary tracers were necessary to identify food web influences. Through combined Hg, C, and N stable isotopic analyses, we were able to differentiate between a shift in Hg sources to fish and periods when energetic transitions (from dreissenid mussels) led to the assimilation of contrasting Hg pools (2000 to present). In the late 1980s, lake trout δ 202 Hg increased (0.4‰) from regulatory reductions in regional Hg emissions. After 2000, C and N isotopes ratios revealed altered food web pathways, resulting in a benthic energetic shift and changes to Hg bioaccumulation. Continued increases in δ 202 Hg indicate fish are responding to several United States mercury emission mitigation strategies that were initiated circa 1990 and continued through the 2011 promulgation of the Mercury and Air Toxics Standards rule. Unlike archives of sediments, this fish archive tracks Hg sources susceptible to bioaccumulation in Great Lakes fisheries. Analysis reveals that trends in fish Hg concentrations can be substantially affected by shifts in trophic structure and dietary preferences initiated by invasive species in the Great Lakes. This does not diminish the benefits of declining emissions over this period, as fish Hg concentrations would have been higher without these actions. 

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3. Observed in-plume gaseous elemental mercury depletion suggests significant mercury scavenging by volcanic aerosols

   https://doi.org/10.1039/D3EA00063J  

   Koenig, Alkuin M.; Magand, Olivier; Rose, Clemence; Di Muro, Andrea; Miyazaki, Yuzo; Colomb, Aurelie; Rissanen, Matti; Lee, Christopher F.; Koenig, Theodore K.; Volkamer, Rainer; et al (October 2023, Environmental Science: Atmospheres)

   Terrestrial volcanism is known to emit mercury (Hg) into the atmosphere. However, despite many years of investigation, its net impact on the atmospheric Hg budget remains insufficiently constrained, in part because the transformations of Hg in volcanic plumes as they age and mix with background air are poorly understood. Here we report the observation of complete gaseous elemental mercury (GEM) depletion events in dilute and moderately aged (∼3–7 hours) volcanic plumes from Piton de la Fournaise on Réunion Island. While it has been suggested that co-emitted bromine could, once photochemically activated, deplete GEM in a volcanic plume, we measured low bromine concentrations in both the gas- and particle-phase and observed complete GEM depletion even before sunrise, ruling out a leading role of bromine chemistry here. Instead, we hypothesize that the GEM depletions were mainly caused by gas–particle interactions with sulfate-rich volcanic particles (mostly of submicron size), abundantly present in the dilute plume. We consider heterogeneous GEM oxidation and GEM uptake by particles as plausible manifestations of such a process and derive empirical rate constants. By extrapolation, we estimate that volcanic aerosols may scavenge 210 Mg y−1 (67–480 Mg y−1) of Hg from the atmosphere globally, acting effectively as atmospheric mercury sink. While this estimate is subject to large uncertainties, it highlights that Hg transformations in aging volcanic plumes must be better understood to determine the net impact of volcanism on the atmospheric Hg budget and Hg deposition pathways. 

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4. A new mechanism for atmospheric mercury redox chemistry: implications for the global mercury budget

   https://doi.org/10.5194/acp-17-6353-2017  

   Horowitz, Hannah M.; Jacob, Daniel J.; Zhang, Yanxu; Dibble, Theodore S.; Slemr, Franz; Amos, Helen M.; Schmidt, Johan A.; Corbitt, Elizabeth S.; Marais, Eloïse A.; Sunderland, Elsie M. (January 2017, Atmospheric Chemistry and Physics)

   Abstract. Mercury (Hg) is emitted to the atmosphere mainly as volatile elemental Hg⁰. Oxidation to water-soluble Hg^II plays a major role in Hg deposition to ecosystems. Here, we implement a new mechanism for atmospheric Hg⁰∕Hg^II redox chemistry in the GEOS-Chem global model and examine the implications for the global atmospheric Hg budget and deposition patterns. Our simulation includes a new coupling of GEOS-Chem to an ocean general circulation model (MITgcm), enabling a global 3-D representation of atmosphere–ocean Hg⁰∕Hg^II cycling. We find that atomic bromine (Br) of marine organobromine origin is the main atmospheric Hg⁰ oxidant and that second-stage HgBr oxidation is mainly by the NO₂ and HO₂ radicals. The resulting chemical lifetime of tropospheric Hg⁰ against oxidation is 2.7 months, shorter than in previous models. Fast Hg^II atmospheric reduction must occur in order to match the  ∼ 6-month lifetime of Hg against deposition implied by the observed atmospheric variability of total gaseous mercury (TGM ≡ Hg⁰+Hg^II(g)). We implement this reduction in GEOS-Chem as photolysis of aqueous-phase Hg^II–organic complexes in aerosols and clouds, resulting in a TGM lifetime of 5.2 months against deposition and matching both mean observed TGM and its variability. Model sensitivity analysis shows that the interhemispheric gradient of TGM, previously used to infer a longer Hg lifetime against deposition, is misleading because Southern Hemisphere Hg mainly originates from oceanic emissions rather than transport from the Northern Hemisphere. The model reproduces the observed seasonal TGM variation at northern midlatitudes (maximum in February, minimum in September) driven by chemistry and oceanic evasion, but it does not reproduce the lack of seasonality observed at southern hemispheric marine sites. Aircraft observations in the lowermost stratosphere show a strong TGM–ozone relationship indicative of fast Hg⁰ oxidation, but we show that this relationship provides only a weak test of Hg chemistry because it is also influenced by mixing. The model reproduces observed Hg wet deposition fluxes over North America, Europe, and China with little bias (0–30%). It reproduces qualitatively the observed maximum in US deposition around the Gulf of Mexico, reflecting a combination of deep convection and availability of NO₂ and HO₂ radicals for second-stage HgBr oxidation. However, the magnitude of this maximum is underestimated. The relatively low observed Hg wet deposition over rural China is attributed to fast Hg^II reduction in the presence of high organic aerosol concentrations. We find that 80% of Hg^II deposition is to the global oceans, reflecting the marine origin of Br and low concentrations of organic aerosols for Hg^II reduction. Most of that deposition takes place to the tropical oceans due to the availability of HO₂ and NO₂ for second-stage HgBr oxidation. 

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5. Evaluation of cation exchange membrane performance under exposure to high Hg⁰ and HgBr₂ concentrations

   https://doi.org/10.5194/amt-12-1207-2019  

   Miller, Matthieu B.; Dunham-Cheatham, Sarrah M.; Gustin, Mae Sexauer; Edwards, Grant C. (January 2019, Atmospheric Measurement Techniques)

   null (Ed.)

   Abstract. Reactive mercury (RM), the sum of both gaseous oxidized Hg and particulatebound Hg, is an important component of the global atmospheric mercury cycle,but measurement currently depends on uncalibrated operationally definedmethods with large uncertainty and demonstrated interferences and artifacts.Cation exchange membranes (CEMs) provide a promising alternative methodologyfor quantification of RM, but method validation and improvements are ongoing.For the CEM material to be reliable, uptake of gaseous elemental mercury(GEM) must be negligible under all conditions and RM compounds must becaptured and retained with high efficiency. In this study, the performance ofCEM material under exposure to high concentrations of GEM (1.43×106 to 1.85×106 pg m−3) and reactive gaseous mercurybromide (HgBr2 ∼5000 pg m−3) was explored using acustom-built mercury vapor permeation system. Quantification of totalpermeated Hg was measured via pyrolysis at 600 ∘C and detectionusing a Tekran® 2537A. Permeation tests wereconducted over 24 to 72 h in clean laboratory air, with absolute humiditylevels ranging from 0.1 to 10 g m−3 water vapor. GEM uptake by the CEMmaterial averaged no more than 0.004 % of total exposure for all testconditions, which equates to a non-detectable GEM artifact for typicalambient air sample concentrations. Recovery of HgBr2 on CEM filters wason average 127 % compared to calculated total permeated HgBr2 based onthe downstream Tekran® 2537A data. The lowHgBr2 breakthrough on the downstream CEMs (< 1 %) suggests thatthe elevated recoveries are more likely related to suboptimal pyrolyzerconditions or inefficient collection on the Tekran® 2537A gold traps. 

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