An Updated Review of Atmospheric Mercury

The atmosphere is a key component of the biogeochemical cycle of mercury, acting as a reservoir, transport mechanism, and facilitator of chemical reactions. The chemical and physical behavior of atmospheric mercury determines how, when, and where emitted mercury pollution impacts ecosystems. In this review, we provide current information about what is known and what remains uncertain regarding mercury in the atmosphere. We discuss new ambient, laboratory, and theoretical information about the chemistry of mercury in various atmospheric media. We review what is known about mercury in and on solid- and liquid-phase aerosols. We present recent findings related to wet and dry deposition and spatial and temporal trends in atmospheric mercury concentrations. We also review atmospheric measurement methods that are in wide use and those that are currently under development

Constraints from observations and modeling on atmosphere-surface exchange of mercury in eastern North America

Atmosphere-surface exchange of mercury, although a critical component of its global cycle, is currently poorly constrained. Here we use the GEOS-Chem chemical transport model to interpret atmospheric Hg-0 (gaseous elemental mercury) data collected during the 2013 summer Nitrogen, Oxidants, Mercury and Aerosol Distributions, Sources and Sinks (NOMADSS) aircraft campaign as well as ground-and ship-based observations in terms of their constraints on the atmosphere-surface exchange of Hg-0 over eastern North America. Model-observation comparison suggests that the Northwest Atlantic may be a net source of Hg-0, with high evasion fluxes in summer (our best sensitivity simulation shows an average oceanic Hg-0 flux of 3.3 ng m(-2) h(-1) over the Northwest Atlantic), while the terrestrial ecosystem in the summer of the eastern United States is likely a net sink of Hg-0 (our best sensitivity simulation shows an average terrestrial Hg-0 flux of -0.6 ng m(-2) h(-1) over the eastern United States). The inferred high Hg-0 fluxes from the Northwest Atlantic may result from high wet deposition fluxes of oxidized Hg, which are in turn related to high precipitation rates in this region. We also find that increasing simulated terrestrial fluxes of Hg-0 in spring compared to other seasons can better reproduce observed seasonal variability of Hg-0 concentration at ground-based sites in eastern North America.Peer reviewe

Long-term Atmospheric Mercury Wet Deposition at Underhill, Vermont

Section 112(m) of the 1990 Clean Air Act Amendments, referred to as the Great Waters Program, mandated an assessment of atmospheric deposition of hazardous air pollutants (HAPs) to Lake Champlain. Mercury (Hg) was listed as a priority HAP and has continued to be a high priority for a number of national and international programs. An assessment of the magnitude and seasonal variation of atmospheric Hg levels and deposition in the Lake Champlain basin was initiated in December 1992 which included event precipitation collection, as well as collection of vapor and particle phase Hg in ambient air. Sampling was performed at the Proctor Maple Research Center in Underhill Center, VT. The range in the annual volume-weighted mean concentration for Hg in precipitation was 7.8–10.5 ng/l for the 11-year sampling period and the average amount of Hg deposited with each precipitation event was 0.10 μg/m 2 . The average amount of Hg deposited through precipitation each year from 1993 to 2003 was 9.7 μg/m 2 /yr. A seasonal pattern for Hg in precipitation is clearly evident, with increased Hg concentrations and deposition observed during spring and summer months. While a clear trend in the 11-year event deposition record at Underhill was not observed, a significant decrease in the event max-to-monthly ratio was observed suggesting that a major source influence was controlled over time. Discrete precipitation events were responsible for significant fractions of the monthly and annual loading of Hg to the forested ecosystem in Vermont. Monthly-averaged temperatures were found to be moderately correlated with monthly volume-weighted mean Hg concentrations ( r 2 =0.61) and Hg deposition ( r 2 =0.67) recorded at the Vermont site. Meteorological analysis indicated the highest levels of Hg in precipitation were associated with regional transport from the west, southwest, and south during the warmer months.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/44444/1/10646_2004_Article_6260.pd

Identification of Atmospheric Mercury Sources and Transport Pathways on Local and Regional Scales.

Mercury (Hg) is a hazardous air pollutant and bioaccumulative neurotoxin whose intricate atmospheric chemistry complicates our ability to define Hg source-receptor relationships on all scales. Our detailed measurements of Hg in its different forms together with atmospheric tracers have improved our understanding of Hg chemistry and transport. Daily-event precipitation samples collected from 1995 to 2006 in Underhill, VT were examined to identify Hg wet deposition trends and source influences. Analysis revealed that annual Hg deposition at this remote location did not vary significantly over the 12-year period. While a decreasing trend in volume-weighted mean Hg concentration was observed, Hg wet deposition did not decline as transport of emissions from the Midwest and along the Atlantic Coast consistently contributed to the largest observed Hg wet deposition events. Receptor modeling of Hg and trace elements in precipitation indicated that ~60% of Hg wet deposition at Underhill could be attributed to emissions from coal-fired utility boilers (CFUBs), and their contribution to Hg wet deposition did not change significantly over time. Hybrid-receptor modeling further defined these CFUBs to be located predominantly in the Midwestern U.S. Atmospheric Hg chemistry and transport from the Chicago urban/industrial area was the focus of speciated Hg measurements performed in the southern Lake Michigan basin during summer 2007. Transport from Chicago, IL to Holland, MI occurred during 27% of the study period, resulting in a five-fold increase in divalent reactive gaseous Hg (RGM) at the downwind Holland site. Dispersion modeling of case study periods demonstrated that under southwesterly flow approximately half of the RGM in Holland could be attributed to primary RGM emissions from Chicago after transport and dispersion, with the remainder due to elemental Hg oxidation in the atmosphere en route. Precipitation and ambient vapor phase samples were also collected in Chicago, Holland, and Dexter, MI and analyzed for Hg isotopes. The Hg isotopic fractionation observed in atmospheric samples was in contrast to a recently published report which predicted that aqueous photoreduction may be a dominant source of atmospheric Hg. Our results suggest that other redox reactions and source related processes likely contribute to isotopic fractionation of atmospheric Hg.Ph.D.Atmospheric and Space SciencesUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/77733/1/lgratz_1.pd

Assessing the Emission Sources of Atmospheric Mercury in Wet Deposition Across Illinois, USA

From August 2007 to August 2009, we collected event-based precipitation samples for mercury (Hg) and trace element analysis at four sites in Illinois, USA. The objectives of these measurements were to quantify the levels of Hg wet deposition across the state, and to assess the contributions to Hg in precipitation from major local and regional emission sources. The measurement sites were located in Chicago, Peoria, Nilwood, and Carbondale, IL. We were not able to identify a clear spatial gradient in Hg wet deposition among the sites. At all four locations we frequently observed Hg concentrations in precipitation > 25 ng/L, while each site received > 10 μg/m2 of Hg wet deposition annually, suggesting a substantial impact from local and regional anthropogenic emission sources. We applied the multivariate statistical receptor model Positive Matrix Factorization (PMF) to the measured Hg and trace element wet deposition amounts at the four sites. The results suggested that 60-83% of total Hg deposition at each site could be attributed to coal combustion emissions. Although we identified other source signatures in the precipitation composition, including cement manufacturing, metal smelting / waste incineration, and iron-steel production, these sources contributed substantially less to the measured amounts of Hg wet deposition. We also applied the hybrid receptor model Quantitative Transport Bias Analysis (QTBA) to the Hg wet deposition data from each site to identify the major source regions associated with the measured values. Results suggested that sources in the Chicago/Gary, St. Louis, and Ohio River Valley urban/industrial areas had a substantial impact on Hg wet deposition, strongly supporting the conclusion that local and regional coal combustion was the largest source of Hg wet deposition in Illinois

Ambient Mercury Observations near a Coal-Fired Power Plant in a Western U.S. Urban Area

We report on the continuous ambient measurements of total gaseous mercury (TGM) and several ancillary air quality parameters that were collected in Colorado Springs, CO. This urban area, which is located adjacent to the Front Range of the Rocky Mountains, is the second largest metropolitan area in Colorado and has a centrally located coal-fired power plant that installed mercury (Hg) emission controls the year prior to our study. There are few other Hg point sources within the city. Our results, which were obtained from a measurement site < 1 km from the power plant, show a distinct diel pattern in TGM, with peak concentrations occurring during the night (1.7 ± 0.3 ng m−3) and minimum concentrations mid-day (1.5 ± 0.2 ng m−3). The TGM concentrations were not correlated with wind originating from the direction of the plant or with sulfur dioxide (SO2) mixing ratios, and they were not elevated when the atmospheric mixing height was above the effective stack height. These findings suggest that the current Hg emissions from the CFPP did not significantly influence local TGM, and they are consistent with the facility’s relatively low reported annual emissions of 0.20 kg Hg per year. Instead, variability in the regional signal, diurnal meteorological conditions, and/or near-surface emission sources appears to more greatly influence TGM at this urban site

Isotopic Composition and Fractionation of Mercury in Great Lakes Precipitation and Ambient Air

Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/155689/1/Gratz_et_al_2010_Isotopic_composition.pd

The use of Pb, Sr, and Hg isotopes in Great Lakes precipitation as a tool for pollution source attribution

Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/155739/1/Sherman_et_al_2014_Use_of_Pb.pd