Mercury Deposition Network Research Articles

Modeling the high-mercury wet deposition in the southeastern US with WRF-GC-Hg v1.0

Abstract. High-mercury wet deposition in the southeastern United States has been noticed for many years. Previous studies came up with a theory that it was associated with high-altitude divalent mercury scavenged by convective precipitation. Given the coarse resolution of previous models (e.g., GEOS-Chem), this theory is still not fully tested. Here we employed a newly developed WRF-GEOS-Chem (WRF-GC; WRF: Weather Research Forecasting) model implemented with mercury simulation (WRF-GC-Hg v1.0). We conduct extensive model benchmarking by comparing WRF-GC with different resolutions (from 50 to 25 km) to GEOS-Chem output (4∘ × 5∘) and data from the Mercury Deposition Network (MDN) in July–September 2013. The comparison of mercury wet deposition from two models presents high-mercury wet deposition in the southeastern United States. We divided simulation results by heights (2, 4, 6, 8 km), different types of precipitation (large-scale and convective), and combinations of these two variations together and find most mercury wet deposition concentrates on higher level and is caused by convective precipitation. Therefore, we conclude that it is the deep convection that caused enhanced mercury wet deposition in the southeastern United States.

Long-Term Trends in Regional Wet Mercury Deposition and Lacustrine Mercury Concentrations in Four Lakes in Voyageurs National Park

Although anthropogenic mercury (Hg) releases to the environment have been substantially lowered in the United States and Canada since 1990, concerns remain for contamination in fish from remote lakes and rivers where atmospheric deposition is the predominant source of mercury. How have aquatic ecosystems responded? We report on one of the longest known multimedia data sets for mercury in atmospheric deposition: aqueous total mercury (THgaq), methylmercury (MeHgaq), and sulfate from epilimnetic lake-water samples from four lakes in Voyageurs National Park (VNP) in northern Minnesota; and total mercury (THg) in aquatic biota from the same lakes from 2001–2018. Wet Hg deposition at two regional Mercury Deposition Network sites (Fernberg and Marcell, Minnesota) decreased by an average of 22 percent from 1998–2018; much of the decreases occurred prior to 2009, with relatively flat trends since 2009. In the four VNP lakes, epilimnetic MeHgaq concentrations declined by an average of 44 percent and THgaq by an average of 27 percent. For the three lakes with long-term biomonitoring, temporal patterns in biotic THg concentrations were similar to patterns in MeHgaq concentrations; however, biotic THg concentrations declined significantly in only one lake. Epilimnetic MeHgaq may be responding both to a decline in atmospheric Hg deposition as well as a decline in sulfate deposition, which is an important driver of mercury methylation in the environment. Results from this case study suggest that regional- to continental-scale decreases in both mercury and sulfate emissions have benefitted aquatic resources, even in the face of global increases in mercury emissions.

Resolving a paradox-high mercury deposition, but low bioaccumulation in northeastern Puerto Rico.

At a "clean air" trade winds site in northeastern Puerto Rico, we found an apparent paradox: atmospheric total mercury (THg) deposition was highest of any site in the USA Mercury Deposition Network, but assimilation into the local food web was quite low. Avian blood THg concentrations (n = 31, from eight species in five foraging guilds) ranged widely from 0.2 to 32 ng g-1 (median of 4.3 ng g-1). Within this population, THg was significantly greater at a low-elevation site near a wetland compared to an upland montane site, even when the comparison was limited to a single species. Overall, however, THg concentrations were approximately an order of magnitude lower than comparable populations in the continental U.S. In surface soil and sediment, potential rates of demethylation were 3 to 9-fold greater than those for Hg(II)-methylation (based on six radiotracer amendment incubations), but rates of change of ambient MeHg pools showed a slight net positive Hg(II)-methylation. Thus, the resolution of the paradox is that MeHg degradation approximately keeps pace with MeHg production in this landscape. Further, any net production of MeHg is subject to frequent flushing by high rainfall on chronically wet soils. The interplay of these microbial processes and hydrology appears to shield the local food web from adverse effects of high atmospheric mercury loading. This scenario may play out in other humid tropical ecosystems as well, but it is difficult to evaluate because coordinated studies of Hg deposition, methylation, and trophic uptake have not been conducted at other tropical sites.

Subtropical subsidence and surface deposition of oxidized mercury produced in the free troposphere

Abstract. Oxidized mercury (Hg(II)) is chemically produced in the atmosphere by oxidation of elemental mercury and is directly emitted by anthropogenic activities. We use the GEOS-Chem global chemical transport model with gaseous oxidation driven by Br atoms to quantify how surface deposition of Hg(II) is influenced by Hg(II) production at different atmospheric heights. We tag Hg(II) chemically produced in the lower (surface–750 hPa), middle (750–400 hPa), and upper troposphere (400 hPa–tropopause), in the stratosphere, as well as directly emitted Hg(II). We evaluate our 2-year simulation (2013–2014) against observations of Hg(II) wet deposition as well as surface and free-tropospheric observations of Hg(II), finding reasonable agreement. We find that Hg(II) produced in the upper and middle troposphere constitutes 91 % of the tropospheric mass of Hg(II) and 91 % of the annual Hg(II) wet deposition flux. This large global influence from the upper and middle troposphere is the result of strong chemical production coupled with a long lifetime of Hg(II) in these regions. Annually, 77–84 % of surface-level Hg(II) over the western US, South America, South Africa, and Australia is produced in the upper and middle troposphere, whereas 26–66 % of surface Hg(II) over the eastern US, Europe, and East Asia, and South Asia is directly emitted. The influence of directly emitted Hg(II) near emission sources is likely higher but cannot be quantified by our coarse-resolution global model (2° latitude × 2.5° longitude). Over the oceans, 72 % of surface Hg(II) is produced in the lower troposphere because of higher Br concentrations in the marine boundary layer. The global contribution of the upper and middle troposphere to the Hg(II) dry deposition flux is 52 %. It is lower compared to the contribution to wet deposition because dry deposition of Hg(II) produced aloft requires its entrainment into the boundary layer, while rain can scavenge Hg(II) from higher altitudes more readily. We find that 55 % of the spatial variation of Hg wet deposition flux observed at the Mercury Deposition Network sites is explained by the combined variation of precipitation and Hg(II) produced in the upper and middle troposphere. Our simulation points to a large role of the dry subtropical subsidence regions. Hg(II) present in these regions accounts for 74 % of Hg(II) at 500 hPa over the continental US and more than 60 % of the surface Hg(II) over high-altitude areas of the western US. Globally, it accounts for 78 % of the tropospheric Hg(II) mass and 61 % of the total Hg(II) deposition. During the Nitrogen, Oxidants, Mercury, and Aerosol Distributions, Sources, and Sinks (NOMADSS) aircraft campaign, the contribution of Hg(II) from the dry subtropical regions was found to be 75 % when measured Hg(II) exceeded 250 pg m−3. Hg(II) produced in the upper and middle troposphere subsides in the anticyclones, where the dry conditions inhibit the loss of Hg(II). Our results highlight the importance the subtropical anticyclones as the primary conduits for the production and export of Hg(II) to the global atmosphere.

Mercury Wet Scavenging and Deposition Differences by Precipitation Type.

We analyze the effect of precipitation type on mercury wet deposition using a new database of individual rain events spanning the contiguous United States. Measurements from the Mercury Deposition Network (MDN) containing single rainfall events were identified and classified into six precipitation types. Mercury concentrations in surface precipitation follow a power law of precipitation depth that is modulated by precipitation system morphology. After controlling for precipitation depth, the highest mercury deposition occurs in supercell thunderstorms, with decreasing deposition in disorganized thunderstorms, quasi-linear convective systems (QLCS), extratropical cyclones, light rain, and land-falling tropical cyclones. Convective morphologies (supercells, disorganized, and QLCS) enhance wet deposition by a factor of at least 1.6 relative to nonconvective morphologies. Mercury wet deposition also varies by geographic region and season. After controlling for other factors, we find that mercury wet deposition is greater over high-elevation sites, seasonally during summer, and in convective precipitation.

Regional Air Quality Model Application of the Aqueous-Phase Photo Reduction of Atmospheric Oxidized Mercury by Dicarboxylic Acids

In most ecosystems, atmospheric deposition is the primary input of mercury. The total wet deposition of mercury in atmospheric chemistry models is sensitive to parameterization of the aqueous-phase reduction of divalent oxidized mercury (Hg2+). However, most atmospheric chemistry models use a parameterization of the aqueous-phase reduction of Hg2+ that has been shown to be unlikely under normal ambient conditions or use a non mechanistic value derived to optimize wet deposition results. Recent laboratory experiments have shown that Hg2+ can be photochemically reduced to elemental mercury (Hg) in the aqueous-phase by dissolved organic matter and a mechanism and the rate for Hg2+ photochemical reduction by dicarboxylic acids (DCA) has been proposed. For the first time in a regional scale model, the DCA mechanism has been applied. The HO2-Hg2+ reduction mechanism, the proposed DCA reduction mechanism, and no aqueous-phase reduction (NAR) of Hg2+ are evaluated against weekly wet deposition totals, concentrations and precipitation observations from the Mercury Deposition Network (MDN) using the Community Multiscale Air Quality (CMAQ) model version 4.7.1. Regional scale simulations of mercury wet deposition using a DCA reduction mechanism evaluated well against observations, and reduced the bias in model evaluation by at least 13% over the other schemes evaluated, although summertime deposition estimates were still biased by −31.4% against observations. The use of the DCA reduction mechanism physically links Hg2+ reduction to plausible atmospheric processes relevant under typical ambient conditions.

A Great Lakes Atmospheric Mercury Monitoring network: Evaluation and design

As many as 51 mercury (Hg) wet-deposition-monitoring sites from 4 networks were operated in 8 USA states and Ontario, Canada in the North American Great Lakes Region from 1996 to 2010. By 2013, 20 of those sites were no longer in operation and approximately half the geographic area of the Region was represented by a single Hg-monitoring site. In response, a Great Lakes Atmospheric Mercury Monitoring (GLAMM) network is needed as a framework for regional collaboration in Hg-deposition monitoring. The purpose of the GLAMM network is to detect changes in regional atmospheric Hg deposition related to changes in Hg emissions. An optimized design for the network was determined to be a minimum of 21 sites in a representative and approximately uniform geographic distribution. A majority of the active and historic Hg-monitoring sites in the Great Lakes Region are part of the National Atmospheric Deposition Program (NADP) Mercury Deposition Network (MDN) in North America and the GLAMM network is planned to be part of the MDN.To determine an optimized network design, active and historic Hg-monitoring sites in the Great Lakes Region were evaluated with a rating system of 21 factors that included characteristics of the monitoring locations and interpretations of Hg data. Monitoring sites were rated according to the number of Hg emissions sources and annual Hg emissions in a geographic polygon centered on each site. Hg-monitoring data from the sites were analyzed for long-term averages in weekly Hg concentrations in precipitation and weekly Hg-wet deposition, and on significant temporal trends in Hg concentrations and Hg deposition. A cluster analysis method was used to group sites with similar variability in their Hg data in order to identify sites that were unique for explaining Hg data variability in the Region. The network design included locations in protected natural areas, urban areas, Great Lakes watersheds, and in proximity to areas with a high density of annual Hg emissions and areas with high average weekly Hg wet deposition. In a statistical analysis, relatively strong, positive correlations in the wet deposition of Hg and sulfate were shown for co-located NADP Hg-monitoring and acid-rain monitoring sites in the Region. This finding indicated that efficiency in regional Hg monitoring can be improved by adding new Hg monitoring to existing NADP acid-rain monitoring sites.Implementation of the GLAMM network design will require Hg-wet-deposition monitoring to be: (a) continued at 12 MDN sites active in 2013 and (b) restarted or added at 9 NADP sites where it is absent in 2013. Ongoing discussions between the states in the Great Lakes Region, the Lake Michigan Air Directors Consortium (a regional planning entity), the NADP, the U.S. Environmental Protection Agency, and the U.S. Geological Survey are needed for coordinating the GLAMM network.

Method development estimating ambient oxidized mercury concentration from monitored mercury wet deposition

Abstract. To quantify mercury dry deposition, the Atmospheric Mercury Network (AMNet) of the National Atmospheric Deposition Program (NADP) was established recently to monitor the speciated atmospheric mercury (i.e. gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM) and particulate-bound mercury (PBM)). However, the spatial coverage of AMNet is far less than the long-established Mercury Deposition Network (MDN) for wet deposition monitoring. The present study describes the first attempt linking ambient concentration of the oxidized mercury (GOM + PBM) with wet deposition aiming to estimate GOM + PBM roughly at locations and/or times where such measurement is not available but where wet deposition is monitored. The beta distribution function is used to describe the distribution of GOM + PBM and is used to predict GOM + PBM from monitored wet deposition. The mean, median, mode, standard deviation, and skewness of the fitted beta distribution parameters were generated using data collected in 2009 at multiple monitoring superstations. The established beta distribution function from the 2009 GOM + PBM data is used to construct a model that predicts GOM + PBM from wet deposition data. The model is validated using 2010 data at multiple stations, and the predicted monthly GOM + PBM concentrations agree reasonably well with measurements. The model has many potential applications after further improvements and validation using different data sets.

Model analyses of atmospheric mercury: present air quality and effects of transpacific transport on the United States

Abstract. Atmospheric mercury is a toxic air and water pollutant that is of significant concern because of its effects on human health and ecosystems. A mechanistic representation of the atmospheric mercury cycle is developed for the state-of-the-art global climate-chemistry model, CAM-Chem (Community Atmospheric Model with Chemistry). The model simulates the emission, transport, transformation and deposition of atmospheric mercury (Hg) in three forms: elemental mercury (Hg(0)), reactive mercury (Hg(II)), and particulate mercury (PHg). Emissions of mercury include those from human, land, ocean, biomass burning and volcano related sources. Land emissions are calculated based on surface solar radiation flux and skin temperature. A simplified air–sea mercury exchange scheme is used to calculate emissions from the oceans. The chemistry mechanism includes the oxidation of Hg(0) in gaseous phase by ozone with temperature dependence, OH, H2O2 and chlorine. Aqueous chemistry includes both oxidation and reduction of Hg(0). Transport and deposition of mercury species are calculated through adapting the original formulations in CAM-Chem. The CAM-Chem model with mercury is driven by present meteorology to simulate the present mercury air quality during the 1999–2001 period. The resulting surface concentrations of total gaseous mercury (TGM) are then compared with the observations from worldwide sites. Simulated wet depositions of mercury over the continental United States are compared to the observations from 26 Mercury Deposition Network stations to test the wet deposition simulations. The evaluations of gaseous concentrations and wet deposition confirm a strong capability for the CAM-Chem mercury mechanism to simulate the atmospheric mercury cycle. The general reproduction of global TGM concentrations and the overestimation on South Africa indicate that model simulations of TGM are seriously affected by emissions. The comparison to wet deposition indicates that wet deposition patterns of mercury are more affected by the spatial variability of precipitation. The sensitivity experiments show that 22% of total mercury deposition and 25% of TGM concentrations in the United States result from domestic anthropogenic sources, but only 9% of total mercury deposition and 7% of TGM concentrations are contributed by transpacific transport. However, the contributions of domestic and transpacific sources on the western United States levels of mercury are of comparable magnitude.

Decreases in Mercury Wet Deposition over the United States during 2004–2010: Roles of Domestic and Global Background Emission Reductions

Wet deposition of mercury (Hg) across the United States is influenced by changes in atmospheric conditions, domestic emissions and global background emissions. We examine trends in Hg precipitation concentrations at 47 Mercury Deposition Network (MDN) sites during 2004–2010 by using the GEOS-Chem nested-grid Hg simulation. We run the model with constant anthropogenic emissions and subtract the model results from the observations. This helps to remove the variability in observed Hg concentrations caused by meteorological factors, including precipitation. We find significant decreasing trends in Hg concentrations in precipitation at MDN sites in the Northeast (−4.1 ± 0.49% yr−1) and Midwest (−2.7 ± 0.68% yr−1). Over the Southeast (−0.53 ± 0.59% yr−1), trends are weaker and not significant, while over the West, trends are highly variable. We conduct model simulations assuming a 45% decrease in Hg emissions from domestic sources in the modeled period and a uniform 12% decrease in background atmospheric Hg concentrations. The combination of domestic emission reductions and decreasing background concentrations explains the observed trends over the Northeast and Midwest, with domestic emission reductions accounting for 58–46% of the decreasing trends. Over the Southeast, we overestimate the observed decreasing trend, indicating potential issues with our assumption of uniformly decreasing background Hg concentrations.

Bulk Atmospheric Mercury Fluxes for the Northern Great Plains, USA

Total atmospheric bulk mercury (Hg) concentration and deposition were measured from August 2008 to November 2010 at nine locations in the Northern Great Plains, USA using passive bulk mercury samplers. Monthly mercury concentrations ranged from 1.3 to 51.0 ng L−1 with an overall volume weighted mean of 12.9 ng L−1. Normalized daily Hg fluxes ranged from 0.43 to 110 ng m−2 day−1 with higher rates occurring during high precipitation months as rainfall during spring and summer. Annual deposition rates ranged from 5.82 to 9.21 μg m−2 year−1 and were comparable to studies performed at similar latitudes and to estimates from the Mercury Deposition Network (MDN). There was no significant difference (p > 0.05) between measured atmospheric mercury for one colocated bulk Hg sampler and an existing MDN wet-only sampler at Eagle Butte, South Dakota, demonstrating measurement unity between the two sampling techniques in this geographic area.

Mercury wet deposition in the eastern United States: characteristics and scavenging ratios

Wet deposition is an important atmospheric mercury (Hg) pathway between air and terrestrial ecosystems. It is measured at numerous locations in the United States (U. S.) as part of the Mercury Deposition Network (MDN). The annual Hg wet deposition flux in 2009 at four locations in the northeastern U. S. (MDN sites MD08, VT99, NY20, and NY43) ranged from 6.4 to 13.4 μg per m(2) year which is higher than modeled reactive Hg (RM) dry deposition for this region. The highest ambient RM concentrations were seen at MD08, which is closest to significant anthropogenic sources; however, the volume-weighted mean Hg concentrations in precipitation were similar at these four sites. Mass based scavenging ratios (SC) of RM ranged from 1700 to 4500. Differences in SCs were likely a result of differences in meteorological conditions, the forms of RM in the atmosphere, vertical concentration variations, and measurement uncertainties, including precipitation depth and RM concentrations. RM SCs were higher than those reported for other soluble species. Multiple linear regression suggests that gaseous oxidized Hg is responsible for the majority of the scavenged RM.

Nested-grid simulation of mercury over North America

Abstract. We have developed a new nested-grid mercury (Hg) simulation over North America with a 1/2° latitude by 2/3° longitude horizontal resolution employing the GEOS-Chem global chemical transport model. Emissions, chemistry, deposition, and meteorology are self-consistent between the global and nested domains. Compared to the global model (4° latitude by 5° longitude), the nested model shows improved skill at capturing the high spatial and temporal variability of Hg wet deposition over North America observed by the Mercury Deposition Network (MDN) in 2008–2009. The nested simulation resolves features such as higher deposition due to orographic precipitation, land/ocean contrast and and predicts more efficient convective rain scavenging of Hg over the southeast United States. However, the nested model overestimates Hg wet deposition over the Ohio River Valley region (ORV) by 27%. We modify anthropogenic emission speciation profiles in the US EPA National Emission Inventory (NEI) to account for the rapid in-plume reduction of reactive to elemental Hg (IPR simulation). This leads to a decrease in the model bias to −2.3% over the ORV region. Over the contiguous US, the correlation coefficient (r) between MDN observations and our IPR simulation increases from 0.60 to 0.78. The IPR nested simulation generally reproduces the seasonal cycle in surface concentrations of speciated Hg from the Atmospheric Mercury Network (AMNet) and Canadian Atmospheric Mercury Network (CAMNet). In the IPR simulation, annual mean gaseous and particulate-bound Hg(II) are within 140% and 11% of observations, respectively. In contrast, the simulation with unmodified anthropogenic Hg speciation profiles overestimates these observations by factors of 4 and 2 for gaseous and particulate-bound Hg(II), respectively. The nested model shows improved skill at capturing the horizontal variability of Hg observed over California during the ARCTAS aircraft campaign. The nested model suggests that North American anthropogenic emissions account for 10–22% of Hg wet deposition flux over the US, depending on the anthropogenic emissions speciation profile assumed. The modeled percent contribution can be as high as 60% near large point sources in ORV. Our results indicate that the North American anthropogenic contribution to dry deposition is 13–20%.

Testing the use of passive sampling systems for understanding air mercury concentrations and dry deposition across Florida, USA

This paper describes the use of passive sampling systems and surrogate surfaces for monitoring atmospheric mercury (Hg) concentrations and dry deposition, respectively, in Florida,USA. Although this area has been reported to have low air concentrations, wet deposition values, reported by the Mercury Deposition Network, are some of the highest in the United States, and little is known about the magnitude of dry deposition to the region. To address this uncertainty, dry deposition of gaseous oxidized mercury (GOM) was estimated based on data collected using surrogate surfaces and through the application of a dry deposition model that utilized Tekran® Mercury Analyzer data for three sites (Davie near Fort Lauderdale, Tampa and Pensacola) over a year (July 2009-July 2010). Passive sampler systems for monitoring GOM and total gaseous mercury (TGM) concentrations were also deployed. In general, higher surrogate surface deposition, and GOM and TGM passive sampler uptake were observed at the DVE location. Across all sites, empirically derived dry deposition was higher than that determined using modeled values. Tekran® Instrument derived GOM concentrations, as well as modeled deposition rates, followed the same seasonal and spatial patterns as that measured by the samplers, however there were some spatial and temporal trends captured by the samplers that were not seen in the Tekran® derived data. Results indicate that these samplers may be applied to identify spatial and temporal trends in air Hg concentrations and potential deposition at sites with low and fairly constant GOM concentrations as reported by the Tekran® system (2–8pgm-3). When viewed collectively, trends in sampler and Tekran® derived data also suggest the potential for different forms of GOM in air. Using empirical and modeled values, dry deposition in Florida during the year of this study could account for 1.5 to 14% of total annual Hg deposition (wet+dry).

Litterfall mercury dry deposition in the eastern USA

Mercury (Hg) in autumn litterfall from predominately deciduous forests was measured in 3 years of samples from 23 Mercury Deposition Network sites in 15 states across the eastern USA. Annual litterfall Hg dry deposition was significantly higher (median 12.3 micrograms per square meter (μg/m 2), range 3.5–23.4 μg/m 2) than annual Hg wet deposition (median 9.6 μg/m 2, range 4.4–19.7 μg/m 2). The mean ratio of dry to wet Hg deposition was 1.3–1. The sum of dry and wet Hg deposition averaged 21 μg/m 2 per year and 55% was litterfall dry deposition. Methylmercury was a median 0.8% of Hg in litterfall and ranged from 0.6 to 1.5%. Annual litterfall Hg and wet Hg deposition rates differed significantly and were weakly correlated. Litterfall Hg dry deposition differed among forest-cover types. This study demonstrated how annual litterfall Hg dry deposition rates approximate the lower bound of annual Hg dry fluxes.

Atmospheric deposition of mercury and major ions to the Pensacola (Florida) watershed: spatial, seasonal, and inter-annual variability

Abstract. Atmospheric deposition was measured at three sites in the Pensacola Bay watershed, Florida, between November 2004 and December 2007. Mercury deposition in the Pensacola Bay watershed was similar to that from nearby Mercury Deposition Network sites along the Northern Gulf of Mexico coast. Mercury deposition during the summer months is higher than other months due to higher concentrations in rainfall throughout the region. Deposition of constituents like H+, sulfate, nitrate, ammonium, chloride and sodium, were much higher in Pensacola Bay that at National Atmospheric Deposition Program (NADP) sites. Chloride and sodium deposition are higher because Pensacola Bay sites are closer to the Gulf of Mexico which is a source of sea salt aerosols. Acid rain constituents, H+, sulfate, nitrate and ammonium are most likely higher at Pensacola Bay sites because these sites are much closer to emission sources of these constituents than NADP sites, particularly two Florida NADP sites, FL14 and FL23, which are located in rural counties far from major industrial activities.

Mercury trends in fish from rivers and lakes in the United States, 1969–2005

A national dataset on concentrations of mercury in fish, compiled mainly from state and federal monitoring programs, was used to evaluate trends in mercury (Hg) in fish from US rivers and lakes. Trends were analyzed on data aggregated by site and by state, using samples of the same fish species and tissue type, and using fish of similar lengths. Site-based trends were evaluated from 1969 to 2005, but focused on a subset of the data from 1969 to 1987. Data aggregated by state were used to evaluate trends in fish Hg concentrations from 1988 to 2005. In addition, the most recent Hg fish data (1996-2005) were compared to wet Hg deposition data from the Mercury Deposition Network (MDN) over the same period. Downward trends in Hg concentrations in fish from data collected during 1969-1987 exceeded upward trends by a ratio of 6 to 1. Declining Hg accumulation rates in sediment and peat cores reported by many studies during the 1970s and 1980s correspond with the period when the most downward trends in fish Hg concentrations occurred. Downward Hg trends in both sediment cores and fish were also consistent with the implementation of stricter regulatory controls of direct releases of Hg to the atmosphere and surface waters during the same period. The southeastern USA had more upward Hg trends in fish than other regions for both site and state aggregated data. Upward Hg trends in fish from the southeastern USA were associated with increases in wet deposition in the region and may be attributed to a greater influence of global atmospheric Hg emissions in the southeastern USA. No significant trends were found in 62% of the fish species from six states from 1996 to 2005. A lack of Hg trends in fish in the more recent data was consistent with the lack of trends in wet Hg deposition at MDN sites and with relatively constant global emissions during the same time period. Although few significant trends were observed in the more recent Hg concentrations in fish, it is anticipated that Hg concentrations in fish will respond to changes in atmospheric Hg deposition, however, the magnitude and timing of the response is uncertain.

Wet deposition mercury fluxes in the Canadian sub-Arctic and southern Alberta, measured using an automated precipitation collector adapted to cold regions

This paper reports mercury (Hg) concentrations and fluxes in precipitation that was collected from 2006 to 2008 at three sites in Canada: sub-Arctic boreal forest, sub-Arctic coast, and southern Alberta, using cold-adapted precipitation collectors which operated reliably at temperatures below −30 °C during the study. The southern Alberta site (Crossfield) may be influenced by Calgary urban air, whereas the sub-Arctic coastal (Churchill, Manitoba) and boreal forest (Fort Vermilion, Alberta) sites are in more remote northern areas. Annual mean Hg concentrations in precipitation (5.0–9.2 ng L −1) at the study sites were in the lower half of the range reported for southern Canada and the USA by the Mercury Deposition Network (MDN). But owing to typically low precipitation rates, gross wet Hg fluxes (0.54–2.0 μg m −2 yr −1) were among the lowest reported by MDN, with Crossfield having about twice the flux in 2007 of the other two sites. Flux was significantly correlated with precipitation, and thus was highest in summer (June–August) and lowest during winter, a pattern typical of other temperate continental locations. There was no evidence of higher wet Hg fluxes or concentrations in springtime at Churchill where atmospheric mercury depletion events (AMDEs) occur. Measured gross deposition fluxes at the study locations were ∼2–8 times lower than estimated by GEOS-Chem and GRAHM atmospheric models. The largest discrepancy occurred for Churchill, which raises the question of how well Hg deposition from AMDEs is described by current models. Better agreement between measurements and models was obtained from MDN stations in Alberta and Alaska, where wet Hg fluxes were 2–10 times higher than the study sites either because of power plant emissions (Alberta), or because of high precipitation rates (Alaska).

Wet deposition of mercury in the U.S. and Canada, 1996–2005: Results and analysis of the NADP mercury deposition network (MDN)

One of the most critical measurements needed to understand the biogeochemical cycle of mercury, and to verify atmospheric models, is the rate of mercury wet-deposition. The Mercury Deposition Network (MDN) operates sites across North America to monitor total mercury in wet-deposition. MDN's primary goal is to provide both spatial and temporal continental-scale observations of mercury wet-deposition fluxes to support researchers, modelers, policy-makers and the public interest. MDN represents the only continental-scale mercury deposition database with a >10-year record of continuous values. This study provides analysis and interpretation of MDN observations at 10 years (1996–2005) with an emphasis on investigating whether rigorous, statistically-significant temporal trends and spatial patterns were present and where they occurred. Wet deposition of mercury ranges from more than 25 μg m −2 yr in south Florida to less than 3 μg m −2 yr in northern California. Volume-weighted total mercury concentrations are statistically different between defined regions overall (Southeast ≈ Midwest > Ohio River > Northeast), with the highest in Florida, Minnesota, and several Southwest locations (10–16 ng L −1). Total mercury wet-deposition is significantly different between defined regions (Southeast > Ohio River > Midwest > Northeast). Mercury deposition is strongly seasonal in eastern North America. The average mercury concentration is about two times higher in summer than in winter, and the average deposition is approximately more than three times greater in summer than in winter. Forty-eight sites with validated datasets of five years or more were tested for trends using the non-parametric seasonal Kendall trend test. Significant decreasing mercury wet-deposition concentration trends were found at about half of the sites, particularly across Pennsylvania and extending up through the Northeast.

An analysis of simulated wet deposition of mercury from the North American Mercury Model Intercomparison Study

A previous intercomparison of atmospheric mercury models in North America has been extended to compare simulated and observed wet deposition of mercury. Three regional‐scale atmospheric mercury models were tested: the Community Multiscale Air Quality (CMAQ) model, the Regional Modeling System for Aerosols and Deposition (REMSAD), and the Trace Element Analysis Model (TEAM). These models were each employed using three sets of lateral boundary conditions to test their sensitivity to intercontinental transport of mercury. The same meteorological and pollutant emission data were used in each simulation. Observations of wet deposition were obtained from the National Atmospheric Deposition Program's Mercury Deposition Network. The regional models can explain 50–70% of the site‐to‐site variance in annual mercury wet deposition. CMAQ was found to have slightly superior agreement with observations of annual mercury deposition flux in terms of the mean value for all monitoring sites, but REMSAD showed the best correlation when measured by the coefficient of determination (r2). With the exception of one CMAQ simulation, all of the models tended to simulate more wet deposition of mercury than was observed. TEAM exceeded the observed average annual wet deposition by 50% or more in all three of its simulations. CMAQ and REMSAD were better able to reproduce the observed seasonal distribution of mercury wet deposition than was TEAM, but TEAM showed the highest correlation for weekly wet deposition samples. An analysis of model accuracy at each observation site showed no obvious geographic patterns for correlation, bias, or error. Adjusting simulated mercury deposition on the basis of the difference between observed and simulated precipitation data improved the correlation and error scores for all of the models.