Nested-grid simulation of mercury over North America

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 (<i>r</i>) 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%

The Atmospheric Mercury Network: measurement and initial examination of an ongoing atmospheric mercury record across North America

The National Atmospheric Deposition Program (NADP) developed and operates a collaborative network of atmospheric-mercury-monitoring sites based in North America &ndash; the Atmospheric Mercury Network (AMNet). The justification for the network was growing interest and demand from many scientists and policy makers for a robust database of measurements to improve model development, assess policies and programs, and improve estimates of mercury dry deposition. Many different agencies and groups support the network, including federal, state, tribal, and international governments, academic institutions, and private companies. AMNet has added two high-elevation sites outside of continental North America in Hawaii and Taiwan because of new partnerships forged within NADP. Network sites measure concentrations of atmospheric mercury fractions using automated, continuous mercury speciation systems. The procedures that NADP developed for field operations, data management, and quality assurance ensure that the network makes scientifically valid and consistent measurements. AMNet reports concentrations of hourly gaseous elemental mercury (GEM), two-hour gaseous oxidized mercury (GOM), and two-hour particulate-bound mercury less than 2.5 microns in size (PBM2.5). As of January 2012, over 450 000 valid observations are available from 30 stations. AMNet also collects ancillary meteorological data and information on land use and vegetation, when available. We present atmospheric mercury data comparisons by time (3 yr) at 21 individual sites and instruments. Highlighted are contrasting values for site locations across the network: urban versus rural, coastal versus high elevation and the range of maximum observations. The data presented should catalyze the formation of many scientific questions that may be answered through further in-depth analysis and modeling studies of the AMNet database. All data and methods are publically available through an online database on the NADP website (http://nadp.sws.uiuc.edu/amn/). Future network directions are to foster new network partnerships and continue to collect, quality assure, and post data, including dry deposition estimates, for each fraction

seasonal and multivariate analysis study of total gaseous mercury data from the Canadian Atmospheric Mercury Measurement Network (CAMNet), Atmos

Abstract Long-term monitoring data of total gaseous mercury (TGM) concentrations from the Canadian Atmospheric Mercury Measurement Network (CAMNet) were analysed for temporal trends, seasonality and comparability within the network and compared to other network and model results. Data collected from 11 Canadian measurement sites between 1995 and 2005 were analysed. Sites within CAMNet were characterized by principle component analysis (PCA) into four main categories. For the first time since automated TGM measurements have been made within CAMNet, this paper reveals statistically significant decreasing TGM concentrations from rural locations in Canada during this time period. The largest declines were observed close to the urban areas of Toronto and Montreal, where levels fell by 17% at Point Petre, and 13% at St. Anicet, respectively. Many of the TGM changes are comparable with the overall trends observed in total mercury concentrations in precipitation, for similar time periods, at co-located or nearby National Atmospheric Deposition programme&apos;s Mercury Deposition Network (NADP-MDN) sites. The results show that these changes are mostly driven by local or regional changes in mercury emissions. Other sites within CAMNet reflect reported changes in hemispherical global background concentrations of airborne mercury, where slight decreases or no statistically significant trend in TGM concentrations exist over the same time period.

Ten-year trends of atmospheric mercury in the high Arctic compared to Canadian sub-Arctic and mid-latitude sites

Global emissions of mercury continue to change at the same time as the Arctic is experiencing ongoing climatic changes. Continuous monitoring of atmospheric mercury provides important information about long-term trends in the balance between transport, chemistry, and deposition of this pollutant in the Arctic atmosphere. Ten-year records of total gaseous mercury (TGM) from 2000 to 2009 were analyzed from two high Arctic sites at Alert (Nunavut, Canada) and Zeppelin Station (Svalbard, Norway); one sub-Arctic site at Kuujjuarapik (Nunavik, Québec, Canada); and three temperate Canadian sites at St. Anicet (Québec), Kejimkujik (Nova Scotia) and Egbert (Ontario). Five of the six sites examined showed a decreasing trend over this time period. Overall trend estimates at high latitude sites were: −0.9% yr&lt;sup&gt;−1&lt;/sup&gt; (95% confidence limits: −1.4, 0) at Alert and no trend (−0.5, +0.7) at Zeppelin Station. Faster decreases were observed at the remainder of the sites: −2.1% yr&lt;sup&gt;−1&lt;/sup&gt; (−3.1, −1.1) at Kuujjuarapik, −1.9% yr&lt;sup&gt;−1&lt;/sup&gt; (−2.1, −1.8) at St. Anicet, −1.6% yr&lt;sup&gt;−1&lt;/sup&gt; (−2.4, −1.0) at Kejimkujik and −2.2% yr&lt;sup&gt;−1&lt;/sup&gt; (−2.8, −1.7) at Egbert. Trends at the sub-Arctic and mid-latitude sites agree with reported decreases in background TGM concentration since 1996 at Mace Head, Ireland, and Cape Point, South Africa, but conflict with estimates showing an increase in global anthropogenic emissions over a similar period. Trends in TGM at the two high Arctic sites were not only less negative (or neutral) overall but much more variable by season. Possible reasons for differences in seasonal and overall trends at the Arctic sites compared to those at lower latitudes are discussed, as well as implications for the Arctic mercury cycle. The first calculations of multi-year trends in reactive gaseous mercury (RGM) and total particulate mercury (TPM) at Alert were also performed, indicating increases from 2002 to 2009 in both RGM and TPM in the spring when concentrations are highest

Gaseous mercury emissions from natural sources in Canadian landscapes

Field measurements of mercury air-surface exchange from natural settings were made in various Canadian landscapes. Soil and water samples were analyzed for mercury concentrations, and air-surface exchange fluxes from these substrates were determined using dynamic chamber, micrometeorological, or modeling methods. Environmental variables, including air and soil/water temperature, solar radiation, humidity, and wind speed, were monitored concurrently with the air-surface exchange to better understand the processes affecting the environmental cycling of mercury. Average mercury fluxes from aquatic landscapes ranged from 0.0 to 5.0 ng m⁻² h⁻¹ with total mercury concentration in water ranging from 0.3 to 6.5 ng L⁻¹. A significant correlation (R² = 0.47) was found between gaseous Hg fluxes and total Hg concentration in water. Mean gaseous Hg fluxes from forest soils varied from −0.4 to 2.2 ng m⁻² h⁻¹, while those from agricultural fields ranged from 1.1 to 2.9 ng m⁻² h⁻¹. Non-mineralized bedrock, sand, and till sites yielded fluxes ranging from −0.03 to 5.9 ng m⁻² h⁻¹. Mean fluxes from mercuriferous geological substrates at various locations were large compared to non-mercuriferous sites, ranging from 9.1 to 1760 ng m⁻² h⁻¹, and represent natural emissions. The corresponding total mercury substrate concentrations ranged from 0.360 to 180 ppm. A significant correlation (R² = 0.66) was found between Hg fluxes and total Hg concentrations in mineralized and non-mineralized substrates. These gaseous Hg flux measurements represent a significant contribution to understanding natural mercury cycling, but there are still insufficient data and knowledge of processes to properly scale up fluxes from natural sources in Canada.13 page(s

Modeling the global atmospheric transport and deposition of mercury to the Great Lakes

Mercury contamination in the Great Lakes continues to have important public health and wildlife ecotoxicology impacts, and atmospheric deposition is a significant ongoing loading pathway. The objective of this study was to estimate the amount and source-attribution for atmospheric mercury deposition to each lake, information needed to prioritize amelioration efforts. A new global, Eulerian version of the HYSPLIT-Hg model was used to simulate the 2005 global atmospheric transport and deposition of mercury to the Great Lakes. In addition to the base case, 10 alternative model configurations were used to examine sensitivity to uncertainties in atmospheric mercury chemistry and surface exchange. A novel atmospheric lifetime analysis was used to characterize fate and transport processes within the model. Model-estimated wet deposition and atmospheric concentrations of gaseous elemental mercury (Hg(0)) were generally within ∼10% of measurements in the Great Lakes region. The model overestimated non-Hg(0) concentrations by a factor of 2–3, similar to other modeling studies. Potential reasons for this disagreement include model inaccuracies, differences in atmospheric Hg fractions being compared, and the measurements being biased low. Lake Erie, downwind of significant local/regional emissions sources, was estimated by the model to be the most impacted by direct anthropogenic emissions (58% of the base case total deposition), while Lake Superior, with the fewest upwind local/regional sources, was the least impacted (27%). The U.S. was the largest national contributor, followed by China, contributing 25% and 6%, respectively, on average, for the Great Lakes. The contribution of U.S. direct anthropogenic emissions to total mercury deposition varied between 46% for the base case (with a range of 24–51% over all model configurations) for Lake Erie and 11% (range 6–13%) for Lake Superior. These results illustrate the importance of atmospheric chemistry, as well as emissions strength, speciation, and proximity, to the amount and source-attribution of mercury deposition