Atmospheric Mercury Network Research Articles

Total gaseous mercury (TGM) concentration over Lake Superior and Lake Michigan

Mercury-contaminated fish are a serious problem in the Great Lakes basin, because mercury is a potent neurotoxin that poses a danger to both humans and wildlife. Lake Superior lake trout and walleye have the highest mercury concentrations of the five Great Lakes. Because the atmosphere is the major source of mercury to the Great Lakes, information on the over-water mercury concentration is essential to model the mercury biogeochemical cycle. For the first time in the peer-reviewed literature, this paper presents total gaseous mercury (TGM) measurements made over Lake Superior and Lake Michigan. The Lake Superior aircraft measurements were made at an altitude of 300 m, and the Lake Michigan aircraft measurements at a variable altitude of 30–300 m. The over-water Lake Superior TGM of 1.02 ± 0.34 ng/m3 is much lower than the TGM from nine stations in the Canadian Atmospheric Mercury Measurement Network (CAMNet) and six stations in the Atmospheric Mercury Network (AMNet). The land-based TGM concentrations average range from 1.25 to 1.75 ng/m3 which are in good agreement with current global average values of 1.3–1.6 ng/m3. The over-water Lake Michigan TGM is 1.65 ± 0.61 ng/m3. We also present Lake Superior over-water measurements of volatile organic compounds (VOC), ozone (O3), nitrogen oxide (NOy), and particulate matter. Elemental carbon (EC) is a tracer for mercury because mercury is released during the combustion of coal. EC is significantly correlated with TGM over both Lake Superior and Lake Michigan. TGM over Lake Michigan is also significantly correlated with organic carbon, sulfate, nitrate and ammonium.

Gaseous Elemental Mercury Concentrations along the Northern Gulf of Mexico Using Passive Air Sampling, with a Comparison to Active Sampling

Mercury is a toxic element that is dispersed globally through the atmosphere. Accurately measuring airborne mercury concentrations aids understanding of the pollutant’s sources, distribution, cycling, and trends. We deployed MerPAS® passive air samplers (PAS) for ~4 weeks during each season, from spring 2019 to winter 2020, to determine gaseous elemental mercury (GEM) levels at six locations along the northern Gulf of Mexico, where the pollutant is of particular concern due to high mercury wet deposition rates and high concentrations in local seafood. The objective was to (1) evaluate spatial and seasonal trends along the Mississippi and Alabama coast, and (2) compare active and passive sampling methods for GEM at Grand Bay National Estuarine Research Reserve, an Atmospheric Mercury Network site. We observed higher GEM levels (p < 0.05) in the winter (1.53 ± 0.03 ng m−3) compared to other seasons at all sites; with the general pattern being: winter > spring > summer ≈ fall. Average GEM levels (all deployment combined) were highest at Bay St. Louis (1.36 ± 0.05 ng m−3), the western-most site nearest the New Orleans metropolitan area, and lowest at Cedar Point (1.07 ± 0.09 ng m−3), a coastal marsh with extensive vegetation that can uptake GEM. The MerPAS units compared reasonably well with the established active monitoring system, but gave slightly lower concentrations, except in the winter when the two methods were statistically similar. Both the passive and active sampling methods showed the same seasonal trends and the difference between them for each season was <15%, acceptable for evaluating larger spatial and temporal trends. Overall, this work demonstrates that PASs can provide insight into GEM levels and the factors affecting them along coastal regions.

Long-Term Observations of Atmospheric Speciated Mercury at a Coastal Site in the Northern Gulf of Mexico during 2007–2018

Atmospheric mercury species (gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and particulate-bound mercury (PBM)), trace pollutants (O3, SO2, CO, NO, NOY, and black carbon), and meteorological parameters have been continuously measured since 2007 at an Atmospheric Mercury Network (AMNet) site that is located on the northern coast of the Gulf of Mexico in Moss Point, Mississippi. For the data that were collected between 2007 and 2018, the average concentrations and standard deviations are 1.39 ± 0.22 ng m−3 for GEM, 5.1 ± 10.2 pg m−3 for GOM, 5.9 ± 13.0 pg m−3 for PBM, and 309 ± 407 ng m−2 wk−1 for mercury wet deposition, with interannual trends of −0.009 ng m−3 yr−1 for GEM, −0.36 pg m−3 yr−1 for GOM, 0.18 pg m−3 yr−1 for PBM, and 2.8 ng m−2 wk−1 yr−1 for mercury wet deposition. The diurnal variation of GEM shows lower concentrations in the early morning due to GEM depletion, likely due to plant uptake in high humidity events and slight elevation during the day, likely due to downward mixing to the surface of higher concentrations of GEM in the air aloft. The seasonal variation of GEM shows higher levels in winter and spring and lower levels in summer and fall. Diurnal variations of both GOM and PBM show broad peaks in the afternoon likely due to the photochemical oxidation of GEM. Seasonally, PBM measurements exhibit higher levels in winter and early spring and lower levels in summer with rising levels in fall, while GOM measurements show high levels in late spring/early summer and late fall and low levels in winter. The seasonal variation of mercury wet deposition shows higher values in summer and lower values in winter, due to larger rainfall amounts in summer than in winter. As expected, anticorrelation between mercury wet deposition and the sum of GOM and PBM, but positive correlation between mercury wet deposition and rainfall were observed. Correlation among GOM, ozone, and SO2 suggests possible different GOM sources: direct emissions and photochemical oxidation of GEM, with the possible influence of boundary layer dynamics and seasonal variability. This study indicates that the monitoring site experiences are impacted from local and regional mercury sources as well as large scale mercury cycling phenomena.

Effects of Brownfield Remediation on Total Gaseous Mercury Concentrations in an Urban Landscape.

In order to obtain a better perspective of the impacts of brownfields on the land–atmosphere exchange of mercury in urban areas, total gaseous mercury (TGM) was measured at two heights (1.8 m and 42.7 m) prior to 2011–2012 and after 2015–2016 for the remediation of a brownfield and installation of a parking lot adjacent to the Syracuse Center of Excellence in Syracuse, NY, USA. Prior to brownfield remediation, the annual average TGM concentrations were 1.6 ± 0.6 and 1.4 ± 0.4 at the ground and upper heights, respectively. After brownfield remediation, the annual average TGM concentrations decreased by 32% and 22% at the ground and the upper height, respectively. Mercury soil flux measurements during summer after remediation showed net TGM deposition of 1.7 suggesting that the site transitioned from a mercury source to a net mercury sink. Measurements from the Atmospheric Mercury Network (AMNet) indicate that there was no regional decrease in TGM concentrations during the study period. This study demonstrates that evasion from mercury-contaminated soil significantly increased local TGM concentrations, which was subsequently mitigated after soil restoration. Considering the large number of brownfields, they may be an important source of mercury emissions source to local urban ecosystems and warrant future study at additional locations.

Uncertainty Assessment of Gaseous Oxidized Mercury Measurements Collected by Atmospheric Mercury Network.

Gaseous oxidized mercury (GOM) measurement uncertainties undoubtedly impact the understanding of mercury biogeochemical cycling; however, there is a lack of consensus on the uncertainty magnitude. The numerical method presented in this study provides an alternative means of estimating the uncertainties of previous GOM measurements. Weekly GOM in ambient air was predicted from measured weekly mercury wet deposition using a scavenging ratio approach, and compared against field measurements of 2-4 hly GOM to estimate the measurement biases of the Tekran speciation instruments at 13 Atmospheric Mercury Network (AMNet) sites. Multiyear average GOM measurements were estimated to be biased low by more than a factor of 2 at six sites, between a factor of 1.5 and 1.8 at six other sites, and below a factor of 1.3 at one site. The differences between predicted and observed were significantly larger during summer than other seasons potentially because of higher ozone concentrations that may interfere with GOM sampling. The analysis data collected over six years at multiple sites suggests a systematic bias in GOM measurements, supporting the need for further investigation of measurement technologies and identifying the chemical composition of GOM.

An approach estimating bidirectional air‐surface exchange for gaseous elemental mercury at AMNet sites

AbstractThe bidirectional air‐surface exchange for gaseous elemental mercury (GEM) and existing measurements of the compensation points over a variety of canopy types are reviewed. Deposition and emission of GEM are dependent on several factors such as the type of canopy, temperature, season, atmospheric GEM concentrations, and meteorological conditions, with compensation points varying between 0.5 and 33 ng m−3. Emissions tend to increase from the spring to summer seasons, as the GEM accumulates in the foliage of the vegetation. A strong dependence on solar radiation has been observed, with higher emissions under light conditions. A bidirectional air‐surface exchange flux model is proposed for estimating GEM fluxes at a two‐hourly time resolution for the National Atmospheric Deposition Program's, Atmospheric Mercury Network (AMNet) sites. Compared to the unidirectional dry deposition model used in Zhang et al. (2012), two additional parameters, stomatal and soil emission potential, were needed in the bidirectional model and were chosen based on knowledge gained in the literature review and model sensitivity test results. Application of this bidirectional model to AMNet sites have produced annual net deposition fluxes comparable to those estimated in Zhang et al. (2012) at the majority of the sites. In this study, the net GEM dry deposition has been estimated separately for each dominant land use type surrounding each site, and this approach is also recommended for future calculations for easy application of the results to assessments of the mercury effects on various ecosystems.

Mercury Speciation at a Coastal Site in the Northern Gulf of Mexico: Results from the Grand Bay Intensive Studies in Summer 2010 and Spring 2011

During two intensive studies in summer 2010 and spring 2011, measurements of mercury species including gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and particulate-bound mercury (PBM), trace chemical species including O3, SO2, CO, NO, NOY, and black carbon, and meteorological parameters were made at an Atmospheric Mercury Network (AMNet) site at the Grand Bay National Estuarine Research Reserve (NERR) in Moss Point, Mississippi. Surface measurements indicate that the mean mercury concentrations were 1.42 ± 0.12 ng∙m−3 for GEM, 5.4 ± 10.2 pg∙m−3 for GOM, and 3.1 ± 1.9 pg∙m−3 for PBM during the summer 2010 intensive and 1.53 ± 0.11 ng∙m−3 for GEM, 5.3 ± 10.2 pg∙m−3 for GOM, and 5.7 ± 6.2 pg∙m−3 for PBM during the spring 2011 intensive. Elevated daytime GOM levels (>20 pg∙m−3) were observed on a few days in each study and were usually associated with either elevated O3 (>50 ppbv), BrO, and solar radiation or elevated SO2 (>a few ppbv) but lower O3 (~20–40 ppbv). This behavior suggests two potential sources of GOM: photochemical oxidation of GEM and direct emissions of GOM from nearby local sources. Lack of correlation between GOM and Beryllium-7 (7Be) suggests little influence on surface GOM from downward mixing of GOM from the upper troposphere. These data were analyzed using the HYSPLIT back trajectory model and principal component analysis in order to develop source-receptor relationships for mercury species in this coastal environment. Trajectory frequency analysis shows that high GOM events were generally associated with high frequencies of the trajectories passing through the areas with high mercury emissions, while low GOM levels were largely associated the trajectories passing through relatively clean areas. Principal component analysis also reveals two main factors: direct emission and photochemical processes that were clustered with high GOM and PBM. This study indicates that the receptor site, which is located in a coastal environment of the Gulf of Mexico, experienced impacts from mercury sources that are both local and regional in nature.

Overview of the NADP’s atmospheric mercury network (AMNet)

Overview of the NADP’s atmospheric mercury network (AMNet)

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

Abstract. The National Atmospheric Deposition Program (NADP) developed and operates a collaborative network of atmospheric-mercury-monitoring sites based in North America – 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.

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.

Seasonal and diurnal variations of atmospheric mercury across the US determined from AMNet monitoring data

Abstract. Speciated atmospheric mercury observations collected over the period from 2008 to 2010 at the Environmental Protection Agency and National Atmospheric Deposition Program Atmospheric Mercury Network sites (AMNet) were analyzed for its spatial, seasonal, and diurnal characteristics across the US. Median values of gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM) and particulate bound mercury (PBM) at 11 different AMNet sites ranged from 148–226 ppqv (1.32–2.02 ng m−3), 0.05–1.4 ppqv (0.47–12.4 pg m−3) and 0.18–1.5 ppqv (1.61–13.7 pg m−3), respectively. Common characteristics of these sites were the similar median levels of GEM as well as its seasonality, with the highest mixing ratios occurring in winter and spring and the lowest in fall. However, discernible differences in monthly average GEM were as large as 30 ppqv, which may be caused by sporadic influence from local emission sources. The largest diurnal variation amplitude of GEM occurred in the summer. Seven rural sites displayed similar GEM summer diurnal patterns, in that the lowest levels appeared in the early morning, and then the GEM mixing ratio increased after sunrise and reached its maxima at noon or in the early afternoon. Unlike GEM, GOM exhibited higher mixing ratios in spring and summer. The largest diurnal variation amplitude of GOM occurred in spring for most AMNet sites. The GOM diurnal minima appeared before sunrise and maxima appeared in the afternoon. The increased GOM mixing ratio in the afternoon indicated a photochemically driven oxidation of GEM resulting in GOM formation. PBM exhibited diurnal fluctuations in summertime. The summertime PBM diurnal pattern displayed daily maxima in the early afternoon and lower mixing ratios at night, implying photochemical production of PBM in summer.

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%.

Is mercury increasing in the atmosphere? The need for an atmospheric mercury network (AMNET)

Is mercury increasing in the atmosphere? The need for an atmospheric mercury network (AMNET)