Matthieu B. Miller

Do We Understand What the Mercury Speciation Instruments Are Actually Measuring? Results of RAMIX

From August 22 to September 16, 2012, atmospheric mercury (Hg) was measured from a common manifold in the field during the Reno Atmospheric Mercury Intercomparison eXperiment. Data were collected using Tekran systems, laser induced fluorescence, and evolving new methods. The latter included the University of Washington-Detector for Oxidized Mercury, the University of Houston Mercury instrument, and a filter-based system under development by the University of Nevada-Reno. Good transmission of total Hg was found for the manifold. However, despite application of standard protocols and rigorous quality control, systematic differences in operationally defined forms of Hg were measured by the sampling systems. Concentrations of reactive Hg (RM) measured with new methods were at times 2-to-3-fold higher than that measured by Tekran system. The low RM recovery by the latter can be attributed to lack of collection as the system is currently configured. Concentrations measured by all instruments were influenced by their sampling location in-the-manifold and the instrument analytical configuration. On the basis of collective assessment of the data, we hypothesize that reactions forming RM were occurring in the manifold. Results provide a new framework for improved understanding of the atmospheric chemistry of Hg.

Comparison of Gaseous Oxidized Hg Measured by KCl-Coated Denuders, and Nylon and Cation Exchange Membranes

The chemical compounds that make up gaseous oxidized mercury (GOM) in the atmosphere, and the reactions responsible for their formation, are not well understood. The limitations and uncertainties associated with the current method applied to measure these compounds, the KCl-coated denuder, are not known due to lack of calibration and testing. This study systematically compared the uptake of specific GOM compounds by KCl-coated denuders with that collected using nylon and cation exchange membranes in the laboratory and field. In addition, a new method for identifying different GOM compounds using thermal desorption is presented. Different GOM compounds (HgCl2, HgBr2, and HgO) were found to have different affinities for the denuder surface and the denuder underestimated each of these compounds. Membranes measured 1.3 to 3.7 times higher GOM than denuders in laboratory and field experiments. Cation exchange membranes had the highest collection efficiency. Thermodesorption profiles for the release of GOM compounds from the nylon membrane were different for HgO versus HgBr2 and HgCl2. Application of the new field method for collection and identification of GOM compounds demonstrated these vary as a function of location and time of year. Understanding the chemistry of GOM across space and time has important implications for those developing policy regarding this environmental contaminant.

Empirical Models for Estimating Mercury Flux from Soils

Multiple parameters have been suggested to influence the exchange of mercury (Hg) between the atmosphere and soils. However, models applied for estimating soil Hg flux are simple and do not consider the potential synergistic and antagonist relationships between factors controlling the exchange. This study applied a two-level factorial experimental design in a gas exchange chamber (GEC) to investigate the individual and combined effects of three environmental factors (temperature, light, and soil moisture) on soil Hg flux. It was shown that individually irradiation, soil moisture, and air temperature all significantly enhance Hg evasive flux (by 90-140%). Synergistic effects (20-30% of additional flux enhancement) were observed for all two-factor interactions, with air temperature/soil moisture and air temperature/irradiation being the most significant. Results from the factorial experiments suggest that a model incorporating the second-order interactions can appropriately explain the flux response to the changes of the studied factors. Based on the factorial experiment results and using the flux data for twelve soil materials measured with a dynamic flux chamber (DFC) at various temperatures, soil moisture contents, solar radiation exposures, and soil Hg contents, two empirical models for estimating Hg flux from soils were developed. Model verification with ambient flux data not used to develop the models suggested that the models were capable of estimating dry soil Hg flux with a high degree of predictability (r ∼ 0.9).

Measurement of surface mercury fluxes at active industrial gold mines in Nevada (USA).

Mercury (Hg) may be naturally associated with the rock units hosting precious and base metal deposits. Active gold mines are known to have point source releases of Hg associated with ore processing facilities. The nonpoint source release of Hg to the air from the large area (hundreds to thousands of hectares) of disturbed and processed material at industrial open pit gold mines has not been quantified. This paper describes the field data collected as part of a project focused on estimating nonpoint source emissions of Hg from two active mines in Nevada, USA. In situ Hg flux data were collected on diel and seasonal time steps using a dynamic flux chamber from representative mine surfaces. Hg fluxes ranged from <1500 ng m(-2) day(-1) for waste rock piles (0.6-3.5 μg g(-1)) to 684,000 ng m(-2) day(-1) for tailings (2.8-58 μg g(-1)). Releases were positively correlated with material Hg concentrations, surface grain size, and moisture content. Highest Hg releases occurred from materials under active cyanide leaching and from tailings impoundments containing processed high-grade ore. Data collected indicate that as mine sites are reclaimed and material disturbance ceases, emissions will decline. Additionally local cycling of atmospheric Hg (deposition and re-emission) was found to occur.

Scaling Non-Point-Source Mercury Emissions from Two Active Industrial Gold Mines: Influential Variables and Annual Emission Estimates

Open-pit gold mines encompass thousands of hectares of disturbed materials that are often naturally enriched in mercury (Hg). The objective of this study was to estimate annual non-point-source Hg emissions from two active gold mines in Nevada. This was achieved by measuring diel and seasonally representative Hg fluxes from mesocosms of materials collected from each mine. These measurements provided a framework for scaling emissions over space and time at each mine by identifying the important variables correlated with Hg flux. The validity of these correlations was tested by comparisons with measurements conducted in situ at the mines. Of the average diel fluxes obtained in situ (92 daily flux measurements), 81% were within the 95% prediction limits of the regressions developed from the laboratory-derived data. Some surfaces at the mines could not be simulated in the laboratory setting (e.g., material actively leached by cyanide solution and tailings saturated with cyanide solution), and as such in situ data were applied for scaling. Based on the surface areas of the materials and environmental conditions at the mines during the year of study, non-point-source Hg releases were estimated to be 19 and 109 kg·year(-1). These account for 56% and 14%, respectively, of the overall emissions from each mine (point + nonpoint sources). Material being heap-leached and active tailings impoundments were the major contributors to the releases (>60% combined) suggesting that as mining operations cease, releases will decline.

Investigation of mercury deposition and potential sources at six sites from the Pacific Coast to the Great Basin, USA

The Western Airborne Contaminants Assessment Project showed that USA National Parks had fish mercury (Hg) concentrations above threshold concentrations set for wildlife. Since significant areas of the Western USA are arid, we hypothesized that dry deposition would be important. The primary question was whether sources of Hg were local and thus, easily addressed, or regional (from within the United States), or global (long range transport), and more difficult to address. To investigate this, surrogate surfaces and passive samplers for the measurement of GOM deposition and concentration, respectively, were deployed from the coast of California to the eastern edge of Nevada. Meteorological data, back trajectory modeling, and ozone concentrations were applied to better understand potential sources of Hg. Lowest seasonal mean Hg deposition (0.2 to 0.4 ng m(-2)h(-1)) was observed at low elevation (<100 m) Pacific Coast sites. Highest values were recorded at Lick Observatory, a high elevation coastal site (1,279 m), and Great Basin National Park (2,062 m) in rural eastern Nevada (1.5 to 2.4 ng m(-2)h(-1)). Intermediate values were recorded in Yosemite and Sequoia National Parks (0.9 to 1.2 ng m(-2)h(-1)). Results indicate that local, regional and global sources of air pollution, specifically oxidants, are contributing to observed deposition. At Great Basin National Park air chemistry was influenced by regional urban and agricultural emissions and free troposphere inputs. Dry deposition contributed ~2 times less Hg than wet deposition at the coastal locations, but 3 to 4 times more at the higher elevation sites. Based on the spatial trends, oxidation in the marine boundary layer or ocean sources contributed ~0.4 ng m(-2)h(-1) at the coastal locations. Regional pollution and long range transport contributed 1 to 2 ng m(-2)h(-1) to other locations, and the source of Hg is global and as such, all sources are important to consider.

Measurement and scaling of air–surface mercury exchange from substrates in the vicinity of two Nevada gold mines

The state of Nevada has extensive mineral resources, and is the largest producer of gold in the USA as well as fourth in world gold production. Mercury (Hg) is often present in the hydrothermal systems that produce gold deposits, and can be found in elevated concentrations in gold ore. As a result, mining of gold ore in Nevada has been shown to release Hg to the atmosphere from point and non-point sources. This project focused on measurement of air-soil Hg exchange associated with undisturbed soils and bedrock outcrops in the vicinity of two large gold mines. Field and laboratory data collected were used to identify the important variables controlling Hg flux from these surfaces, and to estimate a net flux from the areas adjacent to the active mines as well as that occurring from the mined area pre-disturbance. Mean daily flux by substrate type ranged from 9 ng m(-2) day(-1) to 140 ng m(-2) day(-1). Periods of net deposition of elemental Hg were observed when air masses originating from a mine site moved over sampling locations. Based on these observations and measured soil Hg concentrations we suggest that emissions from point and non-point sources at the mines are a source of Hg to the surrounding substrates with the amount deposited not being of an environmental concern but of interest mainly with respect to the cycling of atmospheric elemental Hg. Observations indicate that while some component of the deposited Hg is sequestered in the soil, this Hg is gradually released back to the atmosphere over time. Estimated pre-disturbance emissions from the current mine footprints based on field data were 0.1 and 1.7 kg yr(-1), compared to that estimated for the current non-point mining sources of 19 and 109 kg yr(-1), respectively.

The Nevada Rural Ozone Initiative (NVROI): Insights to understanding air pollution in complex terrain

The Nevada Rural Ozone Initiative (NVROI) was established to better understand O3 concentrations in the Western United States (US). The major working hypothesis for development of the sampling network was that the sources of O3 to Nevada are regional and global. Within the framework of this overarching hypothesis, we specifically address two conceptual meteorological hypotheses: (1) The high elevation, complex terrain, and deep convective mixing that characterize Nevada, make this state ideally located to intercept polluted parcels of air transported into the US from the free troposphere; and (2) site specific terrain features will influence O3 concentrations observed at surface sites. Here, the impact of complex terrain and site location on observations are discussed. Data collected in Nevada at 6 sites (1385 to 2082 m above sea level (asl)) are compared with that collected at high elevation sites in Yosemite National Park and the White Mountains, California. Average daily maximum 1-hour concentrations of O3 during the first year of the NVROI ranged from 58 to 69 ppbv (spring), 53 to 62 ppbv (summer), 44 to 49 ppbv (fall), and 37 to 45 ppbv (winter). These were similar to those measured at 3 sites in Yosemite National Park (2022 to 3031 m asl), and at 4 sites in the White Mountains (1237 to 4342 m asl) (58 to 67 ppbv (summer) and 47 to 58 ppbv (fall)). Results show, that in complex terrain, collection of data should occur at high and low elevation sites to capture surface impacts, and site location with respect to topography should be considered. Additionally, concentrations measured are above the threshold reported for causing a reduction in growth and visible injury for plants (40 ppbv), and sustained exposure at high elevation locations in the Western USA may be detrimental for ecosystems.

Variability and sources of surface ozone at rural sites in Nevada, USA: Results from two years of the Nevada Rural Ozone Initiative.

Ozone (O3) has been measured at Great Basin National Park (GBNP) since September 1993. GBNP is located in a remote, rural area of eastern Nevada. Data indicate that GBNP will not comply with a more stringent National Ambient Air Quality Standard (NAAQS) for O3, which is based upon the 3-year average of the annual 4th highest Maximum Daily 8-h Average (MDA8) concentration. Trend analyses for GBNP data collected from 1993 to 2013 indicate that MDA8 O3 increased significantly for November to February, and May. The greatest increase was for May at 0.38, 0.35, and 0.46 ppb yr(-1) for the 95th, 50th, and 5th percentiles of MDA8 O3 values, respectively. With the exception of GBNP, continuous O3 monitoring in Nevada has been limited to the greater metropolitan areas. Due to the limited spatial detail of O3 measurements in rural Nevada, a network of rural monitoring sites was established beginning in July 2011. For a period ranging from July 2011 to June 2013, maximum MDA8 O3 at 6 sites occurred in the spring and summer, and ranged from 68 to 80ppb. Our analyses indicate that GBNP, in particular, is ideally positioned to intercept air containing elevated O3 derived from regional and global sources. For the 2 year period considered here, MDA8 O3 at GBNP was an average of 3.1 to 12.6 ppb higher than at other rural Nevada sites. Measured MDA8 O3 at GBNP exceeded the current regulatory threshold of 75 ppb on 7 occasions. Analyses of synoptic conditions, model tracers, and air mass back-trajectories on these days indicate that stratospheric intrusions, interstate pollution transport, wildfires, and Asian pollution contributed to elevated O3 observed at GBNP. We suggest that regional and global sources of ozone may pose challenges to achieving a more stringent O3 NAAQS in rural Nevada.

Investigating the influence of long-range transport on surface O3 in Nevada, USA, using observations from multiple measurement platforms

The current United States (US) National Ambient Air Quality Standard (NAAQS) for O3 (75 ppb) is expected to be revised to between 60 and 70 ppb. As the NAAQS becomes more stringent, characterizing the extent of O3 and precursors transported into the US is increasingly important. Given the high elevation, complex terrain, and location in the Intermountain West, the State of Nevada is ideally situated to intercept air transported into the US. Until recently, measurements of O3 and associated pollutants were limited to areas in and around the cities of Las Vegas and Reno. In 2011, the Nevada Rural Ozone Initiative began and through this project 13 surface monitoring sites were established. Also in 2011, the NASA Ames Alpha Jet Atmospheric eXperiment (AJAX) began making routine aircraft measurements of O3 and other greenhouse gases in Nevada. The availability of aircraft and surface measurements in a relatively rural, remote setting in the Intermountain West presented a unique opportunity to investigate sources contributing to the O3 observed in Nevada. Our analyses indicate that stratosphere to troposphere transport, long-range transport of Asian pollution, and regional emissions from urban areas and wildfires influence surface observations. The complexity of sources identified here along with the fact that O3 frequently approaches the threshold being considered for a revised NAAQS indicate that interstate and international cooperation will be necessary to achieve compliance with a more stringent regulatory standard. Further, on a seasonal basis we found no significant difference between daily 1-h maximum O3 at surface sites, which ranged in elevation from 888 to 2307 m, and aircraft measurements of O3 <2500 m which suggests that similar processes influence daytime O3 across rural Nevada and indicates that column measurements from Railroad Valley, NV are useful in understanding these processes.