Atmospheric reactive mercury concentrations in coastal Australia and the Southern Ocean.

Mercury (Hg), especially reactive Hg (RM), data from the Southern Hemisphere (SH) are limited. In this study, long-term measurements of both gaseous elemental Hg (GEM) and RM were made at two ground-based monitoring locations in Australia, the Cape Grim Baseline Air Pollution Station (CGBAPS) in Tasmania, and the Macquarie University Automatic Weather Station (MQAWS) in Sydney, New South Wales. Measurements were also made on board the Australian RV Investigator (RVI) during an ocean research voyage to the East Antarctic coast. GEM was measured using the standard Tekran® 2537 series analytical platform, and RM was measured using cation exchange membranes (CEM) in a filter-based sampling method. Overall mean RM concentrations at CGBAPS and MQAWS were 15.9 ± 6.7 pg m-3 and 17.8 ± 6.6 pg m-3, respectively. For the 10-week austral summer period on RVI, mean RM was 23.5 ± 6.7 pg m-3. RM concentrations at CGBAPS were seasonally invariable, while those at MQAWS were significantly different between summer and winter due to seasonal changes in synoptic wind patterns. During the RVI voyage, RM concentrations were relatively enhanced along the Antarctic coast (up to 30 pg m-3) and GEM concentrations were variable (0.2 to 0.9 ng m-3), suggesting periods of enrichment and depletion. Both RM and GEM concentrations were relatively lower while transiting the Southern Ocean farther north of Antarctica. RM concentrations measured in this study were higher in comparison to most other reported measurements of RM in the global marine boundary layer (MBL), especially for remote SH locations. As observations of GEM and RM concentrations inform global ocean-atmosphere model simulations of the atmospheric Hg budget, our results have important implications for understanding of total atmospheric Hg (TAM).

An innovative approach to bioremediation of mercury contaminated soils from industrial mining operations.

Soils contaminated with mercury (Hg) have proved expensive and logistically difficult to remediate. Research continues into finding suitable environmentally-friendly and efficient ways of achieving this end. Bioremediation is an option, which employs the strategies microorganisms have evolved to deal with Hg. One microbial strategy involves uptake and intracellular volatilisation of mercuric ions, which passively diffuse from the cell and back into the atmosphere. In this work, Pseudomonas veronii cells grown to stationary phase were immobilised in a xanthan gum-based biopolymer via encapsulation. The P. veronii-biopolymer mix was then coated onto natural zeolite granules. Zeolite immobilised cells remained viable for at least 16 weeks stored under ambient room temperature. Furthermore, the immobilised cells were shown to retain both viability and Hg volatilisation functionality after transportation from Australia to the USA, where they were applied to Hg contaminated soil. Maximum flux rates exceeded 10 µg Hg m2 h-1 from mine tailings (≈7 mg kg-1 Hg with 50% v/v water). This was 4 orders of magnitude above background flux levels. It is envisioned that emitted gaseous elemental mercury (GEM) can be readily captured, and transformed back into metallic Hg, which can then be stored appropriately or recycled. This breaks the Hg cycle, as GEM is no longer translocated back to the atmospheric compartment. The immobilising excipients used in this research overcome many logistical issues with delivery of suitable microbial loads to locations of mercury contamination and presents a facile and inexpensive method of augmenting contaminated sites with selected microbial consortia for bioremediation.

Evidence for Different Reactive Hg Sources and Chemical Compounds at Adjacent Valley and High Elevation Locations.

The spatial distribution of chemical compounds and concentration of reactive mercury (RM), defined as the sum of gaseous oxidized mercury (GOM) and <3 µm particulate bound mercury (PBM), are poorly characterized. The objective of this study was to understand the chemistry, concentration, and spatial and temporal distribution of GOM at adjacent locations (12 km apart) with a difference in elevation of ∼1000 m. Atmospheric GOM measurements were made with passive and active samplers using membranes, and at one location, a Tekran mercury measurement system was used. The chemistry of GOM varied across time and location. On the basis of data collected, chemistry at the low elevation site adjacent to a highway was primarily influenced by pollutants generated by mobile sources (GOM = nitrogen and sulfur-based compounds), and the high elevation site (GOM = halogen-based compounds) was affected by long-range transport in the free troposphere over the marine boundary layer into Nevada. Data collected at these two locations demonstrate that different GOM compounds exist depending on the oxidants present in the air. Measurements of GOM made by the KCl denuder in the Tekran instrument located at the low elevation site were lower than that measured using membranes by 1.7-13 times. Accurate measurements of atmospheric concentrations and chemistry of RM are necessary for proper assessment of environmental impacts, and field measurements are essential for atmospheric models, which in turn influence policy decisions.

Identifying sources of ozone to three rural locations in Nevada, USA, using ancillary gas pollutants, aerosol chemistry, and mercury.

Ozone (O3) is a secondary air pollutant of long standing and increasing concern for environmental and human health, and as such, the US Environmental Protection Agency will revise the National Ambient Air Quality Standard of 75 ppbv to ≤ 70 ppbv. Long term measurements at the Great Basin National Park (GBNP) indicate that O3 in remote areas of Nevada will exceed a revised standard. As part of the Nevada Rural Ozone Initiative, measurements of O3 and other air pollutants were made at 3 remote sites between February 2012 and March 2014, GBNP, Paradise Valley (PAVA), and Echo Peak (ECHO). Exceptionally high concentrations of each air pollutant were defined relative to each site as mixing ratios that exceeded the 90th percentile of all hourly data. Case studies were analyzed for all periods during which mean daily O3 exceeded the 90th percentile concurrently with a maximum 8-h average (MDA8) O3 that was "exceptionally high" for the site (65 ppbv at PAVA, 70 ppbv at ECHO and GBNP), and of potential regulatory significance. An MDA8 ≥ 65 ppbv occurred only five times at PAVA, whereas this occurred on 49 and 65 days at GBNP and ECHO, respectively. The overall correlation between O3 and other pollutants was poor, consistent with the large distance from significant primary emission sources. Mean CO at these locations exceeded concentrations reported for background sites in 2000. Trajectory residence time calculations and air pollutant concentrations indicate that exceedances at GBNP and ECHO were promoted by air masses originating from multiple sources, including wildfires, transport of pollution from southern California and the marine boundary layer, and transport of Asian pollution plumes. Results indicate that the State of Nevada will exceed a revised O3 standard due to sources that are beyond their control.

Development of a statistical model to identify spatial and meteorological drivers of elevated O3 in Nevada and its application to other rural mountainous regions.

Measurements of O3 at relatively remote monitoring sites are useful for quantifying baseline O3, and subsequently the magnitude of O3 not controllable by local regulations. As the National Ambient Air Quality Standard (NAAQS) for O3 becomes more stringent, there is an increased need to quantify baseline O3 particularly in the Western US, where regional and global sources can significantly enhance O3 measured at surface sites, yielding baseline mixing ratios approaching or exceeding the NAAQS threshold. Past work has indicated that meteorological conditions as well as site specific spatial characteristics (e.g. elevation, basin size, gradient) are significantly correlated with O3 intercepted at rural monitoring sites. Here, we use 3 years of measurements from sites throughout rural Nevada to develop a categorical tree model to identify spatial and meteorological characteristics that are associated with elevated baseline O3. Data from other sites in the Intermountain Western US are used to test the applicability of the model for sites throughout the region. Our analyses indicate that increased elevation and basin size were associated with increased frequency of elevated O3. On a daily time scale, relative humidity had the strongest association with observed MDA8 O3. Seventy-four percent of MDA8 O3 observations>60 ppbv occurred when daily minimum relative humidity was <15%. Further, we found that including ancillary pollutant data did not improve the predictive accuracy for measurements >60 ppbv whereas including upper air meteorological measurements improved the accuracy of predicting periods when O3 was >60 ppbv. These findings indicate that transport, rather than local production, influences O3 measurements in Nevada, and that high elevation sites in rural Nevada, are representative of baseline conditions in the Intermountain Western US.

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.

Gas-exchange chamber analysis of elemental mercury deposition/emission to alluvium, ore, and mine tailings.

Deposition of mercury (Hg) from the atmosphere is an important source of this contaminant to terrestrial ecosystems. Once deposited, all forms of Hg can be retained or emitted back to the atmosphere. Distinguishing between volatilization of geogenic or indigenous Hg and that deposited from the atmosphere is difficult. Field flux measurements in the general area of two industrial scale gold mining operations, showed local deposition of Hg emitted from point and nonpoint sources, and subsequent re-emission. The work presented in this paper investigated deposition/emission of elemental Hg to and from alluvium and two mine materials before, during, and after exposure to high air concentrations, for both wet and dry conditions, using a laboratory gas exchange chamber and a Hg permeation source. In general, results showed a range in mean elemental Hg deposition velocities ranging from 0.13 to 0.46 cm s(-1) that varied with material. A significant influence of atmospheric ozone (O3) on flux was observed that depended on the material and whether wet or dry. A synergistic relationship existed between O3 and light promoting Hg flux, and flux was also influenced by material grain size, chemistry, and primary mineralogy.

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.

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.

Testing and modeling the influence of reclamation and control methods for reducing nonpoint mercury emissions associated with industrial open pit gold mines.

Industrial gold mining is a significant source of mercury (Hg) emission to the atmosphere. To investigate ways to reduce these emissions, reclamation and dust and mercury control methods used at open pit gold mining operations in Nevada were studied in a laboratory setting. Using this information along with field data, and building off previous work, total annual Hg emissions were estimated for two active gold mines in northern Nevada. Results showed that capping mining waste materials with a low-Hg substrate can reduce Hg emissions from 50 to nearly 100%. The spraying of typical dust control solutions often results in higher Hg emissions, especially as materials dry after application. The concentrated application of a dithiocarbamate Hg control reagent appears to reduce Hg emissions, but further testing mimicking the actual distribution of this chemical within an active leach solution is needed to make a more definitive assessment.

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.

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.

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.