Observations of speciated atmospheric mercury at three sites in Nevada: Evidence for a free tropospheric source of reactive gaseous mercury

Air mercury (Hg) speciation was measured for 11 weeks (June–August 2007) at three sites simultaneously in Nevada, USA. Mean reactive gaseous Hg (RGM) concentrations were elevated at all sites relative to those reported for locations not directly influenced by known point sources. RGM concentrations at all sites displayed a regular diel pattern and were positively correlated with ozone (O3) and negatively correlated with elemental Hg (Hg0) and dew point temperature (Tdp). Superimposed on the diel changes were 2- to 7-day periods when RGM concentrations increased across all three sites, producing significant intersite correlations of RGM daily means (r = 0.53–0.76, p \u3c 0.0001). During these periods, enhanced O3 concentrations and lower Tdp were also observed. Back trajectories were applied to develop gridded frequency distribution (GFD) plots and determine trajectory residence times (TRT) in specific source boxes. The GFD for the upper-quartile RGM daily means at one site showed a contributing airflow regime from the high-altitude subtropics with little precipitation, while that developed for the lower-quartile RGM concentrations indicated predominantly lower-altitude westerly flow and precipitation. Daily mean TRT in a subtropical high-altitude source box (\u3e2 km and \u3c35°N) explained a component of the daily mean RGM at two sites (r2 = 0.37 and 0.27, p\u3c0.05). These observations indicate that long-range transport of RGM from the free troposphere is a potentially important component of Hg input to rural areas of the western United States

Deciphering potential chemical compounds of gaseous oxidized mercury in Florida, USA

The highest mercury (Hg) wet deposition in the United States of America (USA) occurs along the Gulf of Mexico, and in the southern and central Mississippi River Valley. Gaseous oxidized Hg (GOM) is thought to be a major contributor due to high water solubility and reactivity. Therefore, it is critical to understand concentrations, potential for wet and dry deposition, and GOM compounds present in the air. Concentrations and dry-deposition fluxes of GOM were measured and calculated for Naval Air Station Pensacola Outlying Landing Field (OLF) in Florida using data collected by a Tekran® 2537/1130/1135, the University of Nevada Reno Reactive Mercury Active System (UNRRMAS) with cation exchange and nylon membranes, and the Aerohead samplers that use cation-exchange membranes to determine dry deposition. Relationships with Tekran®-derived data must be interpreted with caution, since the GOM concentrations measured are biased low depending on the chemical compounds in air and interferences with water vapor and ozone.Criteria air pollutants were concurrently measured. This allowed for comparison and better understanding of GOM.In addition to other methods previously applied at OLF, use of the UNRRMAS provided a platform for determination of the chemical compounds of GOM in the air. Results from nylon membranes with thermal desorption analyses indicated seven GOM compounds in this area, including HgBr2, HgCl2, HgO, Hg–nitrogen and sulfur compounds, and two unknown compounds. This indicates that the site is influenced by different gaseous phase reactions and sources. Using back-trajectory analysis during a high-GOM event related to high CO, but average SO2, indicated air parcels moved from the free troposphere and across Arkansas, Mississippi, and Alabama at low elevation (&amp;lt; 300 m). This event was initially characterized by HgBr2, followed by a mixture of GOM compounds. Overall, GOM chemistry indicates oxidation reactions with local mobile source pollutants and long-range transport.In order to develop methods to measure GOM concentrations and chemistry, and model dry-deposition processes, the actual GOM compounds need to be known, as well as their corresponding physicochemical properties, such as Henry's Law constants.</html

Development of an Understanding of Reactive Mercury in Ambient Air: A Review

This review focuses on providing the history of measurement efforts to quantify and characterize the compounds of reactive mercury (RM), and the current status of measurement methods and knowledge. RM collectively represents gaseous oxidized mercury (GOM) and that bound to particles. The presence of RM was first recognized through measurement of coal-fired power plant emissions. Once discovered, researchers focused on developing methods for measuring RM in ambient air. First, tubular KCl-coated denuders were used for stack gas measurements, followed by mist chambers and annular denuders for ambient air measurements. For ~15 years, thermal desorption of an annular KCl denuder in the Tekran® speciation system was thought to be the gold standard for ambient GOM measurements. Research over the past ~10 years has shown that the KCl denuder does not collect GOM compounds with equal efficiency, and there are interferences with collection. Using a membrane-based system and an automated system—the Detector for Oxidized mercury System (DOHGS)—concentrations measured with the KCl denuder in the Tekran speciation system underestimate GOM concentrations by 1.3 to 13 times. Using nylon membranes it has been demonstrated that GOM/RM chemistry varies across space and time, and that this depends on the oxidant chemistry of the air. Future work should focus on development of better surfaces for collecting GOM/RM compounds, analytical methods to characterize GOM/RM chemistry, and high-resolution, calibrated measurement systems

Determining sources of reactive mercury compounds in Reno, Nevada, United States

There is much uncertainty regarding the sources of reactive mercury (RM) compounds and atmospheric chemistry driving their formation. This work focused on assessing the chemistry and potential sources of reactive mercury measured in Reno, Nevada, United States, using 1 year of data collected using Reactive Mercury Active System. In addition, ancillary meteorology and criteria air pollutant data, Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) analyses, and a generalized linear model were applied to better understand reactive mercury observations. During the year of sampling, a fire event impacted the sampling site, and gaseous elemental Hg and particulate-bound mercury concentrations increased, as did HgII-S compounds. Data collected on a peak above Reno showed that reactive mercury concentrations were higher at higher elevation, and compounds found in Reno were the same as those measured on the peak. HYSPLIT results demonstrated RM compounds were generated inside and outside of the basin housing Reno. Compounds were sourced from San Francisco, Sacramento, and Reno in the fall and winter, and from long-range transport and the marine boundary layer during the spring and summer. The generalized linear model produced correlations that could be explained; however, when applying the model to similar data collected at two other locations, the Reno model did not predict the observations, suggesting that sampling location chemistry and concentration cannot be generalized

Mercury Biogeochemical Cycling: A Synthesis of Recent Scientific Advances

The focus of this paper is to briefly discuss the major advances in scientific thinking regarding: a) processes governing the fate and transport of mercury in the environment; b) advances in measurement methods; and c) how these advances in knowledge fit in within the context of the Minamata Convention on Mercury. Details regarding the information summarized here can be found in the papers associated with this Virtual Special Issue of STOTEN

A PETROGRAPHIC, GEOCHEMICAL AND STABLE ISOTOPE STUDY OF THE UNITED VERDE OREBODY AND ITS ASSOCIATED ALTERATION, JEROME, ARIZONA

The United Verde orebody, a Proterozoic volcanogenic massive sulfide deposit, is hosted by the Cleopatra Formation. The Cleopatra Formation is subdivided into two distinct members, the Upper and Lower, on the basis of alteration facies, whole rock geochemistry and the chemistry of alteration minerals. The Lower member was deposited prior to ore deposition and consists of five major alteration facies. Facies Bl, the most distant from the orebody represents the recharge area for the ore-forming fluid. Facies B2 surrounds the major discharge area or the chlorite pipe. These three facies contain chlorite and quartz as alteration minerals in variable amounts. Two facies, 81 and S2, contain quartz and sericite as alteration minerals. Mass balance calculations show progressive removal of Na and Ca, and addition of MgO and FeO* from the area of recharge (facies Bl) to facies B2 to the chlorite pipe. Whole rock δ¹⁸O values are high relative to least altered Cleopatra Formation in the recharge area and low in the discharge zone. Mineralogy and geochemistry of samples from the Upper member indicate that it was deposited following ore deposition and interacted with fluids rich in silica and iron. The hydrothermal fluid, which is interpreted to have been seawater, evolved to a high temperature slightly acidic, reduced fluid during water-rock interaction(log a₀₂ = -33 to -41; log a(H2S) = -2.6 to -5.0). The fluid δ¹⁸O and δ¹³C₀₂ values increased. Calculated δ¹³C₀₂ and δ¹⁸O fluid values, and sphalerite and chlorite chemistry imply that mixing of the hydrothermal fluid with seawater occurred in the orebody. the upper The levels of the chlorite pipe and in limited range in δ³⁴S values of sulfides is consistent with the derivation of the oreforming fluids from the reduced basal layer of a stratified basin. The study area represents only a small part of the United Verde circulation cell. Increased δ¹⁸O values of the fluid, and the need for a source of Mg, Fe and other metals suggest that the fluids may have circulated into the Shea Basalt

Determinants of atmospheric mercury concentrations in Reno, Nevada, U.S.A.

Concentrations of gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM) and particulate-bound mercury (PBM) were measured along with ancillary variables 9 km east of downtown Reno, Nevada, U.S.A. from November 2006 through March 2009. Mean two-year (February 2007 through January 2009) GEM, GOM, and PBM concentrations were 2.0 ± 0.7 ng m− 3 (± standard deviation), 18 ± 22 pg m− 3, and 7 ± 7 pg m− 3, respectively. Data collected were compared with observations made at another location just north of the city at 169 m higher elevation. At both locations higher concentrations of GEM and PBM occurred in periods with little atmospheric mixing, indicating that local sources were important for enhancing GEM and PBM concentrations in Reno above that considered continental background. Concentrations of GOM were higher (maximum of 177 pg m− 3) during periods with higher temperature and lower dew point. Higher GOM concentrations at the higher elevation site with less urban impact relative to the valley site, along with other data trends, support the hypothesis that in northern Nevada subsiding dry air from the free troposphere is a source of GOM to the surface

Speciation of atmospheric mercury at two sites in northern Nevada, USA

Gaseous elemental mercury (Hg0), reactive gaseous mercury (RGM), and mercury bound to particles (Hgp) were measured during seasonal 1- or 2-week data collection campaigns at two Mercury Deposition Network sites (NV02 and NV99) in northern Nevada, USA. The sites are rural but are located in an area of diverse natural and anthropogenic mercury sources that include undisturbed and mining mercury-disturbed enriched substrates, coal-fired power plants, ore processing facilities, and industrial facilities. Concentrations of Hg0 averaged over all campaigns were 3.0±1.7 ng m−3 at NV02 and 2.5±3.1 ng m−3 at NV99, higher than has been reported for other rural sites. Hg0 concentrations at the sites were found to be influenced by both local substrate emission and transport from regional source areas. Concentrations of RGM and Hgp were within ranges reported for other rural sites (13±18 and 9±7 pg m−3 at NV02, 7±8 and 13±12 pg m−3 at NV99, respectively). Mercury wet deposition rates measured over 3 years (2003–2005) were similar to other sites in the arid West (3.0±0.7 μg m−2 yr−1 at NV02, 3.9±0.4 μg m−2 yr−1 at NV99)

Atmospheric mercury concentrations and speciation measured from 2004 to 2007 in Reno, Nevada, USA

Atmospheric elemental, reactive and particulate mercury (Hg) concentrations were measured north of downtown Reno, Nevada, USA from November 2004 to November 2007. Three-year mean and median concentrations for gaseous elemental Hg (Hg0) were 1.6 and 1.5 ng m−3 (respectively), similar to global mean Hg0 concentrations. The three-year mean reactive gaseous Hg (RGM) concentration (26 pg m−3) was higher than values reported for rural sites across the western United States. Well defined seasonal and daily patterns in Hg0 and RGM concentrations were observed, with the highest Hg0 concentrations measured in winter and early morning, and RGM concentrations being greatest in the summer and mid-afternoon. Elevated Hg0 concentrations in winter were associated with periods of cold, stagnant air; while a regularly observed early morning increase in concentration was due to local source and surface emissions. The observed afternoon increase and high summer values of RGM can be explained by in situ oxidation of gaseous Hg0 or mixing of RGM derived from the free troposphere to the surface. Because both of these processes are correlated with the same environmental conditions it is difficult to assess their overall contribution to the observed trends