Automated Stable Isotope Sampling of Gaseous Elemental Mercury (ISO-GEM): Insights into GEM Emissions from Building Surfaces.

Atmospheric monitoring networks quantify gaseous elemental mercury (GEM) concentrations, but not isotopic compositions. Here, we present a new method for automated and quantitative stable isotope sampling of GEM (ISO-GEM) at the outlet of a commercial Hg analyzer. A programmable multivalve manifold selects Hg at the analyzer inlet and outlet based on specific criteria (location, time, GEM concentration, auxiliary threshold). Outlet Hg recovery was tested for gold traps, oxidizing acidic solution traps, and activated carbon traps. We illustrate the ISO-GEM method in an exploratory study on the effect of building walls on local GEM. We find that GEM concentrations directly at the building surface (wall inlet) are significantly enhanced (mean 3.8 ± 1.8 ng/m3) compared to 3 m from the building wall (free inlet) (mean 1.5 ± 0.4 ng/m3). GEM δ202Hg (-1.26‰ ± 0.41‰, 1 SD, n = 16) and Δ199Hg (-0.05‰ ± 0.10‰, 1 SD, n = 16) at the wall inlet were different from ambient GEM δ202Hg (0.76‰ ± 0.09‰, 1 SD, n = 16) and Δ199Hg (-0.21‰ ± 0.05‰, 1 SD, n = 16) at the free inlet. The isotopic fingerprint of GEM at the wall inlet suggests that GEM emission from the aluminum building surface affected local GEM concentration measurements. These results illustrate the versatility of the automated Hg isotope sampling.

Testing and application of surrogate surfaces for understanding potential gaseous oxidized mercury dry deposition.

Currently there is no standard method for measurement of atmospheric mercury dry deposition. While all operationally defined forms of atmospheric mercury (elemental, oxidized, and particulate) can be dry deposited, oxidized forms are of concern due to high deposition velocities, water solubility, and reactivity. This paper describes the development of a surrogate surface for characterizing potential dry deposition of gaseous oxidized mercury (GOM). Laboratory tests showed that the surface collected HgCl2, HgBr2, and HgO with equal efficiency, and deposition was not significantly influenced by temperature, humidity, or ozone concentrations. Deposition of mercury to surfaces in field deployments was correlated with GOM concentrations (r2 = 0.84, p < 0.01, n = 326. Weekly mean GOM deposition velocities from surface deployments (1.1 +/- 0.6 cm s(-1)) were higher than modeled values (0.4 +/- 0.2 cm s(-1)) at four field sites, but were within the range reported for direct measurements. Although the surfaces do not simulate the heterogeneity of natural surfaces and need to be validated by direct measurements, they do provide a physical means for estimating temporal trends and spatial variability of dry deposition of GOM.

Estimation of dry deposition of atmospheric mercury in Nevada by direct and indirect methods.

Atmospheric models and limited measurements indicate that dry deposition of atmospheric mercury is an important process by which mercury is input to ecosystems. To begin to fill the measurement data gap, multiple methods were used simultaneously during seasonal campaigns conducted in 2005 and 2006 to estimate dry deposition of atmospheric mercury at two Mercury Deposition Network (MDN) sites in rural Nevada and in Reno, Nevada. Gaseous elemental mercury (Hg0), reactive gaseous mercury (RGM), and particulate-bound mercury (Hgp) concentrations were measured using Tekran 2537A/1130/ 1135 systems. These speciated measurements were combined with on-site meteorological measurements to estimate depositional fluxes of RGM and Hgp using dry deposition models. Modeled fluxes were compared with more direct measurements obtained using polysulfone cation-exchange membranes and foliar surfaces. Dynamic flux chambers were used to measure soil mercury exchange. RGM concentrations were higher during warmer months at all sites, leading to seasonal variation in the modeled importance of RGM as a component of total depositional load. The ratio of dry to wet deposition was between 10 and 90%, and varied with season and with the methods used for dry deposition approximations. This work illustrates the variability of mercury dry deposition with location and time and highlights the need for direct dry deposition measurements.

A synthesis of progress and uncertainties in attributing the sources of mercury in deposition.

A panel of international experts was convened in Madison, Wisconsin, in 2005, as part of the 8th International Conference on Mercury as a Global Pollutant. Our charge was to address the state of science pertinent to source attribution, specifically our key question was: "For a given location, can we ascertain with confidence the relative contributions of local, regional, and global sources, and of natural versus anthropogenic emissions to mercury deposition?" The panel synthesized new research pertinent to this question published over the past decade, with emphasis on four major research topics: long-term anthropogenic change, current emission and deposition trends, chemical transformations and cycling, and modeling and uncertainty. Within each topic, the panel drew a series of conclusions, which are presented in this paper. These conclusions led us to concur that the answer to our question is a "qualified yes," with the qualification being dependent upon the level of uncertainty one is willing to accept. We agreed that the uncertainty is strongly dependent upon scale and that our question as stated is answerable with greater confidence both very near and very far from major point sources, assuming that the "global pool" is a recognizable "source." Many regions of interest from an ecosystem-exposure standpoint lie in between, where source attribution carries the greatest degree of uncertainty.

Concentration and dry deposition of mercury species in arid south central New Mexico (2001-2002).

This research was initiated to characterize atmospheric deposition of reactive gaseous mercury (RGM), particulate mercury (HgP; <2.5 microm), and gaseous elemental mercury (Hg0) in the arid lands of south central New Mexico. Two methods were field-tested to estimate dry deposition of three mercury species. A manual speciation sampling train consisting of a KCl-coated denuder, 2.5 microm quartz fiber filters, and gold-coated quartz traps and an ion-exchange membrane (as a passive surrogate surface) were deployed concurrently over 24-h intervals for an entire year. The mean 24-h atmospheric concentration for RGM was 6.8 pg m(-3) with an estimated deposition of 0.10 ng m(-2) h(-1). The estimated deposition of mercury to the passive surrogate surface was much greater (4.0 ng m(-2) h(-1)) but demonstrated a diurnal pattern with elevated deposition from late afternoon to late evening (1400-2200; 8.0 ng m(-2) h(-1)) and lowest deposition during the night just prior to sunrise (2200-0600; 1.7 ng m(-2) h(-1)). The mean 24-h atmospheric concentrations for HgP and Hg0 were 1.52 pg m(-3) and 1.59 ng m(-3), respectively. Diurnal patterns were observed for RGM with atmospheric levels lowest during the night prior to sunrise (3.8 pg m(-3)) and greater during the afternoon and early evening (8.9 pg m(-3)). Discernible diurnal patterns were not observed for either HgP or Hg0. The total dry deposition of Hg was 5.9 microg m-2 year-' with the contribution from the three species as follows: RGM (0.88 microg m(-2) year(-1)), HgP (0.025 microg m(-2) year(-1)), and Hg0 (5.0 microg m(-2) year(-1)). The annual wet deposition for total mercury throughout the same collection duration was 4.2 microg m(-2) year (-1), resulting in an estimated total deposition of 10.1 microg m(-2) year(-1) for Hg. On one sampling date, enhanced HgP (12 pg m(-3)) was observed due to emissions from a wildfire approximately 250 km to the east.

Development and complete validation of a method for the determination of dimethyl mercury in air and other media.

The rigorous validation of a previously developed research method for the determination of dimethyl mercury ((CH3)2Hg) in environmental samples is presented. During atmospheric analysis, (CH3)2Hg was trapped on Carbotrap™ and analyzed by thermal desorption, isothermal GC separation, and cold vapor atomic fluorescence spectrometry (CVAFS). Water samples were analyzed after direct purging of 100mL aliquots onto Carbotrap™, while sediment and tissue samples were digested with 10mL of 25% KOH in methanol at 60°C and diluted to 40mL with methanol. An ambient air-spiking manifold, which allowed simultaneous replicate sampling, was constructed in a room controlled for temperature and humidity. (CH3)2Hg was introduced into the feed airflow (0.4m3min-1) from a well-calibrated diffusion cell, to obtain a concentration of approximately 5.5ngm-3 as Hg. Samples were collected onto Carbotrap™ columns, and the total volumes quantified by integrating mass flow meters. Trapping efficiency was investigated over a range of sampler flow rates (0.05-0.25Lmin-1), volumes (2-200L), collection temperatures (15-42°C) and relative humidity levels (10-70%). Method detection limits (MDLs), analytical precision and accuracy were quantified for all media. Carbotrap™ was found to be the best choice as a sampling media, whereas Tenax™ was found to be inadequate due to high breakthrough (>70%). This study verified that the method is sufficiently precise, accurate and robust for field sampling at mercury contaminated sites. No interferences were observed from elevated levels of potential co-contaminants, Hg0 (125ngm-3) and H2S (1.27ppmv).

Gaseous elemental mercury in the marine boundary layer: evidence for rapid removal in anthropogenic pollution.

In this study, gas-phase elemental mercury (Hg0) and related species (including inorganic reactive gaseous mercury (RGM) and particulate mercury (PHg)) were measured at Cheeka Peak Observatory (CPO), Washington State, in the marine boundary layer during 2001-2002. Air of continental origin containing anthropogenic pollutants from the urban areas to the east contained on average 5.3% lower Hg0 levels as compared to the marine background. This result is difficult to reconcile since it is known that industrial emissions in our region are sources of Hg0. The rate of removal of Hg0 from a pollution plume necessary to account for our observations is inconsistent with the accepted view of Hg0 as a stable atmospheric pollutant. The largest and most frequent Hg0 loss events occurred in the presence of increased ozone (O3) during the summer. Hg0 and O3 also display diurnal cycles that are out-of-phase with one another. In other seasons Hg0 behavior is less consistent, as we observe weak positive correlations with O3 and occasional Hg0 enhancements in local pollution. RGM and PHg concentrations are enhanced only slightly during Hg0 loss events, comprising a small fraction of the mercury pool (approximately 3%). Long-range transported pollution of Asian origin was also detected at CPO, and this contains both higher and lower levels of Hg0 as compared to the background with maximum changes being <20%. Here, the more photochemically processed the air mass, as determined by propane/ethane ratios, the more likely we are to observe Hg0 loss. Air from the marine background in summer displays a significant diurnal cycle with a phase that matches the diurnal cycles seen in polluted air masses. A Junge lifetime for Hg0 in the clean marine boundary layer is calculated to be 7.1 months, which is on the low end of previous estimates (0.5-2 yr).

Development and characterization of an annular denuder methodology for the measurement of divalent inorganic reactive gaseous mercury in ambient air.

Atmospheric mercury is predominantly present in the gaseous elemental form (Hg0). However, anthropogenic emissions (e.g., incineration, fossil fuel combustion) emit and natural processes create particulate-phase mercury(Hg(p)) and divalent reactive gas-phase mercury (RGM). RGM species (e.g., HgCl2, HgBr2) are water-soluble and have much shorter residence times in the atmosphere than Hg0 due to their higher removal rates through wet and dry deposition mechanisms. Manual and automated annular denuder methodologies, to provide high-resolution (1-2 h) ambient RGM measurements, were developed and evaluated. Following collection of RGM onto KCl-coated quartz annular denuders, RGM was thermally decomposed and quantified as Hg0. Laboratory and field evaluations of the denuders found the RGM collection efficiency to be >94% and mean collocated precision to be <15%. Method detection limits for sampling durations ranging from 1 to 12 h were 6.2-0.5 pg m(-3), respectively. As part of this research, the authors observed that methods to measure Hg(p) had a significant positive artifact when RGM coexists with Hg(p). This artifact was eliminated if a KCl-coated annular denuder preceded the filter. This new atmospheric mercury speciation methodology has dramatically enhanced our ability to investigate the mechanisms of transformation and deposition of mercury in the atmosphere.