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

A Low Cost System for Detecting Fog Events and Triggering an Active Fog Water Collector

A simple method of activating the Caltech Active Strand Cloud-water Collector (CASCC) is described. This system detected the onset of wet deposition events associated with the advection of marine stratus clouds using an optical rain sensor (ORS) and a standard passive fog collector (SFC) in combination with a relative humidity threshold. The system was deployed on a rooftop between May 10 and September 20, 2016 (134 days) at the University of California, Santa Cruz, six km from Pacific Ocean, at 240 m elevation. Twenty-nine fog water samples (daily mean volume = 174 ± 71 mL) were collected for the purposes of quantifying the concentration of monomethylmercury (MMHg) and its possible marine origins. For 20 days during the study, a visibility sensor (VS) was collocated with the ORS and both sensors detected 7 fog events. The ORS detected 2 additional marine stratus drizzle events missed by the VS. The start time of the events detected by the ORS was delayed relative to the onset of visibility reduction in 6 of 7 events by 4.5 ± 3.3 hours. Low wind speeds at night at this location limited the wet deposition to the SFC. Average CASCC sampling time during these events was 6.2 ± 2.8 hours and 4 liquid samples were obtained (80 to \u3e 275 mL). As a comparison, fog water collections at UCSC during the fog seasons of 2014 and 2015 yielded 35 and 12 samples, respectively using a trigger based on relative humidity (RH) and sampling times of \u3e 12 h per day. The main benefit of triggering with the ORS in 2016 was to cut in half the sampling time without loss of sample collection volume. Mean MMHg concentrations between the 3 years were not significantly different suggesting that the SFC/ORS triggering system is appropriate for use at multiple fog collection sites simultaneously

An Updated Review of Atmospheric Mercury

The atmosphere is a key component of the biogeochemical cycle of mercury, acting as a reservoir, transport mechanism, and facilitator of chemical reactions. The chemical and physical behavior of atmospheric mercury determines how, when, and where emitted mercury pollution impacts ecosystems. In this review, we provide current information about what is known and what remains uncertain regarding mercury in the atmosphere. We discuss new ambient, laboratory, and theoretical information about the chemistry of mercury in various atmospheric media. We review what is known about mercury in and on solid- and liquid-phase aerosols. We present recent findings related to wet and dry deposition and spatial and temporal trends in atmospheric mercury concentrations. We also review atmospheric measurement methods that are in wide use and those that are currently under development

Marine fog inputs appear to increase methylmercury bioaccumulation in a coastal terrestrial food web

Coastal marine atmospheric fog has recently been implicated as a potential source of ocean-derived monomethylmercury (MMHg) to coastal terrestrial ecosystems through the process of sea-to-land advection of foggy air masses followed by wet deposition. This study examined whether pumas (Puma concolor) in coastal central California, USA, and their associated food web, have elevated concentrations of MMHg, which could be indicative of their habitat being in a region that is regularly inundated with marine fog. We found that adult puma fur and fur-normalized whiskers in our marine fog-influenced study region had a mean (±SE) total Hg (THg) (a convenient surrogate for MMHg) concentration of 1544 ± 151 ng g−1 (N = 94), which was three times higher (P < 0.01) than mean THg in comparable samples from inland areas of California (492 ± 119 ng g−1, N = 18). Pumas in California eat primarily black-tailed and/or mule deer (Odocoileus hemionus), and THg in deer fur from the two regions was also significantly different (coastal 28.1 ± 2.9, N = 55, vs. inland 15.5 ± 1.5 ng g−1, N = 40). We suggest that atmospheric deposition of MMHg through fog may be contributing to this pattern, as we also observed significantly higher MMHg concentrations in lace lichen (Ramalina menziesii), a deer food and a bioindicator of atmospheric deposition, at sites with the highest fog frequencies. At these ocean-facing sites, deer samples had significantly higher THg concentrations compared to those from more inland bay-facing sites. Our results suggest that fog-borne MMHg, while likely a small fraction of Hg in all atmospheric deposition, may contribute, disproportionately, to the bioaccumulation of Hg to levels that approach toxicological thresholds in at least one apex predator. As global mercury levels increase, coastal food webs may be at risk to the toxicological effects of increased methylmercury burdens.publishedVersio

Total- and Monomethyl-Mercury and Major Ions in Coastal California Fog Water: Results from Two Years of Sampling on Land and at Sea

Marine fog water samples were collected over two summers (2014–2015) with active strand collectors (CASCC) at eight coastal sites from Humboldt to Monterey counties in California, USA, and on four ocean cruises along the California coastline in order to investigate mercury (Hg) cycling at the ocean-atmosphere-land interface. The mean concentration of monomethylmercury (MMHg) in fog water across terrestrial sites for both years was 1.6 ± 1.9 ng L-1 (\u3c0.01–10.4 ng L-1, N = 149), which corresponds to 5.7% (2.0–10.8%) of total Hg (HgT) in fog. Rain water samples from three sites had mean MMHg concentrations of 0.20 ± 0.12 ng L-1 (N = 5) corresponding to 1.4% of HgT. Fog water samples collected at sea had MMHg concentrations of 0.08 ± 0.15 ng L-1 (N = 14) corresponding to 0.4% of HgT. Significantly higher MMHg concentrations in fog were observed at terrestrial sites next to the ocean relative to a site 40 kilometers inland, and the mean difference was 1.6 ng L-1. Using a rate constant for photo-demethylation of MMHg of -0.022 h-1 based on previous demethylation experiments and a coastal-inland fog transport time of 12 hours, a mean difference of only 0.5 ng L-1 of MMHg was predicted between coastal and inland sites, indicating other unknown source and/or sink pathways are important for MMHg in fog. Fog water deposition to a standard passive 1.00 m2 fog collector at six terrestrial sites averaged 0.10 ± 0.07 L m-2 d-1, which was ∼2% of typical rainwater deposition in this area. Mean air-surface fog water fluxes of MMHg and HgT were then calculated to be 34 ± 40 ng m-2 y-1 and 546 ± 581 ng m-2 y-1, respectively. These correspond to 33% and 13% of the rain fluxes, respectively

Total and Monomethyl Mercury in Fog Water from the Central California Coast

[1] Total mercury (HgT) and monomethyl mercury (MMHg) concentrations in fog collected from 4 locations in and around Monterey Bay, California during June-August of 2011 were 10.7 ± 6.8 and 3.4 ± 3.8 ng L−1respectively. In contrast, mean HgT and MMHg concentrations in rain water from March-June, 2011 were 1.8 ± 0.9 and 0.1 ± 0.04 ng L−1 respectively. Using estimates of fog water deposition from 6 sites in the region using a standard fog water collector (SFC), depositions of HgT and MMHg via fog were found to range from 42–4600 and 14–1500 ng m−2 y−1, which accounted for 7–42% of HgT and 61–99% of MMHg in total atmospheric deposition (fog, rain, and dry deposition), estimated for the coastal area. These initial measurements suggest that fog precipitation may constitute an important but previously overlooked input of MMHg to coastal environments. Preliminary comparisons of these data with associated chemical, meteorological and oceanic data suggest that biotically formed MMHg from coastal upwelling may contribute to the MMHg in fog water

Sources of gaseous oxidized mercury and mercury dry deposition at two southeastern U.S. sites

Wet deposition measurements have shown that relative to other parts of the US, the southeastern region has the highest mercury (Hg) inputs. The source of this Hg has been investigated by multiple researchers and is suggested to be derived from local, regional and global sources. Here we focus on trying to understand potential sources of Hg to this area during periods dominated by dry gaseous oxidized mercury (GOM) deposition. Dry deposition of GOM to a surrogate surface was measured in conjunction with speciated atmospheric Hg, and ancillary parameters from September 2007 through September 2008 at two sites located within 25 km of coal-fired power plants (CFPPs) near Yorkville, GA, and Pensacola, FL. Mean weekly GOM dry deposition, daily GOM, and daily sulfur dioxide (SO2) concentrations were significantly (P \u3c 0.01) higher at the Yorkville site by factors of 1.5, 2.0, and 1.8, respectively. At both sites, GOM and SO2 concentrations were significantly correlated (P \u3c 0.05) in every season on hourly and daily time scales. Wind rose diagrams showed significantly enhanced GOM and SO2 concentrations when air moved to the sites from the direction of the nearest CFPPs. Most periods of enhanced GOM concentrations ([GOM] \u3e 98th percentile), were also associated with NOy/SO2 ratios that were within 25% of that reported for the local CFPPs (N = 27 of 33 at Yorkville, N = 18 of 26 at Pensacola). During these events, termed Category 1, mean GOM/SO2 enhancement ratios were 2.4 ± 0.1 and 2.3 ± 0.1 pg m−3 ppb−1 for Yorkville and Pensacola, respectively (range = 0.5 to 5.5). The remaining events at both sites (termed Category 2) displayed significantly lower SO2 concentrations, yet GOM concentrations were not significantly different compared to Category 1 events. The potential sources of GOM during the Category 2 events at OLF were investigated using gridded frequency distributions (GFD) of 72-h atmospheric back trajectories. During these periods there was a greater component of air mass transport from the free troposphere, and less precipitation along the trajectory paths compared to GFDs for Category 1 events. GFDs developed for the weeks when GOM dry deposition was in the upper quartile at both sites simultaneously revealed a similar pattern to the GFDs of Category 2 GOM concentration events, that is, greater free tropospheric transport and relatively little precipitation. Although dry deposition inputs are thought to represent \u3c15% of total annual Hg deposition in this region, we suggest that a significant portion of this Hg could be derived from sources outside the local area

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