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).

Use of multiple tools including lead isotopes to decipher sources of ozone and reactive mercury to urban and rural locations in Nevada, USA.

Ambient air particulate matter (<2.5µm in diameter) samples were collected on two different filter types in 2014 and 2015 over 24h periods and analyzed for reactive mercury (gaseous oxidized mercury+particulate bound mercury) concentrations and lead isotopes to determine sources of pollution to three sites in Nevada, USA. Two sites were located on the western edge of Nevada (Reno, urban, 1370m and Peavine Peak, rural, high elevation, 2515m); the third location was ~485km east in rural Great Basin National Park, NV (2061m). Reactive mercury samples were collected on cation exchange membranes simultaneously with lead samples, collected on Teflon membranes. Lead isotopic ratios have previously identified trans-Pacific lead sources based on the 206/207 and 208/207 lead ratios. Influence from trans-Pacific air masses was higher from March to June associated with long-range transport of pollutants. Spring months are well known for increased transport across the Pacific; however, fall months were also influenced by trans-Pacific air masses in this study. Western North American background ozone concentrations have been measured and modeled at 50 to 55ppbv. Median ozone concentrations at both rural sites in Nevada were within this range. Sources leading to enhancements in ozone of 2 to 18ppbv above monthly medians in Nevada included emissions from Eurasia, regional urban centers, and global and regional wildfires, resulting in concentrations close to the USA air quality standard. At the high elevation locations, ozone was derived from pollutants being transported in the free troposphere that originate around the globe; however, Eurasia and Asia were dominant sources to the Western USA. Negative correlations between reactive mercury and percent Asian lead, Northern Eurasia and East Asia trajectories indicated reactive mercury concentrations at the two high elevation sites were produced by oxidants from local, regional, and marine boundary layer sources.

Development of a Particulate Mass Measurement System for Quantification of Ambient Reactive Mercury.

The Teledyne Advanced Pollution Instrumentation (TAPI) model 602 BetaPlus particulate system provides nondestructive analysis of particulate matter (PM2.5) mass concentration. This instrument was used to determine if measurements made with cation exchange membranes (CEM) were comparable to standard methods, the ß attenuation method at two locations in Reno, NV and an environmental ß attenuation method and gravimetric method at Great Basin National Park, NV. TAPI PM2.5 CEM measurements were statistically similar to the other three PM2.5 methods. Once this was established, the second objective, a destructive method for measurement of reactive mercury (RM = gaseous oxidized and particulate bound Hg), was tested. Samples collected at 16.7 L per min (Lpm) for 24 h on CEM from the TAPI were compared to those measured by the University of Nevada, Reno-Reactive Mercury Active System (UNRRMAS, 1 Lpm) CEM and a Tekran 2537/1130/1135 system (7 Lpm). Given the use of CEM in the TAPI and UNRRMAS, we hypothesized that both should collect RM. Due to the high flow rate and different inlets, TAPI data were systematically lower than the UNRRMAS. Correlation between RM concentrations demonstrated that the TAPI may be used to estimate 24 h resolution RM concentrations in Nevada.

Automated Calibration of Atmospheric Oxidized Mercury Measurements.

The atmosphere is an important reservoir for mercury pollution, and understanding of oxidation processes is essential to elucidating the fate of atmospheric mercury. Several recent studies have shown that a low bias exists in a widely applied method for atmospheric oxidized mercury measurements. We developed an automated, permeation tube-based calibrator for elemental and oxidized mercury, and we integrated this calibrator with atmospheric mercury instrumentation (Tekran 2537/1130/1135 speciation systems) in Reno, Nevada and at Mauna Loa Observatory, Hawaii, U.S.A. While the calibrator has limitations, it was able to routinely inject stable amounts of HgCl2 and HgBr2 into atmospheric mercury measurement systems over periods of several months. In Reno, recovery of injected mercury compounds as gaseous oxidized mercury (as opposed to elemental mercury) decreased with increasing specific humidity, as has been shown in other studies, although this trend was not observed at Mauna Loa, likely due to differences in atmospheric chemistry at the two locations. Recovery of injected mercury compounds as oxidized mercury was greater in Mauna Loa than in Reno, and greater still for a cation-exchange membrane-based measurement system. These results show that routine calibration of atmospheric oxidized mercury measurements is both feasible and necessary.

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.

Eddy covariance flux measurements of gaseous elemental mercury using cavity ring-down spectroscopy.

A newly developed pulsed cavity ring-down spectroscopy (CRDS) system for measuring atmospheric gaseous elemental mercury (GEM) concentrations at high temporal resolution (25 Hz) was used to successfully conduct the first eddy covariance (EC) flux measurements of GEM. GEM is the main gaseous atmospheric form, and quantification of bidirectional exchange between the Earth's surface and the atmosphere is important because gas exchange is important on a global scale. For example, surface GEM emissions from natural sources, legacy emissions, and re-emission of previously deposited anthropogenic pollution may exceed direct primary anthropogenic emissions. Using the EC technique for flux measurements requires subsecond measurements, which so far has not been feasible because of the slow time response of available instrumentation. The CRDS system measured GEM fluxes, which were compared to fluxes measured with the modified Bowen ratio (MBR) and a dynamic flux chamber (DFC). Measurements took place near Reno, NV, in September and October 2012 encompassing natural, low-mercury (Hg) background soils and Hg-enriched soils. During nine days of measurements with deployment of Hg-enriched soil in boxes within 60 m upwind of the EC tower, the covariance of GEM concentration and vertical wind speed was measured, showing that EC fluxes over an Hg-enriched area were detectable. During three separate days of flux measurements over background soils (without Hg-enriched soils), no covariance was detected, indicating fluxes below the detection limit. When fluxes were measurable, they strongly correlated with wind direction; the highest fluxes occurred when winds originated from the Hg-enriched area. Comparisons among the three methods showed good agreement in direction (e.g., emission or deposition) and magnitude, especially when measured fluxes originated within the Hg-enriched soil area. EC fluxes averaged 849 ng m(-2) h(-1), compared to DFC fluxes of 1105 ng m(-2) h(-1) and MBR fluxes of 1309 ng m(-2) h(-1). This study demonstrated that a CRDS system can be used to measure GEM fluxes over Hg-enriched areas, with a conservative detection limit estimate of 32 ng m(-2) h(-1).