Unraveling atmospheric mercury dynamics at Mauna Loa through the isotopic analysis of total gaseous mercury.

Our investigation seeks to uncover the intricate nature of mercury dynamics in the free troposphere through analysis of the isotopic composition of total gaseous elemental mercury (TGM) at the high altitude Mauna Loa Observatory (MLO, 3397 m) in Hawaii, USA. By focusing on this unique site, we aim to provide essential insights into the behavior and cycling of mercury, contributing valuable data to a deeper understanding of its global distribution and environmental impacts. Forty-eight hours of TGM sampling from January to September 2022 revealed significant variations in δ202Hg (-1.86 % to -0.32 %; mean = -1.17 ± 0.65 %, 2 SD, n = 34) and small variations in Δ199Hg (-0.27 % to 0.04 %; mean = -0.13 ± 0.14 %, 2 SD, n = 34) and Δ200Hg (-0.20 % to 0.06 %; mean = -0.05 ± 0.13 %, 2 SD, n = 34). During the sampling period, GEM was negatively correlated with gaseous oxidized mercury (GOM). However, the GOM/GEM ratio was not -1, suggesting that GEM oxidation and subsequent scavenging occurred previously. The δ202Hg isotopic compositions of TGM at MLO were different from those of reported values of high-altitude mountains; the δ202Hg of TGM at MLO was lower than the isotopic ratios that were obtained from other mountain regions. The unique atmospheric conditions at Mauna Loa, with (upslope winds during the day and downslope winds at night, likely result in the) possibly mixing of GEMs from terrestrial (and possibly oceanic GEM emission) sources with and tropospheric sources, influencing and affect the isotopic composition. During the late summer to early fall (September 14-28), negative correlations were found between relative humidity and GOM and between particle number concentrations and Δ199Hg, indicating the gas-to-particle partitioning of the atmospheric mercury during this period. This study will improve our understanding on mercury dynamics of marine origin and high altitudes and shed light on its complex interactions with environmental factors.

Use of Multiple Lines of Evidence to Understand Reactive Mercury Concentrations and Chemistry in Hawai'i, Nevada, Maryland, and Utah, USA.

To advance our understanding of the mercury (Hg) biogeochemical cycle, concentrations and chemistry of gaseous oxidized Hg (GOM), particulate-bound Hg (PBM), and reactive Hg (RM = GOM + PBM) need to be known. The UNR-RMAS 2.0 provides a solution that will advance knowledge. From 11/2017 to 02/2019, the RMAS 2.0 was deployed in Hawai'i, Nevada, Maryland, and Utah to test system performance and develop an understanding of RM at locations impacted by different atmospheric oxidants. Mauna Loa Observatory, Hawai'i, impacted by the free troposphere and the marine boundary layer, had primarily -Br/Cl RM compounds. The Nevada location, directly adjacent to a major interstate highway and experiences inputs from the free troposphere, exhibited -Br/Cl, -N, -S, and organic compounds. In Maryland, compounds observed were -N, -S, and organic-Hg. This site is downwind of coal-fired power plants and located in a forested area. The location in Utah is in a basin impacted by oil and natural gas extraction, multiday wintertime inversion episodes, and inputs from the free troposphere. Compounds were -Br/Cl or -O, -N, and -Br/Cl. The chemical forms of RM identified were consistent with the air source areas, predominant ion chemistry, criterion air pollutants, and meteorology.

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.

The Estimated Six-Year Mercury Dry Deposition Across North America.

Dry deposition of atmospheric mercury (Hg) to various land covers surrounding 24 sites in North America was estimated for the years 2009 to 2014. Depending on location, multiyear mean annual Hg dry deposition was estimated to range from 5.1 to 23.8 µg m-2 yr-1 to forested canopies, 2.6 to 20.8 µg m-2 yr-1 to nonforest vegetated canopies, 2.4 to 11.2 µg m-2 yr-1 to urban and built up land covers, and 1.0 to 3.2 µg m-2 yr-1 to water surfaces. In the rural or remote environment in North America, annual Hg dry deposition to vegetated surfaces is dominated by leaf uptake of gaseous elemental mercury (GEM), contrary to what was commonly assumed in earlier studies which frequently omitted GEM dry deposition as an important process. Dry deposition exceeded wet deposition by a large margin in all of the seasons except in the summer at the majority of the sites. GEM dry deposition over vegetated surfaces will not decrease at the same pace, and sometimes may even increase with decreasing anthropogenic emissions, suggesting that Hg emission reductions should be a long-term policy sustained by global cooperation.

Modification of a commercial cavity ring-down spectroscopy NO2 detector for enhanced sensitivity.

Nitrogen dioxide (NO(2)) plays a central role in atmospheric chemistry, air pollution, and biogeochemical cycles. Many analytical techniques have been developed to detect NO(2), but only chemiluminescence-based instruments are commonly, commercially available. There remains a need for a fast, light, and simple method to directly measure NO(2). In this work we describe the modification and characterization of a small, commercially available cavity ring-down spectroscopy (CRDS) NO(2) detector suitable for surface and aircraft monitoring. A metal oxide scrubber was added to remove NO(2), and provide a chemical zero, improving the detection limit (3sigma of the background noise) from several parts per billion by volume (ppbv) to 0.06 ppbv, integrated over 60 s. Known interferences by water and particles were removed using Nafion tubing and a 1 microm Teflon filter, respectively. A 95% response time of 18+/-1 s was observed for a step change in concentration. The CRDS detector was run in parallel to an ozone chemiluminescence device with photolytic conversion of NO(2) to NO. The two instruments measured ambient air in suburban Maryland. A least-squares fit to the comparison data resulted a slope of 0.960+/-0.002 and R of 0.995, showing agreement within experimental uncertainty.

Summertime ambient formaldehyde in five U.S. metropolitan areas: Nashville, Atlanta, Houston, Philadelphia, and Tampa.

First, we briefly review the atmospheric chemistry and previous intercomparison measurements for HCHO, with special reference to the diffusion scrubber Hantzsch reaction based fluorescence instrument used in the field studies reported herein. Then we discuss summertime HCHO levels in five major U.S. cities measured over 1999-2002, primarily from ground-based measurements. Land-sea breeze circulations play a major role in observed concentrations in coastal cities. Very high HCHO peak mixing ratios were observed in Houston (>47 ppb) where the overall median mixing ratio was 3.3 ppb; the corresponding values in Atlanta were approximately >18 and 7.9 ppb, respectively. The peak and median mixing ratios (9.3 and 2.3 ppb) were the lowest for Tampa, where the land-sea breeze also played an important role. In several cities, replicate HCHO measurements were made by direct spectroscopic instruments; the instruments were located kilometers from each other and addressed very different heights (e.g., 106 vs 10 m). Even under these conditions, there was remarkable qualitative and often quantitative agreement between the different instruments, when they were all sampling the same air mass within a short period of each other. Local chemistry dominates how HCHO is formed and dissipated. The high concentrations in Houston resulted from emissions near the ship channel; the same formaldehyde plume was measured at two sites and clearly ranged over tens of kilometers. Local micrometeorology is another factor. HCHO patterns measured at a high-rise site in downtown Nashville were very much in synchrony with other ground sites 12 km away until July 4 celebrations whence HCHO concentrations at the downtown site remained elevated for several days and nights. The formation and dissipation of HCHO in the different cities are discussed in terms of other concurrently measured species and meteorological vectors. The vertical profiles of HCHO in and around Tampa under several different atmospheric conditions are presented. The extensive data set represented in this paper underscores that urban HCHO measurements can now be made easily; the agreement between disparate instruments (that are independently calibrated or rely on the absolute absorption cross section) further indicates that such measurements can be done reliably and accurately for this very important atmospheric species. The data set presented here can be used as a benchmark for future measurements if the use of formaldehyde precursors such as methanol or methyl tert-butyl ether (MTBE) as oxygenated fuel additives increases in the future.