Tundra uptake of atmospheric elemental mercury drives Arctic mercury pollution.

Anthropogenic activities have led to large-scale mercury (Hg) pollution in the Arctic. It has been suggested that sea-salt-induced chemical cycling of Hg (through 'atmospheric mercury depletion events', or AMDEs) and wet deposition via precipitation are sources of Hg to the Arctic in its oxidized form (Hg(ii)). However, there is little evidence for the occurrence of AMDEs outside of coastal regions, and their importance to net Hg deposition has been questioned. Furthermore, wet-deposition measurements in the Arctic showed some of the lowest levels of Hg deposition via precipitation worldwide, raising questions as to the sources of high Arctic Hg loading. Here we present a comprehensive Hg-deposition mass-balance study, and show that most of the Hg (about 70%) in the interior Arctic tundra is derived from gaseous elemental Hg (Hg(0)) deposition, with only minor contributions from the deposition of Hg(ii) via precipitation or AMDEs. We find that deposition of Hg(0)-the form ubiquitously present in the global atmosphere-occurs throughout the year, and that it is enhanced in summer through the uptake of Hg(0) by vegetation. Tundra uptake of gaseous Hg(0) leads to high soil Hg concentrations, with Hg masses greatly exceeding the levels found in temperate soils. Our concurrent Hg stable isotope measurements in the atmosphere, snowpack, vegetation and soils support our finding that Hg(0) dominates as a source to the tundra. Hg concentration and stable isotope data from an inland-to-coastal transect show high soil Hg concentrations consistently derived from Hg(0), suggesting that the Arctic tundra might be a globally important Hg sink. We suggest that the high tundra soil Hg concentrations might also explain why Arctic rivers annually transport large amounts of Hg to the Arctic Ocean.

Direct detection of atmospheric atomic bromine leading to mercury and ozone depletion.

Bromine atoms play a central role in atmospheric reactive halogen chemistry, depleting ozone and elemental mercury, thereby enhancing deposition of toxic mercury, particularly in the Arctic near-surface troposphere. However, direct bromine atom measurements have been missing to date, due to the lack of analytical capability with sufficient sensitivity for ambient measurements. Here we present direct atmospheric bromine atom measurements, conducted in the springtime Arctic. Measured bromine atom levels reached 14 parts per trillion (ppt, pmol mol-1; 4.2 × 108 atoms per cm-3) and were up to 3-10 times higher than estimates using previous indirect measurements not considering the critical role of molecular bromine. Observed ozone and elemental mercury depletion rates are quantitatively explained by the measured bromine atoms, providing field validation of highly uncertain mercury chemistry. Following complete ozone depletion, elevated bromine concentrations are sustained by photochemical snowpack emissions of molecular bromine and nitrogen oxides, resulting in continued atmospheric mercury depletion. This study provides a breakthrough in quantitatively constraining bromine chemistry in the polar atmosphere, where this chemistry connects the rapidly changing surface to pollutant fate.

Convective forcing of mercury and ozone in the Arctic boundary layer induced by leads in sea ice.

The ongoing regime shift of Arctic sea ice from perennial to seasonal ice is associated with more dynamic patterns of opening and closing sea-ice leads (large transient channels of open water in the ice), which may affect atmospheric and biogeochemical cycles in the Arctic. Mercury and ozone are rapidly removed from the atmospheric boundary layer during depletion events in the Arctic, caused by destruction of ozone along with oxidation of gaseous elemental mercury (Hg(0)) to oxidized mercury (Hg(II)) in the atmosphere and its subsequent deposition to snow and ice. Ozone depletion events can change the oxidative capacity of the air by affecting atmospheric hydroxyl radical chemistry, whereas atmospheric mercury depletion events can increase the deposition of mercury to the Arctic, some of which can enter ecosystems during snowmelt. Here we present near-surface measurements of atmospheric mercury and ozone from two Arctic field campaigns near Barrow, Alaska. We find that coastal depletion events are directly linked to sea-ice dynamics. A consolidated ice cover facilitates the depletion of Hg(0) and ozone, but these immediately recover to near-background concentrations in the upwind presence of open sea-ice leads. We attribute the rapid recoveries of Hg(0) and ozone to lead-initiated shallow convection in the stable Arctic boundary layer, which mixes Hg(0) and ozone from undepleted air masses aloft. This convective forcing provides additional Hg(0) to the surface layer at a time of active depletion chemistry, where it is subject to renewed oxidation. Future work will need to establish the degree to which large-scale changes in sea-ice dynamics across the Arctic alter ozone chemistry and mercury deposition in fragile Arctic ecosystems.

New Constraints on Terrestrial Surface-Atmosphere Fluxes of Gaseous Elemental Mercury Using a Global Database.

Despite 30 years of study, gaseous elemental mercury (Hg(0)) exchange magnitude and controls between terrestrial surfaces and the atmosphere still remain uncertain. We compiled data from 132 studies, including 1290 reported fluxes from more than 200,000 individual measurements, into a database to statistically examine flux magnitudes and controls. We found that fluxes were unevenly distributed, both spatially and temporally, with strong biases toward Hg-enriched sites, daytime and summertime measurements. Fluxes at Hg-enriched sites were positively correlated with substrate concentrations, but this was absent at background sites. Median fluxes over litter- and snow-covered soils were lower than over bare soils, and chamber measurements showed higher emission compared to micrometeorological measurements. Due to low spatial extent, estimated emissions from Hg-enriched areas (217 Mg·a(-1)) were lower than previous estimates. Globally, areas with enhanced atmospheric Hg(0) levels (particularly East Asia) showed an emerging importance of Hg(0) emissions accounting for half of the total global emissions estimated at 607 Mg·a(-1), although with a large uncertainty range (-513 to 1353 Mg·a(-1) [range of 37.5th and 62.5th percentiles]). The largest uncertainties in Hg(0) fluxes stem from forests (-513 to 1353 Mg·a(-1) [range of 37.5th and 62.5th percentiles]), largely driven by a shortage of whole-ecosystem fluxes and uncertain contributions of leaf-atmosphere exchanges, questioning to what degree ecosystems are net sinks or sources of atmospheric Hg(0).

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).

Air impacts of increased natural gas acquisition, processing, and use: a critical review.

During the past decade, technological advancements in the United States and Canada have led to rapid and intensive development of many unconventional natural gas plays (e.g., shale gas, tight sand gas, coal-bed methane), raising concerns about environmental impacts. Here, we summarize the current understanding of local and regional air quality impacts of natural gas extraction, production, and use. Air emissions from the natural gas life cycle include greenhouse gases, ozone precursors (volatile organic compounds and nitrogen oxides), air toxics, and particulates. National and state regulators primarily use generic emission inventories to assess the climate, air quality, and health impacts of natural gas systems. These inventories rely on limited, incomplete, and sometimes outdated emission factors and activity data, based on few measurements. We discuss case studies for specific air impacts grouped by natural gas life cycle segment, summarize the potential benefits of using natural gas over other fossil fuels, and examine national and state emission regulations pertaining to natural gas systems. Finally, we highlight specific gaps in scientific knowledge and suggest that substantial additional measurements of air emissions from the natural gas life cycle are essential to understanding the impacts and benefits of this resource.

Characterization of mercury concentrations in snow and potential sources, Shanghai, China.

This work focused on quantifying the total mercury (HgT) and major ion concentrations in snow samples to understand the importance of this pathway and sources of Hg deposited in Shanghai, China. Rare snow event samples were collected at 26 sites within the city of Shanghai on February 18, 2006, January 27, 2008 and January 20, 2011. The sites were distributed among four main functional area types (i.e., industrial impacted, residential impacted, traffic impacted sites and sites in the city center). Concentrations of HgT and major soluble ions, and pH values were determined for each site. Mean HgT concentrations for all sites were 78±52 ng L(-1), 277±184 ng L(-1), 189±123 ng L(-1) in 2006, 2008 and 2011, respectively. Values were higher in Shanghai than observed in other cities including Beijing which has a smaller population and is less industrial. Principle component analysis (PCA) indicated that secondary aerosols (SO4(2-), NO3(-) and NH4(+)), and biomass combustion (K(+), CH3COO(-), and HCOO(-)) were best related to mercury concentrations in the snow in 2008 and 2011. Although HYSPLIT back trajectory modeling indicated air mass transport from areas with significant coal combustion, results indicate that anthropogenic pollution from within Shanghai was the predominant source of Hg in snow.

Investigation of factors affecting gaseous mercury concentrations in soils.

The purpose of this study was to determine the effects of soil temperature, soil moisture, redox potential (Eh) and soil organic matter (SOM) on the total gaseous mercury (TGM) concentrations in background soils. Our measurements were made in a grass field and deciduous forest at the Piney Reservoir Ambient Air Monitoring Station (PRAAMS) in Garrett County, Maryland. Three plots in each area were sampled every third week from July 2009 to June 2010 at the Oe-A soil horizon interface, the A-E soil horizon interface, and 5 and 10 cm into the E soil horizon. The mean soil TGM concentration for all depths in the forest (2.3 ± 2.2 ng m(-3)) was significantly higher than the mean soil TGM concentration in the grass field (1.5 ± 1.9 ng m(-3)). Soil TGM at all depths was most strongly and consistently correlated to soil temperature. The soil TGM concentrations were highest and most variable at the forest Oe-A soil horizon interface (4.1 ± 2.0 ng m(-3)), ranging from 1.5 to 8.4 ng m(-3). This soil horizon interface had 11 to 26% more SOM and the soil Eh was 100 to 400 mV lower than the other soil depths. Our results suggest that soil temperature, soil Eh and SOM are significant factors affecting TGM concentrations in forest soils. Future studies of TGM dynamics in background soils may benefit from closely monitoring the organic soil horizon.