Alexandra Steffen

Arctic springtime depletion of mercury

The Arctic ecosystem is showing increasing evidence of contamination by persistent, toxic substances, including metals such as mercury, that accumulate in organisms. In January 1995, we began continuous surface-level measurements of total gaseous mercury in the air at Alert, Northwest Territories, Canada (82.5° N, 62.5° W). Here we show that, during the spring (April to early June) of 1995, there were frequent episodic depletions in mercury vapour concentrations, strongly resembling depletions of ozone in Arctic surface air, during the three-month period following polar sunrise (which occurs in March),.

Magnification of atmospheric mercury deposition to polar regions in springtime: The link to tropospheric ozone depletion chemistry

Mercury—in the chemical/physical forms present in the biosphere—is a persistent, toxic, bioaccumulative pollutant that is dispersed throughout the environment on a global scale, mainly via the atmosphere. It is among the “heavy metals” for which the natural biogeochemical cycle has been perturbed by a wide range of human activities, including fossil-fuel combustion and waste incineration. Results of our recent measurements of gaseous elemental mercury (GEM), as well as total particulate-phase mercury (TPM) concentrations in Arctic air, ‘total Hg’ concentrations in Arctic snow, and tropospheric BrO concentrations from an earth-orbiting-satellite platform are presented and discussed. Findings of our research, and the conclusions derived therefrom, are important for environmental protection as well as the health and well-being of aboriginal people in Arctic circumpolar nations.

Worldwide trend of atmospheric mercury since 1977

[1]xa0The inventories of global anthropogenic emissions of mercury for years from 1979/1980 to 1995 suggest a substantial reduction in the 1980s and almost constant emissions afterwards. In contrast to emission inventories, measurements of atmospheric mercury suggest a concentration increase in the 1980s and a decrease in the 1990s. Here we present a first attempt to reconstruct the worldwide trend of atmospheric mercury concentrations from direct measurements since the late 1970s. In combination, long term measurements at 6 sites in the northern, 2 sites in the southern hemispheres, during 8 ship cruises over the Atlantic Ocean (1977–2000) provide a consistent picture, suggesting that atmospheric mercury concentrations increased in the late 1970s to a peak in the 1980s, then decreased to a minimum at about 1996, and have been nearly constant since. The observed trend is not consistent with the published inventories of anthropogenic emissions and the assumed ratios of anthropogenic/natural emissions, and suggests the need to improve the mercury emission inventories and to re-evaluate the contribution of natural sources.

The Arctic: a sink for mercury

Mercury is a persistent, toxic and bio-accumulative pollutant of global interest. Its main mass in the troposphere is in the form of elemental gas-phase mercury. Rapid, near-complete depletion of mercury has been observed during spring in the atmospheric boundary layer of frozen marine areas in Arctic, sub-Arctic and Antarctic locations. It is strongly correlated with ozone depletion. To date, evidence has indicated strongly that chemistry involving halogen gases from surface sea-salt is the mechanism of this destruction. Precisely which halogen gases are the main players has remained unresolved. Our novel kinetic data and multiscale modelling show that Br atoms and BrO radicals are the most effective halogens driving mercury oxidation. The reduction of oxidized mercury deposited in the snow pack back to Hg0 and subsequent diffusion to the atmosphere is observed. However, it cannot compensate for the total deposition, and a net accumulation occurs. We use a unique global atmospheric mercury model to estimate that halogen-driven mercury depletion events result in a 44% increase in the net deposition of mercury to the Arctic. Over a 1-yr cycle, we estimate an accumulation of 325 tons of mercury in the Arctic.

Atmospheric mercury concentrations: measurements and profiles near snow and ice surfaces in the Canadian Arctic during Alert 2000

Abstract Gaseous elemental mercury (GEM) concentration measurements were made during the Alert 2000 campaign in Alert, Nunavut, Canada, between February and May 2000. GEM exhibits dramatic mercury depletion events (MDE) concurrently with ozone in the troposphere during the Arctic springtime. Using a cold regions pyrolysis unit, it was confirmed that GEM is converted to more reactive mercury species during the MDEs. It was determined that on average 48% of this converted GEM was recovered through pyrolysis suggesting that the remaining converted GEM is deposited on the snow surfaces. Samples collected during this campaign showed an approximate 20 fold increase in mercury concentrations in the snow from the dark to light periods. Vertical gradient air profiling experiments were conducted. In the non-depletion periods GEM was found to be invariant in the air column between surface and 1–2xa0m heights. During a depletion period, GEM was found to be invariant in the air column except at the surface where a noticeable increase in the GEM concentration was observed. Concurrent ozone concentration profiles showed a small gradient in the air column but a sharp decrease in ozone concentration at the surface. Other profile studies showed a 41% average GEM concentration difference between the interstitial air in the snow pack and ∼2xa0m above the surface suggesting that GEM is emitted from the snow pack. Further profile studies showed that during MDEs surface level GEM exhibits spikes of mercury concentrations that were over double the ambient GEM concentrations. It is thought that the solar radiation may reduce reactive mercury that is deposited on the snow surface during a MDE back to its elemental form which is then increasingly released from the snow pack as the temperature increases during the day. This is observed when wind speeds are very low.

Vertical distribution of gaseous elemental mercury in Canada

[1]xa0Measurements of gaseous elemental mercury (GEM) were made in three locations in Canada at altitudes from 0.1 to 7 km. In the summer in southeastern Canada, northwesterly winds bring air with a constant mixing ratio of GEM at altitudes up to 7 km, with a concentration near 1.5 nanograms per standard cubic meter of air (ng sm−3). In the winter in southern and central Ontario the mixing ratio is still approximately constant with altitude, but the concentration is 1.7 ng sm−3. In the spring in the Arctic the concentration of gaseous elemental mercury at altitudes above 1 km is near 1.7 ng sm−3; however, there is evidence of episodic depletion of elemental mercury near the surface with mixing of depleted air to altitudes of 1 km. Measurements of GEM in cloud interstitial air and of mercury in cloud water indicate that the influence of a single cycling of air through cloud has little effect on the concentration of GEM. The GEM in air masses transported over the relatively unpopulated terrain of northern Canada during the summer indicates a lower limit of 5000 ng m−2 for an atmospheric column from the surface to 5 km. This gives a global burden of at least 2500 t for that altitude range. These data demonstrate the existence of a vast pool of mercury aloft, provide evidence for a long atmospheric lifetime, and illustrate the potential for long-range atmospheric transport of this metal at altitudes up to at least 7 km.

Atmospheric chemistry of formaldehyde in the Arctic troposphere at Polar Sunrise, and the influence of the snowpack

The role of formaldehyde in the atmospheric chemistry of the Arctic marine boundary layer has been studied during both polar day and night at Alert, Nunavut, Canada. Formaldehyde concentrations were determined during two separate field campaigns (PSE 1998 and ALERT2000) from polar night to the light period. The large differences in the predominant chemistry and transport issues in the dark and light periods are examined here. Formaldehyde concentrations during the dark period were found to be dependent on the transport of air masses to the Alert site. Three regimes were identified during the dark period, including background (free-tropospheric) air, transported polluted air from Eurasia, and halogen-processed air transported across the dark Arctic Ocean. In the light period, background formaldehyde levels were compared to a calculation of the steady-state formaldehyde concentrations under background and low-ozone conditions. We found that, for sunlit conditions, the ambient formaldehyde concentrations cannot be reproduced by known gas-phase chemistry. We suggest that snowpack photochemistry contributes to production and emission of formaldehyde in the light period, which could account for the high concentrations observed at Alert.

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.

A pulse of mercury and major ions in snowmelt runoff from a small Arctic Alaska watershed

Atmospheric mercury (Hg) is deposited to Polar Regions during springtime atmospheric mercury depletion events (AMDEs) that require halogens and snow or ice surfaces. The fate of this Hg during and following snowmelt is largely unknown. We measured Hg, major ions, and stable water isotopes from the snowpack through the entire spring melt runoff period for two years. Our small (2.5 ha) watershed is near Barrow (now Utqiaġvik), Alaska. We measured discharge, made 10u202f000 snow depths, and collected over 100 samples of snow and meltwater for chemical analysis in 2008 and 2009 from the watershed snowpack and ephemeral stream channel. Results show an ionic pulse of mercury and major ions in runoff during both snowmelt seasons, but major ion and Hg runoff concentrations were roughly 50% higher in 2008 than in 2009. Though total discharge as a percent of total watershed snowpack water equivalent prior to the melt was similar in both years (36% in 2008 melt runoff and 34% in 2009), it is possible that record low precipitation in the summer of 2007 led to the higher major ion and Hg concentrations in 2008 melt runoff. Total dissolved Hg meltwater runoff of 14.3 (± 0.7) mg/ha in 2008 and 8.1 (± 0.4) mg/ha in 2009 is five to seven times higher than that reported from other arctic watersheds. We calculate 78% of snowpack Hg was exported with snowmelt runoff in 2008 and 41% in 2009. Our results suggest AMDE Hg complexed with Cl- or Br- may be less likely to be photochemically reduced and re-emitted to the atmosphere prior to snowmelt, and we estimate that roughly 25% of the Hg in snowmelt is attributable to AMDEs. Projected Arctic warming, with more open sea ice leads providing halogen sources that promote AMDEs, may provide enhanced Hg deposition, reduced Hg emission and, ultimately, an increase in snowpack and snowmelt runoff Hg concentrations.