ALBERT

Description: A new sensor based on cavity ring-down spectroscopy (CRDS) has been developed for the measurement of gaseous elemental mercury (Hg0) mass concentration with sub-ng m−3 detection limit and high temporal resolution. Cavity ring-down spectroscopy is a direct absorption technique that utilizes path lengths of up to multiple kilometers in a compact absorption cell and has a significantly higher sensitivity than conventional absorption spectroscopy. Our prototype uses a frequency-doubled, tuneable dye laser emitting pulses at ~253.65 nm with a pulse repetition frequency of 50 Hz. The dye laser incorporates a unique piezo element attached to its tuning grating allowing it to tune the laser on and off the Hg0 absorption line on a pulse to pulse basis to facilitate differential absorption measurements. Hg0 absorption measurements with this CRDS laboratory prototype are highly linearly related to Hg0 concentrations determined by a Tekran 2537B analyzer over a Hg0 concentration range of four orders of magnitude, from 0.2 ng m−3 to 573 ng m−3 implying excellent linearity of both instruments. The current CRDS instrument has a~sensitivity of 0.10 ng m−3 at 10 s time resolution. This tool opens new prospects for the study of Hg0 because of its high temporal resolution and reduced limited sample volume requirements (

Description: Cavity ring-down spectroscopy (CRDS) is a direct absorption technique that utilizes path lengths up to multiple kilometers in a compact absorption cell and has a significantly higher sensitivity than conventional absorption spectroscopy. This tool opens new prospects for study of gaseous elemental mercury (Hg0) because of its high temporal resolution and reduced sample volume requirements (

Description: The chemical cycling and spatiotemporal distribution of mercury in the troposphere is poorly understood. We measured gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particulate mercury (HgP) along with carbon monoxide (CO), ozone (O3), aerosols, and meteorological variables at Storm Peak Laboratory at an elevation of 3200 m a.s.l., in Colorado, from 28 April to 1 July 2008. The mean mercury concentrations were 1.6 ng m−3 (GEM), 20 pg m−3 (RGM) and 9 pg m−3 (HgP). We observed eight events of strongly enhanced atmospheric RGM levels with maximum concentrations up to 137 pg m−3. RGM enhancement events lasted for long time periods of 2 to 6 days showing both enriched level during daytime and nighttime when other tracers (e.g., aerosols) showed different representations of boundary layer air and free tropospheric air. During seven of these events, RGM was inversely correlated to GEM (RGM/GEM regression slope ~−0.1), but did not exhibit correlations with ozone, carbon monoxide, or aerosol concentrations. Relative humidity was the dominant factor affecting RGM levels with high RGM levels always present whenever relative humidity was below 40 to 50%. We conclude that RGM enhancements observed at Storm Peak Laboratory were not induced by pollution events and were related to oxidation of tropospheric GEM. High RGM levels were not limited to upper tropospheric or stratospherically influenced air masses, indicating that entrainment processes and deep vertical mixing of free tropospheric air enriched in RGM may lead to high RGM levels throughout the troposphere and into the boundary layer over the Western United States. Based on backtrajectory analysis and a lack of mass balance between RGM and GEM, atmospheric production of RGM may also have occurred in some distance allowing for scavenging and/or deposition of RGM prior to reaching the laboratory. Our observations provide evidence that the tropospheric pool of mercury is frequently enriched in divalent mercury, that high RGM levels are not limited to upper tropospheric air masses, but that the build-up of high RGM in the troposphere is limited to the presence of dry air.

Description: Gaseous Elemental Mercury (Hg° or GEM) was investigated at Summit Station, Greenland, in the interstitial air extracted from the perennial snowpack (firn) at depths ranging from the surface to 30 m, during summer 2005 and spring 2006. Photolytic production and destruction of Hg° were observed close to the snow surface during summer 2005 and spring 2006, and we observed dark oxidation of GEM up to 270 cm depth in June 2006. Photochemical transformation of gaseous elemental mercury resulted in diel variations in the concentrations of this gas in the near-surface interstitial air, but destruction of Hg° was predominant in June, and production was the main process in July. This seasonal evolution of the chemical mechanisms involving gaseous elemental mercury produces a signal that propagates downward through the firn air, but is unobservably small below 15 m in depth. As a consequence, multi-annual averaged records of GEM concentration should be well preserved in deep firn air at depths below 15 m, and available for the reconstruction of the past atmospheric history of GEM over the last decades.

Description: Atmospheric mercury depletion events (AMDEs) outside the polar region – driven by high levels of gaseous Br and BrO (i.e., BrOx) – were observed recently in the warm Dead Sea boundary layer. The efficient oxidation of gaseous elemental mercury (GEM) under temperate conditions by BrOx was unexpected considering that the thermal back dissociation reaction of HgBr is about 2.5 orders of magnitude higher under Dead Sea temperatures compared to polar temperatures, and hence was expected to significantly slow down GEM oxidation under warm temperatures. The goal of this modelling study was to improve understanding of the interaction of reactive bromine and mercury during Dead Sea AMDEs using numerical simulations based on a comprehensive measurement campaign in summer 2009. Our analysis is focused on daytime AMDE when chemical processes dominate concentration changes. Best agreements between simulations and observations were achieved using rate constants for kHg+Br and kHg+BrO of 2.7 × 10−13 cm3 molecule−1 s−1 and 1.5 × 10−13 cm3 molecule−1 s−1, respectively. Our model also predicted that a rate constant kHg+BrO of 5.0 × 10−14 cm3 molecule−1 s−1 may be considered as a minimum, which is higher than most reported values. These rate constants suggest that BrO could be a more efficient oxidant than Br in the troposphere as long as [Br]/[BrO] ratios are smaller than ~0.2 to 0.5. Under Dead Sea conditions, these kinetics demonstrate a high efficiency and central role of BrOx for AMDEs, with relative contributions to GEM depletion of more than ~90%. Unexpectedly, BrO was found to be the dominant oxidant with relative contributions above 80%. The strong contribution of BrO could explain why the efficiency of GEM oxidation at the Dead Sea does not critically depend on Br and, therefore, is comparable to that in cold polar regions. In order to confirm the suggested kinetics, additional studies, particularly for temperature-dependence of rate constants, are required.

Description: Atmospheric mercury depletion events (AMDEs) outside the polar regions – driven by high levels of reactive bromine species (RBS) – were observed recently in the warm Dead Sea boundary layer. Efficient oxidation of gaseous elemental mercury (GEM) under temperate conditions by RBS was unexpected considering that the thermal back dissociation reaction of HgBr, a proposed key mechanism, is more than 2.5 orders of magnitude higher under Dead Sea temperatures compared with polar temperatures. The goal of this study was to improve understanding of RBS-mercury interactions using numerical simulations based on a comprehensive measurement campaign performed at the Dead Sea during summer 2009. Results demonstrate a high efficiency and central role of BrOx (i.e., Br + BrO) for AMDEs at the Dead Sea, with relative contributions for GEM depletion of more than ~90 %. BrO was found to be the dominant oxidant with relative contribution above 80 %. Best agreement between simulations and observations was achieved by applying rate constants for kHg+Br and kHg+BrO of 2.7×10−13 cm3 molecule−1 s−1 and 1.5 × 10−13 cm3 molecule−1 s−1, respectively – indicating that kHg+BrO is higher than most reported values and that BrO is a more efficient oxidant than Br in the ozone-rich atmosphere (i.e., for [BrO]/[Br] 〉2). This further explains why the efficiency of GEM oxidation by reactive bromine species at the Dead Sea doesn't critically depend on Br and, therefore, is comparable to the efficiency in polar regions even under much higher temperatures. These findings also support the hypothesis identified in a previous study, that Br-induced GEM depletion can be important above oceans in the mid-latitudes and tropics. In the presence of anthropogenic NO2, RBS activity can lead to enhanced NO3 formation, which then causes significant nighttime GEM depletion.

Description: Gaseous Elemental Mercury (GEM) was monitored at the Niwot Ridge (NWT) long-term ecological research (LTER) site (Colorado, USA, 40° N) from interstitial air extracted from the snowpack at depths ranging from the snow surface to 10 cm above the soil. A highly dynamic cycling of mercury (Hg) in this mid-latitude snowpack was observed. Patterns were driven by both GEM production in surface snow and GEM destruction in the deeper snowpack layers. Thorough mixing and vertical transport processes were observed through the snowpack. GEM was photochemically produced near the snow-air interface leading to enhanced GEM levels in interstitial air of surface snow of up to 8 ng m−3. During low wind periods, GEM in surface snow layers remained significantly above ambient air levels at night as well, which may indicate a potential weak GEM production over night. Analysis of vertical GEM gradients in the snowpack show that surface GEM enhancements efficiently propagated down the snowpack, with a temporal lag in peak GEM levels observed with increasing depth. Downward diffusion was responsible for much of these patterns, although vertical advection also contributed to vertical redistribution. Destruction of GEM in the lower snowpack layers was attributed to dark oxidation of GEM. Analysis of vertical GEM/CO2 flux ratios indicated that this GEM destruction occurred in the snow and not in the underlying soil. The strong, diurnal patterns of photochemical GEM production at the surface ultimately lead to re-emission losses of deposited Hg back to the atmosphere. The NWT data show that highest of GEM production and emission occur shortly after fresh snowfall, indicating that fresh snow possibly resupplies photoreducible Hg to the snowpack.

Description: A 182 m ice core was recovered from a borehole drilled into bedrock on the western plateau of Mt. Elbrus (43°20´53.9'' N, 42°25´36.0'' E; 5115 m a.s.l.) in the Caucasus, Russia, in 2009. This is the first ice core in the region that represents a paleoclimate record that is practically undisturbed by seasonal melting. Relatively high snow accumulation rates at the drilling site enabled the analysis of the intraseasonal variability in climate proxies. Borehole temperatures ranged from −17 °C at 10 m depth to −2.4 °C at 182 m. A detailed radio-echo sounding survey showed that the glacier thickness ranged from 45 m near the marginal zone of the plateau up to 255 m at the glacier center. The ice core has been analyzed for stable isotopes (δ18O and δD), major ions (K+, Na+, Ca2+, Mg2+, NH4+, SO42-, NO3-, Cl-, F-), succinic acid (HOOCCH2COOH), and tritium content. The mean annual net accumulation rate of 1455 mm w.e. for the last 140 years was estimated from distinct annual oscillations of δ18O, δD, succinic acid, and NH4+. Annual layer counting also helped date the ice core, agreeing with the absolute markers of the tritium 1963 bomb horizon located at the core depth of 50.7 m w.e. and the sulfate peak of the Katmai eruption (1912) at 87.7 m w.e. According to mathematical modeling results, the ice age at the maximum glacier depth is predicted to be ~ 660 years BP. The 2009 borehole is located downstream from this point, resulting in an estimated basal ice age of less than 350–400 years BP at the drilling site. The glaciological and initial chemical analyses from the Elbrus ice core help reconstruct the atmospheric history of the European region.

Description: A 182 m ice core has been recovered from a borehole drilled through the glacier to the bedrock at the Western Plateau of Mt Elbrus (43°20'53.9'' N, 42°25'36.0'' E; 5115 m a.s.l.), the Caucasus, Russia, in 2009. This is the first ice core in the region which represents a paleoclimate record practically undisturbed by seasonal melting. Relatively high snow accumulation rate at the drilling site enabled analysis of the intra-seasonal climate proxies' variability. Borehole temperatures ranged from −17 °C at 10 m depth and −2.4 °C at 182 m. A detailed radio-echo sounding survey showed that the glacier thickness ranged from 45 m near marginal zone of the plateau up to 255 m at the central part. The ice core has been analyzed for stable isotopes (δ18O and δ D), major ions (K+, Na+, Ca2+, Mg2+, NH4+, SO42-, NO3-, Cl-, F-), succinic acid (HOOCCH2COOH), and tritium content. The mean annual net accumulation rate was estimated from distinct annual oscillations of δ18O, δ D, succinic acid, and NH4+ and is 1455 mm w.e. for the last 140 years. Using annual layer counting also for the dating of the ice core, a good agreement with the absolute markers of the tritium 1963 bomb test time horizon located at the core depth of 50.7 m w.e. and the sulfate peak of the Katmai eruption (1912) at 87.7 m w.e. was obtained. According to mathematical modeling results, the bottom ice age at the maximal glacier depth is predicted to be about 660 years BP. As the 2009 borehole was situated downstream of this point, the estimated bottom ice age of the drilling site does not exceed 350–400 years BP. Taking into account the information that we have acquired on the Western Plateau Elbrus glacier and first results of the ice core analysis, these data can be used to reconstruct the atmospheric history of the European region.