Search

It was discovered in 1995 that, during the spring time, unexpectedly low concentrations of gaseous elemental mercury (GEM) occurred in the Arctic air. This was surprising for a pollutant known to have a long residence time in the atmosphere; however conditions appeared to exist in the Arctic that promoted this depletion of mercury (Hg). This phenomenon is termed atmospheric mercury depletion events (AMDEs) and its discovery has revolutionized our understanding of the cycling of Hg in Polar Regions while stimulating a significant amount of research to understand its impact to this fragile ecosystem. Shortly after the discovery was made in Canada, AMDEs were confirmed to occur throughout the Arctic, sub-Artic and Antarctic coasts. It is now known 10 that, through a series of photochemically initiated reactions involving halogens, GEM is converted to a more reactive species and is subsequently associated to particles in the air and/or deposited to the polar environment. AMDEs are a means by which Hg is transferred from the atmosphere to the environment that was previously unknown. In this article we review the history of Hg in Polar Regions, the methods used to collect Hg in different environmental media, research results of the current understanding of AMDEs from field, laboratory and modeling work, how Hg cycles around the environment after AMDEs, gaps in our current knowledge and the future impacts that AMDEs may have on polar environments. The research presented has shown that while considerable improvements in methodology to measure Hg have been made the main limitation remains knowing the speciation of Hg in the various media. The processes that drive AMDEs and how they occur are discussed. As well, the roles that the snow pack, oceans, fresh water and the sea ice play in the cycling of Hg are presented. It has been found that deposition of Hg from AMDEs occurs at marine coasts and not far inland and that a fraction of the deposited Hg does not remain in the same form in the snow. Kinetic studies undertaken have demonstrated that bromine is the major oxidant depleting Hg in the atmosphere. Modeling results demonstrate that there is a significant deposition of Hg to Polar Regions as a result of AMDEs. Models have also shown that Hg is readily transported to the Arctic from source regions, at times during springtime when this environment is actively transforming Hg from the atmosphere to the snow and ice surfaces. The presence of significant amounts of methyl Hg in snow in the Arctic surrounding AMDEs is important because this species is the link between the environment and impacts to wildlife and humans. Further, much work on methylation and demethylation processes have occurred but are not yet fully understood. Recent changes in the climate and sea ice cover in Polar Regions are likely to have strong effects on the cycling of Hg in this environment; however more research is needed to understand Hg processes in order to formulate meaningful predictions of these changes. [ABSTRACT FROM AUTHOR]

The oxidation of elemental mercury (Hg0) to the divalent gaseous mercury dibromide (HgBr2) has been proposed to account for the removal of Hg0 during depletion events in the springtime Arctic. The mechanism of this process is explored in this paper by theoretical calculations of the relevant rate coefficients. Rice -- Ramsberger -- Kassel -- Marcus (RRKM) theory, together with ab initio quantum calculations where required, are used to estimate the following: recombination rate coefficients of Hg with Br, I, and O; the thermal dissociation rate coefficient of HgBr; and the recombination rate coefficients of HgBr with Br, I, OH, and O2. A mechanism based on the initial recombination of Hg with Br, followed by the addition of a second radical (Br, I, or OH) in competition with thermal dissociation of HgBr, is able to account for the observed rate of Hg0 removal, both in Arctic depletion events and at lower latitudes. [ABSTRACT FROM AUTHOR]

Mercury concentrations are clearly elevated in the surface and sub-surface layers of peat cores collected from a minerotrophic (“groundwater-fed”) fen in southern Greenland (GL) and an ombrotrophic (“rainwater-fed”) bog in Denmark (DK). Using 14C to precisely date samples since ca. AD 1950 using the “atmospheric bomb pulse,” the chronology of Hg accumulation in GL is remarkably similar to the bog in DK where Hg was supplied only by atmospheric deposition: this suggests not only that Hg has been supplied to the surface layers of the minerotrophic core (GL) primarily by atmospheric inputs, but also that the peat cores have preserved a consistent record of the changing rates of atmospheric Hg accumulation. The lowest Hg fluxes in the GL core (0.3 to 0.5 μg/m2/yr) were found in peats dating from AD 550 to AD 975, compared to the maximum of 164 μg/m2/yr in AD 1953. Atmospheric Hg accumulation rates have since declined, with the value for 1995 (14 μg/m2/yr) comparable to the value for 1995 obtained by published studies of atmospheric transport modelling (12 μg/m2/yr).The greatest rates of atmospheric Hg accumulation in the DK core are also found in the sample dating from AD 1953 and are comparable in magnitude (184 μg/m2/yr) to the GL core; again, the fluxes have since gone into strong decline. The accumulation rates recorded by the peat core for AD 1994 (14 μg/m2/yr) are also comparable to the value for 1995 obtained by atmospheric transport modelling (18 μg/m2/yr). Comparing the Pb/Ti and As/Ti ratios of the DK samples with the corresponding crustal ratios (or “natural background values” for preanthropogenic peat) shows that the samples dating from 1953 also contain the maximum concentration of “excess” Pb and As. The synchroneity of the enrichments of all three elements (Hg, Pb, and As) suggests a common source, with coal-burning the most likely candidate. Independent support for this interpretation was obtained from the Pb isotope data (206Pb/207Pb = 1.1481 ± 0.0002 in the leached fraction and 1.1505 ± 0.0002 in the residual fraction) which is too radiogenic to be explained in terms of gasoline lead alone, but compares well with values for U.K. coals. In contrast, the lowest values for 206Pb/207Pb in the DK profile (1.1370 ± 0.0003 in the leached fraction and 1.1408 ± 0.0003 in the residual fraction) are found in the sample dating from AD 1979: this shows that the maximum contribution of leaded gasoline occurred approximately 25 yr after the zenith in total anthropogenic Pb deposition. [Copyright &y& Elsevier]

For the in situ resource utilization (ISRU) of asteroids, the cost-mass conundrum needs to be solved, and technologies may need to be conceptualised from first principals. By using this approach, this Review seeks to illustrate how chemical process intensification can help with the development of disruptive technologies and business matters, how this might influence space-industry start-ups, and even industrial transformations on Earth. The disruptive technology considered is continuous microflow solvent extraction and, as another disruptive element therein, the use of ionic liquids. The space business considered is asteroid mining, as it is probably the most challenging resource site, and the focus is on its last step: the purification of adjacent metals (cobalt versus nickel). The key economic barrier is defined as the reduction in the amount of water used in the asteroid mining process. This Review suggests a pathway toward water savings up to the technological limit of the best Earth-based processes and their physical limits., (© 2020 Wiley-VCH GmbH.)

This review compares the reconstruction of atmospheric Hg deposition rates and historical trends over recent decades in the Arctic, inferred from Hg profiles in natural archives such as lake and marine sediments, peat bogs and glacial firn (permanent snowpack), against those predicted by three state-of-the-art atmospheric models based on global Hg emission inventories from 1990 onwards. Model veracity was first tested against atmospheric Hg measurements. Most of the natural archive and atmospheric data came from the Canadian-Greenland sectors of the Arctic, whereas spatial coverage was poor in other regions. In general, for the Canadian-Greenland Arctic, models provided good agreement with atmospheric gaseous elemental Hg (GEM) concentrations and trends measured instrumentally. However, there are few instrumented deposition data with which to test the model estimates of Hg deposition, and these data suggest models over-estimated deposition fluxes under Arctic conditions. Reconstructed GEM data from glacial firn on Greenland Summit showed the best agreement with the known decline in global Hg emissions after about 1980, and were corroborated by archived aerosol filter data from Resolute, Nunavut. The relatively stable or slowly declining firn and model GEM trends after 1990 were also corroborated by real-time instrument measurements at Alert, Nunavut, after 1995. However, Hg fluxes and trends in northern Canadian lake sediments and a southern Greenland peat bog did not exhibit good agreement with model predictions of atmospheric deposition since 1990, the Greenland firn GEM record, direct GEM measurements, or trends in global emissions since 1980. Various explanations are proposed to account for these discrepancies between atmosphere and archives, including problems with the accuracy of archive chronologies, climate-driven changes in Hg transfer rates from air to catchments, waters and subsequently into sediments, and post-depositional diagenesis in peat bogs. However, no general consensus in the scientific community has been achieved., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Traditional peat sample preparation methods such as drying at high temperatures and milling may be unsuitable for Hg concentration determination in peats due to the possible presence of volatile Hg species, which could be lost during drying. Here, the effects of sample preparation and natural variation on measured Hg concentrations are investigated. Slight increases in mercury concentrations were observed in samples dried at room temperature and at 30 degrees C (6.7 and 2.48 ng kg(-1) h(-1), respectively), and slight decreases were observed in samples dried at 60, 90 and 105 degrees C (2.36, 3.12 and 8.52 ng kg(-1) h(-1), respectively). Fertilising the peat slightly increased Hg loss (3.08 ng kg(-1) h(-1) in NPK-fertilised peat compared to 0.28 ng kg(-1) h(-1) in unfertilised peat, when averaged over all temperatures used). Homogenising samples by grinding in a machine also caused a loss of Hg. A comparison of two Hg profiles from an Arctic peat core, measured in frozen samples and in air-dried samples, revealed that no Hg losses occurred upon air-drying. A comparison of Hg concentrations in several plant species that make up peat, showed that some species (Pinus mugo, Sphagnum recurvum and Pseudevernia furfuracea) are particularly efficient Hg retainers. The disproportionally high Hg concentrations in these species can cause considerable variation in Hg concentrations within a peat slice. The variation of water content (1.6% throughout 17-cm core, 0.97% in a 10 x 10 cm slice), bulk density (40% throughout 17-cm core, 15.6% in a 10 x 10 cm slice) and Hg concentration (20% in a 10 x 10 cm slice) in ombrotrophic peat were quantified in order to determine their relative importance as sources of analytical error. Experiments were carried out to determine a suitable peat analysis program using the Leco AMA 254, capable of determining mercury concentrations in solid samples. Finally, an analytical protocol for the determination of Hg concentrations in solid peat samples is proposed. This method allows correction for variation in factors such as vegetation type, bulk density, water content and Hg concentration in individual peat slices. Several subsamples from each peat slice are air dried, combined and measured for Hg using the AMA254, using a program of 30 s (drying), 125 s (decomposition) and 45 s (waiting). Bulk density and water content measurements are performed on every slice using separate subsamples.

Gaseous elemental mercury (Hg0) is a globally distributed air toxin with a long atmospheric residence time. Any process that reduces its atmospheric lifetime increases its potential accumulation in the biosphere. Our data from Barrow, AK, at 71 degrees N show that rapid, photochemically driven oxidation of boundary-layer Hg0 after polar sunrise, probably by reactive halogens, creates a rapidly depositing species of oxidized gaseous mercury in the remote Arctic troposphere at concentrations in excess of 900 pg m(-3). This mercury accumulates in the snowpack during polar spring at an accelerated rate in a form that is bioavailable to bacteria and is released with snowmelt during the summer emergence of the Arctic ecosystem. Evidence suggests that this is a recent phenomenon that may be occurring throughout the earth's polar regions.