Lead Isotopic Constraints on the Provenance of Antarctic Dust and Atmospheric Circulation Patterns Prior to the Mid-Brunhes Event (~430 kyr ago).

A lead (Pb) isotopic record, covering the two oldest glacial-interglacial cycles (~572 to 801 kyr ago) characterized by lukewarm interglacials in the European Project for Ice Coring in Antarctica Dome C ice core, provides evidence for dust provenance in central East Antarctic ice prior to the Mid-Brunhes Event (MBE), ~430 kyr ago. Combined with published post-MBE data, distinct isotopic compositions, coupled with isotope mixing model results, suggest Patagonia/Tierra del Fuego (TdF) as the most important sources of dust during both pre-MBE and post-MBE cold and intermediate glacial periods. During interglacials, central-western Argentina emerges as a major contributor, resulting from reduced dust supply from Patagonia/TdF after the MBE, contrasting to the persistent dominance of dust from Patagonia/TdF before the MBE. The data also show a small fraction of volcanic Pb transferred from extra-Antarctic volcanoes during post-MBE interglacials, as opposed to abundant transfer prior to the MBE. These differences are most likely attributed to the enhanced wet removal efficiency with the hydrological cycle intensified over the Southern Ocean, associated with a poleward shift of the southern westerly winds (SWW) during warmer post-MBE interglacials, and vice versa during cooler pre-MBE ones. Our results highlight sensitive responses of the SWW and the associated atmospheric conditions to stepwise Antarctic warming.

A 300-Year High-Resolution Greenland Ice Record of Large-Scale Atmospheric Pollution by Arsenic in the Northern Hemisphere.

We report the first high-resolution record of arsenic (As) observed in Greenland snow and ice for the periods 1711-1970 and 2003-2009 AD. The results show well-defined large-scale atmospheric pollution by this toxic element in the northern hemisphere, beginning as early as the 18th century. The most striking feature is an abrupt, unprecedented enrichment factor (EF) peak in the late 1890s, with an ∼30-fold increase in the mean value above the Holocene natural level. Highly enriched As was evident until the late 1910s; a sharp decline was observed after the First World War, reaching a minimum in the early 1930s during the Great Depression. A subsequent increase lasted until the mid-1950s, before decreasing again. Comparisons between the observed variations and Cu smelting data indicate that Cu smelting in Europe and North America was the likely source of early anthropogenic As in Greenland. Despite a significant reduction of ∼80% in concentration and ∼60% in EF from the 1950s to the 2000s, more than 80% of present-day As in Greenland is of anthropogenic origin, probably due to increasing As emissions from coal combustion in China. This highlights the demand for the implementation of national and international environmental regulations to further reduce As emissions.

Recent decline in atmospheric Pb deposition and isotopic constraints on changes in source contributions in snow from northwestern Greenland.

We present lead (Pb) concentrations and isotope ratios in a continuous series of 38 snow samples from a 1.9-m snow pit, covering the period from winter 2012 to summer 2017, at the East Greenland Ice-core Project (EGRIP) ice core drill site in northwestern Greenland. Pb concentrations were highly variable, ranging from 1.53 to 94.9 pg g-1 (mean value of 10.6 pg g-1), with higher concentrations during winter and spring and lower concentrations during summer and fall. Our results show a substantial reduction in the Pb concentration of ∼50% between the 2000s and 2010s, reaching a level close to that observed in the mid-18th century, that is, the time of the Industrial Revolution. Remarkably low radiogenic Pb isotope compositions were observed in our samples compared to previously reported values during the 2000s. The Pb isotope mixing model results indicated a decreasing Chinese contribution from the 2000s onwards, while Europe/Russia emerged as a relatively more important contributor to the anthropogenic Pb input to central Greenland during the corresponding period. Thus, we hypothesized that the reduction in Pb pollution in central Greenland is largely due to a decreasing contribution from Chinese sources in response to the effectiveness of stringent emission control measures in China.

Meteoric smoke fallout over the Holocene epoch revealed by iridium and platinum in Greenland ice.

An iridium anomaly at the Cretaceous/Tertiary boundary layer has been attributed to an extraterrestrial body that struck the Earth some 65 million years ago. It has been suggested that, during this event, the carrier of iridium was probably a micrometre-sized silicate-enclosed aggregate or the nanophase material of the vaporized impactor. But the fate of platinum-group elements (such as iridium) that regularly enter the atmosphere via ablating meteoroids remains largely unknown. Here we report a record of iridium and platinum fluxes on a climatic-cycle timescale, back to 128,000 years ago, from a Greenland ice core. We find that unexpectedly constant fallout of extraterrestrial matter to Greenland occurred during the Holocene, whereas a greatly enhanced input of terrestrial iridium and platinum masked the cosmic flux in the dust-laden atmosphere of the last glacial age. We suggest that nanometre-sized meteoric smoke particles, formed from the recondensation of ablated meteoroids in the atmosphere at altitudes >70 kilometres, are transported into the winter polar vortices by the mesospheric meridional circulation and are preferentially deposited in the polar ice caps. This implies an average global fallout of 14 +/- 5 kilotons per year of meteoric smoke during the Holocene.

Simultaneous determination of picogram per gram concentrations of Ba, Pb and Pb isotopes in Greenland ice by thermal ionisation mass spectrometry.

A technique has been developed to simultaneously measure picogram per gram concentrations of Ba and Pb by isotope dilution mass spectrometry, as well as Pb isotopic ratios in polar ice by thermal ionisation mass spectrometry. BaPO2(+) and Pb+ ions were employed for these determinations. A calibrated mixture of enriched 205Pb and 137Ba was added to the samples providing an accuracy of better than approximately 2% for Pb/Ba element ratio determinations. Interference by molecular ions in the Pb mass spectrum occurred only at 204Pb and 205Pb, but these contributions were negligible in terms of precisions expected on picogram-sized Pb samples. The technique is illustrated with measurements on Greenland firn, using a drill-core section that includes the Laki volcanic eruption of 1783-1784. The data show deviations from the element concentrations indicating volatile metal enrichments, but the Pb isotopic signature of the Laki lava could not be identified.

Atmospheric pollution for trace elements in the remote high-altitude atmosphere in central Asia as recorded in snow from Mt. Qomolangma (Everest) of the Himalayas.

A series of 42 snow samples covering over a one-year period from the fall of 2004 to the summer of 2005 were collected from a 2.1-m snow pit at a high-altitude site on the northeastern slope of Mt. Everest. These samples were analyzed for Al, V, Cr, Mn, Co, Ni, Cu, Zn, As, Rb, Sr, Cd, Sb, Pb, and Bi in order to characterize the relative contributions from anthropogenic and natural sources to the fallout of these elements in central Himalayas. Our data were also considered in the context of monsoon versus non-monsoon seasons. The mean concentrations of the majority of the elements were determined to be at the pg g(-1) level with a strong variation in concentration with snow depth. While the mean concentrations of most of the elements were significantly higher during the non-monsoon season than during the monsoon season, considerable variability in the trace element inputs to the snow was observed during both periods. Cu, Zn, As, Cd, Sb, and Bi displayed high crustal enrichment factors (EFc) in most samples, while Cr, Ni, Rb, and Pb show high EFc values in some of the samples. Our data indicate that anthropogenic inputs are potentially important for these elements in the remote high-altitude atmosphere in the central Himalayas. The relationship between the EFc of each element and the Al concentration indicates that a dominant input of anthropogenic trace elements occurs during both the monsoon and non-monsoon seasons, when crustal contribution is relatively minor. Finally, a comparison of the trace element fallout fluxes calculated in our samples with those recently obtained at Mont Blanc, Greenland, and Antarctica provides direct evidence for a geographical gradient of the atmospheric pollution with trace elements on a global scale.

Atmospheric particle evolution during a nighttime atmospheric mercury depletion event in sub-Arctic at Kuujjuarapik/Whapmagoostui, Québec, Canada.

During a field experiment at Kuujjuarapik/Whapmagoostui (55.31 degrees N, 77.75 degrees W), Quebec, we observed increases of concentrations of particles with diameters larger than 0.3 microm in the ambient air during a nighttime atmospheric mercury depletion event (AMDE). These increases were strongly correlated with decreases of ozone and atmospheric mercury, and we also observed a change in the particle size distribution during this AMDE. Assuming that these phenomena imply either a chemical link or an association through transport, we also studied the nature of this AMDE. We hypothesize that the observed AMDE was a result of an influx of already depleted air masses and that it was not a product of local chemical reactions.

Mercury speciation in the French seasonal snow cover.

Snow samples have been collected in the French Alps in 1998, 1999 and 2000 in order to measure both total Hg (HgT) and reactive Hg (HgR). Concentrations of HgT were between 13 and 130 pg g(-1) and HgR concentrations were below the detection limit (approximately 0.8 pg g(-1)). Hg speciation in snow was evaluated on the basis of ionic complexation equilibrium with chloride, hydroxide, oxalate. The pH of the snow was found to be an important parameter for Hg speciation. For pH values near 3, HgC2O4 is predominant in snow samples except for snow strongly influenced by anthropogenic sources (in which case HgCl2 predominates). When pH > 4, Hg(OH)2 and HgOHCl are predominant. These latter pH values are observed for precipitation not influenced by anthropogenic sources but more by soil erosion, e.g. Saharan dusts. The knowledge of Hgr speciation in snow is a key question for understanding the mechanisms of transformation of these complexes in snow after precipitation.

Influence of anthropogenic sources on total gaseous mercury variability in Grenoble suburban air (France).

Total gaseous mercury (TGM) has been monitored at Champ sur Drac, a suburban site of Grenoble in southern east France. TGM measurements have been made over 4 periods of approximately 10 days throughout 1999-2000 using cold vapour atomic fluorescence absorption technique. The first monitoring campaign was initiated on November 4, 1999, followed by three other campaigns respectively on January 12, 2000, April 10, 2000 and July 17, 2000. Concurrent monitoring of O3, NO, NO2, SO2 and of meteorological parameters have also been performed. The mean TGM concentration was 3.4 ng m(-3) with maximum hourly mean concentration of 37.1 ng m(-3). Although mean TGM concentration was not greatly different from those previously measured in the troposphere, the greater TGM variability as well as the occurrence of high TGM concentration linked to particular wind conditions suggested the strong influence of anthropogenic sources. The chlor-alkali plant located nearby, the others chemical industries using fuel combustion and the municipal waste incinerator were thought to contribute to mercury pollution events.

Isotopic signatures for natural versus anthropogenic Pb in high-altitude Mt. Everest ice cores during the past 800 years.

A long-term record, extending back 800 years (1205 to 2002 AD), of the Pb isotopic composition ((206)Pb/(207)Pb and (208)Pb/(207)Pb) as well as Pb concentrations from high altitude Mt. Everest ice cores has the potential to identify sources and source regions affecting natural and anthropogenic Pb deposition in central Asia. The results show that the regional natural background Pb isotope signature (~1.20 for (206)Pb/(207)Pb and ~2.50 for (208)Pb/(207)Pb) in the central Himalayas was dominated by mineral dust over the last ~750 years from 1205 to 1960s, mostly originating from local sources with occasional contributions of long-range transported dust probably from Sahara desert and northwestern India. Since the 1970s, the Pb isotope ratios are characterized by a continuous decline toward less radiogenic ratios with the least mean ratios of 1.178 for (206)Pb/(207)Pb and 2.471 for (208)Pb/(207)Pb in the period 1990-1996. The depression of the (206)Pb/(207)Pb and (208)Pb/(207)Pb values during the corresponding periods is most likely due to an increasing influence of less radiogenic Pb of anthropogenic origin mainly from leaded gasoline used in South Asia (India as well as possibly Bangladesh and Nepal). From 1997 to 2002, isotopic composition tends to show a shift to slightly more radiogenic signature. This is likely attributed to reducing Pb emissions from leaded gasoline in source regions, coinciding with the nationwide reduction of Pb in gasoline and subsequent phase-out of leaded gasoline in South Asia since 1997. An interesting feature is the relatively high levels of Pb concentrations and enrichment factors (EF) between 1997 and 2002. Although the reason for this feature remains uncertain, it would be probably linked with an increasing influence of anthropogenic Pb emitted from other sources such as fossil fuel combustion and non-ferrous metal production.

An 800-year record of atmospheric As, Mo, Sn, and Sb in central Asia in high-altitude ice cores from Mt. Qomolangma (Everest), Himalayas.

As, Mo, Sn, and Sb have been determined by inductively coupled plasma sector field mass spectrometry (ICP-SFMS) in 143 depth intervals of high-altitude ice cores from Mt. Everest, covering an 800-year time period from 1205 to 2002 AD. The results clearly demonstrate the long-term historical record of atmospheric transport and deposition of As, Mo, Sn, and Sb that has prevailed at high altitudes in the central Himalayas. Natural contributions, mainly from mineral dust, have dominated the atmospheric cycles of As, Mo, Sn, and to some extent Sb during the 700 years prior to the 20th century. Compared to those of the pre-1900 period, pronounced increases of both concentrations and crustal enrichment factors are observed since the 1970s, with the highest increase factor for Sn and the lowest for As. Such increases are attributed to anthropogenic emissions of these elements, largely from stationary fossil fuel combustion and nonferrous metals production, particularly in India. Our central Himalayan ice core record provides an explicit recognition of rising atmospheric As, Mo, Sn, and Sb pollution in response to rapid economic growth in central Asia.

An ultra-clean technique for accurately analysing Pb isotopes and heavy metals at high spatial resolution in ice cores with sub-pg g(-1) Pb concentrations.

Measurements of Pb isotope ratios in ice containing sub-pg g(-1) concentrations are easily compromised by contamination, particularly where limited sample is available. Improved techniques are essential if Antarctic ice cores are to be analysed with sufficient spatial resolution to reveal seasonal variations due to climate. This was achieved here by using stainless steel chisels and saws and strict protocols in an ultra-clean cold room to decontaminate and section ice cores. Artificial ice cores, prepared from high purity water were used to develop and refine the procedures and quantify blanks. Ba and In, two other important elements present at pg g(-1) and fg g(-1) concentrations in Polar ice, were also measured. The final blank amounted to 0.2+/-0.2 pg of Pb with (206)Pb/(207)Pb and (208)Pb/(207)Pb ratios of 1.16+/-0.12 and 2.35+/-0.16, respectively, 1.5+/-0.4 pg of Ba and 0.6+/-2.0 fg of In, most of which probably originates from abrasion of the steel saws by the ice. The procedure was demonstrated on a Holocene Antarctic ice core section and was shown to contribute blanks of only approximately 5%, approximately 14% and approximately 0.8% to monthly resolved samples with respective Pb, Ba and In concentrations of 0.12 pg g(-1), 0.3 pg g(-1) and 2.3 fg g(-1). Uncertainties in the Pb isotopic ratio measurements were degraded by only approximately 0.2%.

Glacial-interglacial changes in the occurrence of Pb, Cd, Cu and Zn in Vostok Antarctic ice from 240 000 to 410 000 years BP.

Lead (Pb), cadmium (Cd), copper (Cu) and zinc (Zn) have been measured by electrothermal atomic absorption spectrometry in various sections of the 3623 m deep ice core drilled at Vostok, in central East Antarctica. The sections were dated from 240 to 410 kyear BP (Marine Isotopic Stages (MIS) 7.5 to 11.3), which corresponds to the 3rd and 4th glacial-interglacial cycles before present. Concentrations are found to have varied greatly during this 170 kyear time period, with high concentration values during the coldest climatic stages such as MIS 8.4 and 10.2 and much lower concentration values during warmer periods, such as the interglacials MIS 7.5, 9.3 and 11.3. Rock and soil dust were the dominant sources for Pb, whatever the period, and for Zn and Cu and possibly Cd during cold climatic stages. The contribution from volcanic emissions was important for Cd during all periods and might have been significant for Cu and Zn during warm periods.

First investigation of an original device dedicated to the determination of gaseous mercury in interstitial air in snow.

The GAMAS (gaseous mercury in interstitial air in snow) instrument developed in our laboratory is a new device devoted to sampling and determination of gaseous mercury concentration in interstitial air in snow. Sampling probes inserted in the snowpack, coupled with a Gardis mercury vapour analyser, provide reliable and original data of vertical profiles of both snow temperature and gaseous mercury concentration at several depths in a snow mantle. This instrument has been tested successfully in Station Nord in Greenland in February-March 2002. A description of this instrument, of the sampling area and its setting up is presented with precise details. Illustrations of the first investigations are given showing a rapid decrease of gaseous mercury concentration simultaneously with depth. A concentration of 0.10 ng/m(3) is reached at 120 cm depth. It may be the result of fast oxidation processes occurring within the snowpack. Gaseous mercury behaviour in the snowpack is a central parameter to elucidate the fate of deposited mercury after mercury depletion events in polar regions. With our new device, we have now the opportunity to determine this key parameter.

Diurnal cycles of gaseous mercury within the snowpack at Kuujjuarapik/Whapmagoostui, Québec, Canada.

Mercury is a globally dispersed and toxic pollutant that can be transported far from its emission sources. In polar and subpolar regions, recent research activities have demonstrated its ability to be converted and deposited rapidly onto snow surfaces during the so-known Mercury Depletion Events (MDEs). The fate of mercury once deposited onto snow surfaces is still unclear: a part could be re-emitted to the atmosphere, the other part could contaminate water systems at the snowmelt. Its capacity to transform to more toxic form and to bioaccumulate in the food chain has consequently made mercury a threat for Arctic ecosystems. The snowpack is a medium that greatly interacts with a variety of atmospheric gases. Its role in the understanding of the fate of deposited mercury is crucial though it is poorly understood. In April 2002, we studied an environmental component of mercury, which is interstitial gaseous mercury (IGM) present in the air of the snowpack at Kuujjuarapik/Whapmagoostui (55 degrees N, 77 degrees W), Canada on the east shore of the Hudson Bay. We report here for the first time continuous IGM measurements at various depths inside a seasonal snowpack. IGM concentrations exhibit a well-marked diurnal cycle with uninterrupted events of Hg0 depletion and production within the snowpack. A possible explanation of Hg0 depletion within the snowpack may be Hg0 oxidation processes. Additionally, we assume that the notable production of Hg0 during the daytime may be the results of photoreduction and photoinitiated reduction of Hg(II) complexes. These new observations show that the snowpack plays undoubtedly a role in the global mercury cycle.