Reliable Ultra Trace Analysis of Cd, U and Zn Concentrations in Greenland Snow and Ice by Using Ultraclean Methods for Contamination Control.

This study presents ultraclean procedures used in the challenging task of determining trace elements at or below the pg/g concentration level encountered in Greenland snow and ice. In order to validate these ultraclean procedures, recent snowfall and Holocene ice from northwest Greenland were analyzed for Cd, U, and Zn concentrations. The total procedural blanks brought through the entire measurement procedure proved to be negligible, compared to trace element concentrations, measured in snow and ice samples. This validates the overall practicality of the proposed ultraclean procedures, thereby ensuring the reliable measurements of ultra-trace analysis. A comparison between our study and published data shows that improper procedures employed throughout all stages, from field sampling to analysis to elevate the concentrations by several orders of magnitude, relative to the reliable concentration ranges. The risk of contamination exposure for selected trace elements appears to increase in the order of U < As ≤ Pb < Cd < Zn. Reliable measurements of Cd, U, and Zn concentrations in snow and ice allowed us to interpret the data in terms of seasonal variations in the inputs of crustal and anthropogenic sources to Greenland ice sheet.

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.

Comparison of acid extraction and total digestion methods for measuring Cd isotope ratios of environmental samples.

To evaluate the pretreatment processing for Cd isotope analysis of environmental samples, acid extractions and total digestions were examined with various environmental certified reference materials. Four certified reference material samples, including fly ash, polluted soil, domestic sludge, and industrial sludge, were digested by six different acid extraction and total digestion methods, and then Cd was separated to remove other matrix by anion-exchange column. The Cd recovery rates of the acid extraction methods were 2.6-89.1%, while those of the total digestion methods were 21.6-88.7%. In these results, the Cd recovery rates were dependent on the sample type. More than 80% of the Cd in the polluted soil and domestic sludge samples could be recovered regardless of the decomposition method, except one method. On the other hand, the Cd recovery rate from fly ash was low when total digestion was performed using a HF mixture, and the recovery rate by total digestion methods for industrial sludge was higher than that by acid extraction. In our results, Cd isotope ratios tended to be more positive by increasing the Cd recovery rates, suggesting that the light isotope of Cd was decomposed preferentially during the decomposition procedures. However, when more than 80% of the Cd in the samples was recovered, the Cd isotope ratios were determined to be similar. This indicated that at least 80% of the Cd should be recovered from environmental samples to accurately measure the Cd isotopic ratio of environmental samples.

Tracing lead pollution sources in abandoned mine areas using stable Pb isotope ratios.

This study focused on Pb isotope ratios of sediments in areas around an abandoned mine to determine if the ratios can be used as a source tracer. For pretreatment, sediment samples were dissolved with mixed acids, and a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS, Nu plasma II) was used to investigate the Pb isotopic composition of the samples. The measured isotope ratios were then corrected for instrumental mass fractionation by measuring the (203)Tl/(205)Tl ratio. Repeated measurements with the NIST SRM 981 reference material showed that the precision of all ratios was below 104 ppm (±2σ) for 50 ng/g. The isotope ratios ((207)Pb/(206)Pb) found were 0.85073 ± 0.0004~0.85373 ± 0.0003 for the main stream, while they were 0.83736 ± 0.0010 for the tributary and 0.84393 ± 0.0002 for the confluence. A binary mixing equation for isotope ratios showed that the contributions of mine lead to neighboring areas were up to 60%. Therefore, Pb isotope ratios can be a good source tracer for areas around abandoned mines.

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.

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.

High-resolution isotopic evidence for a potential Saharan provenance of Greenland glacial dust.

Dust concentrations in Greenland ice show pronounced glacial/interglacial variations with almost two orders of magnitude increase during the Last Glacial Maximum. Greenland glacial dust was previously sourced to two East Asian deserts: the Taklimakan and Gobi deserts. Here we report the first high-resolution Pb and Sr isotopic evidence for a significant Saharan dust influence in Greenland during the last glacial period, back to ~31 kyr ago, from the Greenland NEEM ice core. We find that during Greenland Stadials 3-5.1 (~31 to 23 kyr ago), the primary dust provenance was East Asia, as previously proposed. Subsequently, the Saharan isotopic signals emerge during Greenland Stadials 2.1a-2.1c (~22.6 to 14.7 kyr ago) and from the late Bølling-Allerød to the Younger Dryas periods (~13.6 to 12 kyr ago), coincident with increased aridity in the Sahara and efficient northward transport of dust during these cold periods. A mixing isotopic model proposes the Sahara as an important source, accounting for contribution to Greenland glacial dust of up to 50%, particularly during Greenland Stadial 2.1b and the late Bølling-Allerød to the Younger Dryas periods. Our findings provide new insights into climate-related dust provenance changes and essential paleoclimatic constraints on dust-climate feedbacks in northern high latitudes.

Seasonal variation in the input of atmospheric selenium to northwestern Greenland snow.

Oxygen isotope ratio (δ(18)O) and concentrations of Al, Na(+), methanesulfonic acid (MSA), SO4(2-), and selenium (Se) in a continuous series of 70 snow samples from a 3.2-m snow pit at a site in northwestern Greenland were determined using ultraclean procedures. Well-defined depth profiles of δ(18)O, Al, and sea-salt-Na(+) allowed the determination of chronology of the snow pit that spanned approximately 6 years from spring 2003 to summer 2009. Se concentrations were at a low pg/g level, ranging from 7.2 to 45 pg/g, and exhibited high variability with generally higher values during winter and spring and lower values during summer and fall. Very high crustal enrichment factors (EFc) of Se averaging approximately 26,600 for the entire time period indicate a small contribution from crust dust. High Se/MSA ratios are generally observed in the winter and spring snow layers, in which the Se concentrations were relatively high (>20 pg/g). This suggests that a significant component of the Se present in the snow layers is of anthropogenic origin. During the summer season, however, high EFc values are accompanied with low Se/MSA, indicating an increased contribution of marine biogenic sources. Significant correlations between Se, Al, and non-sea-salt SO4(2-) highlight that significant inputs of Se to the snow are likely controlled by the seasonality in the transport efficiency of anthropogenic Se from the source regions to the site. Based on the seasonal changes in Se concentrations, Se/MSA, and Se/S ratios observed in the samples, the input of anthropogenic Se to the site appears to be governed by the long-range transportation of Se emitted from coal combustion in East Asian countries, especially in China.

Determination of lead isotopes in a new Greenland deep ice core at the sub-picogram per gram level by thermal ionization mass spectrometry using an improved decontamination method.

An improved decontamination method and ultraclean analytical procedures have been developed to minimize Pb contamination of processed glacial ice cores and to achieve reliable determination of Pb isotopes in North Greenland Eemian Ice Drilling (NEEM) deep ice core sections with concentrations at the sub-picogram per gram level. A PL-7 (Fuso Chemical) silica-gel activator has replaced the previously used colloidal silica activator produced by Merck and has been shown to provide sufficiently enhanced ion beam intensity for Pb isotope analysis for a few tens of picograms of Pb. Considering the quantities of Pb contained in the NEEM Greenland ice core and a sample weight of 10 g used for the analysis, the blank contribution from the sample treatment was observed to be negligible. The decontamination and analysis of the artificial ice cores and selected NEEM Greenland ice core sections confirmed the cleanliness and effectiveness of the overall analytical process.

Seasonal variations in the sources of natural and anthropogenic lead deposited at the East Rongbuk Glacier in the high-altitude Himalayas.

Lead (Pb) isotopic compositions and concentrations, and barium (Ba) and indium (In) concentrations have been analysed at sub-annual resolution in three sections from a <110 m ice core dated to the 18th and 20th centuries, as well as snow pit samples dated to 2004/2005, recovered from the East Rongbuk Glacier in the high-altitude Himalayas. Ice core sections indicate that atmospheric chemistry prior to ~1,953 was controlled by mineral dust inputs, with no discernible volcanic or anthropogenic contributions. Eighteenth century monsoon ice core chemistry is indicative of dominant contributions from local Himalayan sources; non-monsoon ice core chemistry is linked to contributions from local (Himalayan), regional (Indian/Thar Desert) and long-range (North Africa, Central Asia) sources. Twentieth century monsoon and non-monsoon ice core data demonstrate similar seasonal sources of mineral dust, however with a transition to less-radiogenic isotopic signatures that suggests local and regional climate/environmental change. The snow pit record demonstrates natural and anthropogenic contributions during both seasons, with increased anthropogenic influence during non-monsoon times. Monsoon anthropogenic inputs are most likely sourced to South/South-East Asia and/or India, whereas non-monsoon anthropogenic inputs are most likely sourced to India and Central Asia.

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.

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.