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Interior Antarctica is among the most remote places on Earth and was thought to be beyond the reach of human impacts when Amundsen and Scott raced to the South Pole in 1911. Here we show detailed measurements from an extensive array of 16 ice cores quantifying substantial toxic heavy metal lead pollution at South Pole and throughout Antarctica by 1889 - beating polar explorers by more than 22 years. Unlike the Arctic where lead pollution peaked in the 1970s, lead pollution in Antarctica was as high in the early 20(th) century as at any time since industrialization. The similar timing and magnitude of changes in lead deposition across Antarctica, as well as the characteristic isotopic signature of Broken Hill lead found throughout the continent, suggest that this single emission source in southern Australia was responsible for the introduction of lead pollution into Antarctica at the end of the 19(th) century and remains a significant source today. An estimated 660 t of industrial lead have been deposited over Antarctica during the past 130 years as a result of mid-latitude industrial emissions, with regional-to-global scale circulation likely modulating aerosol concentrations. Despite abatement efforts, significant lead pollution in Antarctica persists into the 21(st) century.

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., (Copyright © 2014 Elsevier B.V. All rights reserved.)

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%.

Interior Antarctica is among the most remote places on Earth and was thought to be beyond the reach of human impacts when Amundsen and Scott raced to the South Pole in 1911. Here we show detailed measurements from an extensive array of 16 ice cores quantifying substantial toxic heavy metal lead pollution at South Pole and throughout Antarctica by 1889 - beating polar explorers by more than 22 years. Unlike the Arctic where lead pollution peaked in the 1970s, lead pollution in Antarctica was as high in the early 20(th) century as at any time since industrialization. The similar timing and magnitude of changes in lead deposition across Antarctica, as well as the characteristic isotopic signature of Broken Hill lead found throughout the continent, suggest that this single emission source in southern Australia was responsible for the introduction of lead pollution into Antarctica at the end of the 19(th) century and remains a significant source today. An estimated 660 t of industrial lead have been deposited over Antarctica during the past 130 years as a result of mid-latitude industrial emissions, with regional-to-global scale circulation likely modulating aerosol concentrations. Despite abatement efforts, significant lead pollution in Antarctica persists into the 21(st) century.

Abstract: Pb and Ba concentrations and Pb isotopic compositions are reported for firn core and snow pit samples from Victoria Land, Antarctica, dating from 1872 AD to 1994 AD. From variations in Pb/Ba ratios and Pb isotopic compositions, two periods of major Pb enhancements were identified, from 1891 to 1908 AD and from 1948 to 1994 AD. The earlier pollution event is attributed to Pb emissions from non-ferrous metal production and coal combustion in the Southern Hemisphere and is in excellent agreement with coincident pollution inputs reported in firn/ice cores from two other regions of Antarctica, at Coats Land and Law Dome. Using Pb isotopic systematics, it was calculated that ∼50% of Pb deposited in Victoria Land in 1897 originated from anthropogenic emission sources. The more recent period of Pb enhancements, from 1948 to 1994 AD, corresponds to the introduction and widespread use of gasoline alkyl Pb additives in automobiles in the Southern Hemisphere, with anthropogenic Pb inputs averaging 60% of total Pb but with large uncertainty. Intra- and inter-annual variations in Pb concentrations and isotopic compositions were evaluated in snow pits samples corresponding to the period 1991–1994. Substantial variations in Pb/Ba and 206Pb/207Pb ratios were detected but the absence of a regular seasonal pattern for these parameters suggests that the transport and deposition of aerosols to the Antarctic ice sheet are complex and vary from year to year. [Copyright &y& Elsevier]

We report Pb concentrations and isotopic compositions measured in plume aerosol and Pele''s hair (lava) samples collected from Masaya volcano, Nicaragua, to provide the first data pertaining to Pb emissions from the Central American volcanic arc. Lead isotopic compositions, determined by Thermal Ionisation Mass Spectrometry, in the Pele''s hair samples were found to be 206Pb/207Pb∼1.196, 208Pb/207Pb∼2.46 and 206Pb/204Pb∼18.6. Mean Pb fluxes from Masaya were calculated to be 1.0 ton Pb yr−1 with a mean plume Pb/S(gas) ratio of 1.3×10−5. Also, it was found that the majority of Pb emitted was present in the fine aerosol (<2.5 μm diameter) fraction but that the percentage of Pb in the fine aerosol fraction decreased from 96% in the dry daytime plume to 61% in the condensed night-time plume. The contribution from the filter blank was usually a substantial fraction of the total amount of Pb measured, requiring the data to be corrected for blank contributions using Pb isotopic systematics. [Copyright &y& Elsevier]

Lead, Ba and Bi concentrations and Pb isotopic compositions have been measured in Antarctic Law Dome (66.8°S, 112.4°E) ice dated from 1814 AD to 1819 AD by thermal ionisation mass spectrometry to investigate the possible deposition of heavy metals from the 1815 AD eruption of Tambora volcano (8.5°S, 117.4°E) in Indonesia. Although volcanic S emissions from Tambora (observed as SO42−) are present in the Antarctic ice core record, there are grounds to question the origin of the Pb and Bi also deposited at Law Dome from late 1817, as the Pb isotope data suggest this Pb originated from Mount Erebus (77.5°S, 167.2°E) on Ross Island, Antarctica. It is shown that at least 97% of any Pb and Bi emitted from Tambora was removed from the atmosphere within the 1.6 year period required to transport aerosols from Indonesia to Antarctica. Consequently, increased Pb and Bi concentrations observed in Law Dome ice about 1818 AD are attributed to either increased heavy metal emissions from Mount Erebus, or increased fluxes of heavy metals to the Antarctic ice sheet resulting from climate and meteorological modifications following the Tambora eruption. Elevated Ba concentrations, observed from mid-1816 to mid-1818, indicate increased atmospheric loading of rock and soil dust also occurred at the time. [Copyright &y& Elsevier]

Techniques for Pb measurements have reached the stage where Antarctic ice with sub-picogram per gram concentrations can be reliably analysed for isotopic composition. Here, particular attention has been given to measuring the quantity of Pb added during the decontamination and sample storage stages of the sample preparation process because of their impact on accuracy at low concentrations. These stages, including the use of a stainless steel chisel for the decontamination, contributed ∼5.2 pg to the total sample analysed, amounting to a concentration increase of ∼13 fg g−1, which is significantly less than expected. Consequently, the corrections to the isotopic ratios and concentration were also smaller. Other contributions to the blank, such as Pb fallout onto critical working areas in the HEPA-filtered air laboratories, were also relatively small as was the amount of Pb leached from preconditioned perfluoroalkoxy (PFA) beakers during sample processing. The ion source contributed typically 89±19 fg to the blank. Although this was relatively large, its influence depended upon the amount of Pb available for analysis and it had the greatest impact when small volumes of samples with a very low concentration were analysed. A 15 months investigation of the leaching characteristics of Pb from a low-density polyethylene (LDPE) sample storage bottle showed 11 fg cm−2 per day was released immediately following the initial 2 months cleaning process, but this decreased to immeasurable values after a further 3 months of cleaning. [Copyright &y& Elsevier]