Paul Vallelonga

The lead pollution history of Law Dome, Antarctica, from isotopic measurements on ice cores: 1500 AD to 1989 AD

Abstract Lead isotopic compositions and Pb and Ba concentrations have been measured in ice cores from Law Dome, East Antarctica, covering the past 6500 years. ‘Natural’ background concentrations of Pb (∼0.4 pg/g) and Ba (∼1.3 pg/g) are observed until 1884 AD, after which increased Pb concentrations and lowered 206Pb/207Pb ratios indicate the influence of anthropogenic Pb. The isotopic composition of ‘natural’ Pb varies within the range 206Pb/207Pb=1.20–1.25 and 208Pb/207Pb=2.46–2.50, with an average rock and soil dust Pb contribution of 8–12%. A major pollution event is observed at Law Dome between 1884 and 1908 AD, elevating the Pb concentration four-fold and changing 206Pb/207Pb ratios in the ice to ∼1.12. Based on Pb isotopic systematics and Pb emission statistics, this is attributed to Pb mined at Broken Hill and smelted at Broken Hill and Port Pirie, Australia. Anthropogenic Pb inputs are at their greatest from ∼1900 to ∼1910 and from ∼1960 to ∼1980. During the 20th century, Ba concentrations are consistently higher than ‘natural’ levels and are attributed to increased dust production, suggesting the influence of climate change and/or changes in land coverage with vegetation.

Post 17th century changes of European lead emissions recorded in high-altitude Alpine snow and ice

The occurrence of organic pollutants in European Alpine snow/ice has been reconstructed over the past three centuries using a new online extraction method for polycyclic aromatic hydrocarbons (PAH) followed by liquid chromatographic determination. The meltwater flow from a continuous ice core melting system was split into two aliquots, with one aliquot directed to an inductively coupled plasma quadrupole mass spectrometer for continuous trace elements determinations and the second introduced into a solid phase C18 (SPE) cartridge for semicontinuous PAH extraction. The depth resolution for PAH extractions ranged from 40 to 70 cm, and corresponds to 0.7-5 years per sample. The concentrations of 11 PAH were determined in dated snow/ice samples to reconstruct the atmospheric concentration of these compounds in Europe for the last 300 years. The PAH pattern is dominated by phenanthrene (Phe), fluoranthene (Fla), and pyrene (Pyr), which represent 60-80% of the total PAH mass. Before 1875 the sum of PAH concentration (SigmaPAH) was very low with total mean concentrations less than 2 ng/kg and 0.08 ng/kg for the heavier compounds (SigmaPAH*, more than four aromatic rings). During the first phase of the industrial revolution (1770-1830) the PAH deposition showed a weak increase which became much greater from the start of the second phase of the industrial revolution at the end of 19th Century. In the 1920s, economic recession in Europe decreased PAH emissions until the 1930s when they increased again and reached a maximum concentration of 32 ng/kg from 1945 to 1955. From 1955 to 1975 the PAH concentrations decreased significantly, reflecting improvements in emission controls especially from major point sources, while from 1975 to 2003 they rose to levels equivalent to those in 1910. The Fla/(Fla+Pyr) ratio is often used for source assignment and here indicates an increase in the relative contribution of gasoline and diesel combustion with respect to coal and wood burning from 1860 to the 1980s. This trend was reversed during the last two decades.

Optimization of high-resolution continuous flow analysis for transient climate signals in ice cores

Over the past two decades, continuous flow analysis (CFA) systems have been refined and widely used to measure aerosol constituents in polar and alpine ice cores in very high-depth resolution. Here we present a newly designed system consisting of sodium, ammonium, dust particles, and electrolytic meltwater conductivity detection modules. The system is optimized for high-resolution determination of transient signals in thin layers of deep polar ice cores. Based on standard measurements and by comparing sections of early Holocene and glacial ice from Greenland, we find that the new system features a depth resolution in the ice of a few millimeters which is considerably better than other CFA systems. Thus, the new system can resolve ice strata down to 10 mm thickness and has the potential of identifying annual layers in both Greenland and Antarctic ice cores throughout the last glacial cycle.

Antarctic-wide array of high-resolution ice core records reveals pervasive lead pollution began in 1889 and persists today

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 20th 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 19th 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 21st century.

A 220 kyr record of Pb isotopes at Dome C Antarctica from analyses of the EPICA ice core

Pb isotopic compositions and Pb and Ba concentrations are reported in EPICA Dome C ice core samples dating to 220 kyr BP, indicating that Pb isotopic compositions in Antarctic ice vary with changing climate. 206Pb/207Pb ratios decrease during glacial periods, with the lowest values occurring during colder climatic periods (stages 2, 4 and 6) and the Holocene. Low Pb concentrations ( 10 pg/g) were found during cold climatic periods. Ba, a proxy for mineral dust, was used to determine that dust usually accounts for ∼70% of Pb in Dome C ice, while the remaining ∼30% was attributed to volcanic emissions. Pb isotopic compositions at Dome C differ from those reported in pre-industrial ice from other Antarctic locations, due to greater proportions of dust Pb at Dome C.

Determination of Fe2+ and Fe3+ species by FIA-CRC-ICP-MS in Antarctic ice samples

Iron is an element of great interest due to its role in primary production and in oceanic carbon cycle regulation, such that past changes in iron deposition may have influenced oceanic sequestration of atmospheric CO2 on millennial time scales. The behavior of iron in biological and environmental contexts depends strongly on its oxidation state. Solubility in water and the capacity to form complexes are just two important characteristics that are species dependent. Distinguishing between the two iron species, Fe(II) and Fe(III), is necessary to evaluate bioavailability, as Fe(II) is more soluble and therefore more readily available for phytoplankton uptake and growth. Here, we present a novel analytical method for iron speciation analysis using Collision Reaction Cell-Inductively Coupled Plasma-Mass Spectrometry (CRC-ICP-MS) and apply it to ice core samples from Talos Dome, Antarctica. The method detection limit is 0.01 ng g−1. A chelating resin, Ni-NTA Superflow, was used to separate the Fe species. At pH 2 the resin is capable of retaining Fe3+ with no retention of Fe2+. After the initial separation, we oxidized the Fe2+ using H2O2, and determined the Fe2+ concentration as the difference between the two measurements. Our preliminary results demonstrate higher Fe2+ concentrations during glacial periods than during interglacial periods. This elevated concentration of Fe2+ suggests that more iron was available for phytoplankton growth during the Last Glacial Maximum, than would be expected from measurements of proxies such as dust mass or total Fe.

Lead, Ba and Bi in Antarctic Law Dome ice corresponding to the 1815 AD Tambora eruption: an assessment of emission sources using Pb isotopes

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.

Greenland 2012 melt event effects on CryoSat‐2 radar altimetry

CryoSat-2 data are used to study elevation changes over an area in the interior part of the Greenland Ice Sheet during the extreme melt event in July 2012. The penetration of the radar signal into dry snow depends heavily on the snow stratigraphy, and the rapid formation of refrozen ice layers can bias the surface elevations obtained from radar altimetry. We investigate the change in CryoSat-2 waveforms and elevation estimates over the melt event and interpret the findings by comparing in situ surface and snow pit observations from the North Greenland Eemian Ice Drilling Project camp. The investigation shows a major transition of scattering properties around the area, and an apparent elevation increase of 56 ± 26 cm is observed in reprocessed CryoSat-2 data. We suggest that this jump in elevation can be explained by the formation of a refrozen melt layer that raised the reflective surface, introducing a positive elevation bias.

Widespread pollution of the South American atmosphere predates the industrial revolution by 240 y

Significance An exceptionally detailed ice core from the high-altitude location of Quelccaya (Peru) contains compelling evidence that the well-known metallurgic activities performed during the Inca Empire (A.D. 1438−1532) had a negligible impact on the South American atmosphere. In contrast, atmospheric emissions of a variety of toxic trace elements in South America started to have a widespread environmental impact around A.D. 1540, ∼240 y before the industrial revolution when colonial metallurgy began to pollute the Andean atmosphere. 20th century atmospheric pollution levels were the highest on record and remain unprecedented over the entirety of human history. In the Southern Hemisphere, evidence for preindustrial atmospheric pollution is restricted to a few geological archives of low temporal resolution that record trace element deposition originating from past mining and metallurgical operations in South America. Therefore, the timing and the spatial impact of these activities on the past atmosphere remain poorly constrained. Here we present an annually resolved ice core record (A.D. 793–1989) from the high-altitude drilling site of Quelccaya (Peru) that archives preindustrial and industrial variations in trace elements. During the precolonial period (i.e., pre-A.D. 1532), the deposition of trace elements was mainly dominated by the fallout of aeolian dust and of ash from occasional volcanic eruptions, indicating that metallurgic production during the Inca Empire (A.D. 1438−1532) had a negligible impact on the South American atmosphere. In contrast, a widespread anthropogenic signal is evident after around A.D. 1540, which corresponds with the beginning of colonial mining and metallurgy in Peru and Bolivia, ∼240 y before the Industrial Revolution. This shift was due to a major technological transition for silver extraction in South America (A.D. 1572), from lead-based smelting to mercury amalgamation, which precipitated a massive increase in mining activities. However, deposition of toxic trace metals during the Colonial era was still several factors lower than 20th century pollution that was unprecedented over the entirety of human history.

Elemental indicators of natural and anthropogenic aerosol inputs to Law Dome, Antarctica

Abstract A selection of elements (Bi, Ca, Cd, Co, Cu, Mn, Na, Sr, U, V, Zn) were measured by high-resolution inductively coupled plasma sector-field mass spectrometry in firn- and ice-core samples from Law Dome, Antarctica, corresponding to the period 4500 BC to AD 1989. Concentrations of rock dust and sea salts were calculated for each sample and then used to determine concentrations of each element originating from crustal and marine aerosol emissions, respectively. Where calculated contributions from crustal and marine aerosol sources failed to account for the total measured concentration of an element, the remainder was apportioned to volcanic and/or anthropogenic sources and defined as an enrichment. On this basis, it was determined that Bi and Cd concentrations in Law Dome ice are overwhelmingly influenced by volcanic emissions (enrichments 150–250x crustal and marine inputs); Co, Cu, Pb and Zn concentrations in Law Dome ice are largely influenced by volcanic emissions (enrichments 16–36x crustal and marine inputs); and Mn, Sr, U and V concentrations in Law Dome ice are minimally influenced by volcanic emissions (enrichments 1.5–4x crustal and marine inputs). During the 20th century, enrichments of Pb and Cu concentrations were observed to be greater than in earlier centuries, consistent with increasing anthropogenic emissions of Pb and Cu in the Southern Hemisphere over that period.