Hemispheric-scale heavy metal pollution from South American and Australian mining and metallurgy during the Common Era.

Records from polar and alpine ice reflect past changes in background and industrial toxic heavy metal emissions. While Northern Hemisphere records have been used to evaluate environmental effects and linkages to historical events such as foreign conquests, plagues, economic downturns, and technological developments during the past three millennia, little is known about the magnitude and environmental effects of such emissions in the Southern Hemisphere or their historical linkages, especially prior to late 19th century industrialization. Here we used detailed measurements of the toxic heavy metals lead, cadmium, and thallium, as well as non-toxic bismuth, cerium, and sulfur in an array of five East Antarctic ice cores to investigate hemispheric-scale pollution during the Common Era. While thallium showed no anthropogenic increases, the other three metals increased by orders of magnitude in recent centuries after accounting for crustal and volcanic components. These first detailed records indicate that East Antarctic lead pollution started in the 13th century coincident with Late Intermediate Period metallurgy in the Andes and was pervasive during the Spanish Colonial period in parallel with large-scale exploitation of Andean silver and other ore deposits. Lead isotopic variations suggest that 19th-century increases in lead, cadmium, and bismuth resulted from Australian lead and Bolivian tin mining emissions, with 20th century pollution largely the result of the latter. As in the Northern Hemisphere, variations in heavy metal pollution coincided with plagues, cultural and technological developments, as well as global economic and political events including the Great Depression and the World Wars. Estimated atmospheric heavy metal emissions from Spanish Colonial-era mining and smelting during the late 16th and early 17th century were comparable to estimated European emissions during the 1st-century apex of the Roman Empire, with atmospheric model simulations suggesting hemispheric-scale toxic heavy metal pollution during the past five centuries as a result.

Abrupt climate fluctuations in Tibet as imprints of multiple meltwater events during the early to mid-Holocene.

Understanding the impact of meltwater discharge during the final stage of the Laurentide Ice Sheet (LIS) has important implications for predicting sea level rise and climate change. Here we present a high-resolution ice-core isotopic record from the central Tibetan Plateau (TP), where the climate is sensitive to the meltwater forcing, and explore possible signals of the climate response to potential LIS meltwater discharges in the early to mid-Holocene. The record shows four abrupt large fluctuations during the 7-9 ka BP (kiloannum before present), reflecting large shifts of the mid-latitude westerlies and the Indian summer monsoon (ISM) over this period, and they corresponded to possible LIS freshwater events documented in other paleoclimate records. Our study suggests that multiple rapid meltwater discharge events might have occurred during the final stage of LIS. The finding implies the possibility of rapid sea level rise and unstable climate in the transition zone between the mid-latitude westerlies and the ISM due to fast polar ice retreat under the anthropogenic global warming.

Industrial-era decline in Arctic methanesulfonic acid is offset by increased biogenic sulfate aerosol.

Marine phytoplankton are primary producers in ocean ecosystems and emit dimethyl sulfide (DMS) into the atmosphere. DMS emissions are the largest biological source of atmospheric sulfur and are one of the largest uncertainties in global climate modeling. DMS is oxidized to methanesulfonic acid (MSA), sulfur dioxide, and hydroperoxymethyl thioformate, all of which can be oxidized to sulfate. Ice core records of MSA are used to investigate past DMS emissions but rely on the implicit assumption that the relative yield of oxidation products from DMS remains constant. However, this assumption is uncertain because there are no long-term records that compare MSA to other DMS oxidation products. Here, we share the first long-term record of both MSA and DMS-derived biogenic sulfate concentration in Greenland ice core samples from 1200 to 2006 CE. While MSA declines on average by 0.2 µg S kg-1 over the industrial era, biogenic sulfate from DMS increases by 0.8 µg S kg-1. This increasing biogenic sulfate contradicts previous assertions of declining North Atlantic primary productivity inferred from decreasing MSA concentrations in Greenland ice cores over the industrial era. The changing ratio of MSA to biogenic sulfate suggests that trends in MSA could be caused by time-varying atmospheric chemistry and that MSA concentrations alone should not be used to infer past primary productivity.

An upgraded CFA - FLC - MS/MS system for the semi-continuous detection of levoglucosan in ice cores.

A new Continuous Flow Analysis (CFA) system coupled with Fast Liquid Chromatography - tandem Mass Spectrometry (FLC-MS/MS) has been recently developed for determining organic markers in ice cores. In this work we present an upgrade of this innovative technique, optimized for the detection of levoglucosan in ice cores, a crucial tracer for reconstructing past fires. The upgrade involved a specific optimization of the chromatographic and mass spectrometric parameters, allowing for a higher sampling resolution (down to 1 cm) and the simultaneous collection of discrete samples, for off-line analysis of water stable isotopes and additional chemical markers. The robustness and repeatability of the method has been tested by the analysis of multiple sticks of ice cut from the same shallow alpine ice core, and running the system for several hours on different days. The results show similar and comparable trends between the ice sticks. With this upgraded system, a higher sensitivity and a lower limit of detection (LOD) was achieved compared to discrete analysis of alpine samples for levoglucosan measurements. The new LOD was as low as 66 ng L-1, a net improvement over the previous LOD of 600 ng L-1.

Identifying the provenance and quantifying the contribution of dust sources in EPICA Dronning Maud Land ice core (Antarctica) over the last deglaciation (7-27 kyr BP): A high-resolution, quantitative record from a new Rare Earth Element mixing model.

Antarctic ice cores have revealed the interplay between dust and climate in the Southern Hemisphere. Yet, so far, no continuous record of dust provenance has been established through the last deglaciation. Here, using a new database of 207 Rare Earth Element (REE) patterns measured in dust and sediments/soils from well-known potential source areas (PSA) of the Southern Hemisphere, we developed a statistical model combining those inputs to provide the best fit to the REE patterns measured in EPICA Dronning Maud Land (EDML) ice core (E. Antarctica). Out of 398 samples measured in the EDML core, 386 samples have been un-mixed with statistical significance. Combined with the total atmospheric deposition, we quantified the dust flux from each PSA to EDML between 7 and 27 kyr BP. Our results reveal that the dust composition was relatively uniform up until 14.5 kyr BP despite a large drop in atmospheric deposition at ∼18 kyr with a large contribution from Patagonia yielding ∼68 % of total dust deposition. The remaining dust was supplied from Australia (14-15 %), Southern Africa (∼9 %), New Zealand (∼3-4 %) and Puna-Altiplano (∼2-3 %). The most striking change occurred ∼14.5 kyr BP when Patagonia dropped below 50 % on average while low-latitude PSA increased their contributions to 21-23 % for Southern Africa, 13-21 % for Australia and âˆ¼ 4-10 % for Puna-Altiplano. We argue that this shift is linked to long-lasting changes in the hydrology of Patagonian rivers and to sudden acceleration of the submersion of Patagonian shelf at 14.5 kyr BP, highlighting a relationship between dust composition and eustatic sea level. Early Holocene dust composition is highly variable, with Patagonian contribution being still prevalent, at ∼50 % on average. Provided a good coverage of local and distal PSA, our statistical model based on REE pattern offers a straightforward and cost-effective method to trace dust source in ice cores.

The Unusual Dominance of the Yeast Genus Glaciozyma in the Deeper Layer in an Antarctic Permafrost Core (Adélie Cove, Northern Victoria Land) Is Driven by Elemental Composition.

Rock glaciers are relatively common in Antarctic permafrost areas and could be considered postglacial cryogenic landforms. Although the extensive presence of rock glaciers, their chemical-physical and biotic composition remain scarce. Chemical-physical parameters and fungal community (by sequencing the ITS2 rDNA, Illumina MiSeq) parameters of a permafrost core were studied. The permafrost core, reaching a depth of 6.10 m, was divided into five units based on ice content. The five units (U1-U5) of the permafrost core exhibited several significant (p < 0.05) differences in terms of chemical and physical characteristics, and significant (p < 0.05) higher values of Ca, K, Li, Mg, Mn, S, and Sr were found in U5. Yeasts dominated on filamentous fungi in all the units of the permafrost core; additionally, Ascomycota was the prevalent phylum among filamentous forms, while Basidiomycota was the dominant phylum among yeasts. Surprisingly, in U5 the amplicon sequence variants (ASVs) assigned to the yeast genus Glaciozyma represented about two-thirds of the total reads. This result may be considered extremely rare in Antarctic yeast diversity, especially in permafrost habitats. Based on of the chemical-physical composition of the units, the dominance of Glaciozyma in the deepest unit was correlated with the elemental composition of the core.

Importance of precipitation and dust storms in regulating black carbon deposition on remote Himalayan glaciers.

Black carbon (BC) can be transported over long distances and is an important trigger of climate warming and glacier melting at remote high mountains and polar regions. It is normally assumed that the variation of BC flux in remote regions is dominated by its emissions. However, after a comprehensive investigation of potential influencing factors on temporal variations of BC from ice cores of the Himalayas, this short communication shows that in addition to BC emissions, contributions from dust storms and precipitation are also important (up to 56% together) in regulating the variation of BC deposition flux and concentrations derived from remote Himalayan ice core measurements. Therefore, besides BC emissions, the influence of precipitation and BC transported by dust storms should also be considered to better quantify the lifetime and behavior of BC during its long-range transport from source to sink regions as well as to quantify the climatic effects of BC over remote Himalayan glaciers.

Greenland Ice Core Record of Last Glacial Dust Sources and Atmospheric Circulation.

Abrupt and large-scale climate changes have occurred repeatedly and within decades during the last glaciation. These events, where dramatic warming occurs over decades, are well represented in both Greenland ice core mineral dust and temperature records, suggesting a causal link. However, the feedbacks between atmospheric dust and climate change during these Dansgaard-Oeschger events are poorly known and the processes driving changes in atmospheric dust emission and transport remain elusive. Constraining dust provenance is key to resolving these gaps. Here, we present a multi-technique analysis of Greenland dust provenance using novel and established, source diagnostic isotopic tracers as well as results from a regional climate model including dust cycle simulations. We show that the existing dominant model for the provenance of Greenland dust as sourced from combined East Asian dust and Pacific volcanics is not supported. Rather, our clay mineralogical and Hf-Sr-Nd and D/H isotopic analyses from last glacial Greenland dust and an extensive range of Northern Hemisphere potential dust sources reveal three most likely scenarios (in order of probability): direct dust sourcing from the Taklimakan Desert in western China, direct sourcing from European glacial sources, or a mix of dust originating from Europe and North Africa. Furthermore, our regional climate modeling demonstrates the plausibility of European or mixed European/North African sources for the first time. We suggest that the origin of dust to Greenland is potentially more complex than previously recognized, demonstrating more uncertainty in our understanding dust climate feedbacks during abrupt events than previously understood.

Westerly drives long-distance transport of radionuclides from nuclear events to glaciers in the Third Pole.

Major nuclear bomb tests and nuclear power plant incidents release large amounts of radionuclides. This study investigates beta (ß) activities of radionuclides from four ice cores in the Third Pole (TP) to understand the transport routes and related atmospheric processes affecting the radionuclides deposition in glaciers of the region. All the ice cores show three major ß activity peaks in the ice layers corresponding to 1963, 1986, and 2011. The ß activity peak in the 1963 ice layer is referred to as the well-known 1962 Nuclear Bomb Test. Beta activity peaks in 1986 and 2011 ice layers from the Chernobyl and Fukushima Nuclear Incidents (CNI, FNI). Hysplit forward and backward trajectory analyses suggest that the radionuclides were transported by the westerly into the stratosphere and then to the high elevation TP glaciers. In the FNI case, the radionuclides traveled over Japan, the Pacific Ocean, Europe, and central Asia before being deposited in the TP glaciers. Investigations of the atmospheric circulation confirm that the stronger northern branch of westerly is responsible for high radionuclides during the FNI in the TP. Less precipitation with water vapor flux component divergence after the FNI also contributed to the enriched radionuclides.

A Tibetan ice core covering the past 1,300 years radiometrically dated with 39Ar.

Ice cores from alpine glaciers are unique archives of past global and regional climate conditions. However, recovering climate records from these ice cores is often hindered by the lack of a reliable chronology, especially in the age range of 100 to 500 anni (a) for which radiometric dating has not been available so far. We report on radiometric 39Ar dating of an ice core from the Tibetan Plateau and the construction of a chronology covering the past 1,300 a using the obtained 39Ar ages. This is made possible by advances in the analysis of 39Ar using the laser-based detection method atom trap trace analysis, resulting in a twofold increase in the upper age limit of 39Ar dating. By measuring the anthropogenic 85Kr along with 39Ar we quantify and correct modern air contamination, thus removing a major systematic uncertainty of 39Ar dating. Moreover, the 85Kr data for the top part of the ice core provide information on firn processes, including the age difference between the ice and its enclosed gas. This first application of 39Ar and 85Kr to an ice core facilitates further ice cores from nonpolar glaciers to be used for recovering climate records of the Common Era, a period including pronounced anomalies such as the Little Ice Age and the Medieval Warm Period.

Provenance of Anthropogenic Pb and Atmospheric Dust to Northwestern North America.

Industrial activities release aerosols containing toxic metals into the atmosphere, where they are transported far from their sources, impacting ecosystems and human health. Concomitantly, long-range-transported mineral dust aerosols play a role in Earth's radiative balance and supply micronutrients to iron-limited ecosystems. To evaluate the sources of dust and pollutant aerosols to Alaska following the 2001 phase-out of leaded gasoline in China, we measured Pb-Sr-Nd isotopic compositions of particles collected in 2016 from snow pits across an elevational transect (2180-5240 m-a.s.l) in Denali National Park, USA. We also determined Pb flux and enrichment from 1991-2011 in the Denali ice core (3870 m-a.s.l). Chinese coal-burning and non-ferrous metal smelting account for up to 64% of Pb deposition at our sites, a value consistent across the western Arctic. Pb isotope ratios in the aerosols did not change between 2001 and 2016, despite the ban on lead additives. Emissions estimates demonstrate that industrial activities have more than compensated for the phase-out of leaded gasoline, with China emitting ∼37,000 metric tons year-1 of Pb during 2013-2015, approximately 78% of the Pb from East Asia. The Pb flux to Alaska now equals that measured in southern Greenland during peak pollution from North America.

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.

Overestimation of anthropogenic contribution of heavy metals in precipitation than those of aerosol samples due to different treatment methods.

Due to increased anthropogenic activities in recent decades, many heavy metal elements have been emitted into the atmosphere and transported to remote regions. The Enrichment factors (EFs) is a normally used method for evaluating the source of heavy metal elements. However, because of some flaws of this method (e.g., higher solubility of heavy metals elements than reference elements in dilute acid), the anthropogenic contributions of some heavy metal elements in the precipitation sample were overestimated. To address this issue, EFs of heavy metal elements of aerosol, precipitation and snowpit samples in a typical remote area of the Tibetan Plateau (TP) were compared. The results showed that the EF values of many heavy metal elements in precipitation and snowpit samples were close to that of aerosol samples treated with dilute acid but usually much higher than those of totally dissolved aerosol samples. Moreover, EF values of most heavy metal elements in the ice core at the margin of the TP were higher than those at central TP, indicating that signal of long-range transport anthropogenic emitted heavy metal elements is weak and may be covered by natural mineral dust sources at glacier region. Therefore, the threshold EF values for determining anthropogenic sources of heavy metal elements in precipitation and ice core samples should be higher than those of aerosols. This study provides new knowledge on investigating anthropogenic sources of heavy metals in precipitation samples at both the TP and other regions of the world.

Ice-core based assessment of nitrogen deposition in the central Tibetan Plateau over the last millennium.

Atmospheric nitrogen deposition is a unique source of bioavailable nitrogen for ecosystems in remote regions, and has vital impacts on ecological processes. Understanding variations of atmospheric nitrogen deposition in these regions remains challenging due to a lack of observations. Ice cores contain records of nitrogen species of nitrate (NO3-) and ammonium (NH4+), hence provide valuable long-term data to study past variations of atmospheric nitrogen deposition. In this study, we present an annually resolved record of NH4+ and NO3- over the past millennium, derived from the Zangser Kangri (ZK) ice core in the central Tibetan Plateau. The concentration peaks of NH4+ and NO3- coincide with those of Ca2+ (a dust tracer), indicating that variation of nitrogen species in the ZK ice core is largely driven by dust activities. An EOF analysis for all chemical species (Cl-, SO42-, NO3-, Na+, NH4+, K+, Mg2+, Ca2+) reveals significant but separate loadings of NH4+ and NO3- on EOF 2, suggesting an additional source of nitrogen, likely from biogenic emissions of terrestrial ecosystems. Over the past millennium, the EOF 2 series has relatively high values around 1300 CE and 1600 CE, and has increased significantly since the Industrial Revolution. These variations are likely driven by temperature-dependent biogenic emissions on the Tibetan Plateau. Analyses of seasonal air mass backward trajectories and wind fields find that the chemical concentrations in the ZK ice core are mostly influenced by the westerly, but South Asia summer monsoon plays an important role in the transport of nitrogen species generated from biogenic emissions. This is further confirmed by the significant correlation between EOF 2 series and the South Asian summer monsoon index. This study provides new insight into the preindustrial sources, natural variabilities and major drivers of nitrogen deposition on the Tibetan Plateau.

Different patterns and origins between northwestern and southeastern Tibetan ice core glaciochemical records over the past century.

Atmospheric circulation systems differ between the northern and southern Tibetan Plateau (TP) and are characterized by prevailing westerly winds and the Indian monsoon, respectively. This leads to spatial differences between glaciochemical records in the northwestern and southeastern TP. We compared the spatial differences in major soluble ion concentrations (Ca2+, SO42-, NO3-, NH4+, Cl-, Na+, K+, and Mg2+) during the last century in the Aru (northwestern TP) and East Rongbuk (ER; southeastern TP) ice cores. Ca2+ exhibited the largest difference between the ice cores (2371 ppb in the Aru ice core and 65 ppb in the ER ice core), indicating that crustal processes were more dominant in the Aru ice core. NH4+ accounted for 17% of the total ion concentration in the ER ice core but only 3% in the Aru ice core, which may be related to the Indian monsoon traveling over NH3 emission zones in southern Asia. The major soluble ion concentrations exhibited decreasing trends in the Aru ice core but increasing trends in the ER ice core (P < 0.01). Empirical orthogonal function and backward trajectory analyses indicated that the major soluble ions in the Aru ice core originated from crustal sources in central Asia; those in the ER ice core had crustal, anthropogenic, and oceanic sources from southern Asia. The results from the Aru ice core suggest that dust events and enhanced prevailing westerly winds promoted the deposition of dust aerosols from the Taklamakan Desert and arid and semi-arid regions of central Asia. Contrastingly, the results from the ER ice core suggest that the Indian monsoon transported crustal and anthropogenic sources from southern Asia and oceanic sources from the Bay of Bengal and Arabian Sea. This study contributes to the comprehensive understanding of the differences in glaciochemical records and their causes between the northwestern and southeastern TP.

Iron in the NEEM ice core relative to Asian loess records over the last glacial-interglacial cycle.

Mineral dust can indirectly affect the climate by supplying bioavailable iron (Fe) to the ocean. Here, we present the records of dissolved Fe (DFe) and total Fe (TDFe) in North Greenland Eemian Ice Drilling (NEEM) ice core over the past 110 kyr BP. The Fe records are significantly negatively correlated with the carbon-dioxide (CO2) concentrations during cold periods. The results suggest that the changes in Fe fluxes over the past 110 kyr BP in the NEEM ice core are consistent with those in Chinese loess records because the mineral-dust distribution is controlled by the East Asian deserts. Furthermore, the variations in the dust input on a global scale are most likely driven by changes in solar radiation during the last glacial-interglacial cycle in response to Earth's orbital cycles. In the last glacial-interglacial cycle, the DFe/TDFe ratios were higher during the warm periods (following the post-Industrial Revolution and during the Holocene and last interglacial period) than during the main cold period (i.e. the last glacial maximum (LGM)), indicating that the aeolian input of iron and the iron fertilization effect on the oceans have a non-linear relationship during different periods. Although the burning of biomass aerosols has released large amounts of DFe since the Industrial Revolution, no significant responses are observed in the DFe and TDFe variations during this period, indicating that severe anthropogenic contamination has no significant effect on the DFe (TDFe) release in the NEEM ice core.

High-Resolution Tritium Profile in an Ice Core from Camp Century, Greenland.

We measure 3H in an ice core from Camp Century. The temporal distribution of 3H concentration in the ice core corresponds generally well with the historical record of explosive yields of atmospheric nuclear weapons tests. Maximum 3H values observed in 1962-1963 are comparable to those in ice core or precipitation in many other locations in the Northern Hemisphere. There is no indication that significant 3H contamination was locally released into the air during the operation of the Camp Century reactor. It is, however, somewhat surprising that several prominent 3H peaks are still observed after 1980. We suggest that these are associated with airborne 3H releases from the civil nuclear industry. A wavelet analysis during 1970-2017 indicates the primary frequency of variability in the 3H record is annual 3H peaks. These annual peaks can be combined with the 3H spikes from global fallout of known nuclear weapons tests to benchmark and evaluate theoretical ice core dating scales back to the 1950s. A positive correlation is observed between annual 3H average concentration and variability of Arctic Oscillation (AO). This highlights the value of 3H as a potential tracer for air masses and airborne pollutants in the Arctic.

North Atlantic jet stream projections in the context of the past 1,250 years.

Reconstruction of the North Atlantic jet stream (NAJ) presents a critical, albeit largely unconstrained, paleoclimatic target. Models suggest northward migration and changing variance of the NAJ under 21st-century warming scenarios, but assessing the significance of such projections is hindered by a lack of long-term observations. Here, we incorporate insights from an ensemble of last-millennium water isotope-enabled climate model simulations and a wide array of mean annual water isotope ([Formula: see text]O) and annually accumulated snowfall records from Greenland ice cores to reconstruct North Atlantic zonal-mean zonal winds back to the 8th century CE. Using this reconstruction we provide preobservational constraints on both annual mean NAJ position and intensity to show that late 20th- and early 21st-century NAJ variations were likely not unique relative to natural variability. Rather, insights from our 1,250 year reconstruction highlight the overwhelming role of natural variability in thus far masking the response of midlatitude atmospheric dynamics to anthropogenic forcing, consistent with recent large-ensemble transient modeling experiments. This masking is not projected to persist under high greenhouse gas emissions scenarios, however, with model projected annual mean NAJ position emerging as distinct from the range of reconstructed natural variability by as early as 2060 CE.

A multimillion-year-old record of Greenland vegetation and glacial history preserved in sediment beneath 1.4 km of ice at Camp Century.

Understanding the history of the Greenland Ice Sheet (GrIS) is critical for determining its sensitivity to warming and contribution to sea level; however, that history is poorly known before the last interglacial. Most knowledge comes from interpretation of marine sediment, an indirect record of past ice-sheet extent and behavior. Subglacial sediment and rock, retrieved at the base of ice cores, provide terrestrial evidence for GrIS behavior during the Pleistocene. Here, we use multiple methods to determine GrIS history from subglacial sediment at the base of the Camp Century ice core collected in 1966. This material contains a stratigraphic record of glaciation and vegetation in northwestern Greenland spanning the Pleistocene. Enriched stable isotopes of pore-ice suggest precipitation at lower elevations implying ice-sheet absence. Plant macrofossils and biomarkers in the sediment indicate that paleo-ecosystems from previous interglacial periods are preserved beneath the GrIS. Cosmogenic 26Al/10Be and luminescence data bracket the burial of the lower-most sediment between <3.2 ± 0.4 Ma and >0.7 to 1.4 Ma. In the upper-most sediment, cosmogenic 26Al/10Be data require exposure within the last 1.0 ± 0.1 My. The unique subglacial sedimentary record from Camp Century documents at least two episodes of ice-free, vegetated conditions, each followed by glaciation. The lower sediment derives from an Early Pleistocene GrIS advance. 26Al/10Be ratios in the upper-most sediment match those in subglacial bedrock from central Greenland, suggesting similar ice-cover histories across the GrIS. We conclude that the GrIS persisted through much of the Pleistocene but melted and reformed at least once since 1.1 Ma.

First discrete iron(II) records from Dome C (Antarctica) and the Holtedahlfonna glacier (Svalbard).

Fe(II) is more soluble and bioavailable than Fe(III) species, therefore the investigation of their relative abundance and redox processes is relevant to better assess the supply of bioavailable iron to the ocean and its impact on marine productivity. In this context, we present a discrete chemiluminescence-based method for the determination of Fe(II) in firn matrices. The method was applied on discrete samples from a snow pit collected at Dome C (DC, Antarctica) and on a shallow firn core from the Holtedahlfonna glacier (HDF, Svalbard), providing the first Fe(II) record from both Antarctica and Svalbard. The method showed low detection limits (0.006 ng g-1 for DC and 0.003 ng g-1 for the HDF) and a precision ranging from 3% to 20% RSD. Fe(II) concentrations ranged between the LoD and 0.077 ng g-1 and between the LoD and 0.300 ng g-1 for the Antarctic and Arctic samples, respectively. The Fe(II) contribution with respect to the total dissolved Fe was comparable in both sites accounting, on average, for 5% and 3%, respectively. We found that Fe(II) correctly identified the Pinatubo/Cerro Hudson eruption in the DC record, demonstrating its reliability as volcanic tracer, while, on the HDF core, we provided the first preliminary insight on the processes that might influence Fe speciation in firn matrices (i.e. organic ligands and pH influences).