Four Years of Active Sampling and Measurement of Atmospheric Polycyclic Aromatic Hydrocarbons and Oxygenated Polycyclic Aromatic Hydrocarbons in Dronning Maud Land, East Antarctica.

Antarctica, protected by its strong polar vortex and sheer distance from anthropogenic activity, was always thought of as pristine. However, as more data on the occurrence of persistent organic pollutants on Antarctica emerge, the question arises of how fast the long-range atmospheric transport takes place. Therefore, polycyclic aromatic hydrocarbons (PAHs) and oxygenated (oxy-)PAHs were sampled from the atmosphere and measured during 4 austral summers from 2017 to 2021 at the Princess Elisabeth station in East Antarctica. The location is suited for this research as it is isolated from other stations and activities, and the local pollution of the station itself is limited. A high-volume sampler was used to collect the gas and particle phase (PM10) separately. Fifteen PAHs and 12 oxy-PAHs were quantified, and concentrations ranging between 6.34 and 131 pg m3 (Σ15PAHs-excluding naphthalene) and between 18.8 and 114 pg m3 (Σ13oxy-PAHs) were found. Phenanthrene, pyrene, and fluoranthene were the most abundant PAHs. The gas-particle partitioning coefficient log(Kp) was determined for 6 compounds and was found to lie between 0.5 and -2.5. Positive matrix factorization modeling was applied to the data set to determine the contribution of different sources to the observed concentrations. A 6-factor model proved a good fit to the data set and showed strong variations in the contribution of different air masses. During the sampling campaign, a number of volcanic eruptions occurred in the southern hemisphere from which the emission plume was detected. The FLEXPART dispersion model was used to confirm that the recorded signal is indeed influenced by volcanic eruptions. The data was used to derive a transport time of between 11 and 33 days from release to arrival at the measurement site on Antarctica.

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.

High-pressure synthesis and storage of solid organic compounds in active subduction zones.

Recent thermodynamic and experimental studies have suggested that volatile organic compounds (e.g., methane, formate, and acetate) can be produced and stabilized in subduction zones, potentially playing an important role in the deep carbon cycle. However, field evidence for the high-pressure production and storage of solid organic compounds is missing. Here, we examine forearc serpentinite clasts recovered by drilling mud volcanoes above the Mariana subduction zone. Notable correlations between carbon and iron stable-isotope signatures and fluid-mobile element (B, As and Sb) concentrations provide evidence for the percolation of slab-derived CO2-rich aqueous fluids through the forearc mantle. The presence of carbonaceous matter rich in aliphatic moieties within high-temperature clasts (>350°C) demonstrates that molecular hydrogen production associated with forearc serpentinization is an efficient mechanism for the reduction and conversion of slab-derived CO2-rich fluids into solid organic compounds. These findings emphasize the need to consider the forearc mantle as an important reservoir of organic carbon on Earth.

Laboratory study of iron isotope fractionation during dissolution of mineral dust and industrial ash in simulated cloud water.

Atmospheric deposition is a key mode of iron (Fe) input to ocean regions where low concentrations of this micronutrient limit marine primary production. Various natural particles (e.g., mineral dust, volcanic ash) and anthropogenic particles (e.g., from industrial processes, biomass burning) can deliver Fe to the ocean, and assessment of their relative importance in supplying Fe to seawater requires knowledge of both their deposition flux and their Fe solubility (a proxy for Fe bioavailability). Iron isotope (54Fe, 56Fe, 57Fe, 58Fe) analysis is a potential tool for tracing natural and anthropogenic Fe inputs to the ocean. However, it remains uncertain how the distinct Fe isotopic signatures (δ56Fe) of these particles may be modified by physicochemical processes (e.g., acidification, photochemistry, condensation-evaporation cycles) that are known to enhance Fe solubility during atmospheric transport. In this experimental study, we measure changes over time in both Fe solubility and δ56Fe of a Tunisian soil dust and an Fe-Mn alloy factory industrial ash exposed under irradiation to a pH 2 solution containing oxalic acid, the most widespread organic complexing agent in cloud- and rainwater. The Fe released per unit surface area of the ash (∼1460 µg Fe m-2) is ∼40 times higher than that released by the dust after 60 min in solution. Isotopic fractionation is also observed, to a greater extent in the dust than the ash, in parallel with dissolution of the solid particles and driven by preferential release of 54Fe into solution. After the initial release of 54Fe, the re-adsorption of A-type Fe-oxalate ternary complexes on the most stable surface sites of the solid particles seems to impair the release of the heavier Fe isotopes, maintaining a relative enrichment in the light Fe isotope in solution over time. These findings provide new insights on Fe mobilisation and isotopic fractionation in mineral dust and industrial ash during atmospheric processing, with potential implications for ultimately improving the tracing of natural versus anthropogenic contributions of soluble Fe to the ocean.

Inter-comparison of stable iron, copper and zinc isotopic compositions in six reference materials of biological origin.

There is a lack of certified reference materials with an organic matrix for which metal isotope ratios have been certified. Here, we have determined the iron, copper and zinc stable isotopic compositions for six reference materials of biological origin with diverse matrices, i.e. BCR-380R (whole milk), BCR-383 (beans), ERM-CE464 (tuna fish), SRM-1577c (bovine liver), DORM-4 (fish protein) and TORT-3 (lobster hepatopancreas) in three different labs. The concentrations for six major and sixteen trace elements, spanning almost four orders of magnitude, were also measured and the results obtained show an excellent agreement with certified values, demonstrating that the dissolution step was quantitative for all the standards. By taking literature data into account, 39 possible pair-wise comparisons of mean iron, copper and zinc isotopic values (δ values) could be made. Results of Tukey multiple comparisons of means yielded 11 significantly different pairs. Most of these differences are of the same order of magnitude as the estimated mean expanded uncertainties (U, k = 2) (±0.10‰, ±0.05‰, and ±0.05‰ for the δ56Fe, δ65Cu and δ66Zn values, respectively). The present inter-comparison study finally proposes nineteen new preferred values for the Cu, Zn and Fe isotopic compositions of six reference materials of biological origin.

Analysis of the Stable Isotope Ratios (18O/16O, 17O/16O, and D/H) in Glacier Water by Laser Spectrometry.

A compact isotope ratio sensor based on laser absorption spectroscopy at 2.7 µm was developed for high precision and simultaneous measurements of the D/H, 18O/16O and 17O/16O isotope ratios in glacier water. Measurements of the oxygen and hydrogen isotope ratios in glacier water demonstrate a 1σ precision of 0.3‰ for δ18O, 0.2‰ for δ17O, and 0.5‰ for δ2H, respectively. The δ values of the working standard glacier water obtained by the calibrated sensor system is basically identical to the IRMS measurement results with a very high calibration accuracy from 0.17‰ to 0.75‰. Preliminary results on the reproducibility measurements display a standard deviation of 0.13‰ for δ18O, 0.13‰ for δ17O, and 0.64‰ for δ2H, respectively.

Towards a biologically available strontium isotope baseline for Ireland.

Strontium isotopes are used in archaeology, ecology, forensics, and other disciplines to study the origin of artefacts, humans, animals and food items. Strontium in animal and human tissues such as bone and teeth originates from food and drink consumed during life, leaving an isotopic signal corresponding to their geographical origin (i.e. where the plants grew, the animals grazed and the drinking water passed through). To contextualise the measurements obtained directly on animal and human remains, it is necessary to have a sound baseline of the isotopic variation of biologically available strontium in the landscape. In general, plants represent the main source of strontium for humans and animals as they usually contain much higher strontium concentrations than animal products (meat and milk) or drinking water. The observed difference between the strontium isotope composition of geological bedrock, soils and plants from the same locality warrants direct measurement of plants to create a reliable baseline. Here we present the first baseline of the biologically available strontium isotope composition for the island of Ireland based on 228 measurements on plants from 140 distinct locations. The isoscape shows significant variation in strontium isotope composition between different areas of Ireland with values as low as 0.7067 for the basalt outcrops in County Antrim and values of up to 0.7164 in the Mourne Mountains. This variability confirms the potential for studying mobility and landscape use of past human and animal populations in Ireland. Furthermore, in some cases, large differences were observed between different types of plants from the same location, highlighting the need to measure more than one plant sample per location for the creation of BASr baselines.

Human bones tell the story of atmospheric mercury and lead exposure at the edge of Roman World.

Atmospheric metal pollution is a major health concern whose roots pre-date industrialization. This study pertains the analyses of ancient human skeletons and compares them with natural archives to trace historical environmental exposure at the edge of the Roman Empire in NW Iberia. The novelty of our approach relies on the combination of mercury, lead and lead isotopes. We found over a 700-year period that rural Romans incorporated two times more mercury and lead into their bones than post-Romans inhabiting the same site, independent of sex or age. Atmospheric pollution sources contributed on average 57% (peaking at 85%) of the total lead incorporated into the bones in Roman times, which decreased to 24% after the decline of Rome. These values and accompanying changes in lead isotopic composition mirror changes in atmospheric Pb deposition recorded in local peatlands. Thus, skeletons are a time-transgressive archive reflecting contaminant exposure.

Strontium isotope analysis on cremated human remains from Stonehenge support links with west Wales.

Cremated human remains from Stonehenge provide direct evidence on the life of those few select individuals buried at this iconic Neolithic monument. The practice of cremation has, however, precluded the application of strontium isotope analysis of tooth enamel as the standard chemical approach to study their origin. New developments in strontium isotopic analysis of cremated bone reveal that at least 10 of the 25 cremated individuals analysed did not spend their lives on the Wessex chalk on which the monument is found. Combined with the archaeological evidence, we suggest that their most plausible origin lies in west Wales, the source of the bluestones erected in the early stage of the monument's construction. These results emphasise the importance of inter-regional connections involving the movement of both materials and people in the construction and use of Stonehenge.

Mobility during the neolithic and bronze age in northern ireland explored using strontium isotope analysis of cremated human bone.

OBJECTIVES: As many individuals were cremated in Neolithic and Bronze Age Ireland, they have not featured in investigations of individual mobility using strontium isotope analysis. Here, we build on recent experiments demonstrating excellent preservation of biogenic (87) Sr/(86) Sr in calcined bone to explore mobility in prehistoric Northern Ireland. MATERIALS AND METHODS: A novel method of strontium isotope analysis is applied to calcined bone alongside measurements on tooth enamel to human remains from five Neolithic and Bronze Age sites in Northern Ireland. We systematically sampled modern vegetation around each site to characterize biologically available strontium, and from this calculated expected values for humans consuming foods taken from within 1, 5, 10 and 20 Km catchments. This provides a more nuanced way of assessing human use of the landscape and mobility than the 'local' vs. 'non-local' dichotomy that is often employed. RESULTS: The results of this study 1) provide further support for the reliability of strontium isotope analysis on calcined bone, and 2) demonstrate that it is possible to identify isotopic differences between individuals buried at the same site, with some consuming food grown locally (within 1-5 Km) while others clearly consumed food from up to 50 Km away from their burial place. DISCUSSION: Hints of patterning emerge in spite of small sample numbers. At Ballynahatty, for instance, those represented by unburnt remains appear to have consumed food growing locally, while those represented by cremated remains did not. Furthermore, it appears that some individuals from Ballynahatty, Annaghmare and Clontygora either moved in the last few years of their life or their cremated remains were brought to the site. These results offer new insights into the choice behind coterminous cremation and inhumation rites in the Neolithic. Am J Phys Anthropol 160:397-413, 2016. © 2016 Wiley Periodicals, Inc.

Earliest evidence of pollution by heavy metals in archaeological sites.

Homo species were exposed to a new biogeochemical environment when they began to occupy caves. Here we report the first evidence of palaeopollution through geochemical analyses of heavy metals in four renowned archaeological caves of the Iberian Peninsula spanning the last million years of human evolution. Heavy metal contents reached high values due to natural (guano deposition) and anthropogenic factors (e.g. combustion) in restricted cave environments. The earliest anthropogenic pollution evidence is related to Neanderthal hearths from Gorham's Cave (Gibraltar), being one of the first milestones in the so-called "Anthropocene". According to its heavy metal concentration, these sediments meet the present-day standards of "contaminated soil". Together with the former, the Gibraltar Vanguard Cave, shows Zn and Cu pollution ubiquitous across highly anthropic levels pointing to these elements as potential proxies for human activities. Pb concentrations in Magdalenian and Bronze age levels at El Pirulejo site can be similarly interpreted. Despite these high pollution levels, the contaminated soils might not have posed a major threat to Homo populations. Altogether, the data presented here indicate a long-term exposure of Homo to these elements, via fires, fumes and their ashes, which could have played certain role in environmental-pollution tolerance, a hitherto neglected influence.

Calcined bone provides a reliable substrate for strontium isotope ratios as shown by an enrichment experiment.

RATIONALE: Strontium isotopes ((87) Sr/(86) Sr) are used in archaeological and forensic science as markers of residence or mobility because they reflect the local geological substrate. Currently, tooth enamel is considered to be the most reliable tissue, but it rarely survives heating so that in cremations only calcined bone fragments survive. We set out to test the proposition that calcined bone might prove resistant to diagenesis, given its relatively high crystallinity, as the ability to measure in vivo (87) Sr/(86) Sr from calcined bone would greatly extend application to places and periods in which cremation was the dominant mortuary practice, or where unburned bone and enamel do not survive. METHODS: Tooth enamel and calcined bone samples were exposed to a (87) Sr-spiked solution for up to 1 year. Samples were removed after various intervals, and attempts were made to remove the contamination using acetic acid washes and ultrasonication. (87) Sr/(86) Sr was measured before and after pre-treatment on a Nu Plasma multi-collector induced coupled plasma mass spectrometer using NBS987 as a standard. RESULTS: The strontium isotopic ratios of all samples immersed in the spiked solution were strongly modified showing that significant amounts of strontium had been adsorbed or incorporated. After pre-treatment the enamel samples still contained significant amounts of (87) Sr-enriched contamination while the calcined bone fragments did not. CONCLUSIONS: The results of the artificial enrichment experiment demonstrate that calcined bone is more resistant to post-mortem exchange than tooth enamel, and that in vivo strontium isotopic ratios are retained in calcined bone.

Impact of root-induced mobilization of zinc on stable Zn isotope variation in the soil-plant system.

Stable Zn isotopes are increasingly used to trace the source of metal pollution in the environment and to gain a better understanding of the biogeochemical cycle of Zn. In this work, we investigated the effect of plants on Zn isotope fractionation in the soil-plant system of the surface horizon of two Zn-rich Technosols (pH 6.73-7.51, total Zn concentration = 9470-56600 mg kg(-1)). In a column experiment, the presence of Agrostis capillaris L. significantly increased the mobilization of Zn from soil to leachate, predominantly as a result of root-induced soil acidification. The zinc isotope compositions of plants and leachates indicated that the Zn uptake by A. capillaris did not fractionate Zn isotopes as compared to the leachates. Within the plant, heavier Zn isotopes were preferentially retained in roots (Δ66Znroot - shoot=+0.24 to +0.40 ‰). More importantly, the Zn released in leachates due to root-induced mobilization was isotopically heavier than the Zn released in the absence of plants (Δ66Zn=+0.16 to +0.18 ‰). This indicates that the rhizosphere activity of A. capillaris mobilized Zn from another pool than the one that spontaneously releases Zn upon contact with the percolating solution. Mobilization of Zn by the roots might thus exert a stronger influence on the Zn isotope composition in the soil solution than the Zn uptake by the plant. This study highlights the key role of the rhizosphere activity in Zn release in soil and demonstrates that stable Zn isotopes provide a useful proxy for the detection of Zn mobilization in soil-plant systems.

Anthropogenic impacts in North Poland over the last 1300 years--a record of Pb, Zn, Cu, Ni and S in an ombrotrophic peat bog.

Lead pollution history over Northern Poland was reconstructed for the last ca. 1300 years using the elemental and Pb isotope geochemistry of a dated Polish peat bog. The data show that Polish Pb-Zn ores and coal were the main sources of Pb, other heavy metals and S over Northern Poland up until the industrial revolution. After review of the potential mobility of each element, most of the historical interpretation was based on Pb and Pb isotopes, the other chemical elements (Zn, Cu, Ni, S) being considered secondary indicators of pollution. During the last century, leaded gasoline also contributed to anthropogenic Pb pollution over Poland. Coal and Pb-Zn ores, however, remained important sources of pollution in Eastern European countries during the last 50 years, as demonstrated by a high (206)Pb/(207)Pb ratio (1.153) relative to that of Western Europe (ca. 1.10). The Pb data for the last century were also in good agreement with modelled Pb inventories over Poland and the Baltic region.

Iron isotopic fractionation in industrial emissions and urban aerosols.

A study on tropospheric aerosols involving Fe particles with an industrial origin is tackled here. Aerosols were collected at the largest exhausts of a major European steel metallurgy plant and around its near urban environment. A combination of bulk and individual particle analysis performed by SEM-EDX provides the chemical composition of Fe-bearing aerosols emitted within the factory process (hematite, magnetite and agglomerates of these oxides with sylvite (KCl), calcite (CaCO(3)) and graphite carbon). Fe isotopic compositions of those emissions fall within the range (0.08 per thousand

Stable iron isotopes and microbial mediation in red pigmentation of the Rosso Ammonitico (mid-late Jurassic, Verona area, Italy).

The iron (Fe) isotopic composition of 17 Jurassic limestones from the Rosso Ammonitico of Verona (Italy) have been analyzed by Multiple-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS). Such analysis allowed for the recognition of a clear iron isotopic fractionation (mean -0.8 per thousand, ranging between -1.52 to -0.06 per thousand) on a millimeter-centimeter scale between the red and grey facies of the studied formation. After gentle acid leaching, measurements of the Fe isotopic compositions gave delta(56)Fe values that were systematically lower in the red facies residues (median: -0.84 per thousand, range: -1.46 to +0.26 per thousand) compared to the grey facies residues (median: -0.08 per thousand, range: -0.34 to +0.23 per thousand). In addition, the red facies residues were characterized by a lighter delta(56)Fe signal relative to their corresponding leachates. These Fe isotopic fractionations could be a sensitive fingerprint of a biotic process; systematic isotopic differences between the red and grey facies residues, which consist of hematite and X-ray amorphous iron hydroxides, respectively, are hypothesized to have resulted from the oxidizing activity of iron bacteria and fungi in the red facies. The grey Fe isotopic data match the Fe isotopic signature of the terrestrial baseline established for igneous rocks and low-C(org) clastic sedimentary rocks. The Fe isotopic compositions of the grey laminations are consistent with the influx of detrital iron minerals and lack of microbial redox processes at the water-interface during deposition. Total Fe concentration measurements were performed by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) (confirmed by concentration estimations obtained by MC-ICP-MS analyses of microdrilled samples) on five samples, and resultant values range between 0.30% (mean) in the grey facies and 1.31% (mean) in the red facies. No correlation was observed between bulk Fe content and pigmentation or between bulk Fe content and Fe isotopic compositions. The rapid transformation of the original iron oxyhydroxides to hematite could have preserved the original isotopic composition if it had occurred at about the same temperature. This paper supports the use of Fe isotopes as sensitive tracers of biological activities recorded in old sedimentary sequences that contain microfossils of iron bacteria and fungi. However, a careful interpretation of the iron isotopic fractionation in terms of biotic versus abiotic processes requires supporting data or direct observations to characterize the biological, (geo)chemical, or physical context in relation to the geologic setting. This will become even more pertinent when Fe isotopic studies are expanded to the interplanetary realm.

High-accuracy determination of iron in seawater by isotope dilution multiple collector inductively coupled plasma mass spectrometry (ID-MC-ICP-MS) using nitrilotriacetic acid chelating resin for pre-concentration and matrix separation.

In the present paper we describe a robust and simple method to measure dissolved iron (DFe) concentrations in seawater down to <0.1 nmol L(-1) level, by isotope dilution multiple collector inductively coupled plasma mass spectrometry (ID-MC-ICP-MS) using a (54)Fe spike and measuring the (57)Fe/(54)Fe ratio. The method provides for a pre-concentration step (100:1) by micro-columns filled with the resin NTA Superflow of 50 mL seawater samples acidified to pH 1.9. NTA Superflow is demonstrated to quantitatively extract Fe from acidified seawater samples at this pH. Blanks are kept low (grand mean 0.045+/-0.020 nmol L(-1), n=21, 3 x S.D. limit of detection per session 0.020-0.069 nmol L(-1) range), as no buffer is required to adjust the sample pH for optimal extraction, and no other reagents are needed than ultrapure nitric acid, 12 mM H(2)O(2), and acidified (pH 1.9) ultra-high purity (UHP) water. We measured SAFe (sampling and analysis of Fe) reference seawater samples Surface-1 (0.097+/-0.043 nmol L(-1)) and Deep-2 (0.91+/-0.17 nmol L(-1)) and obtained results that were in excellent agreement with their DFe consensus values: 0.118+/-0.028 nmol L(-1) (n=7) for Surface-1 and 0.932+/-0.059 nmol L(-1) (n=9) for Deep-2. We also present a vertical DFe profile from the western Weddell Sea collected during the Ice Station Polarstern (ISPOL) ice drift experiment (ANT XXII-2, RV Polarstern) in November 2004-January 2005. The profile shows near-surface DFe concentrations of approximately 0.6 nmol L(-1) and bottom water enrichment up to 23 nmol L(-1) DFe.

Precise measurement of Fe isotopes in marine samples by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS).

A novel analytical technique for isotopic analysis of dissolved and particulate iron (Fe) from various marine environments is presented in this paper. It combines coprecipitation of dissolved Fe (DFe) samples with Mg(OH)(2), and acid digestion of particulate Fe (PFe) samples with double pass chromatographic separation. Isotopic data were obtained using a Nu Plasma MC-ICP-MS in dry plasma mode, applying a combination of standard-sample bracketing and external normalization by Cu doping. Argon interferences were determined prior to each analysis and automatically subtracted during analysis. Sample size can be varied between 200 and 600 ng of Fe per measurement and total procedural blanks are better than 10 ng of Fe. Typical external precision of replicate analyses (1S.D.) is +/-0.07 per thousand on delta(56)Fe and +/-0.09 per thousand on delta(57)Fe while typical internal precision of a measurement (1S.E.) is +/-0.03 per thousand on delta(56)Fe and +/-0.04 per thousand on delta(57)Fe. Accuracy and precision were assured by the analysis of reference material IRMM-014, an in-house pure Fe standard, an in-house rock standard, as well as by inter-laboratory comparison using a hematite standard from ETH (Zürich). The lowest amount of Fe (200 ng) at which a reliable isotopic measurement could still be performed corresponds to a DFe or PFe concentration of approximately 2 nmol L(-1) for a 2 L sample size. To show the versatility of the method, results are presented from contrasting environments characterized by a wide range of Fe concentrations as well as varying salt content: the Scheldt estuary, the North Sea, and Antarctic pack ice. The range of DFe and PFe concentrations encountered in this investigation falls between 2 and 2000 nmol L(-1) Fe. The distinct isotopic compositions detected in these environments cover the whole range reported in previous studies of natural Fe isotopic fractionation in the marine environment, i.e. delta(56)Fe varies between -3.5 per thousand and +1.5 per thousand. The largest fractionations were observed in environments characterized by redox changes and/or strong Fe cycling. This demonstrates the potential use of Fe isotopes as a tool to trace marine biogeochemical processes involving Fe.

Atmospheric lead and heavy metal pollution records from a Belgian peat bog spanning the last two millenia: human impact on a regional to global scale.

Europe has been continuously polluted throughout the last two millennia. During the Roman Empire, these pollutions were mainly from ore extraction and smelting across Europe. Then, during the Middle Ages and the Early times of Industrial revolution (i.e. 1750), these pollutions extended to coal burning and combustion engine. Belgian ombrotrophic peat bogs have proved an effective archive of these pollutants and provide the opportunity to reconstruct the history of atmospheric deposition in NW Europe. The results of recent and past trace metal accumulation and Pb isotopes from a one-meter peat core (in the Misten peat bog) have been derived using XRF and Nu-plasma MC-ICP-MS. Combined with (14)C and (210)Pb dates these data have enabled us to trace fluxes in anthropogenic pollution back to original Roman times. Several periods of well-known Pb pollution events are clearly recorded including the Early and Late Roman Empire, the Middle Ages and the second industrial revolution. Also recorded is the introduction of leaded gasoline, and more recently the introduction of unleaded gasoline. Lead isotopes in this site have also enabled us to fingerprint several regional and global sources of anthropogenic particles.