Release and mobility of hexavalent chromium in contaminated soil with chemical factory waste: Experiments, Cr isotope analysis and reactive transport modeling.

Our study focused on the leaching processes in soil contaminated with hexavalent chromium (Cr(VI)), traced to industrial waste from a disused site and resulting in groundwater contamination. Mineral and geochemical characterization of the soil by means of XRD, SEM-EDS, total digestion and sequential extractions revealed that the main Cr content was from solid waste located in the upper meter of the soil profile. Flow-through and column experiments were carried out to investigate the processes responsible for Cr(VI) release. Cr(VI) mobility along the soil profile was also assessed. Moreover, Cr isotope signatures were used to evaluate a potential Cr(VI) reduction process, which preferably could immobilize toxic Cr(VI) complexes. One-dimensional (1D) numerical simulations reproduced the Cr(VI) release from the flow-through experiment containing the Cr(VI) rich-solid waste and also the Cr(VI) mobility along the column experiment. These results enabled us to interpret quantitatively the processes resulting in Cr(VI) contamination and mobility along the soil profile. Cr(VI) was released from dissolving Cr(VI)-rich phases (e.g., sodium chromate, Cr(VI)-hydrocalumite and Cr(VI)-ettringite) of the solid waste layer. Cr(VI) reduction and Cr(VI) adsorption did not take place along the column. Such accurate characterization of these processes is necessary for the mitigation of Cr(VI) mobility in contaminated soils.

The proper choice of proxies for relevant strontium isotope baselines used for provenance and mobility studies in glaciated terranes - Important messages from Denmark.

Strontium (Sr) isotope based provenance and mobility studies of ancient humans and animals necessitate representative isoscapes/baselines. However, regions/terranes that were shaped and affected by glaciers during the last Ice Ages and are covered by glaciogenic sediments present a challenge with regards to the choice of suitable surface proxy archives. Recent studies proposed that only 87Sr/86Sr signatures from pristine areas are relevant for this purpose. To test this theory, 160 new Sr concentrations [Sr] and 87Sr/86Sr signatures composed from ~960 subsamples of soil leachates and plants, complemented with 55 surface waters from agriculturally unaffected pristine forest sites from all over Denmark (island of Bornholm excluded) were analyzed. The results reveal that average 87Sr/86Sr signatures of all three proxies (plants: 0.7115 ± 0.0025; 2σ, n = 162; soil leachates: 0.7118 ± 0.0037; 2σ; n = 161, surface waters: 0.7104 ± 0.0030; 2σ, n = 55) are elevated compared to larger water bodies (creeks, rivers, lakes). In mixing diagrams, the data converge in a shared high [Sr] low 87Sr/86Sr endmember, which points to either remnant natural carbonates and/or organic components retaining carbonate Sr in the studied Podzols/Luvisols. The indications for more abundant carbonates in the past, compared to today's acid leached soils, implies that 87Sr/86Sr values measured from pristine forest locations and heathlands do not adequately reflect the biosphere compositions that prevailed ~12,000-2000 thousand years ago. Consequently, pristine forests in Denmark seem to be unsuitable proxy archive environments for constructing Sr isotope baselines for determining the provenance and mobility of ancient humans and animals. Hence, 87Sr/86Sr values measured in these pristine areas are non-representative and inadequate, and their use will lead to wrong interpretations. Finally, our study sheds light on the complexity of defining relevant and representative isoscapes/baselines in significantly changing environments and areas where the surface biosphere conditions do not necessary reflect the underlying geology.

Cadmium isotopes in Bahamas platform carbonates: A base for reconstruction of past surface water bioproductivity and their link with chromium isotopes.

The distribution of cadmium (Cd) within the oceans strongly suggests that it is used as a nutrient by marine phytoplankton. Biologically induced removal of Cd from modern surface waters is accompanied by an isotopic fractionation leaving surface-waters enriched in isotopically heavy Cd. This first study focusses on tying the Cd isotopic record preserved in modern shallow platform carbonates of the Great Bahama Bank (GBB) to conditions in the upper water column, and provides a base for future studies aiming at reconstructing past bioproductivity levels in ancient ocean/basin surface waters. In addition, we compare δ114Cd values with previously published chromium (Cr) isotope values and link signals of bioproductivity with redox conditions in the surface waters. The GBB core samples yield [Cd] (21-188 µg/kg), which increases with depth alongside changes in carbonate mineralogy related to sediment supply and diagenesis. The δ114Cd values of these carbonates are mainly positively fractionated with an average of 0.11‰ ± 0.17 (2σ; n = 17) relative to the NIST 3108 reference standard. Unlike previously observed for Cr isotopes, there is no control of δ114Cd values by relative abundances of the carbonate polymorphs aragonite and calcite in the studied profile. Likewise, δ114Cd values are not correlated to major and trace element (e.g. Ca, Mg, Mn and Sr) contents. We postulate that the burial and diagenetic processes of carbonate cannot modify the Cd isotope signals. Using the experimental fractionation factor for Cd into calcite (-0.45‰), calculated seawater δ114Cd of +0.56 ± 0.17‰ is in agreement with values for modern North Atlantic Surface Seawater. This study's results suggest that δ114Cd values in carbonates are a reliable tool for reconstruction of bioproductivity levels in past surface seawaters, and open new possibilities in combination with Cr isotopes to link these with past ocean redox.

Goldilocks at the dawn of complex life: mountains might have damaged Ediacaran-Cambrian ecosystems and prompted an early Cambrian greenhouse world.

We combine U-Pb in-situ carbonate dating, elemental and isotope constraints to calibrate the synergy of integrated mountain-basin evolution in western Gondwana. We show that deposition of the Bambuí Group coincides with closure of the Goiás-Pharusian (630-600 Ma) and Adamastor (585-530 Ma) oceans. Metazoans thrived for a brief moment of balanced redox and nutrient conditions. This was followed, however, by closure of the Clymene ocean (540-500 Ma), eventually landlocking the basin. This hindered seawater renewal and led to uncontrolled nutrient input, shallowing of the redoxcline and anoxic incursions, fueling positive productivity feedbacks and preventing the development of typical Ediacaran-Cambrian ecosystems. Thus, mountains provide the conditions, such as oxygen and nutrients, but may also preclude life development if basins become too restricted, characterizing a Goldilocks or optimal level effect. During the late Neoproterozoic-Cambrian fan-like transition from Rodinia to Gondwana, the newborn marginal basins of Laurentia, Baltica and Siberia remained open to the global sea, while intracontinental basins of Gondwana became progressively landlocked. The extent to which basin restriction might have affected the global carbon cycle and climate, e.g. through the input of gases such as methane that could eventually have collaborated to an early Cambrian greenhouse world, needs to be further considered.

The geographic distribution of bioavailable strontium isotopes in Greece - A base for provenance studies in archaeology.

Sr isotopes are a powerful tool used to reconstruct human mobility in archaeology. This requires extensive bioavailable 87Sr/86Sr baselines used as reference for deciphering potential areas of origin. We define the first extensive bioavailable Sr isotope baselines for the different geographical regions and surface lithologies of Greece by combining new Sr data with previously published bioavailable 87Sr/86Sr data. We present 82 new Sr concentrations and 87Sr/86Sr signatures of plants, soil leachates, surface waters and spring waters from Central Greece and combine these with published baseline values from all over Greece. We define individual baselines for ten of the thirteen geographical regions of Greece. We also provide soil leachate 87Sr/86Sr ratios from the two archaeological Bronze Age sites of Kirrha and Ayios Vasileios in Central and Southern Greece and demonstrate the validity and applicability of the new baselines for these sites. The bioavailable 87Sr/86Sr compositions of Central Greece define a narrow range of 87Sr/86Sr values between 0.70768 - 0.71021, with the widest range observed for the soil leachates. Sr derived from carbonate weathering appears to be the most important Sr source sampled by the proxies. There is an overall larger variability in baseline ranges of the different geographical regions, the narrowest is that for West Greece and the widest that for West Macedonia. In addition, we computed statistical Sr isotope ranges for the five main surface lithological groups characterising the sampling sites of the various proxies. Narrowly ranged, unradiogenic bioavailable Sr isotope signatures are typical of areas characterised by igneous outcrops as well as by Cenozoic and Mesozoic sediments. Areas, where Palaeozoic and Precambrian bedrock outcrops dominate, produce significantly wider ranges. Our study promotes the usefulness of multi-proxy baselines for geographical reference purposes and thus their promising applicability for future human mobility studies.

Testing Late Bronze Age mobility in southern Sweden in the light of a new multi-proxy strontium isotope baseline of Scania.

The Bronze Age of Sweden's southernmost region, Scania, is complex and intriguing. One could say that Scania represented in many ways a gateway for people, ideas and material culture connecting continental Europe with Sweden. Shedding light on the dynamics of human mobility in this region requires an in depth understanding of the local archaeological contexts across time. In this study, we present new archaeological human data from the Late Bronze Age Simris II site, located in an area of Scania showing a dynamic environment throughout the Late Bronze Age, thus likely involving various forms of mobility. Because the characterization of solid strontium isotope baselines is vital for delineating human mobility in prehistory using the strontium isotope methodology, we introduce the first environmentally based multi-proxy (surface water-, plant- and soil leachates) strontium isotope baselines for sub-regions of Scania. Our results show, that the highly complex and spatially scattered lithologies characterising Scania does not allow for a spatially meaningful, geology-based grouping of multi-proxy data that could be beneficial for provenance studies. Instead, we propose sub-regional baselines for areas that don't necessarily fully correspond and reflect the immediate distribution of bedrock lithologies. Rather than working with a Scania-wide multi-proxy baseline, which we define as 87Sr/86Sr = 0.7133 ± 0.0059 (n = 102, 2σ), we propose sub-regional, multi-proxy baselines as follows: Area 1, farthest to the north, by 87Sr/86Sr = 0.7184 ± 0.0061 (n = 16, 2σ); Area 2, comprising the mid and western part of Scania, with 87Sr/86Sr = 0.7140 ± 0.0043 (n = 48, 2σ); Area 3-4, roughly corresponding to a NW-SE trending zone dominated by horst-graben tectonics across Scania, plus the carbonate dominated south western part of Scania with 87Sr/86Sr = 0.7110 ± 0.0030 (n = 39, 2σ). Our results also reflect that the complexity of the geology of Scania requires systematic, high density, statistically sound sampling of multiple proxies to adequately constrain the baseline ranges, particularly of those areas dominated by Precambrian lithologies. The averaging effect of biosphere Sr in surface water might be beneficial for the characterization of baselines in such terranes. Our sub-regional, area-specific baselines allow for a first comparison of different baseline construction strategies (single-proxy versus multi-proxy; Scania-wide versus sub-regional). From the Late Bronze Age Simris II site, we identified six individuals that could be analysed for Sr isotopes, to allow for an interpretation of their provenance using the newly established, environmental strontium isotope baselines. All but one signature agrees with the local baselines, including the 87Sr/86Sr value we measured for a young individual buried in a house urn, typically interpreted as evidence for long distance contacts. The results are somewhat unexpected and provides new aspects into the complexity of Scandinavian Bronze Age societies.

Microbially induced chromium isotope fractionation and trace elements behavior in lower Cambrian microbialites from the Jaíba Member, Bambuí Basin, Brazil.

In east-central Brazil, the Ediacaran-Cambrian Bambuí Basin has the potential to provide a record of unique geochemical responses of Earth's ocean and atmosphere evolution during this key time interval. From this perspective, we studied an interval of the upper Bambuí Basin using sedimentologic, stratigraphic, and chemostratigraphic tools. The lower Cambrian Jaíba Member of the uppermost Serra da Saudade Formation is an interval of up to 60 m-thick of carbonate rocks disposed into two shallowing upward trends. Inner to outer ramp and high-energy shoal deposits are described, in which laminated microbialites are the prevailing sedimentary facies. REE + Y data suggest contamination by iron (oxy)hydroxides that are dissociated from the riverine detritic flux. Sedimentary iron enrichment may be related to the settling of iron nanoparticles in coastal environments, diagenetic iron mobilization, or both. MREE enrichment is caused by microbial degradation of organic matter in the iron reduction zone during the anoxic early-diagenetic stage. Chromium isotopes yielded negatively fractionated values (δ53 Cr = -0.69 to -0.27‰), probably resulting from biotic and abiotic reduction of dissolved Cr(VI) to light and less toxic Cr(III) within pores of microbial mats. The δ53 Cr data of the Jaíba microbialite are thus a product of metabolic reactions in microbial mats and do not reflect seawater signal. The isotopic offset from seawater is feasible from molecular diffusion of Cr into pore water and reduction reactions occurring deep inside the mat, although the exact mechanism and consequences are not yet fully understood due to the poor preservation of metabolic reactions in the geological record. Our study suggests that Cr isotopes can be used to reconstruct Cr and other metals cycling within ancient microbial mats, and that caution should be taken when using past microbialites to infer seawater Cr records and redox state of the atmosphere and ocean.

Allosteric targeting of the FFA2 receptor (GPR43) restores responsiveness of desensitized human neutrophils.

The G protein-coupled free fatty acid receptor 2 (FFA2R) is highly expressed on neutrophils and was previously described to regulate neutrophil activation. Allosteric targeting of G protein-coupled receptors (GPCRs) is increasingly explored to create distinct pharmacology compared to endogenous, orthosteric ligands. The consequence of allosteric versus orthosteric FFA2R activation for neutrophil response, however, is currently largely elusive. Here, different FFA2R desensitization profiles in human neutrophils following allosteric or orthosteric activation are reported. Using a set of neutrophil functional assays to measure calcium flux, pERK1/2, chemotaxis, cellular degranulation, and oxidative burst together with holistic and pathway-unbiased whole cell sensing based on dynamic mass redistribution, it is found that the synthetic positive allosteric modulator agonist 4-CMTB potently activates neutrophils and simultaneously alters FFA2R responsiveness toward the endogenous, orthosteric agonist propionic acid (C3) after homologous and heterologous receptor desensitization. Stimulation with C3 or the hierarchically superior chemokine receptor activator IL-8 led to strong FFA2R desensitization and rendered neutrophils unresponsive toward repeated stimulation with C3. In contrast, stimulation with allosteric 4-CMTB engaged a distinct composition of signaling pathways as compared to orthosteric receptor activation and was able to activate neutrophils that underwent homologous and heterologous desensitization with C3 and IL-8, respectively. Moreover, allosteric FFA2R activation could re-sensitize FFA2 toward the endogenous agonist C3 after homologous and heterologous desensitization. Given the fact that receptor desensitization is critical in neutrophils to sense and adapt to their current environment, these findings are expected to be useful for the discovery of novel pharmacological mechanisms to modulate neutrophil responsiveness therapeutically.

Ediacaran Doushantuo-type biota discovered in Laurentia.

The Ediacaran period (635-541 Ma) was a time of major environmental change, accompanied by a transition from a microbial world to the animal world we know today. Multicellular, macroscopic organisms preserved as casts and molds in Ediacaran siliciclastic rocks are preserved worldwide and provide snapshots of early organismal, including animal, evolution. Remarkable evolutionary advances are also witnessed by diverse cellular and subcellular phosphatized microfossils described from the Doushantuo Formation in China, the only source showing a diversified assemblage of microfossils. Here, we greatly extend the known distribution of this Doushantuo-type biota in reporting an Ediacaran Lagerstätte from Laurentia (Portfjeld Formation, North Greenland), with phosphatized animal-like eggs, embryos, acritarchs, and cyanobacteria, the age of which is constrained by the Shuram-Wonoka anomaly (c. 570-560 Ma). The discovery of these Ediacaran phosphatized microfossils from outside East Asia extends the distribution of the remarkable biota to a second palaeocontinent in the other hemisphere of the Ediacaran world, considerably expanding our understanding of the temporal and environmental distribution of organisms immediately prior to the Cambrian explosion.

Enhanced soil quality with reduced tillage and solid manures in organic farming - a synthesis of 15 years.

Demands upon the sustainability of farming are increasing in step with climate change and diversity loss. Organic farming offers a viable approach. To further improve organic management, three strategies with potential to enhance soil quality are being tested in a long-term trial since 2002 on a clay loam in temperate Switzerland: reduced tillage vs. ploughing, solid vs. liquid manures and biodynamic preparations. A synthesis of 15 years reveals an increase in topsoil organic carbon (SOC, +25%), microbial biomass (+32%) and activity (+34%) and a shift in microbial communities with conversion from ploughing to reduced tillage. Soils under reduced tillage are more stratified in SOC and nutrients. Additional application of composted manure has increased SOC by 6% compared to pure slurry application, with little impact on soil microbes. Biodynamic preparations have had a minor impact on soil quality. Fertilisation and biodynamic preparations did not affect yields. Both higher and lower yields were harvested in the reduced tillage system in relation to ploughing. The main yield determinants were N supply and higher weed infestation under reduced tillage. Continuously reduced tillage in organic farming has been proven to enhance soil quality at this site, while also presenting more challenges in management.

Characterisation of the natural attenuation of chromium contamination in the presence of nitrate using isotopic methods. A case study from the Matanza-Riachuelo River basin, Argentina.

The groundwater contamination by hexavalent chromium (Cr(VI)) in a site of the Matanza-Riachuelo River basin (MRB), Argentina, has been evaluated by determining the processes that control the natural mobility and attenuation of Cr(VI) in the presence of high nitrate (NO3-) contents. The groundwater Cr(VI) concentrations ranged between 1.9E-5 mM and 0.04 mM, while the NO3- concentrations ranged between 0.5 mM and 3.9 mM. In order to evaluate the natural attenuation of Cr(VI) and NO3- in the MRB groundwater, Cr and N isotopes were measured in these contaminants. In addition, laboratory batch experiments were performed to determine the isotope fractionation (ε) during the reduction of Cr(VI) under denitrifying conditions. While the Cr(VI) reduction rate is not affected by the presence of NO3-, the NO3- attenuation is slower in the presence of Cr(VI). Nevertheless, no significant differences on ε values were observed when testing the absence or presence of each contaminant. The ε53Cr determined in the batch experiments describe a two- stage trend, in which Stage I is characterized by ε53Cr ~-1.8‰ and Stage II by ε53Cr ~-0.9‰. The respective ε15NNO3 obtained is -23.9‰ whereas ε18ONO3 amount to -25.7‰. Using these ε values and a Rayleigh fractionation model we estimate that an average of 60% of the original Cr(VI) is removed from the groundwater of the contaminated site. Moreover, the average degree of NO3- attenuation by denitrification is found to be about 20%. This study provides valuable information about the dynamics of a complex system that can serve as a basis for efficient management of contaminated groundwater in the most populated and industrialized basin of Argentina.

A strontium isotope baseline of Cyprus. Assessing the use of soil leachates, plants, groundwater and surface water as proxies for the local range of bioavailable strontium isotope composition.

In this study, a strontium isotope baseline for Cyprus is presented. The aim of the study was two-fold; first to provide an environmental multi-proxy-based baseline (water/plants/soil leachates) suitable for archaeological provenance and mobility studies, food source authentication, and forensic investigations; and second, to contribute to the debate around which proxy (or combination of proxies) might be most suitable to define bioavailable fractions of strontium in geologically complex areas also exposed to sea-spray and other Sr-bearing aerosols. Lowest bioavailable strontium isotope signatures range is found within terranes dominated by ophiolites, where 87Sr/86Sr ratios range from 0.7055 to 0.7081, however, results reveal a high degree of variability in bioavailable 87Sr/86Sr ratios, both spatially, along depth profiles and amongst the different proxies. A narrower range of bioavailable Sr isotope signatures is observed within the Circum Troodos Sedimentary Successions (C.T.S.S.), both in spatial distribution and between different proxies. Observed range is 87Sr/86Sr = 0.7079 to 0.7089 in areas dominated by pre-Quaternary C.T.S.S., and 87Sr/86Sr ratios = 0.7076 to 0.7086 in areas covered by Quaternary C.T.S.S., revealing the lithologies to be very homogenous with respect to bioavailable strontium ratios. Intra-site variations in three archaeological sites (multiple samples from each site from within a 500 m radius) within the pre-Quaternary and Quaternary C.T.S.S. are smaller than inter-site variations, suggesting that tracing studies inferred from baselines sampled within a limited spatial area could lead to erroneous conclusions regarding provenance. The study points to the necessity for conducting multi-proxy, spatially extensive sampling to adequately characterize complex geological areas, if these should serve as reliable reference areas in provenance studies.

Subtle Cr isotope signals track the variably anoxic Cryogenian interglacial period with voluminous manganese accumulation and decrease in biodiversity.

Earth's atmosphere experienced a step of profound oxygenation during the Neoproterozoic era, accompanied by diversification of animals. However, during the Cryogenian period (720-635 million years ago) Earth experienced its most severe glaciations which likely impacted marine ecosystems and multicellular life in the oceans. In particular, large volumes of Mn and Fe accumulated during the interglacial intervals of the Cryogenian glaciations, indicating large anoxic marine metal reservoirs. Here we present chromium isotope-, rare earth element-, and redox-sensitive trace element data of sedimentary rocks from the interglacial Datangpo Formation deposited between the Sturtian and Marinoan glaciations in South China, in an attempt to investigate the oxidation state of the oceans and atmosphere. Both the Cr isotope and trace element data indicate mainly anoxic water conditions with cryptic oxic surface water incursions after the Sturtian glaciation. Glacial-fed manganese precipitated as manganese carbonate in anoxic basins, and the non-fractionated δ53Cr record of -0.10 ± 0.06‰ identifies anoxic conditions with a cryptic component of slightly fractionated Cr isotope composition in manganese ore, in line with distinctly fractionated Mo isotope composition. Both the manganese carbonate ore and the black shales exhibit very low redox-sensitive element concentrations. Our study demonstrates that the oxygenation of the seawater, and inferably of the atmosphere, at the beginning of the Cryogenian interglacial interval was much subdued. The post-glacial rebound then allowed the Ediacaran biological diversity.

East Greenland ice core dust record reveals timing of Greenland ice sheet advance and retreat.

Accurate estimates of the past extent of the Greenland ice sheet provide critical constraints for ice sheet models used to determine Greenland's response to climate forcing and contribution to global sea level. Here we use a continuous ice core dust record from the Renland ice cap on the east coast of Greenland to constrain the timing of changes to the ice sheet margin and relative sea level over the last glacial cycle. During the Holocene and the previous interglacial period (Eemian) the dust record was dominated by coarse particles consistent with rock samples from central East Greenland. From the coarse particle concentration record we infer the East Greenland ice sheet margin advanced from 113.4 ± 0.4 to 111.0 ± 0.4 ka BP during the glacial onset and retreated from 12.1 ± 0.1 to 9.0 ± 0.1 ka BP during the last deglaciation. These findings constrain the possible response of the Greenland ice sheet to climate forcings.

Mapping human mobility during the third and second millennia BC in present-day Denmark.

We present results of the largest multidisciplinary human mobility investigation to date of skeletal remains from present-day Denmark encompassing the 3rd and 2nd millennia BC. Through a multi-analytical approach based on 88 individuals from 37 different archaeological localities in which we combine strontium isotope and radiocarbon analyses together with anthropological investigations, we explore whether there are significant changes in human mobility patterns during this period. Overall, our data suggest that mobility of people seems to have been continuous throughout the 3rd and 2nd millennia BC. However, our data also indicate a clear shift in mobility patterns from around 1600 BC onwards, with a larger variation in the geographical origin of the migrants, and potentially including more distant regions. This shift occurred during a transition period at the beginning of the Nordic Bronze Age at a time when society flourished, expanded and experienced an unprecedented economic growth, suggesting that these aspects were closely related.

Bioavailable 87Sr/86Sr in European soils: A baseline for provenancing studies.

We present 87Sr/86Sr isotope ratios for ~1200 selected soil samples, collected by the GEMAS consortium from grazing (Gr) and agricultural (Ap) soils in Europe with the aim to better understand the strontium isotope distribution in the bioavailable fraction of the top-soil and its potential for provenancing applications. Spatial analysis shows that there is a clear distinction between coastal (<100 km) and non-coastal (>100 km) samples in their variance and that this variance is mirrored in the sodium concentration, suggesting an important but highly variable contribution from seaspray. We present two 87Sr/86Sr maps at 25 km × 25 km scale: one based solely on the measured data using a classical kriging approach and one based on a Random Forest model using complementary GEMAS data to predict the strontium isotope composition at the remaining 3000+ GEMAS sampling locations, including appropriate uncertainty assessment. Using a forensic Bayesian likelihood ratio approach, a tool was developed in R to create provenancing likelihood ratio maps. The maps delineate areas of high and low likelihood and allow investigators to direct their resources to areas of interest. For actual forensic case work either the measured or the modelled data can be used as reference data for the overall distribution of 87Sr/86Sr values in Europe.

Highly fractionated chromium isotopes in Mesoproterozoic-aged shales and atmospheric oxygen.

The history of atmospheric oxygen through the Mesoproterozoic Era is uncertain, but may have played a role in the timing of major evolutionary developments among eukaryotes. Previous work using chromium isotopes in sedimentary rocks has suggested that Mesoproterozoic Era atmospheric oxygen levels were too  low in concentration (<0.1% of present-day levels (PAL)) for the expansion of eukaryotic algae and for the evolution of crown-group animals that occurred later in the Neoproterozoic Era. In contrast, our new results on chromium isotopes from Mesoproterozoic-aged sedimentary rocks from the Shennongjia Group from South China is consistent with atmospheric oxygen concentrations of >1% PAL and thus the possibility that a permissive environment existed long before the expansion of various eukaryotic clades.

Environmentally available hexavalent chromium in soils and sediments impacted by dispersed fly ash in Sarigkiol basin (Northern Greece).

Hexavalent chromium is one of the most toxic and carcinogenic species known and can be released into the environment from several sources. In Sarigkiol basin (N Greece) the presence of Cr(VI) in soil, sediments and groundwater may originate from both natural (ophiolitic rocks and their weathering products) and anthropogenic (dispersed fly ash produced from lignite power plants) sources. In this study, the distribution of contents and origin of environmentally available Cr(VI) in soils, sediments, regoliths and fly ash of Sarigkiol basin is presented. Detailed geochemical and mineralogical studies were performed on soil samples (up to 1 m) and regoliths, while leaching tests were also applied to fresh and old fly ash samples. Leachable chromium from soil and sediment samples generally increased with depth and the highest concentrations were observed near to the power plant of Agios Dimitrios. The speciation of chromium in leachates revealed that Cr(VI) concentrations accounted for more than 96% of total Cr. Leaching tests of regoliths established that the natural contribution of Cr(VI) is up to 14 µg kg-1. Therefore, the measurement of higher concentrations (up to 80 µg kg-1) of environmentally available Cr(VI) in soils and sediments can be attributed to the impact/presence of dispersed fly ash in the soils and sediments of the same area. This was also supported by the low correlation recorded between environmentally available chromium and Cr-bearing minerals (mainly serpentine and talc). The influenced zone is located in the eastern part of the basin near the local power plant and surrounds an open conveyor belt that transfers fly ash to an open temporary storage pit. This zone overlies an unconfined porous aquifer thus explaining the elevated concentrations of Cr(VI) in groundwater (up to 120 µg L-1) previously reported in this area.

A matter of months: High precision migration chronology of a Bronze Age female.

Establishing the age at which prehistoric individuals move away from their childhood residential location holds crucial information about the socio dynamics and mobility patterns in ancient societies. We present a novel combination of strontium isotope analyses performed on the over 3000 year old "Skrydstrup Woman" from Denmark, for whom we compiled a highly detailed month-scale model of her migration timeline. When combined with physical anthropological analyses this timeline can be related to the chronological age at which the residential location changed. We conducted a series of high-resolution strontium isotope analyses of hard and soft human tissues and combined these with anthropological investigations including CT-scanning and 3D visualizations. The Skrydstrup Woman lived during a pan-European period characterized by technical innovation and great social transformations stimulated by long-distance connections; consequently she represents an important part of both Danish and European prehistory. Our multidisciplinary study involves complementary biochemical, biomolecular and microscopy analyses of her scalp hair. Our results reveal that the Skrydstrup Woman was between 17-18 years old when she died, and that she moved from her place of origin -outside present day Denmark- to the Skrydstrup area in Denmark 47 to 42 months before she died. Hence, she was between 13 to 14 years old when she migrated to and resided in the area around Skrydstrup for the rest of her life. From an archaeological standpoint, this one-time and one-way movement of an elite female during the possible "age of marriageability" might suggest that she migrated with the aim of establishing an alliance between chiefdoms. Consequently, this detailed multidisciplinary investigation provides a novel tool to reconstruct high resolution chronology of individual mobility with the perspective of studying complex patterns of social and economic interaction in prehistory.

Oxidative elemental cycling under the low O2 Eoarchean atmosphere.

The Great Oxidation Event signals the first large-scale oxygenation of the atmosphere roughly 2.4 Gyr ago. Geochemical signals diagnostic of oxidative weathering, however, extend as far back as 3.3-2.9 Gyr ago. 3.8-3.7 Gyr old rocks from Isua, Greenland stand as a deep time outpost, recording information on Earth's earliest surface chemistry and the low oxygen primordial biosphere. Here we find fractionated Cr isotopes, relative to the igneous silicate Earth reservoir, in metamorphosed banded iron formations (BIFs) from Isua that indicate oxidative Cr cycling 3.8-3.7 Gyr ago. Elevated U/Th ratios in these BIFs relative to the contemporary crust, also signal oxidative mobilization of U. We suggest that reactive oxygen species were present in the Eoarchean surface environment, under a very low oxygen atmosphere, inducing oxidative elemental cycling during the deposition of the Isua BIFs and possibly supporting early aerobic biology.