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The Montecristo district, northern Chile, is one of the few places worldwide where there is a direct relationship between magnetite-(apatite) (MtAp) mineralization and iron oxide-copper-gold (IOCG) mineralization. The MtAp mineralization includes Ti-poor magnetite, fluorapatite, and actinolite and is crosscut and partially replaced by a younger IOCG mineralization that includes a second generation of actinolite and magnetite with quartz, chalcopyrite, pyrite, and molybdenite. The MtAp stage at Montecristo is interpreted as the crystallized iron-rich melts that used the pre-existing structures of the Atacama Fault System as conduits. These rocks later acted as a trap for hydrothermal IOCG mineralization. Geochronology data at Montecristo indicate that the host diorite (U-Pb zircon 153.3 ± 1.8 Ma, 2-sigma), MtAp mineralization (40Ar-39Ar in actinolite, 154 ± 2 Ma and 153 ± 4 Ma, 2-sigma), and the IOCG event (Re-Os on molybdenite, 151.8 ± 0.6 Ma, 2-sigma) are coeval within error and took place in a time span of less than 3.4 Ma. The εHfi and εNdi values of the host diorite are + 8.0 to + 9.8 and + 4.3 to + 5.4, respectively. The whole-rock 87Sr/86Sri values of the IOCG mineralization (0.70425 to 0.70442) are in the lower end of those of the MtAp mineralization (0.70426-0.70629). In contrast, εNdi values for the IOCG mineralization (+ 5.4 and + 5.7) fall between those of the MtAp rocks (+ 6.6 to + 7.2) and the host diorite, which suggests that the IOCG event was related to fluids having a more crustal Nd (εNdi < + 5.7) composition than the MtAp mineralization. This likely reflects the mixing of Nd from the MtAp protolith and a deep magmatic-hydrothermal source, very likely an unexposed intrusion equivalent to the host diorite. Sulfur isotope compositions (δ34S, + 0.3 to + 3.4) are consistent with a magmatic source. Supplementary Information: The online version contains supplementary material available at 10.1007/s00126-023-01172-0.
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Near-equilibrium calcite dissolution in seawater contributes significantly to the regulation of atmospheric [Formula: see text] on 1,000-y timescales. Despite many studies on far-from-equilibrium dissolution, little is known about the detailed mechanisms responsible for calcite dissolution in seawater. In this paper, we dissolve 13C-labeled calcites in natural seawater. We show that the time-evolving enrichment of [Formula: see text] in solution is a direct measure of both dissolution and precipitation reactions across a large range of saturation states. Secondary Ion Mass Spectrometer profiles into the 13C-labeled solids confirm the presence of precipitated material even in undersaturated conditions. The close balance of precipitation and dissolution near equilibrium can alter the chemical composition of calcite deeper than one monolayer into the crystal. This balance of dissolution-precipitation shifts significantly toward a dissolution-dominated mechanism below about [Formula: see text] Finally, we show that the enzyme carbonic anhydrase (CA) increases the dissolution rate across all saturation states, and the effect is most pronounced close to equilibrium. This finding suggests that the rate of hydration of [Formula: see text] is a rate-limiting step for calcite dissolution in seawater. We then interpret our dissolution data in a framework that incorporates both solution chemistry and geometric constraints on the calcite solid. Near equilibrium, this framework demonstrates a lowered free energy barrier at the solid-solution interface in the presence of CA. This framework also indicates a significant change in dissolution mechanism at [Formula: see text], which we interpret as the onset of homogeneous etch pit nucleation.
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More than 100,000 community wells have been installed in the 150-300 m depth range throughout Bangladesh over the past decade to provide low-arsenic drinking water (<10 µg/L As), but little is known about how aquifers tapped by these wells are recharged. Within a 25 km2 area of Bangladesh east of Dhaka, groundwater from 65 low-As wells in the 35-240 m depth range was sampled for tritium (3H), oxygen and hydrogen isotopes of water (18O/16O and 2H/1H), carbon isotope ratios in dissolved inorganic carbon (DIC, 14C/12C and 13C/12C), noble gases, and a suite of dissolved constituents, including major cations, anions, and trace elements. At shallow depths (<90 m), 24 out of 42 wells contain detectable 3H of up to 6 TU, indicating the presence of groundwater recharged within 60 years. Radiocarbon (14C) ages in DIC range from modern to 10 kyr. In the 90-240 m depth range, however, only 5 wells shallower than 150 m contain detectable 3H (<0.3 TU) and 14C ages of DIC cluster around 10 kyr. The radiogenic helium (4He) content in groundwater increases linearly across the entire range of 14C ages at a rate of 2.5×10-12 ccSTP 4He g-1 yr-1. Within the samples from depths >90 m, systematic relationships between 18O/16O, 2H/1H, 13C/12C and 14C/12C, and variations in noble gas temperatures, suggest that changes in monsoon intensity and vegetation cover occurred at the onset of the Holocene, when the sampled water was recharged. Thus, the deeper low-As aquifers remain relatively isolated from the shallow, high-As aquifer.
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BACKGROUND: The paper presents a quantification of main (hydrogen sulfide and sulfate), as well as of intermediate sulfur species (zero-valent sulfur (ZVS), thiosulfate, sulfite, thiocyanate) in the Yellowstone National Park (YNP) hydrothermal springs and pools. We combined these measurements with the measurements of quadruple sulfur isotope composition of sulfate, hydrogen sulfide and zero-valent sulfur. The main goal of this research is to understand multiple sulfur isotope fractionation in the system, which is dominated by complex, mostly abiotic, sulfur cycling. RESULTS: Water samples from six springs and pools in the Yellowstone National Park were characterized by pH, chloride to sulfate ratios, sulfide and intermediate sulfur species concentrations. Concentrations of sulfate in pools indicate either oxidation of sulfide by mixing of deep parent water with shallow oxic water, or surface oxidation of sulfide with atmospheric oxygen. Thiosulfate concentrations are low (<6 µmol L(-1)) in the pools with low pH due to fast disproportionation of thiosulfate. In the pools with higher pH, the concentration of thiosulfate varies, depending on different geochemical pathways of thiosulfate formation. The δ(34)S values of sulfate in four systems were close to those calculated using a mixing line of the model based on dilution and boiling of a deep hot parent water body. In two pools δ(34)S values of sulfate varied significantly from the values calculated from this model. Sulfur isotope fractionation between ZVS and hydrogen sulfide was close to zero at pH < 4. At higher pH zero-valent sulfur is slightly heavier than hydrogen sulfide due to equilibration in the rhombic sulfur-polysulfide - hydrogen sulfide system. Triple sulfur isotope ((32)S, (33)S, (34)S) fractionation patterns in waters of hydrothermal pools are more consistent with redox processes involving intermediate sulfur species than with bacterial sulfate reduction. Small but resolved differences in ∆(33)S among species and between pools are observed. CONCLUSIONS: The variation of sulfate isotopic composition, the origin of differences in isotopic composition of sulfide and zero-valent sulfur, as well as differences in ∆(33)S of sulfide and sulfate are likely due to a complex network of abiotic redox reactions, including disproportionation pathways.
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This study presents the mineralogy and strontium isotope ratio (87Sr/86Sr) of 21 pathological biominerals (bladder and kidney stones) collected from patients admitted between 2018 and 2020 at the Department of Urology of the San Pio Hospital (Benevento, southern Italy). Urinary stones belong to the calcium oxalate, purine or calcium phosphate mineralogy types. Their corresponding 87Sr/86Sr range from 0.707607 for an uricite sample to 0.709970 for a weddellite one, and seem to be partly discriminated based on the mineralogy. The comparison with the isotope characteristics of 38 representative Italian bottled and tap drinking waters show a general overlap in 87Sr/86Sr with the biominerals. However, on a smaller geographic area (Campania Region), we observe small 87Sr/86Sr differences between the biominerals and local waters. This may be explained by external Sr inputs for example from agriculture practices, inhaled aerosols (i.e., particulate matter), animal manure and sewage, non-regional foods. Nevertheless, biominerals of patients that stated to drink and eat local water/wines and foods every day exhibited a narrower 87Sr/86Sr range roughly matching the typical isotope ratios of local geological materials and waters, as well as those of archaeological biominerals from the same area. Finally, we conclude that the strontium isotope signature of urinary stones may reflect that of the environmental matrices surrounding patients, but future investigations are recommended to ultimately establish the potential for pathological biominerals as reliable biomonitoring proxies, taking into the account the contribution of the external sources of Sr.
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Água Potável , Cálculos Urinários , Animais , Humanos , Isótopos de Estrôncio/análise , Isótopos , Agricultura , EstrôncioRESUMO
The understanding of global carbon has rarely extended to small-scale tropical river basins. To address these uncertainties, this study aims to investigate the importance of rock weathering and organic matter turnover in the carbon cycle in a terrain dominated by crystalline silicate rocks. The geochemical composition of the dissolved and particulate carbon phases (DIC, DOC and POC) and their stable carbon isotopes were studied in the Deduru Oya River in Sri Lanka. Dissolved inorganic carbon (DIC) was the most dominant carbon phase and its contribution to the total carbon pool varied between 67 and 89 %. Furthermore, the δ13CDIC values in the river varied between -1.1 and -16.5 . The lithological characteristics and molar ratios between Ca2+, Mg2+ and HCO3- indicated rock weathering mainly by CO2 and carbonic acid. The δ13CDIC values for groundwater input were -15.9 , while for carbonate weathering, mainly due to fertiliser input, they reached a value of -12.7 . This input was fed into an isotope mass balance to determine the relative contributions. However, the isotope mass balance was only plausible after correcting for the effects on δ13CDIC caused by degassing and photosynthesis. Our study demonstrated that carbonate weathering and organic matter turnover are essential components of the river carbon cycle even in a silicate dominated catchment. They can represent up to 60 % of the DIC pool. Combined with the higher organic matter turnover and high pCO2 in the river water, it can be suggested that the Deduru Oya River acts as a net source of CO2 in the atmosphere. Our study shows that CO2 degassing and in-stream photosynthesis in tropical river systems need to be considered along with chemical weathering to account for carbon transport and turnover in tropical rivers.
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Stable isotope ratios of nitrogen and oxygen (15N/14N and 18O/16O) of nitrate (NO3-) are excellent tracers for developing systematic understanding of sources, conversions, and deposition of reactive atmospheric nitrogen (Nr) in the environment. Despite recent analytical advances, standardized sampling of NO3-) isotopes in precipitation is still lacking. To advance atmospheric studies on Nr species, we propose best-practice guidelines for accurate and precise sampling and analysis of NO3- isotopes in precipitation based on the experience obtained from an international research project coordinated by the International Atomic Energy Agency (IAEA). The precipitation sampling and preservation strategies yielded a good agreement between the NO3- concentrations measured at the laboratories of 16 countries and at the IAEA. Compared to conventional methods (e.g., bacterial denitrification), we confirmed the accurate performance of the lower cost Ti(III) reduction method for isotope analyses (15N and 18O) of NO3- in precipitation samples. These isotopic data depict different origins and oxidation pathways of inorganic nitrogen. This work emphasized the capability of NO3- isotopes to assess the origin and atmospheric oxidation of Nr and outlined a pathway to improve laboratory capability and expertise at a global scale. The incorporation of other isotopes like 17O in Nr is recommended in future studies.
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Nitratos , Poluentes Químicos da Água , Nitratos/análise , Isótopos de Nitrogênio/análise , Monitoramento Ambiental/métodos , Poluentes Químicos da Água/análise , Nitrogênio/análise , China , Isótopos de Oxigênio/análiseRESUMO
Natural stable metal isotopes have shown utility in differentiation between healthy and diseased brain states (e.g. Alzheimer's disease, AD). While the AD brain accumulates some metals, it purges others, namely K (accompanied by increased serum K, suggesting brain-blood transferal). Here, K isotope compositions of Göttingen minipig brain regions for two AD models at midlife are reported. Results indicate heavy K isotope enrichment where amyloid beta (Aß) accumulation is observed, and this enrichment correlates with relative K depletion. These results suggest preferential efflux of isotopically light K+ from the brain, a linkage between brain K concentrations and isotope compositions, and linkage to Aß (previously shown to purge cellular brain K+). Brain K isotope compositions differ from that for serum and brain K is much more abundant than in serum, suggesting that changes in brain K may transfer a measurable K isotope excursion to serum, thereby generating an early AD biomarker.
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Doença de Alzheimer , Suínos , Animais , Humanos , Peptídeos beta-Amiloides/metabolismo , Porco Miniatura/metabolismo , Encéfalo/metabolismo , Metais , IsótoposRESUMO
To addresshow parent materials are affecting organic carbon dynamics in a soil profile, soils from a lithosequence comprising six parent lithologies under a rangeland ecosystem have been explored at three depth intervals for soil organic carbon (SOC) content and its 13C depth trends. Studied parent materials ranged from metamorphic (foliated: FM and non-foliated: NFM) to sedimentary (clastic carbonate: CCS) to plutonic (intermediate: IP, felsic: FP and intermediate felsic: IFP) geological contexts. The relationship between SOC concentration and its isotopic signatures to a depth of 50â cm in FM, NFM, FP and IFP profiles was well described by the kinetic fractionation of SOC during biodegradation. For CCS and IP lithologies, strong divergence from the Rayleigh equation was observed suggesting that the 13C enrichments in these soils resulted from both mixing different SOC pools and isotope fractionation related to the C mineralization. Results suggest that SOC across the lithosequence goes through different isotopic evolutions resulting from different 13C-enriched inputs and pedogenic properties as described by the extended Rayleigh equation (0 ≤ ßC ≤ 0.80). These are presumably caused by the bedrock lithology implying that parent material affects C storage and dynamics.
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Carbono , Solo , Carbono/metabolismo , Isótopos de Carbono , Ecossistema , CinéticaRESUMO
Sodium nitrate ores from the Atacama Desert in South America were economically important as they represented huge natural resources for the fertilizer and explosives industries during the early nineteenth to early twentieth centuries. Nitrogen and oxygen isotope ratios (δ15N and δ18O) of these desert nitrates generally show unique compositions (from close to 0 and up to ca. +50â , respectively). The nitrates indicate the provenance as atmospheric in origin due to the mass-independent photochemical reaction of nitric oxide (NO) with ozone (O3) in the atmosphere to produce nitrate (NO3-). This paper examines the previously existing isotope data for specimens acquired from the Atacama Desert. It then reports new data from dual isotope analysis of historic nitrate specimens archived in museums in the UK. In the stable isotope signatures for nitrates from two areas of the Atacama Desert, Tarapacá in the north and Antofagasta in the south, were examined, and this analysis enabled a more detailed definition of their isotopic compositional ranges. This improved database is useful for tracing the provenance of the historic nitrates used in gunpowder and saltpetre, and also the cause of nitrate pollution in natural environments for which routine chemistry alone cannot provide the definite evidence for the origin.
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Nitratos , Poluentes Químicos da Água , Chile , Monitoramento Ambiental , Museus , Nitratos/análise , Isótopos de Nitrogênio/análise , Isótopos de Oxigênio/análise , Poluentes Químicos da Água/análiseRESUMO
Gas samples were collected from 25 m long horizontal boreholes drilled into the excavation field at 10° inclination to the longwall face in two mining areas, Pesje and Preloge, in the Velenje Coal Mine, Slovenia, from 2013 to 2018. The degassing mechanism of coalbed gas and its stable isotopic composition (δ13CCO2, δ13CCH4, and δ2HCH4) were investigated in boreholes in advance of eight working faces. The major coalbed gas constituents were CO2 and methane. Gas concentrations and isotope values revealed that the methane is biogenic in origin with δ13CCH4 values of -69.4 to -29.5 , δ2HCH4 values of -301 to -222 , and a fractionation factor (αCO2-CH4) of 0.998-1.073, suggesting that methane derives from microbial acetate fermentation and CO2 reduction. The carbon dioxide methane index values ranged from 50.0-98.3 vol.% and δ13CCO2 values from -11.8 to -0.5 , indicating that CO2 is biogenic and endogenic in origin. The degassing mechanism results in isotope fractionation of methane and CO2 for carbon isotopes up to 39.9 and up to 8.5 , respectively, depending on the position of the excavation fields in space, e.g. under pre-mined coal area, fresh overburden.
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Carvão Mineral , Metano , Dióxido de Carbono/análise , Isótopos de Carbono/análise , Metano/análise , EslovêniaRESUMO
Accurately determining the age of hydrothermal ore deposits is difficult, because of lack of suitable mineral chronometers and techniques. Here we present the first LA-MC-ICPMS U-Pb age of carbonates from hydrothermal Sb deposits. Three stages of hydrothermal carbonates from the giant South China Sb metallogenic belt were identified: (1) pre-ore dolomite (Dol-I), (2) syn-ore calcite (Cal-II), and (3) post-ore calcite (Cal-III). The U and Pb isotopic data show that Cal-II yielded a lower intercept age of 115.3 ± 1.5 Ma (MSWD = 2.0), suggesting a Sb mineralization that corresponds to an extension event occurred during the early Cretaceous in South China. Although Cal-III yielded an age of 60.0 ± 0.9 Ma (MSWD = 1.5), indicating a potential tectonothermal event occurred in this belt during the early Cenozoic. Hence, in situ U-Pb dating of calcite offers a new way to determine the age of hydrothermal ore deposits.
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Selenium and oxygen isotope systematics can be useful tools for tracing sources and fate of Se oxyanions in water. In order to measure δ18O values of selenate, SeO4 2- must first be sequestered from water by precipitation as BaSeO4(s). However, other dissolved oxyanions insoluble with Ba2+ require removal. Dissolved selenate was separated from dissolved selenite, carbonate, phosphate, and arsenate by addition of Ce3+ cations that quantitatively removed these oxyanions by precipitation as insoluble Ce2(SeO3)3(s), Ce2(CO3)3(s), CePO4(s), and CeAsO4(s), respectively. δ18O-selenate (-8.19 ± 0.17â ) did not change after four replicates of selenite removal by Ce2(SeO3)3(s) precipitation and Ce3+ removal by cation exchange (-8.20 ± 0.14, -8.32 ± 0.09, -8.17 ± 0.13, and -8.29 ± 0.13â ). δ18O-selenate values (-10.86 ± 0.45â ) were preserved also when selenate was pre-concentrated on anion exchange resin, quantitatively retrieved by elution, and processed with Ce3+ to remove interfering oxyanions (-10.77 ± 0.07â ). The extraction and purification steps developed here successfully isolated dissolved selenate from interfering oxyanions while preserving δ18O-selenate values. This method should be useful for characterizing δ18O-selenate when present with the co-occurring oxyanions above in laboratory experiments and field sites with high Se concentrations, although further research is required for methods to eliminate any co-occurring sulphate.
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Arseniatos/análise , Carbonatos/análise , Isótopos de Oxigênio/análise , Fosfatos/análise , Ácido Selênico/análise , Ácido Selenioso/análise , Poluentes Químicos da Água/análise , Selênio/análise , Soluções , Sulfatos/análiseRESUMO
Comparing two different techniques applied for the extraction of marine pore water samples from sediments, the well-established whole round (WR) method and the more recent Rhizon method, in terms of their effects on stable calcium isotope ratios in extracted pore waters, we recognize a systematic offset between the two sampling methods. Higher δ44/40Ca values are associated with lower Ca concentrations for the Rhizon sampling technique and lower δ44/40Ca values are associated with higher Ca concentrations for the corresponding WR-derived pore water samples. Models involving Rayleigh fractionation and mixing calculation suggest that the observed offset is most likely caused by a combined process of CaCO3 precipitation and ion exchange taking place during Rhizon sampling-induced CO2 degassing. Changing pressure, extraction time or extraction yield during WR pressing does not lead to a variation in δ44/40Ca, indicating that no Ca isotope fractionation takes place during the sampling of pore water. On the basis of analytical and modelling results, WR samples appear to provide δ44/40Ca values that are more representative of the 'true' pore water isotopic composition. While the difference between the sampling techniques is close to the present-day analytical precision of Ca isotope analysis, it may become more relevant with increasing analytical precision in the future.
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Isótopos de Cálcio/análise , Cálcio/análise , Monitoramento Ambiental/métodos , Sedimentos Geológicos/química , Água do Mar/química , Dióxido de Carbono/análise , Fracionamento Químico , Modelos TeóricosRESUMO
A temporal framework for mineral deposits is essential when addressing the history of their formation and conceptualizing genetic models of their origin. This knowledge is critical to understand how crust-forming processes are related to metal accumulations at specific time and conditions of Earth evolution. To this end, high-precision absolute geochronology utilising the rhenium-osmium (Re-Os) radiometric system in specific sulphide minerals is becoming a method of choice. Here, we present a procedure to obtain mineral separates of individual sulphide species that may coexist within specific mineralized horizons in ore deposits. This protocol is based on preliminary petrographic and paragenetic investigations of sulphide and gangue minerals using reflected and transmitted light microscopy. Our approach emphasizes the key role of a stepwise use of a Frantz isodynamic separator to produce mineral separates of individual sulphide species that are subsequently processed for Re-Os and sulphur isotope geochemistry.â¢Detailed method and its graphical illustration modified from an original procedure introduced by [1], [2].â¢Quality control and validation of monophasic mineral separates made by microscopic investigations and qualitative analysis of aliquots embedded in epoxy mounts.â¢The present method, which contributed to the successful results presented in the co-publication by Saintilan et al. (2020), demonstrates why other studies reporting Re-Os isotope data for mixtures of sulphide minerals should be considered with caution.
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Saltpetre (KNO3; potassium nitrate) is one of the major ingredients of gunpowder. Simplex saltpetre (total 126 samples) together with gunpowder (total 93 samples) commodities which are currently prevailing in local markets as used for wildlife hunting and rocket festivals (local name in Lao: Boun Ban Fai) were collected from throughout Lao PDR. Dual isotopic composition of nitrates (δ15N, δ18O) was analyzed by the microbial denitrification method. Binary plotting of the data was conducted to characterize the mode of formation. In Lao PDR, almost all the commodities were imported from neighbouring Thailand, and to a lesser extent from Israel. Binary plotting of δ15N vs. δ18O of nitrates shows their intrinsic origin manufactured by Haber-Bosch and subsequently Ostwald processes. We observed an inverse correlation (δ15Nnitrate: up to + 12â ; δ18Onitrate: down to + 15â ), deviating from the reservoir values (free air) of δ15N (dinitrogen; up to 0â ) and δ18O (oxygen; +23.5â ), interpreted this as an indication of isotope fractionation during manufacture. The most plausible interpretation for this is the fractionation associated with formation of NO following NO2 and finally NO3 products. A nearly comparable inverse relationship is also observed for nitrates in pyrotechnics manufactured in China.
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Monitoramento Ambiental/métodos , Poluentes Ambientais/análise , Nitratos/análise , Isótopos de Nitrogênio/análise , Isótopos de Oxigênio/análise , Compostos de Potássio/análise , Fracionamento Químico , China , Desnitrificação , LaosRESUMO
Open Access (OA) describes the free, unrestricted access to and re-use of research articles. Recently, a new wave of interest, debate, and practice surrounding OA publishing has emerged. In this paper, we provide a simple overview of the trends in OA practice in the broad field of geochemistry. Characteristics of the approach such as whether or not an article processing charge (APC) exists, what embargo periods or restrictions on self-archiving' policies are in place, and whether or not the sharing of preprints is permitted are described. The majority of journals have self-archiving policies that allow authors to share their peer reviewed work via green OA without charge. There is no clear relationship between journal impact and APC. The journals with the highest APC are typically those of the major commercial publishers, rather than the geochemistry community themselves. The rise in OA publishing has potential impacts on the profiles of researchers and tends to devolve costs from organizations to individuals. Until the geochemistry community makes the decision to move away from journal-based evaluation criteria, it is likely that such high costs will continue to impose financial inequities upon research community. However, geochemists could more widely choose legal self-archiving as an equitable and sustainable way to disseminate their research.
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Aquatic plants commonly used in landscaping or as ornaments are subject to a growing worldwide market that is source of trade between countries which can induce the transfer of unwanted invasive alien plant species. To protect national biodiversity and economy, authorities promote the use of local markets without however providing the method to do so. This study deals with the feasibility of using Sr stable isotopes for discriminating the origin of aquatic plants at a worldwide scale. More than 15 aquatic plant species were collected from main producers in four countries (China, Hungary, Germany, France). Each plant was analysed for its 87Sr/86Sr ratio and the results are compared within samples from each producer and between countries. For a given produce, significant 87Sr/86Sr can be measured as a function of the plant species. However, at the scale of Europe, plants from different producers are almost isotopically identical with 87Sr/86Sr ratios of 0.71228 ± 218.10-5, 0.71116 ± 178.10-5 and 0.71066 ± 156.10-5 for France, Hungary and Germany, respectively. These values are clearly distinguishable from those measured in Chinese aquatic plants, which yield a mean 87Sr/86Sr ratio of 0.70591 ± 168.10-5. This Sr isotopic discrimination between European and Chinese aquatic plants is explained by the specific agricultural and hydrogeological environments of the producing countries. Indeed, the cycle of Sr in aquatic plants is studied here for the first time. Natural and anthropic materials of French origin were collected and characterized in terms of 87Sr/86Sr. Mixing models reveal that irrigation water is the main source of Sr for plants (35-85%). Clays from the substrate (4-38%) and fertilizers (5-19%) can also contribute, in proportions depending on the plant species. This model accounts for the small variations in 87Sr/86Sr ratios of species from the same producer and allows a discrimination between producers using different agricultural practices.
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Along the 98 800 km2 Rhône catchment area, 3 million people depend on the river resource and its sustainability. Flow rate monitoring of the French rivers showed the importance of the Swiss part of the Rhône (measured at station 1), the Isere (station 2) and the Durance rivers (station 3) contribution into the Rhône downstream (station 4) during summer when other recharges are decreasing. While their contribution is only of 10-30 % during most of the year, those rivers could contribute to more than 60 % of the Rhône flow rate during the driest period. The current study aims at confirming the key role of Alpine rivers contribution to the Rhône downstream flow by investigating an alternative monitoring tool of high-altitude water contribution. As a suitable tracer of latitude and altitude especially in a contrasted morphology, such as the Rhône watershed, water stable isotopes can be relevant to trace the origin of the recharge contributing to the waterflow. This study is based on a full hydrological cycle survey of the Rhône downstream water isotopes signature complemented by the current flow rate monitoring program of the Alpine rivers. With a linear regression model between both parameters data, the current study evidences the relevance of using water isotope signature to trace the seasonal change of water's origin and evaluate the high altitude waters contribution (RQ AR) into the Rhône river downstream flow rate (δ2H = 26.0 x RQAR - 57.9 with R = 0.88, R2 = 0.79 and a p-value < 0.0001). It also confirms the key role of Alpine waters contribution to the Rhône River during summer with average value of 70 ± 6% and the importance to monitor the sustainability of their contribution in future drier period.
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Elemental and isotopic pattern of n(87Sr)/n(86Sr) and δ88Sr/86SrSRM987 were used to characterise groundwater and recharge of saline ponds in a clastic aquifer in East Austria. Therefore, shallow, artesian and thermal groundwaters of the investigated aquifer along with rainfall and rivers were analysed using (MC) ICP-MS. The n(87Sr)/n(86Sr) ratio and elemental pattern changed with aquifer depth as a result of progressing bedrock leaching and dissolution with increasing groundwater residence time. The n(87Sr)/n(86Sr) ratio of shallow groundwater below saline ponds of 0.71019 ± 0.00044 was significantly different from thermal groundwater of 0.71205 ± 0.00035 (U, k = 2). In contrast to previous theories, this result suggested no recharge of saline ponds by upwelling paleo-seawater. Isotope pattern deconvolution revealed that rainfall accounted to about 60% of the n(87Sr)/n(86Sr) ratio of shallow groundwater below saline ponds. The δ88Sr/86SrSRM987 values of groundwater decreased from about 0.25 in most shallow, to predominantly negative values of about -0.24 in artesian groundwater. This result indicated leaching and dissolution of weathered minerals. In turn, the δ88Sr/86SrSRM987 of deep thermal groundwater showed positive values of about 0.12 , which suggested removal of 86Sr from solution by carbonate precipitation. These results highlight the potential of δ88Sr/86SrSRM987 signature as an additional geochemical tracer.