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1.
Over the last decade it has become apparent that Li isotopes may be a good proxy to trace silicate weathering. However, the exact mechanisms which drive the behaviour of Li isotopes in surface environments are not totally understood and there is a need to better calibrate and characterize this proxy. In this study, we analysed the Li concentrations and isotopic compositions in the various surface reservoirs (soils, rocks, waters and plants) of a small forested granitic catchment located in the Vosges Mountains (Strengbach catchment, France, OHGE http://ohge.u-strasbg.fr). Li fluxes were calculated in both soil profiles and at the basin scale and it was found that even in this forested basin, atmospheric inputs and litter fall represented a minor flux compared to input derived from the weathering of rocks and soil minerals (which together represent a minimum of 70% of dissolved Li). Li isotope ratios in soil pore waters show large depth dependent variations. Average dissolved δ7Li decreases from −1.1‰ to −14.4‰ between 0 and −30 cm, but is +30.7‰ at −60 cm. This range of Li isotopic compositions is very large and it encompasses almost the entire range of terrestrial Li isotope compositions that have been previously reported. We interpret these variations to result from both the dissolution and precipitation of secondary phases. Large isotopic variations were also measured in the springs and stream waters, with δ7Li varying from +5.3‰ to +19.6‰. δ7Li increases from the top to the bottom of the basin and also covaries with discharge at the outlet. These variations are interpreted to reflect isotopic fractionations occurring during secondary phase precipitation along the water pathway through the rocks. We suggest that the dissolved δ7Li increases with increasing residence time of waters through the rocks, and so with increasing time of interaction between waters and solids. A dissolution precipitation model was used to fit the dissolved Li isotopic compositions. It was found that the isotopic compositions of springs and stream waters are explicable by an isotopic fractionation of −5‰ to −14‰ (best fit −10.8‰), in agreement with Li incorporation into clay. In soil solutions, it was found that isotopic fractionation during secondary precipitation is larger (at least −23‰), suggesting a major role for different secondary phases, such as iron oxides that maybe incorporate Li with a higher isotope fractionation.  相似文献   

2.
Li isotope fractionation in peridotites and mafic melts   总被引：4，自引：0，他引：4  
We have measured the Li isotope ratios of a range of co-existing phases from peridotites and mafic magmas to investigate high-temperature fractionations of 7Li/6Li. The Li isotopic compositions of seven mantle peridotites, reconstructed from analyses of mineral separates, show little variation (δ7Li 3.2-4.9‰) despite a wide range in fertility and radiogenic isotopic compositions. The most fertile samples yield a best estimate of δ7Li ∼ 3.5‰ for the upper mantle. Bulk analyses of olivine separates from the xenoliths are typically ∼1.5‰ isotopically lighter than co-existing orthopyroxenes, suggestive of a small, high-temperature equilibrium isotope fractionation. On the other hand, bulk analyses of olivine phenocrysts and their host melts are isotopically indistinguishable. Given these observations, equilibrium mantle melting should generate melts with δ7Li little different from their sources (<0.5‰ lighter). In contrast to olivine and orthopyroxene, that dominate peridotite Li budgets, bulk clinopyroxene analyses are highly variable (δ7Li = 6.6‰ to −8.1‰). Phlogopite separated from a modally metasomatised xenolith yielded an extreme δ7Li of −18.9‰. Such large Li isotope variability is indicative of isotopic disequilibrium. This inference is strongly reinforced by in situ, secondary ion mass-spectrometry analyses which show Li isotope zonation in peridotite minerals. The simplest zoning patterns show isotopically light rims. This style of zoning is also observed in the phenocrysts of holocrystalline Hawaiian lavas. More dramatically, a single orthopyroxene crystal from a San Carlos xenolith shows a W-shaped Li isotope profile with a 40‰ range in δ7Li, close to the isotope variability seen in all terrestrial whole rock analyses. We attribute Li isotope zonation in mineral phases to diffusive fractionation of Li isotopes, within mineral phases and along melt pathways that pervade xenoliths. Given the high diffusivity of Li, the Li isotope profiles we observe can persist, at most, only a few years at magmatic temperatures. Our results thus highlight the potential of Li isotopes as a high-resolution geospeedometer of the final phases of magmatic activity and cooling.  相似文献   

3.
Li concentrations and isotopic compositions of coexisting minerals (ol, opx, and cpx) from peridotite xenoliths entrained in the Hannuoba Tertiary basalts, North China Craton, provide insight into Li isotopic fractionation between mantle minerals during melt-rock interaction in the considerably thinned lithospheric mantle. Bulk analyses of mineral separates show significant enrichment of Li in cpx (2.4-3.6 ppm) relative to olivine (1.2-1.8 ppm), indicating that these peridotites have been affected by mantle metasomatism with mafic silicate melts. Bulk olivine separates (δ7Li ∼ +3.3‰ to +6.4‰) are isotopically heavier than coexisting pyroxenes (δ7Li ∼ −3.3‰ to −8.2‰ in cpx, and −4.0‰ to −6.7‰ in opx). Such large variation suggests Li elemental and isotopic disequilibrium. This conclusion is supported by results from in situ SIMS analyses of mineral grains where significant Li elemental and isotopic zonations exist. The olivine and opx have lower Li concentrations and heavier Li isotopes in the rims than in the cores. This reverse correlation of δ7Li with Li concentrations indicates diffusive fractionation of Li isotopes. However, the zoning patterns in coexisting cpx show isotopically heavier rims with higher Li abundances. This positive correlation between δ7Li and Li concentrations suggests a melt mixing trend. We attribute Li concentration and isotope zonation in minerals to the effects of two-stage diffusive fractionation coupled with melt-rock interaction. The earliest melts may have been derived from the subducted oceanic slab with low δ7Li values produced by isotopic fractionation during the dehydration of the seawater-altered slab. Melts at later stages were derived from the asthenosphere and interacted with the peridotites, producing the Li elemental and isotopic zoning in mineral grains. These data thus provide evidence for multiple-stage peridotite-melt interaction in the lithospheric mantle beneath the northern North China Craton.  相似文献   

4.
Saline groundwaters were recovered from undisturbed (Restigouche deposit) and active (Brunswick #12 mine) Zn-Pb volcanogenic massive sulfide deposits in the Bathurst Mining Camp (BMC), northern New Brunswick, Canada. These groundwaters, along with fresh to brackish meteoric ground and surface waters from the BMC, have been analyzed to determine their major, trace element and stable isotopic (O, H, C, and B) compositions. Saline groundwaters (total dissolved solids = 22-45 g/L) are characterized by relatively high Na/Ca ratios compared to brines from the Canadian Shield and low Na/Clmolar and δ11B isotopic compositions (−2.5‰ to 11.1‰) compared to seawater. Although saline waters from the Canadian Shield commonly have oxygen and hydrogen isotopic compositions that plot to the left of the global meteoric water line, those from the BMC fall close to the water line. Fracture and vein carbonate minerals at the Restigouche deposit have restricted carbon isotopic compositions of around −5‰ to −6‰. The carbon isotopic compositions of the saline waters at the Restigouche deposit (+12‰ δ13CDIC) are the result of fractionation of dissolved inorganic carbon by methanogenesis. We suggest that, unlike previous models for shield brines, the composition of saline waters in the BMC is best explained by prolonged water-rock reaction, with no requirement of precursor seawater. We suggest that elevated Br/Cl ratios of saline waters compared to seawater may be explained by differential uptake of Br and Cl during groundwater evolution through water-rock reaction.  相似文献   

5.
In the present work, the first results are reported for both Li and B isotope ratios in rainwater samples collected over a long time period (i.e. monthly rainfall events over 1 a) at a national scale (from coastal and inland locations). In addition, the stable isotopes of the water molecule (δD and δ18O) are also reported here for the same locations so that the Li and B isotope data can be discussed in the same context. The range of Li and B isotopic variations in these rainwaters were measured to enable the determination of the origin of these elements in rainwaters and the characterization of both the seasonal and spatio-temporal effects for δ7Li and δ11B signatures in rainwaters. Lithium and B concentrations are low in rainwater samples, ranging from 0.004 to 0.292 μmol/L and from 0.029 to 6.184 μmol/L, respectively. δ7Li and δ11B values in rainwaters also show a great range of variation between +3.2‰ and +95.6‰ and between −3.3‰ and +40.6‰ over a period of 1 a, respectively, clearly different from the signature of seawater. Seasonal effects (i.e. rainfall amount and month) are not the main factors controlling element concentrations and isotopic variations. δ7Li and δ11B values in rainwaters are clearly different from one site to another, indicating the variable contribution of sea salts in the rainwater depending on the sampling site (coastal vs. inland: also called the distance-from-the-coast-effect). This is well illustrated when wind direction data (origin of air masses) is included. It was found that seawater is not the main supplier of dissolved atmospheric Li and B, and non-sea-salt sources (i.e. crustal, anthropogenic, biogenic) should also be taken into account when Li and B isotopes are considered in hydrogeochemistry as an input to surface waters and groundwater bodies as recharge. In parallel, the isotopic variations of the water molecule, vector of the dissolved B and Li, are also investigated and reported as a contour map for δ18O values based on compiled data including more than 400 δ18O values from throughout France. This δ18O map could be used as a reference for future studies dealing with δ18O recharge signature in relation to the characterization of surface waters and/or groundwater bodies.  相似文献   

6.
We report lithium (Li) isotopic measurements in seawater-derived waters that were discharged from geothermal wells, thermal springs, and sub-marine springs located in volcanic island arc areas in Guadeloupe (the Bouillante geothermal field) and Martinique (Lamentin plain and the Diamant areas). While Li isotopic signatures of the geothermal fluids collected from deep reservoirs were found to be homogeneous for a given site, the δ7Li signatures for each of these reservoirs were significantly different. The first low temperature (25-250 °C) experiments of Li isotope exchange during seawater/basalt interaction confirmed that Li isotopic exchange is strongly temperature dependent, as previously inferred from natural studies. Li isotopic fractionation ranged from +19.4‰ (Δsolution-solid) at 25 °C to +6.7‰ at 250 °C. These experiments demonstrated the importance of Li isotopic fractionation during the formation of Li-bearing secondary minerals and allowed us to determine the following empirical relationship between isotopic fractionation and temperature: Δsolution-solid = 7847/T − 8.093. Application of experimental results and literature data to the Bouillante area suggested that geothermal water was in equilibrium at 250-260 °C. It likely has a deep and large reservoir located in the upper sheeted dike complex of the oceanic crust, just below the transition zone between andesite volcanic flows and the basaltic dikes. The upper dike section, from which Li is extracted by hydrothermal fluids, was characterized by light Li isotopic values in the rocks, indicating retention of 6Li by the altered rocks. For the Lamentin and Diamant areas, the geothermal fluids appeared to be in equilibrium with reservoir volcano-sedimentary rocks at 90-120 °C and 180 °C, respectively. Further evidence for this argument is provided by the fact that only the Na/Li thermometric relationship determined for sedimentary basins yielded temperature values in agreement with those measured or estimated for the reservoir fluids. This suggests the importance of a sedimentary signature in these reservoir rocks. Altogether, this study highlights that the use of Li isotopic systematics is a powerful tool for characterizing the origin of geothermal waters as well as the nature of their reservoir rocks.  相似文献   

7.
Mg isotope ratios (26Mg/24Mg) are reported in soil pore-fluids, rain and seawater, grass and smectite from a 90 kyr old soil, developed on an uplifted marine terrace from Santa Cruz, California. Rain water has an invariant 26Mg/24Mg ratio (expressed as δ26Mg) at −0.79 ± 0.05‰, identical to seawater δ26Mg. Detrital smectite (from the base of the soil profile, and therefore unweathered) has a δ26Mg value of 0.11‰, potentially enriched in 26Mg by up to 0.3‰ compared to the bulk silicate Earth Mg isotope composition (although within the range of all terrestrial silicates). The soil pore-waters show a continuous profile with depth for δ26Mg, ranging from −0.99‰ near the surface to −0.43‰ at the base of the profile. Shallow pore-waters (<1 m) have δ26Mg values that are similar to, or slightly lower than the rain waters. This implies that the degree of biological cycling of Mg in the pore-waters is relatively small and is quantified as <32%, calculated using the average Mg isotope enrichment factor between grass and rain (δ26Mggrass-δ26Mgrain) of 0.21‰. The deep pore-waters (1-15 m deep) have δ26Mg values that are intermediate between the smectite and rain, ranging from −0.76‰ to −0.43‰, and show a similar trend with depth compared to Sr isotope ratios. The similarity between Sr and Mg isotope ratios confirms that the Mg in the pore-waters can be explained by a mixture between rain and smectite derived Mg, despite the fact that Mg and Sr concentrations may be buffered by the exchangeable reservoir. However, whilst Sr isotope ratios in the pore-waters span almost the complete range between mineral and rain inputs, Mg isotopes compositions are much closer to the rain inputs. If Mg and Sr isotope ratios are controlled uniquely by a mixture, the data can be used to estimate the mineral weathering inputs to the pore-waters, by correcting for the rain inputs. This isotopic correction is compared to the commonly used chloride correction for precipitation inputs. A consistent interpretation is only possible if Mg isotope ratios are fractionated either by the precipitation of a secondary Mg bearing phase, not detected by conventional methods, or selective leaching of 24Mg from smectite. There is therefore dual control on the Mg isotopic composition of the pore-waters, mixing of two inputs with distinct isotopic compositions, modified by fractionation. The data provide (1) further evidence for Mg isotope fractionation at the surface of the Earth and (2) the first field evidence of Mg isotope fractionation during uptake by natural plants. The coherent behaviour of Mg isotope ratios in soil environments is encouraging for the development of Mg isotope ratios as a quantitative tracer of both weathering inputs of Mg to waters, and the physicochemical processes that cycle Mg, a major cation linked to the carbon cycle, during continental weathering.  相似文献   

8.
Magnesium and strontium isotope signatures were determined during different seasons for the main rivers of the Moselle basin, northeastern France. This small basin is remarkable for its well-constrained and varied lithology on a small distance scale, and this is reflected in river water Sr isotope compositions. Upstream, where the Moselle River drains silicate rocks of the Vosges mountains, waters are characterized by relatively high 87Sr/86Sr ratios (0.7128-0.7174). In contrast, downstream of the city of Epinal where the Moselle River flows through carbonates and evaporites of the Lorraine plateau, 87Sr/86Sr ratios are lower, down to 0.70824.Magnesium in river waters draining silicates is systematically depleted in heavy isotopes (δ26Mg values range from −1.2 to −0.7‰) relative to the value presently estimated for the continental crust and a local diorite (−0.5‰). In comparison, δ26Mg values measured in soil samples are higher (∼0.0‰). This suggests that Mg isotope fractionation occurs during mineral leaching and/or formation of secondary clay minerals. On the Lorraine plateau, tributaries draining marls, carbonates and evaporites are characterized by low Ca/Mg (1.5-3.2) and low Ca/Sr (80-400) when compared to local carbonate rocks (Ca/Mg = 29-59; Ca/Sr = 370-2200), similar to other rivers draining carbonates. The most likely cause of the Mg and Sr excesses in these rivers is early thermodynamic saturation of groundwater with calcite relative to magnesite and strontianite as groundwater chemistry progressively evolves in the aquifer. δ26Mg of the dissolved phases of tributaries draining mainly carbonates and evaporites are relatively low and constant throughout the year (from −1.4‰ to −1.6‰ and from −1.2‰ to −1.4‰, respectively), within the range defined for the underlying rocks. Downstream of Epinal, the compositions of the Moselle River samples in a δ26Mg vs. 87Sr/86Sr diagram can be explained by mixing curves between silicate, carbonate and evaporite waters, with a significant contribution from the Vosgian silicate lithologies (>70%). Temporal co-variation between δ26Mg and 87Sr/86Sr for the Moselle River throughout year is also observed, and is consistent with a higher contribution from the Vosges mountains in winter, in terms of runoff and dissolved element flux. Overall, this study shows that Mg isotopes measured in waters, rocks and soils, coupled with other tracers such as Sr isotopes, could be used to better constrain riverine Mg sources, particularly if analytical uncertainties in Mg isotope measurements can be improved in order to perform more precise quantifications.  相似文献   

9.
Boron isotope compositions (δ11B) and B concentrations of rains and snows were studied in order to characterize the sources and fractionation processes during the boron atmospheric cycle. The 11B/10B ratios of instantaneous and cumulative rains and snows from coastal and continental sites show a large range of variations, from −1.5 ± 0.4 to +26.0 ± 0.5‰ and from −10.2 ± 0.5 to +34.4 ± 0.2‰, respectively. Boron concentrations in rains and snows vary between 0.1 and 3.0 ppb. All these precipitation samples are enriched in 10B compared to the ocean value (δ11B = +39.5‰). An empirical rain-vapour isotopic fractionation of +31‰ is estimated from three largely independent methods. The deduced seawater-vapour fractionation is +25.5‰, with the difference between the rain and seawater fractionations principally reflecting changes in the speciation of boron in the liquid with ∼100% B(OH)3 present in precipitations. A boron meteoric water line, δD = 2.6δ11B − 133, is proposed which describes the relationship between δD and δ11B in many, but not all, precipitations. Boron isotopic compositions of precipitations can be related to that of the seawater reservoir by the seawater-vapour fractionation and one or more of (1) the rain-vapour isotopic fractionation, (2) evolution of the δ11B value of the atmospheric vapour reservoir via condensation-precipitation processes (Rayleigh distillation process), (3) any contribution of vapour from the evaporation of seawater aerosols, and (4) any contribution from particulate matter, principally sea salt, continental dust and, perhaps more regionally, anthropogenic sources (burning of biomass and fossil fuels). From the δ11B values of continental precipitations, a sea salt contribution cannot be more than a percent or so of the total B in precipitation over these areas.  相似文献   

10.
The groundwater B concentration in Mesozoic karst, Neogene and alluvial aquifers in the West part of Chalkidiki province in Central Macedonia, Greece reaches 6.45 mg L−1, which exceeds the limit of 1 mg L−1, set by the European Union for drinking water. The high B contents have been detected in this area, not only near the shoreline, where seawater intrusion occurs, but also in the inland part of the basin. Multi isotope (2H, 18O, 34S, 18O(SO4), 11B, 87Sr/86Sr) data from borehole and thermal water springs allow identification of the possible B sources. The B dissolved in groundwater in the Chalkidiki area is mainly geogenic. The low δ11B values, 0–1‰, similar to those of thermal fluids from continental geothermal fields, and the low Cl/B ratio compared to seawater both indicate a geothermal origin for B and reflect deep circulation and interaction with igneous rocks. The 87Sr/86Sr ratio also indicates that the deep-aquifer granodiorite is the predominant rock source of Sr, while the shallow limestone unit has negligible effects on the dissolved Sr budget in these thermal karst waters which O and H isotopes show to be of meteoric origin. The main source of high B in borehole water is mainly mixing with B-rich geothermal water. The mixing between geothermal water and water from the Neogene aquifer is also reflected by isotopic contents of SO4.  相似文献   

11.
The Li isotopic composition of the upper continental crust is estimated from the analyses of well-characterized shales, loess, granites and upper crustal composites (51 samples in total) from North America, China, Europe, Australia and New Zealand. Correlations between Li, δ7Li, and chemical weathering (as measured by the Chemical Index of Alteration (CIA)), and δ7Li and the clay content of shales (as measured by Al2O3/SiO2), reflect uptake of heavy Li from the hydrosphere by clays. S-type granites from the Lachlan fold belt (-1.1 to -1.4‰) have δ7Li indistinguishable from their associated sedimentary rocks (-0.7 to 1.2‰), and show no variation in δ7Li throughout the differentiation sequence, suggesting that isotopic fractionation during crustal anatexis and subsequent differentiation is less than analytical uncertainty (±1‰, 2σ). The isotopically light compositions for both I- and S-type granites from the Lachlan fold belt (-2.5 to + 2.7 ‰) and loess from around the world (-3.1 to + 4.5‰) reflect the influence of weathering in their source regions. Collectively, these lithologies possess a limited range of Li isotopic compositions (δ7Li of −5‰ to + 5‰), with an average (δ7Li of 0 ± 2‰ at 1σ) that is representative of the average upper continental crust. Thus, the Li isotopic composition of the upper continental crust is lighter than the average upper mantle (δ7Li of + 4 ± 2‰), reflecting the influence of weathering on the upper crustal composition. The concentration of Li in the upper continental crust is estimated to be 35 ± 11 ppm (2σ), based on the average loess composition and correlations between insoluble elements (Ti, Nb, Ta, Ga and Al2O3, Th and HREE) and Li in shales. This value is somewhat higher than previous estimates (∼20 ppm), but is probably indistinguishable when uncertainties in the latter are accounted for.  相似文献   

12.
We present whole rock Li and Mg isotope analyses of 33 ultramafic xenoliths from the terrestrial mantle, which we compare with analyses of 30 (mostly chondritic) meteorites. The accuracy of our new Mg isotope ratio measurement protocol is substantiated by a combination of standard addition experiments, the absence of mass independent effects in terrestrial samples and our obtaining identical values for rock standards using two different separation chemistries and three different mass-spectrometric introduction systems. Carbonaceous, ordinary and enstatite chondrites have irresolvable mean stable Mg isotopic compositions (δ25Mg = −0.14 ± 0.06; δ26Mg = −0.27 ± 0.12‰, 2SD), but our enstatite chondrite samples have lighter δ7Li (by up to ∼3‰) than our mean carbonaceous and ordinary chondrites (3.0 ± 1.5‰, 2SD), possibly as a result of spallation in the early solar system. Measurements of equilibrated, fertile peridotites give mean values of δ7Li = 3.5 ± 0.5‰, δ25Mg = −0.10 ± 0.03‰ and δ26Mg = −0.21 ± 0.07‰. We believe these values provide a useful estimate of the primitive mantle and they are within error of our average of bulk carbonaceous and ordinary chondrites. A fuller range of fresh, terrestrial, ultramafic samples, covering a variety of geological histories, show a broad positive correlation between bulk δ7Li and δ26Mg, which vary from −3.7‰ to +14.5‰, and −0.36‰ to + 0.06‰, respectively. Values of δ7Li and δ26Mg lower than our estimate of primitive mantle are strongly linked to kinetic isotope fractionation, occurring during transport of the mantle xenoliths. We suggest Mg and Li diffusion into the xenoliths is coupled to H loss from nominally anhydrous minerals following degassing. Diffusion models suggest that the co-variation of Mg and Li isotopes requires comparable diffusivities of Li and Mg in olivine. The isotopically lightest samples require ∼5-10 years of diffusive ingress, which we interpret as a time since volatile loss in the host magma. Xenoliths erupted in pyroclastic flows appear to have retained their mantle isotope ratios, likely as a result of little prior degassing in these explosive events. High δ7Li, coupled with high [Li], in rapidly cooled arc peridotites may indicate that these samples represent fragments of mantle wedge that has been metasomatised by heavy, slab-derived fluids. If such material is typically stirred back into the convecting mantle, it may account for the heavy δ7Li seen in some oceanic basalts.  相似文献   

13.
This study investigates the application of sulphur isotope ratios (δ34S) in combination with carbon (δ13C) and nitrogen (δ15N) ratios to understand the influence of environmental sulphur on the isotopic composition of archaeological human and faunal remains from Roman era sites in Oxfordshire, UK. Humans (n = 83), terrestrial animals (n = 11), and freshwater fish (n = 5) were analysed for their isotope values from four locations in the Thames River Valley, and a broad range of δ34S values were found. The δ34S values from the terrestrial animals were highly variable (−13.6‰ to +0.5‰), but the δ34S values of the fish were clustered and 34S-depleted (−20.9‰ to −17.3‰). The results of the faunal remains suggest that riverine sulphur influenced the terrestrial sulphur isotopic signatures. Terrestrial animals were possibly raised on the floodplains of the River Thames, where highly 34S-depleted sulphur influenced the soil. The humans show the largest range of δ34S values (−18.8‰ to +9.6‰) from any archaeological context to date. No differences in δ34S values were found between the males (−7.8 ± 6.0‰) and females (−5.3 ± 6.8‰), but the females had a linear correlation (R2 = 0.71; p < 0.0001) between their δ15N and δ34S compositions. These δ34S results suggest a greater dietary variability for the inhabitants of Roman Oxfordshire than previously thought, with some individuals eating solely terrestrial protein resources and others showing a diet almost exclusively based on freshwater protein such as fish. Such large dietary variability was not visible by analysing only the carbon and nitrogen isotope ratios, and this research represents the largest and most detailed application of δ34S analysis to examine dietary practices (including breastfeeding and weaning patterns) during the Romano-British Period.  相似文献   

14.
Deuterium and oxygen isotope fractionations between liquid and vapor water were experimentally-determined during evaporation of a NaCl solution (35 g L−1) as a function of water temperature and wind velocity. In the case of a null wind velocity, slopes of δD-δ18O trajectories of residual waters hyperbolically decrease with increasing water temperatures in the range 23-47 °C. For wind velocities ranging from 0.8 to 2.2 m s−1, slopes of the δD-δ18O trajectories linearly increase with increasing wind velocity at a given water temperature. These experimental results can be modeled by using Rayleigh distillation equations taking into account wind-related kinetics effects. Deuterium and oxygen isotope compositions of water inclusions trapped by the precipitated halite crystals were determined by micro-equilibration techniques.These isotopic compositions accurately reflect those of the surrounding residual waters during halite growth. Isotopic compositions of water inclusions in twenty natural halites from the Messinian Realmonte mine in Sicily suggest precipitation temperatures of that match the homogenization temperatures obtained by microthermometry (median = 34 ± 5 °C). The similarity between the measured and experimental slopes of the δD-δ18O evaporation trajectories suggests that the effect of wind was negligible during the genesis of these halite deposits. Hydrogen and oxygen isotope compositions of water inclusions from Realmonte halite also define a linear trend whose extrapolation until intersection with the Mediterranean Meteoric Water Line allows the characterization of the water source with δD and δ18O values of −70 ± 10‰ and −11.5 ± 1.5‰, respectively. These results reveal that the huge amounts of salts deposited in Sicily result from the evaporation of seawater mixed with a dominant fraction (?50%) of meteoric waters most likely deriving from alpine fluvial discharge.  相似文献   

15.
Evaluation of the extent of volatile element recycling in convergent margin volcanism requires delineating likely source(s) of magmatic volatiles through stable isotopic characterization of sulfur, hydrogen and oxygen in erupted tephra with appropriate assessment of modification by degassing. The climactic eruption of Mt. Mazama ejected approximately 50 km3 of rhyodacitic magma into the atmosphere and resulted in formation of a 10-km diameter caldera now occupied by Crater Lake, Oregon (lat. 43°N, long. 122°W). Isotopic compositions of whole-rocks, matrix glasses and minerals from Mt. Mazama climactic, pre-climactic and postcaldera tephra were determined to identify the likely source(s) of H2O and S. Integration of stable isotopic data with petrologic data from melt inclusions has allowed for estimation of pre-eruptive dissolved volatile concentrations and placed constraints on the extent, conditions and style of degassing.Sulfur isotope analyses of climactic rhyodacitic whole rocks yield δ34S values of 2.8-14.8‰ with corresponding matrix glass values of 2.4-13.2‰. δ34S tends to increase with stratigraphic height through climactic eruptive units, consistent with open-system degassing. Dissolved sulfur concentrations in melt inclusions (MIs) from pre-climactic and climactic rhyodacitic pumices varies from 80 to 330 ppm, with highest concentrations in inclusions with 4.8-5.2 wt% H2O (by FTIR). Up to 50% of the initial S may have been lost through pre-eruptive degassing at depths of 4-5 km. Ion microprobe analyses of pyrrhotite in climactic rhyodacitic tephra and andesitic scoria indicate a range in δ34S from −0.4‰ to 5.8‰ and from −0.1‰ to 3.5‰, respectively. Initial δ34S values of rhyodacitic and andesitic magmas were likely near the mantle value of 0‰. Hydrogen isotope (δD) and total H2O analyses of rhyodacitic obsidian (and vitrophyre) from the climactic fall deposit yielded values οf −103 to −53‰ and 0.23-1.74 wt%, respectively. Values of δD and wt% H2O of obsidian decrease towards the top of the fall deposit. Samples with depleted δD, and mantle δ18O values, have elevated δ34S values consistent with open-system degassing. These results imply that more mantle-derived sulfur is degassed to the Earth’s atmosphere/hydrosphere through convergent margin volcanism than previously attributed. Magmatic degassing can modify initial isotopic compositions of sulfur by >14‰ (to δ34S values of 14‰ or more here) and hydrogen isotopic compositions by 90‰ (to δD values of −127‰ in this case).  相似文献   

16.
We measured Ca stable isotope ratios (δ44/40Ca) in an ancient (2 My), hyperarid soil where the primary source of mobile Ca is atmospheric deposition. Most of the Ca in the upper meter of this soil (3.5 kmol m−2) is present as sulfates (2.5 kmol m−2), and to a lesser extent carbonates (0.4 kmol m−2). In aqueous extracts of variably hydrated calcium sulfate minerals, δ44/40CaE values (vs. bulk Earth) increase with depth (1.4 m) from a minimum of −1.91‰ to a maximum of +0.59‰. The trend in carbonate-δ44/40Ca in the top six horizons resembles that of sulfate-δ44/40Ca, but with values 0.1-0.6‰ higher. The range of observed Ca isotope values in this soil is about half that of δ44/40Ca values observed on Earth. Linear correlation among δ44/40Ca, δ34S and δ18O values indicates either (a) a simultaneous change in atmospheric input values for all three elements over time, or (b) isotopic fractionation of all three elements during downward transport. We present evidence that the latter is the primary cause of the isotopic variation that we observe. Sulfate-δ34S values are positively correlated with sulfate-δ18O values (R2 = 0.78) and negatively correlated with sulfate δ44/40CaE values (R2 = 0.70). If constant fractionation and conservation of mass with downward transport are assumed, these relationships indicate a δ44/40Ca fractionation factor of −0.4‰ in CaSO4. The overall depth trend in Ca isotopes is reproduced by a model of isotopic fractionation during downward Ca transport that considers small and infrequent but regularly recurring rainfall events. Near surface low Ca isotope values are reproduced by a Rayleigh model derived from measured Ca concentrations and the Ca fractionation factor predicted by the relationship with S isotopes. This indicates that the primary mechanism of stable isotope fractionation in CaSO4 is incremental and effectively irreversible removal of an isotopically enriched dissolved phase by downward transport during small rainfall events.  相似文献   

17.
The isotopic compositions of commercially available herbicides were analyzed to determine their respective 15N, 13C and 37Cl signatures for the purposes of developing a discrete tool for tracing and identifying non-point source contaminants in agricultural watersheds. Findings demonstrate that of the agrochemicals evaluated, chlorine stable isotopes signatures range between δ37Cl = −4.55‰ and +3.40‰, whereas most naturally occurring chlorine stable isotopes signatures, including those of road salt, sewage sludge and fertilizers, vary in a narrow range about the Standard Mean Ocean Chloride (SMOC) between −2.00‰ and +1.00‰. Nitrogen stable isotope values varied widely from δ15N = −10.86‰ to +1.44‰ and carbon stable isotope analysis gave an observed range between δ13C = −37.13‰ and −21.35‰ for the entire suite of agro-chemicals analyzed. When nitrogen, carbon and chlorine stable isotope analyses were compared in a cross-correlation analysis, statistically independent isotopic signatures exist suggesting a new potential tracer tool for identifying herbicides in the environment.  相似文献   

18.
Sulfur isotope compositions of pumice and adsorbed volatiles on ash from the first historical eruption of Anatahan volcano (Mariana arc) are presented in order to constrain the sources of sulfur erupted during the period 10-21 May, 2003. The isotopic composition of S extracted from erupted pumice has a narrow range, from δ34SV-CDT +2.6‰ to +3.2‰, while the composition of sulfur adsorbed onto ash has a larger range (+2.8‰ to +5.3‰). Fractionation modeling for closed and open system scenarios suggests that degassing of SO2 raised the δ34SV-CDT value of S dissolved in the melt from an initial composition of between +1.6‰ and +2.6‰ for closed-system degassing, or between −0.5‰ and +1.5‰ for open-system degassing, however closed-system degassing is the preferred model. The calculated values for the initial composition of the magma represent a MORB-like (δ34SV-CDT ∼ 0‰) mantle source with limited contamination by subducted seawater sulfate (δ34SV-CDT +21‰). Modeling also suggests that the δ34SV-CDT value of SO2 gas in closed-system equilibrium with the degassed magma was between +0.9‰ and +2.5‰. The δ34SV-CDT value of sulfate adsorbed onto ash in the eruption plume (+2.8‰ to +5.1‰) is consistent with sulfate formation by oxidation of magmatic SO2 in the eruption column. The sulfur isotope composition of sulfate adsorbed to ash changes from lower δ34S values for ash erupted early in the eruption to higher δ34S values for ash erupted later in the eruption. We interpret the temporal/stratigraphic change in sulfate isotopic composition to primarily reflect a change in the isotopic composition of magmatic SO2 released from the progressively degassing magma and is attributed to the expulsion of an accumulated gas phase at the beginning of the eruption. More efficient oxidation of magmatic SO2 gas to sulfate in the early water-rich eruption plume probably contributed to the change in S isotope compositions observed in the ash leachates.  相似文献   

19.
Ion-microprobe was used to measure Li abundances and isotopic compositions in pyroxenes from three Martian meteorites belonging to the nakhlite family. The profiles performed across augite crystals from Northwest Africa 817 show a large isotopic zoning from crystal cores (δ7Li ∼ 0‰) to rims (δ7Li ∼ +20‰) while Li abundances are almost constant (∼9.2 μg/g). Unlike NWA 817, the pyroxene studied in the Miller Range 03346 nakhlite shows a zoning in Li abundance, with concentrations increasing from ∼2.5 μg/g in the core to ∼9 μg/g in the rim. The augite rim (δ7Li = +7‰) is slightly enriched in 7Li with regard to the core (δ7Li = +4‰), but most of the isotopic variations observed occur at an intermediate position along the profile, where δ7Li falls down to ∼−11‰. In the case of Nakhla, Li concentrations in augite increase from cores (∼3.5 μg/g) to rims (∼6.5 μg/g), while the δ7Li variation is restricted (i.e., between δ7Li = +6.0 and +12.6‰). For the three meteorites the Li abundances were also measured in the groundmass, which was found to be enriched in lithium (∼10 μg/g). Conventional magmatic and post-magmatic processes such as alteration and fractional crystallization, fail to explain the dataset obtained on nakhlites. Degassing processes, which were previously proposed to explain the Li distribution in shergottite crystals, cannot result in the strong decoupling between Li abundances and isotopic composition observed in nakhlites. We suggest that the original magmatic Li distributions (concentrations and isotopic compositions) in nakhlites have been modified by diffusion of Li from the Li-rich groundmass towards the pyroxene crystals during sub-solidus cooling. Diffusion appears to have been efficient for NWA 817 and MIL 03346 but, apparently, did not produce a significant migration of Li in Nakhla, possibly because of the lower abundance of groundmass in the latter. Diffusion induced Li redistributions may also affect terrestrial porphyric rocks but very specific cooling rates are required to quench the diffusion profiles as observed in two of the present nakhlites.  相似文献   

20.
Bottled waters are an increasingly significant product in the human diet. In this work, we present a dataset of stable isotope ratios for bottled waters sampled in Greece. A total of 25 domestic brands of bottled still waters, collected on the Greek market in 2009, were analysed for δ18O and δ2H. The measured stable isotope ratios range from − 9.9‰ to − 6.9‰ for δ18O and from − 67.50‰ to − 46.5‰ for δ2H. Comparison of bottled water isotope ratios with natural spring water isotope ratios demonstrates that on average the isotopic composition of bottled water tends to be similar to the composition of naturally available local water sources, showing that bottled water isotope ratios preserve information about the water sources from which they were derived and suggesting that in many cases bottled water should not be considered as an isotopically distinct component of the human diet. This investigation also helped to determine the natural origin of bottled water, and to indicate differences between the natural and production processes. The production process may influence the isotopic composition of waters. No such modification was observed for sampled waters in this study. The isotopic methods applied can be used for the authentication of bottled waters and for use in the regulatory monitoring of water products.  相似文献   

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