共查询到20条相似文献,搜索用时 31 毫秒
1.
Olaf Nehlich Benjamin T. Fuller Mandy Jay Alice Mora Colin I. Smith Michael P. Richards 《Geochimica et cosmochimica acta》2011,75(17):4963-4977
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
2.
Stephanie A. Ewing Wenbo Yang Greg Michalski Brian W. Stewart Ronald Amundson 《Geochimica et cosmochimica acta》2008,72(4):1096-1110
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
3.
Manuela A. Fehr Per S. Andersson Carl-Magnus Mörth 《Geochimica et cosmochimica acta》2008,72(3):807-826
Holocene sediments from the Gotland Deep basin in the Baltic Sea were investigated for their Fe isotopic composition in order to assess the impact of changes in redox conditions and a transition from freshwater to brackish water on the isotope signature of iron. The sediments display variations in δ56Fe (differences in the 56Fe/54Fe ratio relative to the IRMM-14 standard) from −0.27 ± 0.09‰ to +0.21 ± 0.08‰. Samples deposited in a mainly limnic environment with oxygenated bottom water have a mean δ56Fe of +0.08 ± 0.13‰, which is identical to the mean Fe isotopic composition of igneous rocks and oxic marine sediments. In contrast, sediments that formed in brackish water under periodically euxinic conditions display significantly lighter Fe isotope signatures with a mean δ56Fe of −0.14 ± 0.19‰. Negative correlations of the δ56Fe values with the Fe/Al ratio and S content of the samples suggest that the isotopically light Fe in the periodically euxinic samples is associated with reactive Fe enrichments and sulfides. This is supported by analyses of pyrite separates from this unit that have a mean Fe isotopic composition of −1.06 ± 0.20‰ for δ56Fe. The supply of additional Fe with a light Fe isotopic signature can be explained with the shelf to basin Fe shuttle model. According to the Fe shuttle model, oxides and benthic ferrous Fe that is derived from dissimilatory iron reduction from shelves is transported and accumulated in euxinic basins. The data furthermore suggest that the euxinic water has a negative dissolved δ56Fe value of about −1.4‰ to −0.9‰. If negative Fe isotopic signatures are characteristic for euxinic sediment formation, widespread euxinia in the past might have shifted the Fe isotopic composition of dissolved Fe in the ocean towards more positive δ56Fe values. 相似文献
4.
Magali Bonifacie Vincent Busigny Pascal Philippot Nathalie Jendrzejewski Marc Javoy 《Geochimica et cosmochimica acta》2008,72(1):126-139
Bulk-rock chlorine content and isotopic composition (δ37Cl) were determined in oceanic serpentinites, high-pressure metaperidotites and metasediments in order to gain constraints on the global chlorine cycle associated with hydrothermal alteration and subduction of oceanic lithosphere. The distribution of insoluble chlorine in oceanic serpentinites was also investigated by electron microprobe. The hydrothermally-altered ultramafic samples were dredged along the South West Indian Ridge and the Mid-Atlantic Ridge. The high-pressure metamorphic samples were collected in the Western Alps: metaperidotites in the Erro-Tobbio unit and metasediments in the Schistes Lustrés nappe.Oceanic serpentinites show relatively large variations of bulk-rock Cl contents and δ37Cl values with mean values of 1105 ± 596 ppm and −0.7 ± 0.4‰, respectively (n = 8; 1σ). Serpentines formed after olivine (meshes) show lower Cl content than those formed after orthopyroxene (bastites). In bastites of two different samples, Cl is positively correlated with Al2O3 and negatively correlated with SiO2. These relationships are interpreted as reflecting preferential Cl-incorporation into the bastite structure distorted by Al (substituted for Si) rather than different alteration conditions between olivine and orthopyroxene minerals. High-pressure metaperidotites display relatively homogeneous Cl contents and δ37Cl values with mean values of 467 ± 88 ppm and −1.4 ± 0.1‰, respectively (n = 7; 1σ). A macroscopic high-pressure olivine-bearing vein, formed from partial devolatilization of serpentinites at ∼2.5 GPa and 500-600 °C, shows a Cl content and a δ37Cl value of 603 ppm and −1.6‰, respectively. Metasediments (n = 2) show low whole-rock Cl contents (<15 ppm Cl) that did not allow Cl isotope analyses to be obtained.The range of negative δ37Cl values observed in oceanic serpentinites is likely to result from water-rock interaction with fluids that have negative δ37Cl values. The homogeneity of δ37Cl values from the high-pressure olivine-bearing vein and the metaperidotite samples implies that progressive loss of Cl inherited from oceanic alteration throughout subduction did not significantly fractionate Cl isotopes. Chlorine recycled in subduction zones via metaperidotites should thus show a range of δ37Cl values similar to the range found in oceanic serpentinized peridotites. 相似文献
5.
Weiqiang Li Simon E. Jackson Norman J. Pearson 《Geochimica et cosmochimica acta》2010,74(14):4078-239
Significant, systematic Cu isotopic variations have been found in the Northparkes porphyry Cu-Au deposit, NSW, Australia, which is an orthomagmatic porphyry Cu deposit. Copper isotope ratios have been measured in sulfide minerals (chalcopyrite and bornite) by both solution and laser ablation multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). The results from both methods show a variation in δ65Cu of hypogene sulfide minerals of greater than 1‰ (relative to NIST976). Significantly, the results from four drill holes through two separate ore bodies show strikingly similar patterns of Cu isotope variation. The patterns are characterized by a sharp down-hole decrease from up to 0.8‰ (0.29 ± 0.56‰, 1σ, n = 20) in the low-grade peripheral alteration zones (phyllic-propylitic alteration zone) to a low of ∼−0.4‰ (−0.25 ± 0.36‰, 1σ, n = 30) at the margins of the most mineralized zones (Cu grade >1 wt%). In the high-grade cores of the systems, the compositions are more consistent at around 0.2‰ (0.19 ± 0.14‰, 1σ, n = 40). The Cu isotopic zonation may be explained by isotope fractionation of Cu between vapor, solution and sulfides at high temperature, during boiling and sulfide precipitation processes. Sulfur isotopes also show an isotopically light shell at the margins of the high-grade ore zones, but these are displaced from the low δ65Cu shells, such that there is no correlation between the Cu and S isotope signatures. Fe isotope data do not show any discernable variation along the drill core. This work demonstrates that Cu isotopes show a large response to high-temperature porphyry mineralizing processes, and that they may act as a vector to buried mineralization. 相似文献
6.
The isotopic composition of U in nature is generally assumed to be invariant. Here, we report variations of the 238U/235U isotope ratio in natural samples (basalts, granites, seawater, corals, black shales, suboxic sediments, ferromanganese crusts/nodules and BIFs) of ∼1.3‰, exceeding by far the analytical precision of our method (≈0.06‰, 2SD). U isotopes were analyzed with MC-ICP-MS using a mixed 236U-233U isotopic tracer (double spike) to correct for isotope fractionation during sample purification and instrumental mass bias. The largest isotope variations found in our survey are between oxidized and reduced depositional environments, with seawater and suboxic sediments falling in between. Light U isotope compositions (relative to SRM-950a) were observed for manganese crusts from the Atlantic and Pacific oceans, which display δ238U of −0.54‰ to −0.62‰ and for three of four analyzed Banded Iron Formations, which have δ238U of −0.89‰, −0.72‰ and −0.70‰, respectively. High δ238U values are observed for black shales from the Black Sea (unit-I and unit-II) and three Kupferschiefer samples (Germany), which display δ238U of −0.06‰ to +0.43‰. Also, suboxic sediments have slightly elevated δ238U (−0.41‰ to −0.16‰) compared to seawater, which has δ238U of −0.41 ± 0.03‰. Granites define a range of δ238U between −0.20‰ and −0.46‰, but all analyzed basalts are identical within uncertainties and slightly lighter than seawater (δ238U = −0.29‰).Our findings imply that U isotope fractionation occurs in both oxic (manganese crusts) and suboxic to euxinic environments with opposite directions. In the first case, we hypothesize that this fractionation results from adsorption of U to ferromanganese oxides, as is the case for Mo and possibly Tl isotopes. In the second case, reduction of soluble UVI to insoluble UIV probably results in fractionation toward heavy U isotope compositions relative to seawater. These findings imply that variable ocean redox conditions through geological time should result in variations of the seawater U isotope compositions, which may be recorded in sediments or fossils. Thus, U isotopes might be a promising novel geochemical tracer for paleo-redox conditions and the redox evolution on Earth. The discovery that 238U/235U varies in nature also has implications for the precision and accuracy of U-Pb dating. The total observed range in U isotope compositions would produce variations in 207Pb/206Pb ages of young U-bearing minerals of up to 3 Ma, and up to 2 Ma for minerals that are 3 billion years old. 相似文献
7.
Philip A.E. Pogge von Strandmann Tim Elliott Chris Coath Alistair B. Jeffcoate 《Geochimica et cosmochimica acta》2011,75(18):5247-5268
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
8.
Lithium isotope systematics in a forested granitic catchment (Strengbach, Vosges Mountains, France) 总被引:1,自引:0,他引:1
Emmanuel Lemarchand François Chabaux Marie-Claire Pierret 《Geochimica et cosmochimica acta》2010,74(16):4612-7724
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
9.
Transition metal stable isotope signatures can be useful for tracing both natural and anthropogenic signals in the environment, but only if the mechanisms responsible for fractionation are understood. To investigate isotope fractionations due to electrochemistry (or redox processes), we examine the stable isotope behavior of iron and zinc during the reduction reaction + 2e− = Mmetal as a function of electrochemical driving force, temperature, and time. In all cases light isotopes are preferentially electroplated, following a mass-dependent law. Generally, the extent of fractionation is larger for higher temperatures and lower driving forces, and is roughly insensitive to amount of charge delivered. The maximum fractionations are δ56/54Fe = −4.0‰ and δ66/64Zn = −5.5‰, larger than observed fractionations in the natural environment and larger than those predicted due to changes in speciation. All the observed fractionation trends are interpreted in terms of three distinct processes that occur during an electrochemical reaction: mass transport to the electrode, chemical speciation changes adjacent to the electrode, and electron transfer at the electrode. We show that a large isotope effect adjacent the electrode surface arises from the charge-transfer kinetics, but this effect is attenuated in cases where diffusion of ions to the electrode surface becomes the rate-limiting step. Thus while a general increase in fractionation is observed with increasing temperature, this appears to be a result of thermally enhanced mass transport to the reacting interface rather than an isotope effect associated with the charge-transfer kinetics. This study demonstrates that laboratory experiments can successfully distinguish isotopic signatures arising from mass transport, chemical speciation, and electron transfer. Understanding how these processes fractionate metal isotopes under laboratory conditions is the first step towards discovering what role these processes play in fractionating metal isotopes in natural systems. 相似文献
10.
The effect of early diagenesis on the Fe isotope compositions of porewaters and authigenic minerals in continental margin sediments 总被引:3,自引:0,他引:3
Silke Severmann Clark M. Johnson James McManus 《Geochimica et cosmochimica acta》2006,70(8):2006-2022
Iron isotope compositions in marine pore fluids and sedimentary solid phases were measured at two sites along the California continental margin, where isotope compositions range from δ56Fe = −3.0‰ to +0.4‰. At one site near Monterey Canyon off central California, organic matter oxidation likely proceeds through a number of diagenetic pathways that include significant dissimilatory iron reduction (DIR) and bacterial sulfate reduction, whereas at our other site in the Santa Barbara basin DIR appears to be comparatively small, and production of sulfides (FeS and pyrite) was extensive. The largest range in Fe isotope compositions is observed for Fe(II)aq in porewaters, which generally have the lowest δ56Fe values (minimum: −3.0‰) near the sediment surface, and increase with burial depth. δ56Fe values for FeS inferred from HCl extractions vary between ∼−0.4‰ and +0.4‰, but pyrite is similar at both stations, where an average δ56Fe value of −0.8 ± 0.2‰ was measured. We interpret variations in dissolved Fe isotope compositions to be best explained by open-system behavior that involves extensive recycling of Feflux. This study is the first to examine Fe isotope variations in modern marine sediments, and the results show that Fe isotopes in the various reactive Fe pools undergo isotopic fractionation during early diagenesis. Importantly, processes dominated by sulfide formation produce high-δ56Fe values for porewaters, whereas the opposite occurs when Fe(III)-oxides are present and DIR is a major pathway of organic carbon respiration. Because shelf pore fluids may carry a negative δ56Fe signature it is possible that the Fe isotope composition of ocean water reflects a significant contribution of shelf-derived iron to the open ocean. Such a signature would be an important means for tracing iron sources to the ocean and water mass circulation. 相似文献
11.
We present high-precision measurements of Mg and Fe isotopic compositions of olivine, orthopyroxene (opx), and clinopyroxene (cpx) for 18 lherzolite xenoliths from east central China and provide the first combined Fe and Mg isotopic study of the upper mantle. δ56Fe in olivines varies from 0.18‰ to −0.22‰ with an average of −0.01 ± 0.18‰ (2SD, n = 18), opx from 0.24‰ to −0.22‰ with an average of 0.04 ± 0.20‰, and cpx from 0.24‰ to −0.16‰ with an average of 0.10 ± 0.19‰. δ26Mg of olivines varies from −0.25‰ to −0.42‰ with an average of −0.34 ± 0.10‰ (2SD, n = 18), opx from −0.19‰ to −0.34‰ with an average of −0.25 ± 0.10‰, and cpx from −0.09‰ to −0.43‰ with an average of −0.24 ± 0.18‰. Although current precision (∼±0.06‰ for δ56Fe; ±0.10‰ for δ26Mg, 2SD) limits the ability to analytically distinguish inter-mineral isotopic fractionations, systematic behavior of inter-mineral fractionation for both Fe and Mg is statistically observed: Δ56Feol-cpx = −0.10 ± 0.12‰ (2SD, n = 18); Δ56Feol-opx = −0.05 ± 0.11‰; Δ26Mgol-opx = −0.09 ± 0.12‰; Δ26Mgol-cpx = −0.10 ± 0.15‰. Fe and Mg isotopic composition of bulk rocks were calculated based on the modes of olivine, opx, and cpx. The average δ56Fe of peridotites in this study is 0.01 ± 0.17‰ (2SD, n = 18), similar to the values of chondrites but slightly lower than mid-ocean ridge basalts (MORB) and oceanic island basalts (OIB). The average δ26Mg is −0.30 ± 0.09‰, indistinguishable from chondrites, MORB, and OIB. Our data support the conclusion that the bulk silicate Earth (BSE) has chondritic δ56Fe and δ26Mg.The origin of inter-mineral fractionations of Fe and Mg isotopic ratios remains debated. δ56Fe between the main peridotite minerals shows positive linear correlations with slopes within error of unity, strongly suggesting intra-sample mineral-mineral Fe and Mg isotopic equilibrium. Because inter-mineral isotopic equilibrium should be reached earlier than major element equilibrium via chemical diffusion at mantle temperatures, Fe and Mg isotope ratios of coexisting minerals could be useful tools for justifying mineral thermometry and barometry on the basis of chemical equilibrium between minerals. Although most peridotites in this study exhibit a narrow range in δ56Fe, the larger deviations from average δ56Fe for three samples likely indicate changes due to metasomatic processes. Two samples show heavy δ56Fe relative to the average and they also have high La/Yb and total Fe content, consistent with metasomatic reaction between peridotite and Fe-rich and isotopically heavy melt. The other sample has light δ56Fe and slightly heavy δ26Mg, which may reflect Fe-Mg inter-diffusion between peridotite and percolating melt. 相似文献
12.
Li isotope fractionation in peridotites and mafic melts 总被引:4,自引:0,他引:4
A.B. Jeffcoate T. Elliott S.A. Kasemann K. Cooper 《Geochimica et cosmochimica acta》2007,71(1):202-218
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
13.
Geothermal waters from the Taupo Volcanic Zone,New Zealand: Li,B and Sr isotopes characterization 总被引:2,自引:0,他引:2
Chemical and isotopic data for 23 geothermal water samples collected in New Zealand within the Taupo Volcanic Zone (TVZ) are reported. Major and trace elements including Li, B and Sr and their isotopic compositions (δ7Li, δ11B, 87Sr/86Sr) were determined in high temperature geothermal waters collected from deep boreholes in different geothermal fields (Ohaaki, Wairakei, Mokai, Kawerau and Rotokawa geothermal systems). Lithium concentrations are high (from 4.5 to 19.9 mg/L) and Li isotopic compositions (δ7Li) are homogeneous, ranging between −0.5‰ and +1.4‰. In particular, it is noteworthy that, except for the samples from the Kawerau geothermal field having slightly higher δ7Li values (+1.4%), the other geothermal waters have a near constant δ7Li signature around a mean value of 0‰ ± 0.6 (2σ, n = 21). Boron concentrations are also high and relatively homogeneous for the geothermal samples, falling between 17.5 and 82.1 mg/L. Boron isotopic compositions (δ11B) are all negative, and display a range between −6.7‰ and −1.9‰. These B isotope compositions are in agreement with those of the Ngawha geothermal field in New Zealand. Lithium and B isotope signatures are in a good agreement with a fluid signature mainly derived from water/rock interaction involving magmatic rocks with no evidence of seawater input. On the other hand, Sr concentrations are lower and more heterogeneous and fall between 2 and 165 μg/L. The 87Sr/86Sr ratios range from 0.70549 to 0.70961. These Sr isotope compositions overlap those of the Rotorua geothermal field in New Zealand, confirming that some geothermal waters (with more radiogenic Sr) have interacted with bedrocks from the metasedimentary basement. Each of these isotope systems on their own reveals important information about particular aspects of either water source or water/rock interaction processes, but, considered together, provide a more integrated understanding of the geothermal systems from the TVZ in New Zealand. 相似文献
14.
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
15.
Yan-Jie Tang Hong-Fu Zhang Takuya Moriguti Ji-Feng Ying 《Geochimica et cosmochimica acta》2007,71(17):4327-4341
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
16.
Experimental determination of magnesium isotope fractionation during higher plant growth 总被引:1,自引:0,他引:1
Two higher plant species (rye grass and clover) were cultivated under laboratory conditions on two substrates (solution, phlogopite) in order to constrain the corresponding Mg isotope fractionations during plant growth and Mg uptake. We show that bulk plants are systematically enriched in heavy isotopes relative to their nutrient source. The Δ26Mgplant-source range from 0.72‰ to 0.26‰ for rye grass and from 1.05‰ to 0.41‰ for clover. Plants grown on phlogopite display Mg isotope signatures (relative to the Mg source) ∼0.3‰ lower than hydroponic plants. For a given substrate, rye grass display lower δ26Mg (by ∼0.3‰) relative to clover. Magnesium desorbed from rye grass roots display a δ26Mg greater than the nutrient solution. Adsorption experiments on dead and living rye grass roots also indicate a significant enrichment in heavy isotopes of the Mg adsorbed on the root surface. Our results indicate that the key processes responsible for heavy isotope enrichment in plants are located at the root level. Both species also exhibit an enrichment in light isotopes from roots to shoots (Δ26Mgleaf-root = −0.65‰ and −0.34‰ for rye grass and clover grown on phlogopite respectively, and Δ26Mgleaf-root of −0.06‰ and −0.22‰ for the same species grown hydroponically). This heavy isotope depletion in leaves can be explained by biological processes that affect leaves and roots differently: (1) organo-Mg complex (including chlorophyll) formation, and (2) Mg transport within plant. For both species, a positive correlation between δ26Mg and K/Mg was observed among the various organs. This correlation is consistent with the link between K and Mg internal cycles, as well as with formation of organo-magnesium compounds associated with enrichment in heavy isotopes. Considering our results together with the published range for δ26Mg of natural plants and rivers, we estimate that a significant change in continental vegetation would induce a change of the mean river δ26Mg that is comparable to analytical uncertainties. 相似文献
17.
Charles W. Mandeville James D. Webster Bruce E. Taylor Akira Sasaki Charles R. Bacon 《Geochimica et cosmochimica acta》2009,73(10):2978-3012
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
18.
Wang-Ye Li Fang-Zhen Teng Shan Ke Roberta L. Rudnick Fu-Yuan Wu 《Geochimica et cosmochimica acta》2010,74(23):6867-6884
High-precision Mg isotopic data are reported for ∼100 well-characterized samples (granites, loess, shales and upper crustal composites) that were previously used to estimate the upper continental crust composition. Magnesium isotopic compositions display limited variation in eight I-type granites from southeastern Australia (δ26Mg = −0.25 to −0.15) and in 15 granitoid composites from eastern China (δ26Mg = −0.35 to −0.16) and do not correlate with SiO2 contents, indicating the absence of significant Mg isotope fractionation during differentiation of granitic magma. Similarly, the two S-type granites, which represent the two end-members of the S-type granite spectrum from southeastern Australia, have Mg isotopic composition (δ26Mg = −0.23 and −0.14) within the range of their potential source rocks (δ26Mg = −0.20 and +0.15) and I-type granites, suggesting that Mg isotope fractionation during crustal anatexis is also insignificant. By contrast, δ26Mg varies significantly in 19 A-type granites from northeastern China (−0.28 to +0.34) and may reflect source heterogeneity.Compared to I-type and S-type granites, sedimentary rocks have highly heterogeneous and, in most cases, heavier Mg isotopic compositions, with δ26Mg ranging from −0.32 to +0.05 in nine loess from New Zealand and the USA, from −0.27 to +0.49 in 20 post-Archean Australian shales (PAAS), and from −0.52 to +0.92 in 20 sedimentary composites from eastern China. With increasing chemical weathering, as measured by the chemical index of alternation (CIA), δ26Mg values show a larger dispersion in shales than loess. Furthermore, δ26Mg correlates negatively with δ7Li in loess. These characteristics suggest that chemical weathering significantly fractionates Mg isotopes and plays an important role in producing the highly variable Mg isotopic composition of sedimentary rocks.Based on the estimated proportions of major rock units within the upper continental crust and their average MgO contents, a weighted average δ26Mg value of −0.22 is derived for the average upper continental crust. Our studies indicate that Mg isotopic composition of the upper crust is, on average, mantle-like but highly heterogeneous, with δ26Mg ranging from −0.52 to +0.92. Such large isotopic variation mainly results from chemical weathering, during which light Mg isotopes are lost to the hydrosphere, leaving weathered products (e.g., sedimentary rocks) with heavy Mg isotopes. 相似文献
19.
Romain Millot Emmanuelle Petelet-Giraud Catherine Guerrot Philippe Négrel 《Applied Geochemistry》2010
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
20.
Isotopic variations of dissolved copper and zinc in stream waters affected by historical mining 总被引:4,自引:0,他引:4
Zinc and Cu play important roles in the biogeochemistry of natural systems, and it is likely that these interactions result in mass-dependent fractionations of their stable isotopes. In this study, we examine the relative abundances of dissolved Zn and Cu isotopes in a variety of stream waters draining six historical mining districts located in the United States and Europe. Our goals were to (1) determine whether streams from different geologic settings have unique or similar Zn and Cu isotopic signatures and (2) to determine whether Zn and Cu isotopic signatures change in response to changes in dissolved metal concentrations over well-defined diel (24-h) cycles.Average δ66Zn and δ65Cu values for streams varied from +0.02‰ to +0.46‰ and −0.7‰ to +1.4‰, respectively, demonstrating that Zn and Cu isotopes are heterogeneous among the measured streams. Zinc or Cu isotopic changes were not detected within the resolution of our measurements over diel cycles for most streams. However, diel changes in Zn isotopes were recorded in one stream where the fluctuations of dissolved Zn were the largest. We calculate an apparent separation factor of ∼0.3‰ (66/64Zn) between the dissolved and solid Zn reservoirs in this stream with the solid taking up the lighter Zn isotope. The preference of the lighter isotope in the solid reservoir may reflect metabolic uptake of Zn by microorganisms. Additional field investigations must evaluate the contributions of soils, rocks, minerals, and anthropogenic components to Cu and Zn isotopic fluxes in natural waters. Moreover, rigorous experimental work is necessary to quantify fractionation factors for the biogeochemical reactions that are likely to impact Cu and Zn isotopes in hydrologic systems. This initial investigation of Cu and Zn isotopes in stream waters suggests that these isotopes may be powerful tools for probing biogeochemical processes in surface waters on a variety of temporal and spatial scales. 相似文献