玄武岩标准样品铁铜锌同位素组成

报道了三种玄武岩标准样品(BCR-2、BIR-1a和GBW 07105)的铁铜锌同位素数据。实验使用HNO3-HF混合酸消解玄武岩标准样品;AGMP-1阴离子交换树脂分离提纯样品中的铜铁锌,利用多接收等离子体质谱仪(MC-ICPMS)测定铁铜锌同位素比值,分析过程中使用样品-标准-样品交叉法校正仪器的质量分馏。实验得到BCR-2、BIR-1a和GBW 07105标准样品的高精度铁铜锌同位素组成(95%置信水平的不确定度)分别为:δ56FeBCR-2-IRMM014=0.070‰±0.018‰(2SD),δ65 CuBCR-2-SRM976=0.16‰±0.04‰(2SD),δ66 ZnBCR-2-IRMM3702=-0.072‰±0.020‰(2SD);δ56 FeBIR-1a-IRMM014=0.044‰±0.026‰(2SD),δ65CuBIR-1a-SRM976=0.027‰±0.019‰(2SD),δ66 ZnBIR-1a-IRMM3702=0.085‰±0.032‰(2SD);δ56FeGBW 07105-IRMM014=0.126‰±0.039‰(2SD),δ65 CuGBW 07105-SRM976=0.12‰±0.01‰(2SD),δ66ZnGBW 07105-IRMM3702=0.22‰±0.03‰(2SD)。这些数据在误差(不确定度)范围内与国际上已发表的数据是一致的。三个玄武岩标准样品的铁铜锌同位素组成数据的发表为铁铜锌同位素研究提供了统一的标准,使地质样品的铁铜锌同位素数据的质量监控成为可能。     

Isotopic fractionation of Cu in tektites

Tektites are terrestrial natural glasses of up to a few centimeters in size that were produced during hypervelocity impacts on the Earth’s surface. It is well established that the chemical and isotopic composition of tektites is generally identical to that of the upper terrestrial continental crust. Tektites typically have very low water content, which has generally been explained by volatilization at high temperature; however, the exact mechanism is still debated. Because volatilization can fractionate isotopes, comparing the isotopic composition of volatile elements in tektites with those of their source rocks may help to understand the physical conditions during tektite formation.Interestingly, volatile chalcophile elements (e.g., Cd and Zn) seem to be the only elements for which isotopic fractionation is known so far in tektites. Here, we extend this study to Cu, another volatile chalcophile element. We have measured the Cu isotopic composition for 20 tektite samples from the four known different strewn fields. All of the tektites (except the Muong Nong-types) are enriched in the heavy isotopes of Cu (1.98 < δ⁶⁵Cu < 6.99) in comparison to the terrestrial crust (δ⁶⁵Cu ≈ 0) with no clear distinction between the different groups. The Muong Nong-type tektites and a Libyan Desert Glass sample are not fractionated (δ⁶⁵Cu ≈ 0) in comparison to the terrestrial crust. To refine the Cu isotopic composition of the terrestrial crust, we also present data for three geological reference materials (δ⁶⁵Cu ≈ 0).An increase of δ⁶⁵Cu with decreasing Cu abundance probably reflects that the isotopic fractionation occurred by evaporation during heating. A simple Rayleigh distillation cannot explain the Cu isotopic data and we suggest that the isotopic fractionation is governed by a diffusion-limited regime. Copper is isotopically more fractionated than the more volatile element Zn (δ^66/64Zn up to 2.49‰). This difference of behavior between Cu and Zn is predicted in a diffusion-limited regime, where the magnitude of the isotopic fractionation is regulated by the competition between the evaporative flux and the diffusive flux at the diffusion boundary layer. Due to the difference of ionic charge in silicates (Zn²⁺ vs. Cu⁺), Cu has a diffusion coefficient that is larger than that of Zn by at least two orders of magnitude. Therefore, the larger isotopic fractionation in Cu than in Zn in tektites is due to the significant difference in their respective chemical diffusivity.     

Fe isotope systematics of coexisting amphibole and pyroxene in the alkaline igneous rock suite of the Ilímaussaq Complex,South Greenland

The Ilímaussaq intrusion, South Greenland, provides an exceptional test case for investigating the changes of stable Fe isotope fractionation of solidus phases with changes in the Fe³⁺/∑Fe ratio of an evolving melt. The intrusion comprises a sequence of four melt batches that were fed from the same parental alkali basaltic magma. Differentiation produced cumulate rocks that range from augite syenite (phase I) over peralkaline granite (phase II) to agpaitic syenites (phases IIIa and IIIb). Fe³⁺/∑Fe ratios in amphiboles increase substantially from phase I to phase II and III rocks and mark a major change in the parental magma composition from augite syenites to peralkaline granites and agpaitic syenites. Before this transition, olivine, clinopyroxene, and amphibole in augite syenite, the most primitive rock type in the Ilímaussaq Complex, have a uniform Fe isotope composition that is identical to that of the bulk of igneous crustal rocks and approximated by the average isotopic composition of basalts (δ^56/54Fe_IRMM-014 = 0.072 ± 0.046‰). After the transition, amphiboles in the peralkaline granites and agpaitic syenites yield significantly heavier Fe isotope compositions with δ^56/54Fe_IRMM-014 values ranging from 0.123 to 0.237‰. Contamination of the Ilímaussaq magma by ongoing crustal assimilation as cause for this increase can be excluded on the grounds of Nd isotope data. Large-scale metasomatic overprint with an external fluid can also be dismissed based on amphibole O and Li isotope systematics. Rather, the increase towards heavy Fe isotope compositions most likely reflects the change in chemical compositions of amphiboles (calcic in augite syenite to sodic in the agpaitic syenites) and their Fe³⁺/ΣFe ratios that mirror changes in the chemical composition of the melt and its oxygen fugacity. A sensitive adjustment of equilibrium Fe isotope fractionation factors to amphibole ferric/ferrous ratios is also supported by beta-factors calculated from Mössbauer spetroscopy data. Comparison of the measured isotope fractionation between clinopyroxene and amphibole with that predicted from Mössbauer data reveal Fe isotope systematics close to equilibrium in augite syenites but Fe isotopic disequilibrium between these two phases in phase IIIa agpaitic syenites. These results are in agreement with O and Li isotope systematics. While amphiboles in all Ilímaussaq lithologies crystallized at temperatures between 650 and 850 °C, textural evidence reveals later clinopyroxene crystallization at temperatures as low as 300–400 °C. Therefore, isotopic equilibrium at crystallization conditions between these two phases can not be expected, but importantly, subsolidus reequilibration can also be dismissed.     

Use of isotope ratios to assess sources of Pb and Zn dispersed in the environment during mining and ore processing within the Orlovka–Spokoinoe mining site (Russia)

Element concentrations, element ratios and Pb and Zn isotope data are reported for different geologic samples (barren and ore-bearing granites and host rocks), technogenic products (ore concentrates and tailings) and biologic samples (lichens and birch leaves) from the Orlovka–Spokoinoe mining district, Eastern Transbaikalia, Russia, with the aim to trace the sources of Pb and Zn at a local level within the mining site. Lichens and birch leaves were used as receptors of contamination within the mining site. Pb/Zr and Zn/Zr values indicated Pb and Zn enrichment relative to host rocks. Zn isotope data of 15 geologic and 11 lichen samples showed different Zn isotopic signatures with the total range for the geologic suite of −0.4‰ to +1.2‰ and for lichens of +0.4‰ to +1.4‰ in δ⁶⁶Zn relative to Lyon JMC Zn standard. The source of isotopically heavy Zn within the Orlovka–Spokoinoe mining site could be potentially associated with long-range atmospheric aerosols that also contributed Pb to the studied mining site. Our results demonstrated that Zn isotopes might be used as new tools for Zn source assessment.     

Development of Cu and Zn Isotope MC-ICP-MS Measurements: Application to Suspended Particulate Matter and Sediments from the Scheldt Estuary

The present study evaluates several critical issues related to precision and accuracy of Cu and Zn isotopic measurements with application to estuarine particulate materials. Calibration of reference materials (such as the IRMM 3702 Zn) against the JMC Zn and NIST Cu reference materials were performed in wet and/or dry plasma modes (Aridus I and DSN‐100) on a Nu Plasma MC‐ICP‐MS. Different mass bias correction methods were compared. More than 100 analyses of certified reference materials suggested that the sample‐calibrator bracketing correction and the empirical external normalisation methods provide the most reliable corrections, with long term external precisions of 0.06 and 0.07‰ (2SD), respectively. Investigation of the effect of variable analyte to spike concentration ratios on Zn and Cu isotopic determinations indicated that the accuracy of Cu measurements in dry plasma is very sensitive to the relative Cu and Zn concentrations, with deviations of δ⁶⁵Cu from ?0.4‰ (Cu/Zn = 4) to +0.4‰ (Cu/Zn = 0.2). A quantitative assessment (with instrumental mass bias corrections) of spectral and non‐spectral interferences (Ti, Cr, Co, Fe, Ca, Mg, Na) was performed. Titanium and Cr were the most severe interfering constituents, contributing to inaccuracies of ?5.1‰ and +0.60‰ on δ^68/64Zn, respectively (for 500 μg l^?1 Cu and Zn standard solutions spiked with 1000 μg l^?1 of Ti or Cr). Preliminary isotopic results were obtained on contrasting sediment matrices from the Scheldt estuary. Significant isotopic fractionation of zinc (from 0.21‰ to 1.13‰ for δ⁶⁶Zn) and copper (from ?0.38‰ to 0.23‰ for δ⁶⁵Cu), suggest a control by physical mixing of continental and marine water masses, characterized by distinct Cu and Zn isotopic signatures. These results provide a stepping‐stone to further evaluate the use of Cu and Zn isotopes as biogeochemical tracers in estuarine environments.     

Lithium in tektites and impact glasses: Implications for sources, histories and large impacts

Lithium (Li) abundances and isotope compositions were determined in a representative suite of tektites (moldavites, Muong Nong-type tektites and an australite, Ivory Coast tektites and bediasites), impact-related glasses (Libyan Desert Glass, zhamanshinites and irghizites), a glass fragment embedded in the suevite from the Ries impact crater and sedimentary materials in order to test a possible susceptibility of Li to fractionation during hypervelocity impact events and to de-convolve links to their potential parental sources. The overall data show a large spread in Li abundance (4.7-58 ppm Li) and δ⁷Li values (−3.2‰ to 26.0‰) but individual groups of tektites and impact glasses have distinctive Li compositions.Most importantly, any significant high-temperature Li isotope fractionation can be excluded by comparing sedimentary lithologies from central Europe with moldavites. Instead, we suggest that Li isotope compositions in tektites and impact-related glasses are probably diagnostic of the precursor materials and their pre-impact geological histories. The Muong Nong-type tektites and australite specimen are identical in terms of Li concentrations and δ⁷Li and we tentatively endorse their common origin in a single impact event. Evidence for low-temperature Rayleigh fractionation, which must have operated prior to impact-induced melting and solidification, is provided for a subset of Muong Nong-type tektites. Although Li isotope variations in most tektites are broadly similar to those of the upper continental crust, Libyan Desert Glass carries high δ⁷Li ?24.7‰, which appears to mirror the previous fluvial history of parental material that was perhaps deposited in lacustrine environment or coastal seawater. Lithium isotopes in impact-related glasses from the Zhamanshin crater define a group distinct from all other samples and point to melting of chemically less evolved mafic lithologies, which is also consistent with their major and trace element patterns.Extreme shock pressures and the related extreme post-shock temperatures alone appear not to have any effect on the Li isotope systematics; therefore, useful information on parental lithologies and magmatic processes may be retrieved from analyses of Martian and lunar meteorites. Moreover, lack of significant Li depletion in tektites provides further constraints on the loss of moderately volatile elements during the Moon-forming impact.     

Contrasting Carbon and Oxygen Isotopic Evolution in Metacarbonates from the Kerala Khondalite Belt,Southern India

The Kerala Khondalite belt is a Proterozoic metasupracrustal granulite facies terrain in southern India comprising garnet-biotite gneiss, garnet-sillimanite gneiss and orthopyroxene granulites as major rock types. Calc-silicate rocks and marbles, occurring as minor lithologies in the Kerala Khondalite Belt, show different mineral assemblages and reaction histories of which indicate a metamorphic P-T-fluid history dominated by internal fluid buffering during the peak metamorphism, followed by external fluid influx during decompression. The carbon and oxygen isotopic compositions of calcite from three representative metacarbonate localities show contrasting evolutionary trends. The Ambasamudram marbles exhibit carbon and oxygen isotope ratios (δ¹³C ∼ 0‰ and δ¹⁸O ∼ 20‰) typical of middle to late Proterozoic marine carbonate sediments with minor variation ascribed to the isotopic exchange due to the devolatilization reactions. The δ¹³C and δ¹⁸O values of ∼ −9‰ and 11‰, respectively, for calcite from calc-silicate rocks at Nuliyam are considerably low and heterogeneous. The wollastonite formation here, possibly corresponds to an earlier event of fluid infiltration during prograde to peak metamorphism, which resulted in decarbonation and isotope resetting. Further, petrologic evidence supports a model of late carbonic fluid infiltration that has partially affected the calc-silicate rocks, with subsequent isotope resetting, more towards the contact between calc-silicate rock and charnockite. At Korani, only oxygen isotopes have been significantly lowered (δ¹⁸O ∼ 13‰) and the process involved might be a combination of metamorphic devolatilization accompanied by an aqueous fluid influx, supported by petrologic evidence. The stable isotope signatures obtained from the individual localities, thus indicate heterogeneous patterns of fluid evolution history within the same crustal segment.     

Spatially controlled Fe and Si isotope variations: an alternative view on the formation of the Torres del Paine pluton

We present new Fe and Si isotope ratio data for the Torres del Paine igneous complex in southern Chile. The multi-composition pluton consists of an approximately 1 km vertical exposure of homogenous granite overlying a contemporaneous 250-m-thick mafic gabbro suite. This first-of-its-kind spatially dependent Fe and Si isotope investigation of a convergent margin-related pluton aims to understand the nature of granite and silicic igneous rock formation. Results collected by MC-ICP-MS show a trend of increasing δ⁵⁶Fe and δ³⁰Si with increasing silica content as well as a systematic increase in δ⁵⁶Fe away from the mafic base of the pluton. The marginal Torres del Paine granites have heavier Fe isotope signatures (δ⁵⁶Fe = +0.25 ± 0.02 2se) compared to granites found in the interior pluton (δ⁵⁶Fe = +0.17 ± 0.02 2se). Cerro Toro country rock values are isotopically light in both Fe and Si isotopic systems (δ⁵⁶Fe = +0.05 ± 0.02 ‰; δ³⁰Si = ?0.38 ± 0.07 ‰). The variations in the Fe and Si isotopic data cannot be accounted for by local assimilation of the wall rocks, in situ fractional crystallization, late-stage fluid exsolution or some combination of these processes. Instead, we conclude that thermal diffusion or source magma variation is the most likely process producing Fe isotope ratio variations in the Torres del Paine pluton.     

Application of iron and zinc isotopes to track the sources and mechanisms of metal loading in a mountain watershed

Here the hydrogeochemical constraints of a tracer dilution study are combined with Fe and Zn isotopic measurements to pinpoint metal loading sources and attenuation mechanisms in an alpine watershed impacted by acid mine drainage. In the tested mountain catchment, δ⁵⁶Fe and δ⁶⁶Zn isotopic signatures of filtered stream water samples varied by ∼3.5‰ and 0.4‰, respectively. The inherent differences in the aqueous geochemistry of Fe and Zn provided complimentary isotopic information. For example, variations in δ⁵⁶Fe were linked to redox and precipitation reactions occurring in the stream, while changes in δ⁶⁶Zn were indicative of conservative mixing of different Zn sources. Fen environments contributed distinctively light dissolved Fe (<−2.0‰) and isotopically heavy suspended Fe precipitates to the watershed, while Zn from the fen was isotopically heavy (>+0.4‰). Acidic drainage from mine wastes contributed heavier dissolved Fe (∼+0.5‰) and lighter Zn (∼+0.2‰) isotopes relative to the fen. Upwelling of Fe-rich groundwater near the mouth of the catchment was the major source of Fe (δ⁵⁶Fe ∼ 0‰) leaving the watershed in surface flow, while runoff from mining wastes was the major source of Zn. The results suggest that given a strong framework for interpretation, Fe and Zn isotopes are useful tools for identifying and tracking metal sources and attenuation mechanisms in mountain watersheds.     

Origin of fluids in iron oxide–copper–gold deposits: constraints from δ 37Cl, 87Sr/86Sri and Cl/Br

The origin of the hypersaline fluids (magmatic or basinal brine?), associated with iron oxide (Cu–U–Au–REE) deposits, is controversial. We report the first chlorine and strontium isotope data combined with Cl/Br ratios of fluid inclusions from selected iron oxide–copper–gold (IOCG) deposits (Candelaria, Raúl–Condestable, Sossego), a deposit considered to represent a magmatic end member of the IOCG class of deposit (Gameleira), and a magnetite–apatite deposit (El Romeral) from South America. Our data indicate mixing of a high δ ³⁷Cl magmatic fluid with near 0‰ δ ³⁷Cl basinal brines in the Candelaria, Raúl–Condestable, and Sossego IOCG deposits and leaching of a few weight percent of evaporites by magmatic-hydrothermal (?) fluids at Gameleira and El Romeral. The Sr isotopic composition of the inclusion fluids of Candelaria, Raúl–Condestable, and El Romeral confirms the presence of a non-magmatic fluid component in these deposits. The heavy chlorine isotope signatures of fluids from the IOCG deposits (Candelaria, Raúl–Condestable, Sossego), reflecting the magmatic-hydrothermal component of these fluids, contrast with the near 0‰ δ ³⁷Cl values of porphyry copper fluids known from the literature. The heavy chlorine isotope compositions of fluids of the investigated IOCG deposits may indicate a prevailing mantle Cl component in contrast to porphyry copper fluids, an argument also supported by Os isotopes, or could result from differential Cl isotope fractionation processes (e.g. phase separation) in fluids of IOCG and porphyry Cu deposits.     

The Cu isotopic signature of granites from the Lachlan Fold Belt,SE Australia

This contribution reports our preliminary work to determine Cu isotope ratios for various granite rocks and examine the Cu isotope systematics within granite suites. A chemical procedure, modified from Maréchal [Maréchal, C.N., Télouk, P. and Albarède, F., 1999. Precise analysis of copper and zinc isotopic compositions by plasma-source mass spectrometry. Chemical Geology, 156(1–4): 251–273.], was used to separate Cu from rock matrix. Quantitative recovery (100.6 ± 1.6%), with a low total procedural blank (2.65 ± 0.66 ng) for Cu, has been achieved, allowing Cu isotopic measurements on samples with as little as 10 ppm Cu. The Cu isotope ratios (δ⁶⁵Cu relative to NIST SRM 976) of 32 rock samples, ranging from mafic to felsic compositions, from 3 batholiths (2 I-type, 1 S-type) from the Lachlan Fold Belt in southeastern Australia, vary from ? 0.46‰ to 1.51‰. Most of them cluster around zero, with mean values for the I-type and S-type granites of 0.03 ± 0.15‰ and ? 0.03 ± 0.42‰ (2 sigma) respectively. These data, together with Cu isotope ratios of two loess samples, provide preliminary evidence that the baseline Cu isotopic composition of the crystalline part of upper continental crust is close to zero. The tight clustering of Cu isotope ratios of rocks from the I-type suites suggests that high-temperature magmatic processes do not produce significant Cu isotope fractionation. However, two granites with abnormally heavy Cu isotope signatures (up to 1.51‰) appears to be the result of localized hydrothermal alteration. Measurable variation in Cu isotopic composition of the S-type granite may reflect isotopic heterogeneity in the sedimentary source region as a result of redox processes or may be due to hydrothermal overprinting. Thus, Cu isotope geochemistry may be a useful tracer for studying hydrothermal alteration and source heterogeneity of granitic rocks.     

Redox history of the Three Gorges region during the Ediacaran and Early Cambrian as indicated by the Fe isotope

The Ediacaran-Cambrian transition is characterized by numerous events such as the emergence of large multi-cellular metazoans and surface environmental disturbances.Based on geological evidence,it has been proposed that this transition coincided with the increase in the atmospheric oxygen level that was key to the evolution of life.Even though ancient redox conditions can be inferred from the composition of sedimentary iron mineral species,this method is not necessarily applicable to all rocks.In the Earth system,the cycling of iron is of considerable interest owing to its sensitivity to redox conditions.Information regarding the paleo-oceanic iron cycle is revealed in the iron isotopic composition of ironbearing minerals.Unfortunately,only limited iron isotopic data exists for Ediacaran-to Cambrianperiod oceans.To circumvent this deficiency,we drilled a fossiliferous Ediacaran to Early Cambrian sedimentary succession in the Three Gorges region,South China.We analyzed the iron isotope ratios(δ~(56/54)Fe)of pyrite grains in the drill cores using laser ablation multi collector inductively coupled plasma mass spectrometry.The results demonstrate large variations inδ~(56/54)Fe,from-1.6 to 1.6‰,and positive iron isotope ratios are observed in many successions.The presence of positiveδ~(56/54)Fe in pyrite indicates that the ferrous iron in the seawater was partially oxidized,suggesting that seawater at Three Gorges was ferruginous during the Ediacaran and Early Cambrian periods.However,aggregated pyrite grains in organic carbon-rich black shales at Member 4 of the Doushantuo Formation and the base of the Shuijingtuo Formation yield near-zeroδ~(56/54)Fe values;this suggests that the ocean was transiently dominated by sulfidic conditions during these periods.Notably negativeδ~(56/54)Fe values,lower than-1‰,can be interpreted as a signature of DIR.The DIR also might contribute in part to the re-mineralization of organic matter during the largest negative carbon isotope anomaly in the Ediacaran.     

Variations in the isotopic composition of molybdenum in freshwater lake systems

Variations in molybdenum isotopic composition, spanning the range of ∼ 2.3‰ in the terms of ⁹⁷Mo/⁹⁵Mo ratio, have been measured in sediment cores from three lakes in northern Sweden and north-western Russia. These variations have been produced by both isotopically variable input of Mo into the lakes due to Mo isotopic heterogeneity of bedrock in the drainage basins and fractionation in the lake systems due to temporal variations in limnological conditions. Mo isotope abundances of bedrock in the lake drainage basins have been documented by analysis of Mo isotope ratios of a suite of molybdenite occurrences collected in the studied area and of detrital fractions of the lake sediment cores. The median δ⁹⁷Mo value of the investigated molybdenites is 0.26‰ with standard deviation of 0.43‰ (n = 19), whereas the median δ⁹⁷Mo value of detrital sediment fractions from two lakes is − 0.40‰ with standard deviation of 0.36‰ (n = 15).The isotopic composition of Mo in the sediment cores has been found to be dependent on redox conditions of the water columns and the dominant type of scavenging phases. Hydrous Fe oxides have been shown to be an efficient scavenger of Mo from porewater under oxic conditions. Oxidative precipitation of Fe(II) in the sediments resulted in co-precipitation of Mo and significant authigenic enrichment at the redox boundary. In spite of a pronounced increase in Mo concentration associated with Fe oxides at the redox boundary the isotopic composition of Mo in this zone varies insignificantly, suggesting little or no isotope fractionation during scavenging of Mo by hydrous Fe oxides. In a lake with anoxic bottom water a chironomid-inferred reconstruction of O₂ conditions in the bottom water through the Holocene indicates that increased O₂ concentrations are generally associated with low δ⁹⁷Mo/⁹⁵Mo values of the sediments, whereas lowered O₂ contents of the bottom water are accompanied by relatively high δ⁹⁷Mo/⁹⁵Mo values, thus confirming the potential of Mo isotope data to be a proxy for redox conditions of overlying waters. However, it is pointed out that other processes including input of isotopically heterogeneous Mo and Mn cycling in the redox-stratified water column can be a primary cause of variations in Mo isotopic compositions of lake sediments.     

Crassulacean acid metabolism influences D/H ratio of leaf wax in succulent plants

This study sought to characterize hydrogen isotopic fractionation during biosynthesis of leaf wax n-alkanes in succulent plants capable of crassulacean acid metabolism (CAM). The metabolic and physiological features of CAM represent crucial strategies for survival in hot and dry climates and have been hypothesized to impact hydrogen isotope fractionation. We measured the stable carbon and hydrogen isotopic compositions (δ¹³C and δD, respectively) of individual n-alkanes in 20 species of succulent plants from a global collection of the Huntington Botanical Gardens, San Marino, California. Greenhouse conditions and irrigation with water of constant δD value enabled determination of interspecies differences in net D/H fractionation between source water and leaf wax products. Carbon isotope ratios provide constraints on the extent of CAM vs. C₃ photosynthesis and indicate a wide range of CAM use, with δ¹³C values ranging from −33.01‰ to −18.54‰ (C₂₇–C₃₃ n-alkanes) and −26.66‰ to −17.64‰ (bulk tissue). Despite the controlled growth environment, we observed ca. 90‰ interspecies range in δD values from −193‰ to −107‰. A positive correlation between δ¹³C_bulk and δD_C31 values with R² = 0.60 (δ¹³C_C31 and δD_C31 values with R² = 0.41) implicates a metabolic isotope effect as the dominant cause of interspecies variation in the hydrogen isotopic composition of leaf wax n-alkanes in CAM-intermediate plants.     

Post-Chicxulub depositional and diagenetic history of the northwestern Yucatan Peninsula,Mexico

The Chicxulub Sedimentary Basin of the northwestern Yucatan Peninsula, Mexico, which was formed because of the largest identified Phanerozoic bolide impact on Earth, became a site of deposition of dominantly marine carbonate sediments during most of the Cenozoic Era. This is a study of the filling and diagenetic history of this basin and surrounding areas. The study makes use of lithologic, biostratigraphic, petrographic, and geochemical data obtained on core samples from boreholes drilled throughout the northwestern Yucatan Peninsula.The core sample data indicate that: 1) The Chicxulub Sedimentary Basin concentrated the deposition of pelagic and outer-platform sediments during the Paleocene and Eocene, and, in places, during the Early Oligocene, as well, and filled during the Middle Miocene, 2) deeper-water limestone also is present within the Paleocene and Lower Eocene of the proposed Santa Elena Depression, which is located immediately south of the Basin, 3) shallow-water deposits are relatively more abundant outside the Basin and Depression than inside, 4) the autigenic and allogenic silicates from the Paleogene formations are the most abundant inside the Depression, 5) sediment deposition and diagenesis within the Basin also were controlled by impact crater topography, 6) the abundance of the possible features of subaerial exposure increases upward and outward from the center of the Basin, and 7) the formation of replacive low-magnesium calcite and dolomite, dedolomitization, dissolution, and precipitation of vug-filling calcite and dolomite cement have been more common outside the Basin than inside.δ¹⁸O in whole-rock (excluding vug-filling) calcite from core samples ranges from − 7.14‰ to + 0.85‰ PDB. δ¹³C varies from − 6.92‰ to + 3.30‰ PDB. Both stable isotopes correlate inversely with the abundance of subaerial exposure features indicating that freshwater diagenesis has been extensive especially outside and at the edge of the Chicxulub Sedimentary Basin.δ¹⁸O and δ¹³C in whole-rock (excluding vug-filling) dolomite ranges from − 5.54‰ to + 0.87‰ PDB and − 4.63‰ to + 3.38‰ PDB, respectively. Most dolomite samples have negative δ¹⁸O and positive δ¹³C suggesting that replacive dolomitization involved the presence of a fluid dominated by freshwater and/or an anomalously high geothermal gradient.Most dolomite XRD-determined mole percent CaCO₃ varies between 51 and 56. Replacive dolomite is larger, more euhedral, and less stoichiometric inside the Chicxulub Sedimentary Basin than outside.     

Anatomy of a large Ag–Pb–Zn deposit in the Great Xing'an Range,northeast China: metallogeny associated with Early Cretaceous magmatism

The Bairendaba vein-type Ag–Pb–Zn deposit, hosted in a Carboniferous quartz diorite, is one of the largest polymetallic deposits in the southern Great Xing'an Range. Reserves exceeding 8000 tonnes of Ag and 3 million tonnes of Pb?+?Zn with grades of 30 g/t and 4.5% have been estimated. We identify three distinct mineralization stages in this deposit: a barren pre-ore stage (stage 1), a main-ore stage with economic Ag–Pb–Zn mineralization (stage 2), and a post-ore stage with barren mineralization (stage 3). Stage 1 is characterized by abundant arsenopyrite?+?quartz and minor pyrite. Stage 2 is represented by abundant Fe–Zn–Pb–Ag sulphides and is further subdivided into three substages comprising the calcite–polymetallic sulphide stage (substage 1), the fluorite–polymetallic sulphide stage (substage 2), and the quartz–polymetallic sulphide stage (substage 3). Stage 3 involves an assemblage dominated by calcite with variable pyrite, galena, quartz, fluorite, illite, and chlorite. Fluid inclusion analysis and mineral thermometry indicate that the three stages of mineralization were formed at temperatures of 320–350°C, 200–340°C, and 180–240°C, respectively. Stage 1 early mineralization is characterized by low-salinity fluids (5.86–8.81 wt.% NaCl equiv.) with an isotopic signature of magmatic origin (δ¹⁸O_fluid = 10.45–10.65‰). The main ore minerals of stage 2 precipitated from aqueous–carbonic fluids (4.34–8.81 wt.% NaCl equiv.). The calculated and measured oxygen and hydrogen isotopic compositions of the ore-forming aqueous fluids (δ¹⁸O_fluid = 3.31–8.59‰, δD_fluid?=??132.00‰ to??104.00‰) indicate that they were derived from a magmatic source and mixed with meteoric water. Measured and calculated sulphur isotope compositions of hydrothermal fluids (δ³⁴S_∑S?=??1.2–3.8‰) indicate that the ore sulphur was derived mainly from a magmatic source. The calculated carbon isotope compositions of hydrothermal fluids (δ¹³C_fluid?=??26.52‰ to??25.82‰) suggest a possible contribution of carbon sourced from the basement gneisses. The stage 3 late mineralization is dominated (1.40–8.81 wt.% NaCl equiv.) by aqueous fluids. The fluids show lower δ¹⁸O_fluid (?16.06‰ to??0.70‰) and higher δD_fluid (?90.10‰ to??74.50‰) values, indicating a heated meteoric water signature. The calculated carbon isotope compositions (δ¹³C_fluid?=??12.82‰ to??6.62‰) of the hydrothermal fluids in stage 3 also suggest a possible contribution of gneiss-sourced carbon. The isotopic compositions and fluid chemistry indicate that the ore mineralization in the Bairendaba deposit was related to Early Cretaceous magmatism.     

Copper stable isotopes as tracers of metal-sulphide segregation and fractional crystallisation processes on iron meteorite parent bodies

We report high precision Cu isotope data coupled with Cu concentration measurements for metal, troilite and silicate fractions separated from magmatic and non-magmatic iron meteorites, analysed for Fe isotopes (δ⁵⁷Fe; permil deviation in ⁵⁷Fe/⁵⁴Fe relative to the pure iron standard IRMM-014) in an earlier study (Williams et al., 2006). The Cu isotope compositions (δ⁶⁵Cu; permil deviation in ⁶⁵Cu/⁶³Cu relative to the pure copper standard NIST 976) of both metals (δ⁶⁵Cu_M) and sulphides (δ⁶⁵Cu_FeS) span much wider ranges (−9.30 to 0.99‰ and −8.90 to 0.63‰, respectively) than reported previously. Metal-troilite fractionation factors (Δ⁶⁵Cu_M-FeS = δ⁶⁵Cu_M − δ⁶⁵Cu_FeS) are variable, ranging from −0.07 to 5.28‰, and cannot be explained by equilibrium stable isotope fractionation coupled with either mixing or reservoir effects, i.e. differences in the relative proportions of metal and sulphide in the meteorites. Strong negative correlations exist between troilite Cu and Fe (δ⁵⁷Fe_FeS) isotope compositions and between metal-troilite Cu and Fe (Δ⁵⁷Fe_M-FeS) isotope fractionation factors, for both magmatic and non-magmatic irons, which suggests that similar processes control isotopic variations in both systems. Clear linear arrays between δ⁶⁵Cu_FeS and δ⁵⁷Fe_FeS and calculated Cu metal-sulphide partition coefficients (D_Cu = [Cu]_metal/[Cu]_FeS) are also present. A strong negative correlation exists between Δ⁵⁷Fe_M-FeS and D_Cu; a more diffuse positive array is defined by Δ⁶⁵Cu_M-FeS and D_Cu. The value of D_Cu can be used to approximate the degree of Cu concentration equilibrium as experimental studies constrain the range of D_Cu between Fe metal and FeS at equilibrium to be in the range of 0.05-0.2; D_Cu values for the magmatic and non-magmatic irons studied here range from 0.34 to 1.11 and from 0.04 to 0.87, respectively. The irons with low D_Cu values (closer to Cu concentration equilibrium) display the largest Δ⁵⁷Fe_M-FeS and the lowest Δ⁶⁵Cu_M-FeS values, whereas the converse is observed in the irons with large values D_Cu that deviate most from Cu concentration equilibrium. The magnitudes of Cu and Fe isotope fractionation between metal and FeS in the most equilibrated samples are similar: 0.25 and 0.32‰/amu, respectively. As proposed in an earlier study (Williams et al., 2006) the range in Δ⁵⁷Fe_M-FeS values can be explained by incomplete Fe isotope equilibrium between metal and sulphide during cooling, where the most rapidly-cooled samples are furthest from isotopic equilibrium and display the smallest Δ⁵⁷Fe_M-FeS and largest D_Cu values. The range in Δ⁶⁵Cu_M-FeS, however, reflects the combined effects of partial isotopic equilibrium overprinting an initial kinetic signature produced by the diffusion of Cu from metal into exsolving sulphides and the faster diffusion of the lighter isotope. In this scenario, newly-exsolved sulphides initially have low Cu contents (i.e. high D_Cu) and extremely light δ⁶⁵Cu_FeS values; with progressive equilibrium and fractional crystallisation the Cu contents of the sulphides increase as their isotopic composition becomes less extreme and closer to the metal value. The correlation between Δ⁶⁵Cu_M-FeS and Δ⁵⁷Fe_M-FeS is therefore a product of the superimposed effects of kinetic fractionation of Cu and incomplete equilibrium between metal and sulphide for both isotope systems during cooling. The correlations between Δ⁶⁵Cu_M-FeS and Δ⁵⁷Fe_M-FeS are defined by both magmatic and non-magmatic irons record fractional crystallisation and cooling of metallic melts on their respective parent bodies as sulphur and chalcophile elements become excluded from crystallised solid iron and concentrated in the residual melt. Fractional crystallisation processes at shallow levels have been implicated in the two main classes of models for the origin of the non-magmatic iron meteorites; at (i) shallow levels in impact melt models and (ii) at much deeper levels in models where the non-magmatic irons represent metallic melts that crystallised within the interior of a disrupted and re-aggregated parent body. The presence of non-magmatic irons with a range of Fe and Cu isotope compositions, some of which record near-complete isotopic equilibrium implies crystallisation at a range of cooling rates and depths, which is most consistent with cooling within the interior of a meteorite parent body. Our data therefore lend support to models where the non-magmatic irons are metallic melts that crystallised in the interior of re-aggregated, partially differentiated parent bodies.     

Lithium elemental and isotopic variations in rock-melt interaction

Despite the occurrence of highly variable lithium (Li) elemental distribution and isotopic fractionation in mantle mineral, the mechanism of Li heterogeneity and fractionation remains a controversial issue. We measured Li contents and isotopic compositions of olivine and clinopyroxene xenocrysts and phenocrysts from kamafugite host lavas, as well as minerals in melt pockets occurring as metasomatic products in peridotite xenoliths from the Western Qinling, central China. The olivine xenocrysts in the kamafugites show compositional zonation. The cores have high Mg# (100 × Mg/(Mg+Fe); 91.0–92.2) and Li abundances (5.63–21.7 ppm), low CaO contents (≤0.12 wt%) and low δ⁷Li values (−39.6 to −6.76‰), which overlap with the compositional ranges of the olivines in the melt pockets as well as those in peridotite xenoliths. The rims of the olivine xenocrysts display relatively low Mg# (85.9–88.2), high CaO contents (0.19–0.38 wt%) and high δ⁷Li values (18.3–26.9‰), which are comparable to the olivine phenocrysts (Mg#: 86.4–87.1; CaO: 0.20–0.28 wt%; Li: 12.4–36.8 ppm; δ⁷Li: 18.1–26.0‰) and the silicate-melt metasomatized olivines. The clinopyroxene phenocrysts and clinopyroxenes in the melt pockets have no distinct characteristics with respect to the Li abundances and δ⁷Li values, but show higher and lower CaO contents, respectively, than the clinopyroxenes from silicate and carbonatite metasomatized samples. These features indicate that Li concentration and isotopic signatures of the cores of the xenocrysts recorded carbonatite melt-peridotite reaction (carbonatite metasomatism) at mantle depth, and the variations in the rims probably resulted from xenocryst–host magma interaction during ascent. Our results reveal that the interaction with carbonatite and silicate melts gave rise to an increase in Li abundance in minerals of peridotite xenoliths at mantle depth or during transportation. In terms of δ⁷Li, the carbonatite and silicate melts produced remarkably contrasting δ⁷Li variations in olivine. Based on the systematic variations of Li abundances and Li isotopes in olivines, we suggest that the δ⁷Li value of olivine is a more important indicator than that of clinopyroxene in discriminating carbonatite and silicate melt interaction agents with peridotites.     

Copper and iron isotope fractionation in mine tailings at the Laver and Kristineberg mines,northern Sweden

Previous research has shown that Cu and Fe isotopes are fractionated by dissolution and precipitation reactions driven by changing redox conditions. In this study, Cu isotope composition (⁶⁵Cu/⁶³Cu ratios) was studied in profiles through sulphide-bearing tailings at the former Cu mine at Laver and in a pilot-scale test cell at the Kristineberg mine, both in northern Sweden. The profile at Kristineberg was also analysed for Fe isotope composition (⁵⁶Fe/⁵⁴Fe ratios). At both sites sulphide oxidation resulted in an enrichment of the lighter Cu isotope in the oxidised zone of the tailings compared to the original isotope ratio, probably due to preferential losses of the heavier Cu isotope into the liquid phase during oxidation of sulphides. In a zone with secondary enrichment of Cu, located just below the oxidation front at Laver, δ⁶⁵Cu (compared to ERM-AE633) was as low as −4.35 ± 0.02‰, which can be compared to the original value of 1.31 ± 0.03‰ in the unoxidised tailings. Precipitation of covellite in the secondary Cu enrichment zone explains this fractionation. The Fe isotopic composition in the Kristineberg profile is similar in the oxidised zone and in the unoxidised zone, with average δ⁵⁶Fe values (relative to the IRMM-014) of −0.58 ± 0.06‰ and −0.49 ± 0.05‰, respectively. At the well-defined oxidation front, δ⁵⁶Fe was less negative, −0.24 ± 0.01‰. Processes such as Fe(II)–Fe(III) equilibrium and precipitation of Fe-(oxy)hydroxides at the oxidation front are assumed to cause this Fe isotope fractionation. This field study provides additional support for the importance of redox processes for the isotopic composition of Cu and Fe in natural systems.     

Influencing factors and significance of organic and inorganic nitrogen isotopic compositions in lacustrine sedimentary rocks

Comprehensive nitrogen biogeochemical cycle has been reconstructed for representative lacustrine organic-rich sedimentary rock in China, namely the Triassic Yanchang Formation (YF, 199–230 Ma) in Ordos and the Cretaceous Qingshankou Formation (QF, 86–92 Ma) in Songliao basins, by evaluating the organic and inorganic nitrogen isotopic compositions rather than only organic or bulk nitrogen isotopic compositions. The results indicate that the nitrogen isotope values of bulk rock (δ¹⁵N_bulk) in the non-metamorphic stage are significantly different from that of kerogen, which challenge the conceptual framework of sedimentary nitrogen isotope interpretation. The δ¹⁵N_bulk from the YF and QF were lower than their respective the nitrogen isotope values of kerogen (δ¹⁵N_ker), with offsets up to ～5.1‰, which have the inverse relationship for the metamorphosed rock. Thermal evolution did not significantly modify the δ¹⁵N of bulk rock and kerogen. The δ¹⁵N of sediments from the YF (δ¹⁵N_bulk, 1.6‰–5.6‰) were lower than that of rock from the QF (δ¹⁵N_bulk, 10.2‰–15.3‰). The nitrogen isotope values of silicate incorporated nitrogen (δ¹⁵N_sil) were slightly lower than those of the δ¹⁵N_ker in the YF and obviously lower for the QF. The fact that different nitrogen cycles occur in the YF and QF due to the different depositional redox conditions leads to different isotopic results. The YF water environment dominated by oxic conditions is not conducive to the occurrence of denitrification and anammox, and no abundant N₂ loss leads to the relatively light δ¹⁵N_bulk. In the stratified water for the QF, redox transition zone promotes denitrification and anammox, resulting in the heavy δ¹⁵N_bulk of rock and promotes the DNRA, resulting in heavy δ¹⁵N_ker and low δ¹⁵N_sil.