微量水δ(~(17)O)和δ(~(18)O)CoF_3法线外同时测试新技术

三氧同位素(16O、17O、18O)组成特征可有效示踪天然水循环及其环境效应,微量水δ(17O)和δ(18O)CoF3法同时测试新技术的建立,可为三氧同位素定量研究提供有效的分析手段,特别是能够捕捉到像光合作用、呼吸作用等生物过程中发生的同位素分馏现象。在国内首次建立了微量水δ(17O)和δ(18O)CoF3法线外同时测试新技术,样品量仅需2μL,整个制样时间约40min。采用在质谱测试前对待测样品在100℃下预热10 min,待O2完全解吸后再进行质谱测试的方法,避免了制样和测试过程中的记忆效应及分馏效应,δ(17O)和δ(18O)的分析精度分别达到±0.07‰和±0.14‰。该法使用固体试剂CoF3替代了剧毒的气态氟化物BrF5,使得制样流程更加安全可靠且样品量少,适用性强,具有很大的推广应用价值。     

Automated isotopic measurements of micron-sized dust: application to meteoritic presolar silicon carbide

We report the development of a new analytical system allowing the fully automated measurement of isotopic ratios in micrometer-sized particles by secondary ion mass spectrometry (SIMS) in a Cameca ims-6f ion microprobe. Scanning ion images and image processing algorithms are used to locate individual particles dispersed on sample substrates. The primary ion beam is electrostatically deflected to and focused onto each particle in turn, followed by a peak-jumping isotopic measurement. Automatic measurements of terrestrial standards indicate similar analytical uncertainties to traditional manual particle analyses (e.g., ∼3‰/amu for Si isotopic ratios). We also present an initial application of the measurement system to obtain Si and C isotopic ratios for ∼3300 presolar SiC grains from the Murchison CM2 carbonaceous chondrite. Three rare presolar Si₃N₄ grains were also identified and analyzed. Most of the analyzed grains were extracted from the host meteorite using a new chemical dissolution procedure. The isotopic data are broadly consistent with previous observations of presolar SiC in the same size range (∼0.5-4 μm). Members of the previously identified SiC AB, X, Y, and Z subgroups were identified, as was a highly unusual grain with an extreme ³⁰Si enrichment, a modest ²⁹Si enrichment, and isotopically light C. The stellar source responsible for this grain is likely to have been a supernova. Minor differences in isotopic distributions between the present work and prior data can be partially explained by terrestrial contamination and grain aggregation on sample mounts, though some of the differences are probably intrinsic to the samples. We use the large new SiC database to explore the relationships between three previously identified isotopic subgroups—mainstream, Y, and Z grains—all believed to originate in asymptotic giant branch stars. The isotopic data for Z grains suggest that their parent stars experienced strong CNO-cycle nucleosynthesis during the early asymptotic giant branch phase, consistent with either cool bottom processing in low-mass (M < 2.3M_⊙) parent stars or hot-bottom burning in intermediate-mass stars (M > 4M_⊙). The data provide evidence for a sharp threshold in metallicity, above which SiC grains form with much higher ¹²C/¹³C ratios than below. Above this threshold, the fraction of grains with relatively high ¹²C/¹³C decreases exponentially with increasing ²⁹Si/²⁸Si ratio. This result indicates a sharp increase in the maximum mass of SiC parent stars with decreasing metallicity, in contrast to expectations from Galactic chemical evolution theory.     

Isotopic and Elemental Imaging of Geological Materials by Laser Ablation Inductively Coupled Plasma-Mass Spectrometry

Laser ablation ICP-MS represents a promising new development for the acquisition of elemental and isotopic images from a variety of different materials. Compared to existing methods for imaging, it offers relatively rapid throughput, very wide dynamic range, a relatively clean mass spectrum, utility at a variety of scales (from μm to cm) and multi-element/isotopic capability. Although developing rapidly in the biological sciences, the method has not yet seen widespread application to geological materials. This contribution documents some preliminary experiments aimed at understanding the fundamental aspects of elemental and isotopic image acquisition using laser ablation ICP-MS. In particular, we note that ablation cell designs must be optimised to promote rapid system response, in contrast to the signal-smoothing that is often preferred for simple spot analyses. Furthermore, experimental parameters must be carefully evaluated on a system-by-system basis to avoid the blurring effects of re-sampling phenomena. With careful attention to these details, and development of appropriate data processing software, laser ablation ICP-MS imaging has much to offer workers in the Earth and environmental sciences.     

Heating duration of igneous rim formation on a chondrule in the Northwest Africa 3118 CV3oxA carbonaceous chondrite inferred from micro-scale migration of the oxygen isotopes

Due to their common occurrence in various types of chondrites, igneous rims formed on pre-existing chondrules throughout chondrule-forming regions of the solar nebula. Although the peak temperatures are thought to reach similar values to those achieved during chondrule formation events, the heating duration in chondrule rim formation has not been well defined. We determined the two-dimensional chemical and oxygen isotopic distributions in an igneous rim of a chondrule within the Northwest Africa 3118 CV3_oxA chondrite with sub-micrometer resolution using secondary ion mass spectrometry and scanning electron microscopy. The igneous rim experienced aqueous alteration on the CV parent body. The aqueous alteration resulted in precipitation of the secondary FeO-rich olivine (Fa_40–49) and slightly disturbed the Fe-Mg distribution in the MgO-rich olivine phenocrysts (Fa_11–22) at about a 1 μm scale. However, no oxygen isotopic disturbances were observed at a scale greater than 100 nm. The MgO-rich olivine, a primary phase of igneous rim formation, has δ¹⁷O = −6 ± 3‰ and δ¹⁸O = −1 ± 4‰, and some grains contain extreme ¹⁶O-rich areas (δ¹⁷O, δ¹⁸O = ∼−30‰) nearly 10 μm across. We detected oxygen isotopic migration of approximately 1 μm at the boundaries of the extreme ¹⁶O-rich areas. Using oxygen self-diffusivity in olivine, the heating time of the igneous rim formation could have continued from several hours to several days at near liquidus temperatures (∼2000 K) in the solar nebula suggesting that the rim formed by a similar flash heating event that formed the chondrules.     

The Marl Slate: a model for the precipitation of calcite, dolomite and sulphides in a newly formed anoxic sea

Detailed studies of a new, complete Marl Slate core in South Yorkshire have provided information on isotopic (δ¹³C, δ¹⁸O, δ³⁴S) and geochemical variations (trace elements and C/S ratio) which enable the formulation of a model for carbonate and sulphide precipitation in the Late Permian Zechstein Sea. Calcite and dolomite are intimately associated; the fine lamination, organic character and absence of benthos in the sediments are indicative of anoxic conditions. Lithologically the core can be divided into a lower, predominantly sapropelic Marl Slate (2 m) and an upper Transition Zone (0·65 m) of alternating sapropel and calcite-rich and dolomite-rich carbonates. C/S ratios are 2·22 for the Marl Slate and 1·72 for the Transition Zone respectively, both characteristic of anoxic environments. δ¹⁸O in the carbonates shows a large and systematic variation closely mirrored by variations in calcite/dolomite ratio. The results suggest a fractionation factor equivalent to a depletion of 3·8% for ¹⁸O and 1·5% for ¹³C in calcite. The δ³⁴S values of pyrite are isotopically light (mean value = - 32·7%) suggesting a fractionation factor for the Marl Slate of almost 44%, typical of anoxic basins. The results are related to stratification in the early Zechstein Sea. Calcite was precipitated in oxic upper layers above the halocline. Below the oxic/anoxic boundary framboidal pyrite was precipitated, resulting in lower sulphate concentration and elevated Mg/Ca ratio (due to calcite precipitation). As a result of this, dolomite formation occurred below the oxic/anoxic interface, within the anoxic water column and in bottom sediments. Variations in calcite/dolomite ratios, and isotopic variations, are thus explained by fluctuations in the relative level of the oxic/anoxic boundary in the Zechstein Sea.     

Timescales and mechanisms of fluid infiltration in a marble: an ion microprobe study

Using a recently developed ion microprobe technique, a detailed oxygen isotope map of calcite grains in a coarse-grained marble has been constructed, supported by trace element (Mn, Sr, Fe) analysis and cathodoluminescence (CL) imaging, in order to constrain scales of oxygen isotope equilibrium, timescales and mechanisms of metamorphic fluid infiltration, and fluid sources and pathways. Results are compared with a previous study of this sample (Wada 1988) carried out using a cryo-microtome technique and conventional oxygen isotope analysis. The marble, from the high temperature/low pressure Hida metamorphic belt in north-central Japan, underwent granulite facies followed by amphibolite facies metamorphic events, the latter associated with regional granite intrusion. The CL imaging indicates two types of calcite, a yellow luminescing (YLC) and a purple luminescing (PLC) variety. The YLC, which occupies grain boundaries, fractures, replacement patches, and most of the abundant deformation twin lamellae, post-dates the dominant PLC calcite and maps out fluid pathways. Systematic relationships were established between oxygen isotope and trace element composition, calcite type and texture, based on 74 ¹⁸O/¹⁶O and 17 trace element analyses with 20–30 μ m spatial resolution. The YLC is enriched in Mn and Fe, and depleted in ¹⁸O and Sr compared to PLC, and is much more ¹⁸O depleted than is indicated from conventional analyses. Results are interpreted to indicate infiltration of ¹⁸O-depleted (metamorphic or magmatic) fluid (initial δ¹⁸O = 9‰–10.5‰) along grain boundaries, fractures and deformation twin lamellae, depleting calcite grains in Sr and enriching them in Mn and Fe. The sample is characterised by gross isotopic and elemental disequilibrium, with important implications for the application of chromatographic theory to constrain fluid fluxes in metacarbonate rocks. Areas of PLC unaffected by “short-circuiting” fluid pathways contain oxygen diffusion profiles of ∼10‰/∼200 μm in grain boundary regions or adjacent to fractures/patches. When correction is made for estimated grain boundary/fracture and profile orientation in 3D, profiles are indistinguishable within error. Modelling of these profiles gives consistent estimates of Dt (where D is the diffusion coefficient and t is time) of ∼0.8 × 10⁻⁸ m², from which, using experimental data for oxygen diffusion in calcite, timescales of fluid transport along grain boundaries at amphibolite facies temperatures of ∼10³ to ∼10⁴ years are obtained. These short timescales, which are much shorter than plausible durations of metamorphism, imply that rock permeabilities may be transiently much higher during fluid flow than those calculated from time integrated fluid fluxes or predicted from laboratory measurements. The preservation of ¹⁸O/¹⁶O profiles requires either rapid cooling rates (∼100–600 °C/million years), or, more plausibly, loss of grain boundary fluid such that a dry cooling history followed the transient passage of fluid. The δ¹⁸O/trace element correlations are also consistent with volume diffusion-controlled transport in the PLC. Fluid transport and element exchange occurred by two inter-related mechanisms on short timescales and on different lengthscales – long-distance flow along cracks, grain boundaries and twin lamellae coupled to ∼200 μm-scale volume diffusion of oxygen. Received: 8 December 1997 / Accepted: 18 May 1998     

Oxygen isotope ratios of cellulose-derived phenylglucosazone: An improved paleoclimate indicator of environmental water and relative humidity

Oxygen atoms within fossil wood provide high-resolution records of climate change, particularly for the Quaternary. However, current analysis methods of fossil cellulose do not differentiate between different positions of the oxygen atoms. Here, we propose a refinement to tree-cellulose paleoclimatology modeling, using the cellulose-derived compound phenylglucosazone as the isotopic substrate. Stem samples from trees were collected at northern latitudes as low as 24°37′N and as high as 69°00′N. We extracted stem water and cellulose from each stem sample and analyzed them for their ¹⁸O content. In addition, we derived the cellulose to phenylglucosazone, a compound which lacks the oxygen attached to the second carbon of the cellulose-glucose moieties. Oxygen isotope analysis of phenylglucosazone allowed us to calculate the ¹⁸O content of the oxygen attached to the second carbon of the cellulose-glucose moieties. By way of these analyses, we tested two hypotheses: first, that the ¹⁸O content of the oxygen attached to second carbon will more closely reflect the ¹⁸O content of the stem water, and will not resemble the ¹⁸O content of either cellulose or its derivative phenylglucosazone. Second, tree-ring models that incorporate the variable oxygen isotope fractionation shown here and elsewhere are more accurate than those that do not. Our first hypothesis was rejected on the basis that the oxygen isotope ratios of the oxygen attached to the second carbon of the glucose moieties had a noisy isotopic signal with a large standard deviation and gave the poorest correlation with the oxygen isotope ratios of stem water. Related to this isotopic noise, we observed that the correlation between oxygen isotope ratios of phenylglucosazone with both stem water and relative humidity were higher than those observed for cellulose. Our hypothesis about tree-ring models which account for changes in the oxygen isotopic fractionation during cellulose synthesis was consistent only for the ¹⁸O content of phenylglucosazone. We showed that the tree-ring model based on the ¹⁸O content of phenylglucosazone was an improvement over existing models that are based on whole cellulose. Additionally, this approach may be used in other cellulose based archives such as peat deposits and lacustrine sediments.     

硅酸盐矿物氧同位素组成的激光分析

对于红外激光系统和紫外激光系统 ,由于它们加热样品的反应机理完全不同 ,决定了它们在稳定同位素地球化学分析中的不同使用范围。根据对CO2 激光系统分析地球化学样品的实践 ,发现对结果产生干扰的因素有 :(1)石英的粒径效应 ;(2 )微量样品接收电压过低 ;(3)分子筛的吸附能力 ;(4 )系统中的吸附水 ;(5 ) 14 N19F+ 对δ17O值的影响。由于石英的粒径效应而导致细粒石英 (粒径<2 5 0 μm)的δ18O值偏低 ,可以采用不聚焦激光的快速加热法来解决。由于样品量太少而决定了样品气体接收电压过低 ,导致δ18O值出现系统偏高或偏低 ,可以利用校正曲线对结果进行校正。分子筛吸附性能的下降会产生氧同位素的分馏 ,因此确定分子筛的使用寿命非常重要。系统中的吸附水利用氟化物试剂预氟化来去除 ,重要的是应避免在预氟化的过程中产生大量的HF腐蚀激光系统的BaF2 窗口玻璃并与部分矿物样品发生反应。     

An optimized procedure for boron separation and mass spectrometry analysis for river samples

An optimized procedure for the separation of boron from natural river samples and an improved mass spectrometry determination of boron isotopic ratio are presented. The chemical procedure, based on the use of the boron-specific resin Amberlite IRA 743, is especially efficient in separating boron from natural organic matter-rich samples like river waters.The properties of Amberlite IRA 743 have been investigated. The two factors important in determining the boron affinity for the resin are: the pH value and the ionic strength of the solution from which B is to be extracted. A logarithmic relationship between B partition coefficients and pH values is found. High ionic strength significantly lowers the fixation of B onto the Amberlite resin.The knowledge of the factors controlling the affinity of the resin Amberlite IRA 743 for boron enables us to design a simple and miniaturized chemical separation procedure characterized by (i) three chromatographic steps using, respectively, 50, 10 and 3 μl of resin, (ii) no evaporation step between each column, and (iii) final separation of boron from residual organic matter by sublimation of boric acid at 75 °C.Boron isotopic ratios are measured using an improved cesium metaborate technique, with graphite and mannitol. Adequate loading conditions enable us to obtain typical signal intensities of 5×10⁻¹² A for 250 ng of boron. No in-run isotopic fractionation is observed, the external reproducibility for standards processed through the entire chemical procedure, as well as for samples, corresponds to 0.35‰ (±2σ). According to this precision, a slight, but reproducible isotopic fractionation of 0.4‰ is observed for standards processed through the entire chemical procedure whose origin is discussed, but is still unclear.     

Geochemistry of Suspended Particulate Matter (SPM) in the Murray-Darling River System: A Conceptual Isotopic/Geochemical Model for the Fractionation of Major, Trace and Rare Earth Elements

A conceptual isotopic/geochemical model is presented to explain the variation of major, trace and rare earth element (REE) geochemistry and Sr isotope systematics in suspended particulate matter (SPM) as a function of particle/colloid size. This conceptual model is an extension of a previous investigation of the origin of SPM in the Murray-Darling River system (MDRS) that utilised Sr isotope systematics to examine aspects of SPM (particle/colloid) origin, structure and mineralogy. The geochemical processes that give rise to the often coherent trends in major, trace and REE geochemistry and Sr isotopic signature as a function of particulate (<1 μm) and colloidal (>1 μm) size in the MDRS have been identified using an enhanced SPM size fractionation technique as a basis to not only obtain a broad range of particle/colloid size ranges, but also to provide sufficient material for subsequent geochemical and isotopic analysis. The conceptual isotopic/geochemical model proposed here contains three major components: (i) the differential weathering of micas and alkali (K-) feldspars to form the majority of the particulate (<1 μm) fractions (high 87Sr/86Sr ratio), which have a geochemical and Sr isotopic signature that closely resembles precursor mineralogies, (ii) the differential weathering of Na, Ca-feldspars (plagioclase) which decompose to form clay minerals in the colloidal (>1 μm) fractions (low 87Sr/86Sr ratio), with a range of geochemical signatures related to the relative proportions of inorganic and organic constituents, and (iii) the presence of natural organic matter as coatings on the particulate (<1 μm) and colloidal (>1 μm) matter and possibly as organo-colloids which exert an increasing influence in particular on bulk colloid geochemistry with decreasing colloid size. This conceptual isotopic/geochemical model also accounts for the distinct variation in major, trace and REE geochemistry and Sr isotopic systematics between the particulate (<1 μm) and colloidal (>1 μm) fractions, the variation being primarily a function of the distinctly different precursor mineralogies of the SPM fractions and geochemical fractionation during the weathering and transport. Additionally, this model explains a systematic fractionation of REE apparent within colloidal (>1 μm) fractions. Statisitcal (hierachical cluster) analysis of two particulate and three colloidal fractions from 23 samples from the MDRS is used as a basis to investigate geochemical and mineralogical associations within the particulate and colloidal size fractions and to provide additional supporting evidence for the conceptual isotopic/geochemical model. This revised version was published online in July 2006 with corrections to the Cover Date.     

Karst springs as “natural” pluviometers: Constraints on the isotopic composition of rainfall in the Apennines of central Italy

This paper describes an indirect method to calculate the isotopic composition of rainfall by using the isotopic composition of karst springs fed by waters circulating in the most important regional aquifer of central Italy, i.e. the Mesozoic limestone sequence that forms the backbone of the Apennines. By using δ¹⁸O and δD data and the δ¹⁸O (and/or δD) average gradient for elevation, evaluated through the use of literature rainfall data and new measurements from a typical Alpine valley in northern Italy, the altitude of precipitation of their parent water has been re-calculated. Vertical descents of more than 2000 m, from recharge to discharge, have been assessed in some high flow-rate cold springs in the morphologically steep Adriatic sector of central Italy. A clear correlation between the vertical descents and more negative isotopic compositions at their relative emergence elevations is highlighted. In contrast, in the Tyrrhenian sector lower karstic drops (generally lower than 500 m) correlate with less negative isotopic composition of recharge areas.The δ¹⁸O iso-contour map of the “recalculated” parent rainfall in central Italy is more detailed than any possible isotopic map of rainfall made using pluviometers, unless large number of rainfall collectors were deployed on mountaintops. The data also show that the isotopic composition of rainfall depends on the source of the storm water. In particular, precipitation is isotopically heavier when originating in the Mediterranean Sea, and lighter when formed in the Atlantic Ocean. Consequently, the collision between air masses with such a different isotopic signature results in a relatively small latitudinal fractionation effect. The peninsular part of central Italy is very narrow, with several mountains and massifs more that 2000 m high, and any latitudinal variation in the isotopic composition between rainfall sourced in the Atlantic Ocean and in the Mediterranean Sea is much lower than that due to the isotopic fractionation due to elevation.     

Excimer laser isotope-ratio-monitoring mass spectrometry for in situ oxygen isotope analysis

A technique using isotope-ratio-monitoring gas chromatography-mass spectrometry (irmGCMS) and excimer laser fluorination for in situ oxygen isotope analysis of silicates is described. The irmGCMS and oxygen extraction line is connected by a newly developed interface, reducing the time for a single analysis to less than 10 min. The precision obtained for δ¹⁸O is similar to what has been reported for excimer laser fluorination using dual inlet systems. δ¹⁸O values of two olivine standards had 1σ precision of ±0.14‰ (n=19 and n=10) and that of Dörentrup quartz had ±0.17‰. Eleven analyses of a large zircon crystal had a precision of ±0.12‰. However, between 300 and 600 nmol oxygen was liberated for a single analysis, equivalent to cylindrical laser holes 250 to 350 μm in diameter and depth. In the future it will be feasible to measure the isotope ratio of cylindrical volumes 150 μm in diameter simply by reducing the volume of the extraction line. While this is still significantly larger than what is possible with ion probes, the ratios obtained by excimer laser-irmGCMS are highly accurate and precise without correction. The value of this technique for in situ oxygen isotope measurements is demonstrated with two rock slabs from metamorphic rocks of the Dabie–Sulu ultra-high-pressure belt, China.     

Combining in situ isotopic, trace element and textural analyses of quartz from four magmatic-hydrothermal ore deposits

This study couples in situ ¹⁶O, ¹⁷O and ¹⁸O isotope and in situ trace element analyses to investigate and characterize the geochemical and textural complexity of magmatic-hydrothermal quartz crystals. Euhedral quartz crystals contemporaneous with mineralization were obtained from four magmatic-hydrothermal ore deposits: El Indio Au–Ag–Cu deposit; Summitville Au–Ag–Cu deposit; North Parkes Cu–Au deposit and Kingsgate quartz-Mo–Bi–W deposit. The internal features of the crystals were imaged using cathodoluminescence and qualitative electron microprobe maps. Quantitative isotopic data were collected in situ using 157 nm laser ablation inductively coupled plasma mass spectrometry (for 40 trace elements in quartz) and sensitive high-resolution ion microprobe (for 3 isotopes in quartz). Imaging revealed fine oscillatory zoning, sector zoning, complex “macromosaic” textures and hidden xenocrystic cores. In situ oxygen isotope analyses revealed a δ¹⁸O range of up to 12.4 ± 0.3 ‰ in a single crystal—the largest isotopic range ever ascribed to oscillatory zonation in quartz. Some of these crystals contain a heavier δ¹⁸O signature than expected by existing models. While sector-zoned crystals exhibited strong trace element variations between faces, no evidence for anisotropic isotope fractionation was found. We found: (1) isotopic heterogeneity in hydrothermal quartz crystals is common and precludes provenance analysis (e.g., δD–δ¹⁸O) using bulk analytical techniques, (2) the trace element signature of quartz is not an effective pathfinder toward noble metal mineralization and (3) in three of the four samples, both textural and isotopic data indicate non-equilibrium deposition of quartz.     

Ion microprobe study of intragrain micropermeability in alkali feldspars

Alkali feldspar cleavage fragments from the Klokken layered syenite, South Greenland, were heated to 700°C at 0.1 GPa in 99% H₂ ¹⁸O for 75 h. These samples were then polished and imaged by ion microprobe for ¹⁸O. The feldspars were known to contain areas of pristine, braid micro-perthite which were not turbid and areas of deuteric patch perthite which were turbid. Turbidity is related to the presence of micropores in the feldspars. On imaging the grain, it was found that the ¹⁸O had penetrated into the parts of the grain which were microporous and not into the pristine areas. Micropores are therefore responsible for rendering the feldspars permeable as well as porous. The implications of micropermeable feldspars in several areas of geology are discussed.     

Ion microprobe analysis of oxygen isotope ratios in quartz from Skye granite: healed micro-cracks,fluid flow,and hydrothermal exchange

 Quartz grains in hydrothermally altered granites from the Isle of Skye are highly heterogeneous and not equilibrated in oxygen isotope ratio at the 20 μm scale. Ion microprobe analysis of one grain shows a gradient of 13‰ over 400 μm and a greater range in δ ¹⁸O than all quartz previously analyzed on the Isle of Skye. Other crystals from the same outcrop are homogeneous. Digitized cathodoluminescence images reveal patterns of magmatic zoning and brittle fracturing not otherwise detectable. The ion probe analysis correlates low δ ¹⁸O values on a micro-scale to one set of healed cracks. Thus, quartz exchanges oxygen isotopes primarily by solution and reprecipitation along fractures, in contrast to more reactive feldspar that appears to exchange from the grain boundary inward. Macroscopic models of isotope exchange are not realistic for these rocks; the flow of hydrothermal fluids was heterogeneous, anisotropic and crack controlled. Received: 23 October 1995/Accepted: 9 April 1996     

New data on variations of stable isotopes in the pingo ice core in the southern part of the Tazovsky Peninsula

The aim of this work is to obtain the vertical isotopic profile of the thick Pestsovoe pingo ice core in the southern part of the Tazovsky Peninsula, to determine the oxygen and hydrogen isotopic composition of the ice, and to reveal its formation conditions. Two trends were identified for the isotopic profile of the pingo ice: an insignificant increase of the δ¹⁸O (~1.5‰) and δD (~9‰) values at depths of 12–15 m and a gradual decrease of isotopic values by 3.8 and 23‰ for δ¹⁸O and δD, respectively, at a depth of 15–26 m. The formation of the pingo ice core in the semiclosed system resulted in fractionation of the isotopic composition of oxygen and hydrogen by more than 4 and 20‰, respectively.     

The isotopic composition of Tertiary carbonates from the Mainz Basin: an example of isotopic fractionations in 'closed basins'

The carbon and oxygen isotopic composition of seventy-nine samples of biogenic carbonates from the Mainz Basin Tertiary (Oligocene and Lower Miocene) was analysed. Most samples were mollusc shells still consisting of aragonite. Assuming only small temperature effects, salinity trends derived from isotope data are consistent with palaeontological results from the region: a salinity cycle ranging from fresh water-brackish (Lower Oligocene) towards marine (Middle Oligocene) and brackish-fresh water (Upper Oligocene) was found. Within the Lower Miocene, a trend of decreasing salinities is suggested. Though the isotopic salinity trends coincide rather well with palaeontological salinities, the absolute oxygen isotope ratios indicate an unusual isotopic environment enriched in ¹⁸O. Isotope fractionation is explained by evaporation of a closed basin (Rupelton excluded) with fresh water influx from surrounding land areas in a subtropical climate. Enrichment in ¹⁸O by repeated evaporation processes is paralleled by increasing concentration of Sr. Increasing fresh water influx during the Oligocene is due to climatic changes with a trend of more humid conditions towards the younger rock strata.     

神农架石笋氧同位素的海拔效应

作为古气候代用指标,石笋氧同位素为亚洲季风演化研究提供了一系列可靠的证据。然而,关于石笋氧同位素指示的气候意义一直存在争论。本文选取了位于神农架地区海拔1250～2250m的黑龙洞、青天洞和三宝洞3个洞穴进行对比分析,发现不同海拔洞穴石笋δ18O在波动形式上相同,但绝对值存在约-0.1‰/100m的系统差,而大气降水的在该地的海拔效应约为-0.2‰/100m。为此,我们认为,石笋δ18O除了受季风降雨的影响外,不同海拔的温度梯度也对石笋δ18O具有较大的贡献。结合洞穴年均温度,初步估算石笋δ18O的温度效应约为-0.25‰/℃,与O’Neil的同位素平衡分馏计算结果相同。      

巴丹吉林沙漠石英δ18O值及其物源意义

巴丹吉林沙漠是世界上沙丘最高大的沙漠,其沙源研究对认识沙漠形成、高大沙山发育和防沙治沙工程有重要意义。石英是沙漠沉积物中常见的矿物,其氧同位素值可示踪物源。采集沙漠西北部、东部、东南部高大沙山、丘间低地与湖泊以及雅布赖山前的表层沉积物,测定了样品不同粒级的石英δ18O值。结果表明:①石英δ18O值随粒级减小有增大趋势,同一样品不同粒级石英δ18O值存在较大差异,相同粒级石英δ18O值也有变化。②石英δ18O值介于9.4‰~19.3‰,均值为13.3‰（n=55）;其中沙丘沙的石英δ18O值介于9.5‰~16.6‰,均值为12.9 ‰（n=39）;湖相沉积物的石英δ18O值介于9.4‰~19.3‰,均值为14.2‰（n=16）。③区域内,<16 μm粒级的石英δ18O值与16~64 μm、125~154 μm、200~250 μm、> 300 μm粒级的石英δ18O值都存在显著差异,但200~250 μm与 > 300 μm粒级的石英δ18O值没有显著差异;经区域对比,巴丹吉林沙漠 < 16 μm粒级的石英δ18O值与柴达木盆地沙漠、蒙古戈壁风成沉积物 < 16 μm石英δ18O值无显著差异,但巴丹吉林沙漠16~64 μm粒级的石英δ18O值与蒙古戈壁风成沉积物16~64 μm石英δ18O值存在显著差异;这似乎暗示研究区的细颗粒物质可能是远源的。巴丹吉林沙漠沉积物的石英δ18O值位于火成岩石英、砂岩和变质岩石英δ18O值分布阈值内,受区域地质条件、物源混合、粒级效应等因素的影响,砂粒级的石英δ18O值所指示的母岩成份特征与祁连山区岩石的岩性有较好吻合。     

Calculation of individual isotope equilibrium constants for geochemical reactions

Theory is derived from the work of Urey (Urey H. C. [1947] The thermodynamic properties of isotopic substances. J. Chem. Soc. 562-581) to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by α = (K^ex)^1/n, where n is the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example ¹³C¹⁶O¹⁸O and ¹H²H¹⁸O. The equilibrium constants of the isotope exchange reactions can be expressed as ratios of individual isotope equilibrium constants for geochemical reactions. Knowledge of the equilibrium constant for the dominant isotopic species can then be used to calculate the individual isotope equilibrium constants.Individual isotope equilibrium constants are calculated for the reaction CO_2g = CO_2aq for all species that can be formed from ¹²C, ¹³C, ¹⁶O, and ¹⁸O; for the reaction between ¹²C¹⁸O_2aq and ¹H₂¹⁸O_l; and among the various ¹H, ²H, ¹⁶O, and ¹⁸O species of H₂O. This is a subset of a larger number of equilibrium constants calculated elsewhere (Thorstenson D. C. and Parkhurst D. L. [2002] Calculation of individual isotope equilibrium constants for implementation in geochemical models. Water-Resources Investigation Report 02-4172. U.S. Geological Survey). Activity coefficients, activity-concentration conventions for the isotopic variants of H₂O in the solvent ¹H₂¹⁶O_l, and salt effects on isotope fractionation have been included in the derivations. The effects of nonideality are small because of the chemical similarity of different isotopic species of the same molecule or ion. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors.The derivations can be extended to calculation of individual isotope equilibrium constants for ion pairs and equilibrium constants for isotopic species of other chemical elements. The individual isotope approach calculates the same phase isotopic compositions as existing methods, but also provides concentrations of individual species, which are needed in calculations of mass-dependent effects in transport processes. The equilibrium constants derived in this paper are used to calculate the example of gas-water equilibrium for CO₂ in an acidic aqueous solution.