Fractionation of carbon and hydrogen isotopes by methane-oxidizing bacteria

Carbon isotopic analysis of methane has become a popular technique in the exploration for oil and gas because it can be used to differentiate between thermogenic and microbial gas and can sometimes be used for gas-source rock correlations. Methane-oxidizing bacteria, however, can significantly change the carbon isotopic composition of methane; the origin of gas that has been partially oxidized by these bacteria could therefore be misinterpreted.We cultured methane-oxidizing bacteria at two different temperatures and monitored the carbon and hydrogen isotopic compositions of the residual methane. The residual methane was enriched in both ¹³C and D. For both isotopic species, the enrichment at equivalent levels of conversion was greater at 26°C than at 11.5°C. The change in δD relative to the change in δ¹³C was independent of temperature within the range studied. One culture exhibited a change in the fractionation pattern for carbon (but not for hydrogen) midway through the experiment, suggesting that bacterial oxidation of methane may occur via more than one pathway.The change in the δD value for the residual methane was from 8 to 14 times greater than the change in the δ¹³C value, indicating that combined carbon and hydrogen isotopic analysis may be an effective way of identifying methane which has been subjected to partial oxidation by bacteria.     

Isotopic exchange of carbon-bound hydrogen over geologic timescales

The increasing popularity of compound-specific hydrogen isotope (D/H) analyses for investigating sedimentary organic matter raises numerous questions about the exchange of carbon-bound hydrogen over geologic timescales. Important questions include the rates of isotopic exchange, methods for diagnosing exchange in ancient samples, and the isotopic consequences of that exchange. This article provides a review of relevant literature data along with new data from several pilot studies to investigate such issues. Published experimental estimates of exchange rates between organic hydrogen and water indicate that at warm temperatures (50-100°C) exchange likely occurs on timescales of 10⁴ to 10⁸ yr. Incubation experiments using organic compounds and D-enriched water, combined with compound-specific D/H analyses, provide a new and highly sensitive method for measuring exchange at low temperatures. Comparison of δD values for isoprenoid and n-alkyl carbon skeletons in sedimentary organic matter provides no evidence for exchange in young (<1 Ma), cool sediments, but strong evidence for exchange in ancient (>350 Ma) rocks. Specific rates of exchange are probably influenced by the nature and abundance of organic matter, pore-water chemistry, the presence of catalytic mineral surfaces, and perhaps even enzymatic activity.Estimates of equilibrium fractionation factors between organic H and water indicate that typical lipids will be depleted in D relative to water by ∼75 to 140‰ at equilibrium (30°C). Thus large differences in δD between organic molecules and water cannot be unambiguously interpreted as evidence against hydrogen exchange. A better approach may be to use changes in stereochemistry as a proxy for hydrogen exchange. For example, estimated rates of H exchange in pristane are similar to predicted rates for stereochemical inversion in steranes and hopanes. The isotopic consequences of this exchange remain in question. Incubations of cholestene with D₂O indicate that the number of D atoms incorporated during structural rearrangements can be far less than the number of C-H bonds that are broken. Sample calculations indicate that, for steranes in immature sediments, the D/H ratio imparted by biosynthesis may be largely preserved in spite of significant structural changes.     

Stable isotopic studies on chitin. III. The D/H and 18O/16O ratios in arthropod chitin

Stable hydrogen and oxygen isotope ratios are presented for carbon-bound hydrogen and for oxygen in chitin-derived substrates from 57 arthropod species collected in 50 different locations or grown under controlled conditions in the laboratory. No systematic isotopic differences were found among Insecta, Crustacea, and Merostomata. The determination of infra- and interindividual isotopic variabilities in a lobster and among individuals of crustacean populations yielded small variances of about ±3 per mil for δD values and ±0.3 per mil for δ¹⁸O values. Molting stage and sex of crustaceans showed no systematic effects on isotopic composition. The δD and δ¹⁸O values of ambient water showed only weak correlations with the respective δ values of chitin-derived substrates. Positive correlation was observed between δD values and trophic level. No temperature effects on δ¹⁸O and δD values from marine crustaceans were found that exceed the natural isotopic noise level. Taken together, these observations indicate that reconstruction of water isotopic composition from arthropod chitin δD and δ¹⁸O values will require specific information about the habits and habitats of the species involved in the analysis.     

Hydrogen Isotope Study of Fluid Inclusions in Vein Quartz of the Hishikari Gold Deposits, Japan

Abstract: The origin of mineralizing fluids responsible for the Hishikari vein-type epithermal Au deposits was studied on the basis of the hydrogen isotopic ratio (δD) of the inclusion fluid from vein quartz and adularia. The origin of hydrothermal fluids was estimated by combination of the present δ values and the oxygen isotopic ratios (δ¹⁸O) previously reported by Shikazono and Nagayama (1993). The water in the fluid inclusions was extracted by means of decrepitation of quartz at 500°C. Hydrogen was obtained by reduction of the collected water with Zn shot at 450°C. The δD values were determined by mass spectrometer. The δD values of inclusion fluid obtained from quartz range from –61 to –114%. These are significantly lower than the δD value of the thermal water presently venting from the Hishikari deposits and that of local meteoric water. Hydrogen isotopic fractionation between water and amorphous silica, which might have initially precipitated from the hydrothermal fluids at least partly, is not a probable cause of this isotopic depletion, while some water might have been released from the initial hydrous amorphous silica during recrystallization to quartz observed presently. Thus, a part of ore fluids for the Hishikari deposits is supposed to have been originated from the water having anomalous δD values of lower than –100%. Such D depletion cannot be caused by simple oxygen-shift of meteoric water or by contribution of magmatic volatiles. The δD values of water released from the shale samples of the Shimanto–Supergroup, a major host to the Hishikari veins range from –132 to –148%. Therefore, the anomalous δD values of inclusion fluids from some vein quartz and adularia suggest that the water released from hydrous minerals of the sedimentary basement rocks by dehydration or the groundwater isotopically exchanged with sedimentary rocks at elevated temperatures during circulation, partly contributed to the hydrothermal fluids responsible for the Hishikari deposits.     

Carbon and hydrogen isotopic compositions of New Zealand geothermal gases

Carbon and hydrogen isotopic compositions are reported for methane, hydrogen and carbon dioxide from four New Zealand geothermal areas: Ngawha, Wairakei, Broadlands and Tikitere. Carbon-13 contents are between ?24.4 and ?29.5%. (PDB) for methane, and between ?3.2 and ?9.1%. for carbon dioxide. Deuterium contents are between ?142 and ?197%. (SMOW) for methane and between ?310 and ?600%. for hydrogen. The different areas have different isotopic compositions with some general relationships to reservoir temperature.The isotopic exchange of hydrogen with water indicates acceptable reservoir temperatures of 180–260°C from most spring samples but often higher than measured temperatures in well samples. Indicated temperatures assuming ¹³C equilibria between CH₄ and CO₂ are 100–200°C higher than measured maxima. This difference may be due to partial isotopic equilibration or may reflect the origin of the methane. Present evidence cannot identify whether the methane is primordial, or from decomposing sediments or from reduction of magmatic CO₂. The isotopic equilibria between CH₄, CO₂, H₂ and H₂O are reviewed and a new semi-empirical temperature scale proposed for deuterium exchange between methane and water.     

Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems

Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2 cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using δD values in ethane from several basins in the world are in close agreement with similar predictions based on the δ¹³C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that δD values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that δD values in ethane might be more suitable for modeling than comparable values in methane and propane.     

A reexamination of cellulose carbon-bound hydrogen δD measurements and some factors affecting plant-water D/H relationships

The method of Epstein et al. (1976) for analysis of D/H ratios of cellulose carbon-bound hydrogen has been modified. This modified “renitration” method yields δD values which are in agreement with those obtained by the sodium chlorite delignification method. Comparison of results obtained by the renitration method with the published results of Epstein et al. (1976) indicate some differences in the δD values of individual samples. However, the overall plant-water δD relationship determined by Epstein et al., is not greatly changed upon redetermination by the renitration method. Additional data from a variety of plants representing a wide geographical range reveal that relative humidity is an important variable in determining the δD value of cellulose C-H hydrogen on this inter-regional scale. The role of relative humidity can be reasonably explained by a leaf water model that assumes an isotopic steady-state during transpiration. These results reaffirm the conclusion of Epstein et al., that the δD variations of the source water are the dominant control of the δD variations of cellulose C-H hydrogen from naturally grown plants. Thus, there is an expectation that these cellulose δD variations can have climate significance.     

Isotopic variations of oxygen and hydrogen in groundwater of carbonate aquifer in an arid environment

The stable isotopic characteristics were used together with the total chloride to assess changes in groundwater from recharge zones into the carbonate aquifer in an arid environment. The aquifer under study represents a major source of groundwater and thermal springs in Al-Ain city, which are located at the northern part of Jabal Hafit in the United Arab Emirates (UAE). The relationship between oxygen and hydrogen isotopic composition of groundwater is established and is described by δD?=?2.2δ¹⁸O???9.96. The lower slope and y-intercept of groundwater samples relative to the local meteoric waterline suggests that the isotopic enrichment is due to the evaporation of shallow groundwater after recharge occurs. The majority of the shallow groundwater samples have a negative deuterium excess (d-excess) which might be ascribed to high a degree of evaporation, while most of the groundwater samples from deep wells, have a positive value of d-excess which may be related to a low degree of evaporation. The δ¹⁸O values of the thermal waters suggest enrichment towards δ¹⁸O of the carbonate rocks because of the exchange with oxygen at higher temperatures. A possible mixing between thermal or hot water and shallow groundwater is evident in some samples as reflected by δD vs. Cl and d-excess vs. δ¹⁸O plots.     

The sources of water in Martian meteorites: clues from hydrogen isotopes

H isotope measurements of carbonate, phosphate, feldspathic and mafic glasses, and post-stishovite silica phase in the shergottites Zagami, Shergotty, SaU 005, DaG 476, ALHA 77005 and EETA 79001, as well as in Chassigny and ALH 84001, show that all these phases contain deuterium-enriched water of extraterrestrial origin. The minerals and glasses analyzed may contain an initial primary hydrogen component, but their isotopic composition was modified to varying degrees by three different processes: interaction with a fractionated exchangeable water reservoir on Mars, hydrogen devolatilization by impact melting, and terrestrial contamination. Positive correlations between δD and water abundance in feldspathic glass and post-stishovite silica in Zagami, Shergotty, and SaU 005 is indicative of mixing of a high δD component (3000-4000‰) and a less abundant, low δD component (∼0‰). The high δD component is primarily derived from the Martian exchangable reservoir, but may also have been influenced by isotopic fractionation associated with shock-induced hydrogen loss. The low δD component is either a terrestrial contaminant or a primary “magmatic” component. The negative correlation between δD and water abundances in mafic and feldspathic glasses in ALH 84001, ALHA 77005, and EETA 79001 is consistent with the addition of a low δD terrestrial contaminant to a less abundant high-deuterium Martian component. The low δD of magmatic glass in melt inclusions suggests that the δD of Martian parent magma was low and that the initial H isotope signature of Mars may be similar to that of Earth.     

Hydrogen and oxygen isotope ratios in nodular and bedded cherts

Hydrogen and oxygen isotopic compositions of cherts (δD for hydroxyl hydrogen in the chert, δ¹⁸O for the total oxygen) have been determined for a suite of samples from the central and western United States. When plotted on a δD-δ¹⁸O diagram, Phanerozoic cherts define domains parallel to the meteoric water line which are different for different periods of geologic time. The elongation parallel to the meteoric water line suggests that meteoric waters were involved in the formation of many cherts.The existence of different chert δ-values for different geologic times indicates that once the granular microcrystalline quartz of cherts crystallizes its isotopic composition is preserved with time. An explanation for the change with time of the isotopic composition of cherts involving large changes with time in the isotopic composition of ocean water is unlikely since δ¹⁸O of the ocean would have had to decrease by about 3‰between Carboniferous and Triassic time and then increase about 5%.` from Triassic to Cretaceous time. Such isotopic changes cannot be accounted for by extensive glaciation, sedimentation of hydrous minerals, or input of water from the mantle into the oceans.The variation with time of the chert δ-values can be satisfactorily explained in terms of past climatic temperature fluctuations if the chert-water isotope fractionation with temperature is approximated by 1000 lnα = 3.09 × 10⁶T^?2 – 3.29. Crystallization temperatures so inferred suggest that the average climatic temperatures for the central and western U.S. decreased from about 34 to 20°C through the Paleozoic, increased to 35–40°C in the Triassic, and then decreased through the Mesozoic to Tertiary values of about 17°C. A few data for the Precambrian suggest the possibility that Earth surface temperatures may have reached about 52°C at 1.3 b.y. and about 70°C at 3 b.y.     

Changes in the HOAr isotope composition of clays during retrograde alteration

K-Ar ages of illite alteration associated with Middle Proterozoic Athabasca unconformity-type U deposits in Saskatchewan range from 414 to 1493 Ma. The K-Ar ages correlate with water contents and δD values such that illites with young K-Ar ages have δD values as low as −169 and water contents as high as 7.7 wt.% whereas illites with older ages have δD values near −70 and water contents near 4 wt.%. Water extracted at 400°C from illites with low δD values and high water contents has low δD and δ¹⁸O values similar to those of modern meteoric water suggesting that some of the illites associated with the original deposition of the ore underwent varying degrees of retrograde alteration. The alteration is initiated by hydration of sites in the interlayer region of the illite which results in the partial resetting of the K-Ar ages and introduction of excess structural water in the form of interlamellar water. The interlamellar water is enriched in ¹⁸O by about 7 per mil relative to the water that physically surrounded the clay particle. Further alteration decreases the δD value and increases the δ¹⁸O value of the illite by isotopic exchange between the mineral and the interlamellar water. Although the chemical compositions and XRD patterns of the altered illites indicate that no detectable smectite component is present in the samples, the isotopic results suggest that the altered illites may be an early precursor in the formation of mixed-layer illite/smectite by retrograde alteration of pure illite. The wide variation of δD values of chlorite and kaolinite from these U deposits is analogous to that of the illite suggesting that retrograde alteration of clays by meteoric water can be substantial. The general association of altered clays with areas containing the highest concentrations of U is probably related to localized permeability within the ore zone.     

Extreme 18O-enriched volcanics and 18O-evolved marine water,Aljustrel, Iberian Pyrite Belt: transition from high to low Rayleigh number convective regimes

Quartz-eye keratophyric tuffs at Aljustrel, S. Portugal, Iberian Pyrite Belt possess unusually high, uniform whole rock δ-values up to 18.1%. with a mean of 16.7 ± 0.7%.. Because the quartz eye cores have δ¹⁸O 12.0 to 13.5%. the felsic tuffs may have had an original whole rock oxygen isotope composition of 10 to 11%. The deduced enrichments of up to +8%. in keratophyric derivatives is attributed to isotope exchange with abundant marine water under temperatures which diminished to ≤ 100°C, during thermally driven convective cooling. The isotopic uniformity requires elevated permeability of ～ 10^?8 cm², such that the second critical Rayleigh number was exceeded, and drifting, non steady state convection cells dominated, with relatively smooth thermal structures.In mineralised counterparts of the tuffs beneath the Feitais-Estacao Zn-Pb-Cu massive sulphide orebodies, whole rock δ-values are ~12%. and quartz (13.3–15.4%.)-chlorite (3.2–6.3%.) fractionations correspond to temperatures of 220–270°C, and a calculated fluid δ¹⁸O of 1.4 to 5.7%. This local isotopic overprinting in vent domains of the regionally high ¹⁸O was induced by a stable, second stage convective regime imposed by drastic reduction of permeability accompanying capping of the geothermal discharge by hydrothermal cherts, and/or progressive spilitisation of the tuffs. At lower water/rock coupled with higher temperatures, the recirculating marine water underwent variable ¹⁸O enrichment up to 5.7%. by exchange with the high ¹⁸O tuffs. An upwards increase in δ¹⁸O quartz and δ-quartz reflects progressive cooling of the geothermal discharge from 15.4%. 270°C in the stockwork, through 18.3%. 220–240°C in the orebody, to 20.1%. 110–130°C in overlying hydrothermal cherts, probably induced by entrainment of ambient marine bottom water in sub-seafloor aquifers.     

Inverse relationship between D/H fractionation in cyanobacterial lipids and salinity in Christmas Island saline ponds

Sediments from 28 saline and hypersaline (salinity 13.6-149.2) ponds on Christmas Island (Kiritimati), in the Central tropical Pacific Ocean, were investigated for the effect of salinity on the D/H ratios of lipid biomarkers. Hydrogen isotope ratios (expressed as δD values) of total lipid extracts, and individual hydrocarbons heptadecane, heptadecene, octadecane, octadecene, diploptene, and phytene from cyanobacteria, became increasingly enriched in deuterium as salinity increased, spanning a range of 100‰, while lake water δD values spanned a range of just 12‰. Net D/H fractionation between lipids and source water thus decreased as salinity increased. Isotope fractionation factors (α_lipid-water) were strongly correlated with salinity, and increased in all compound classes studied by up to 0.0967 over a salinity range of 136. Differences in the hydrogen isotopic composition of lipids derived from three biosynthetic pathways (acetogenic, mevalonate, and non-mevalonate) remained similar irrespective of the salinity. This suggests that the mechanism responsible for the observed α_lipid-water-salinity relationship originates prior to the last common biosynthetic branching point, the Calvin Cycle. We propose that a decrease in the exchange of intra- and extra-cellular (ambient) water resulting from down-regulation or closure of water channels (aquaporins) within cyanobacterial cell membranes, and subsequent isotopic enrichment of the intracellular water, likely resulting from metabolic reactions. These findings imply that caution must be exercised when attempting to reconstruct source water δD values using lipid δD values from environments that may have experienced salinity variations. On the other, hand our results can be used to establish a paleo-salinity proxy based on lipid δD, if additional constraints on source water δD values can be made.     

Carbon and hydrogen isotopic compositions of algae and bacteria from hydrothermal environments,Yellowstone National Park

Stromatolites forming today on a small scale in hydrothermal environments are chemical and biological analogues of much larger Precambrian formations. Carbon isotopic composition varied as a function of CO₂ concentration, pH, and species composition. Stratiform, layered stromatolites grew in silica-depositing springs at 55° to 70°C; they consisted mainly of a unicellular alga, Synechococcus, and a filamentous, photosynthetic bacterium, Chloroflexus. These thermophiles become enriched in ¹²C as the concentration of carbon dioxide in the effluent waters increases. At a concentration of 40 ppm total inorganic C, and δ¹³C of organic carbon was ～ ?12%., whereas at 900 ppm total inorganic C, the δ¹³C of similar species was ～ ?25%.. Conical stromatolites or conophytons (principally a filamentous, blue-green alga Phormidium and Chloroflexus) grew at 40°-55°C. In older, broader conophytons, Chloroflexus was the dominant organism. Their δ¹³C values were ～ ?18%. in a variety of hot springs. In carbonate-depositing springs, i.e., carbon dioxide saturated, conophytons and stromatolites consisting of a variety of blue-green algae and photosynthetic bacteria had the most negative δ¹³C values (to ?30%.). These carbon isotope ratios are directly comparable to carbon isotope ratios of kerogen from Precambrian stromatolites. The presence and activity of methanogenic bacteria or heterotrophic, aerobic and anaerobic bacteria did not alter significantly the δ¹³C of the original organic matter.The hydrogen isotopic fractionation between thermophilic organisms and water is 0 to ?74 for temperatures of 85° to 46°C, respectively. Acidophilic algae fractionated hydrogen isotopes to a lesser extent than did the photosynthetic organisms inhabiting neutral pH springs. Because organic matter retains some of its original isotopic signature, relationships of CO₂ levels, pH, temperature, and species composition between modern stromatolites and their environment and those of the Precambrian can be inferred.     

Antiphase hydrogen and oxygen isotope periodicity in chert nodules

Oxygen and hydrogen isotope analyses were made of Jurassic-age chert nodules from the Holy Cross Mountains, SE Poland, along radial transects at high spatial resolution. There is a radial “sigmoidal” periodicity for both isotope ratios, but the two are out of phase, with high δD values corresponding to low δ¹⁸O values. Periodicity for a 100- to 120-mm diameter nodule is approximately 16 mm, increasing slightly toward the rim, with amplitudes approaching 20 and 3.0‰ for hydrogen and oxygen, respectively. The combined hydrogen-oxygen isotope data for one nodule fall on a published curve for chert forming in equilibrium with seawater (Knauth and Epstein, 1976); the range of delta values corresponds to temperature variations of ∼10°C. Data for a second chert fall on a subparallel δD-δ¹⁸O line with δD values that are almost 50‰ lower. The δD-δ¹⁸O patterns for the nodules cannot be explained by periodic mixing of meteoric and ocean water because the hydrogen and oxygen isotope data are out of phase. Two possible explanations for the antiphase periodicity are (a) cyclical temperature variations, perhaps related to an unstable convection system (e.g., Bolton et al., 1999), and (b) self-organizing catalytic precipitation (e.g., Wang and Merino, 1990). The systematic isotopic variations are difficult to explain by diagenesis and strongly suggest that primary isotopic compositions are preserved. The isotopic data provide important information on the thermal history of the sedimentary basin, if temperature variations are the cause of the isotopic periodicity.     

Fractionation of hydrogen and oxygen isotopes of gypsum hydration water and assessment of its geochemical indications

Fundamental knowledge of the isotopic fractionation between the hydration water and the mother solution and whether the primary information recorded in hydration water can be preserved or not in deposits or mines have long been unclear. In order to calculate the accurate hydrogen and oxygen isotopic fractionation factors between gypsum hydration water and its mother solution with new methods, to understand the mechanism of fractionation and synthetically assess the record-keeping abilities of the isotopic composition of hydration water during the process of diagenesis after deposition, experiments on the hydrogen and oxygen isotopic compositions of gypsum hydration water and its mother solution at different isothermal temperatures from 5 to 50°C were systematically conducted. In addition, samples from two typical gypsum deposits formed in different environmental conditions were also determined. Results show that during gypsum crystallisation, both hydrogen and oxygen isotopes show significant fractionation between the hydration water and the mother solution. The calculated hydrogen isotopic fractionation factors are <1, while the oxygen isotopic fractionation factors are >1 at temperatures from 5 to 50°C. The fractionation factors show no functional relationships with temperature. Isotopic compositions of gypsum hydration water in arid lake sediments can be used to trace the source of water and primary deposit environmental information. However, the isotopic composition of the gypsum hydration water can easily be altered by dissolution and secondary precipitation of gypsum during later diagenesis, particularly in areas with humid climate and abundant groundwater. A very careful assessment on record-keeping abilities of the primary isotopic composition of hydration water in gypsum during later diagenesis must be considered before application.     

应用氢氧同位素研究矿床成因的一些问题探讨

成矿热液的氢、氧同位素组成与其水的类型、水/岩交换的岩石成分和同位素组成、水/岩交换时的温度及水/岩交换程度(W/R比值大小)等诸多因素有关,微生物和有机质也对其有一定的影响。因此,仅通过简单投影的方法将成矿热液的氢、氧同位素值与一些所谓的标准值进行类比,由此就推断出热液中水的来源,这种方法是不可取的;尤其当成矿热液的氢、氧同位素值介于大气降水和岩浆水的值之间时,切忌滥用两种水混合成矿模式,因为实际情况往往并不是这样。本文以胶东乳山金矿床为例,展开了这方面的讨论。     

哈尼梯田麻栗寨河流域雨季大气降水氢氧同位素特征及影响因素

以红河哈尼梯田文化景观遗产核心区麻栗寨河流域的雨季大气降水为研究对象,对2014年雨季典型月7月的氢氧同位素组成进行了分析,拟合出大气瞬时降水线方程,并与邻近地区及全国、全球降水线方程进行对比,分析温度、湿度、降水量等气象参数和海拔对氢氧稳定同位素的影响,并初步判断该区的水汽来源。结果表明：（1）研究区雨季大气降水δ¹⁸O值变化范围大,与邻近的昆明、贵阳、成都地区相比,贫化明显;（2）大气降水线方程为δD=7.59δ¹⁸O+3.31,其斜率和截距较小,说明研究区雨季降水量大且蒸发强烈、降水的水汽来源非单一化,除受印度洋、孟加拉湾的变热性热带海洋气团的影响,还受研究区地表水体的二次蒸发影响;（3）研究区降水稳定同位素特征显示不但存在明显的降水量效应,也存在温度效应和海拔效应,但各因素是综合作用的,主导因素不明显。     

Ion microprobe isotopic measurements of individual interplanetary dust particles

Ion microprobe measurements of D/H ratios in individual fragments of eight stratospheric dust particles give δD values ranging from ?386 to +2534‰ relative to SMOW. The δD values in five particles far exceed those in terrestrial samples and prove that the samples are interplanetary dust particles (IDPs). The hydrogen isotopic composition is heterogeneous on a scale of a few microns demonstrating that the dust is unequilibrated. Measurements of D/H ratios in conjunction with elemental and molecular ion signals in different fragments of individual IDPs show that a carbonaceous phase, not water, is the carrier of the D enrichments. Previous infrared transmission measurements have shown that IDPs fall into three main spectral classes. Particles from two of those three IR classes show large D/H ratios. Two particles studied from the third class do not. However, one of these contains solar flare tracks and is extraterrestrial. Thus, most, but not all, IDPs contain hydrogen with a non-terrestrial isotopic composition.Carbon isotopic measurements on fragments of three IDPs give ratios similar to terrestrial values and show a largely uniform isotopic composition for a given particle. Small, but significant, differences in δ¹³C of ~40‰ between particles are seen. No correlations between the hydrogen and carbon isotopic compositions are observed.The magnesium and silicon isotopic compositions of fragments of three IDPs are found to be normal within measurement errors.     

The hydrogen isotope fractionation between kaolinite and water

Hydrogen isotope fractionation factors between kaolinite and water were determined at temperatures between 200° and 352°C. Five-gram samples of kaolinite were heated in contact with 8-mg samples of water in sealed glass reaction tubes. Under these conditions the approach to equilibrium with time will be reflected primarily in the change of the δ D in the water. Also the δ D of the hydrogen in the kaolinite will be relatively constant, subject to minor corrections. About seventy sealed vessels were heated for various times at various temperatures. During four months of heating, ～ 25% of kaolinite hydrogen exchanged with the water at 200°C, whereas 100% exchanged at 352°C. The α-values were estimated assuming equilibrium between exchanged kaolinite and water. The 10³lnα-values are estimated to be ?20, ?15, ?6 and +7 for 352°, 300°, 250° and 200°C, respectively, which are in approximate agreement with reported values previously determined at 400°C using conventional methods as well as those estimated from kaolinite in hydrothermally active systems. The curve representing the relationship between the hydrogen isotope fractionation factor for the kaolinite-water system and temperatures between 400° and 25°C is not monotonic but rather has a maximum at 200°C.