稀有气体同位素的激光探针分析:技术与应用

稀有气体同位素的激光探针分析就是利用激光的集束性和高能性来抽提固体样品中的气体 ,然后将气体净化、分离之后送入质谱计测定其含量和同位素组成。该系统主要由显微监视系统、激光发射系统、位移调节系统、样品处理系统和质谱计组成。薄片样品放入真空样品室后 ,利用显微监视系统可以对薄片进行分析和照相 ,可以对小到 30～ 5 0 μm的微小区域定位分析。该方法的优势主要在于 :(1)系统本底非常低 ;(2 )样品用量较少 ;(3)具有很高的空间分辨率 ;(4 )利用“Q开关” ,可以用作微破裂工具 ;(5 )与熔融法相比 ,分析成本较低。它也有不足之处 :(1)系统的投入成本高 ;(2 )各稀有气体的抽提效率不均一 ,需要校正。     

Kerogen-mineral reactions at raised temperatures in the presence of water

Kerogen has been artificially matured under “hydrous pyrolysis” conditions in the presence of various minerals in order to investigate the influence of the latter on the organic products. In addition to three clay minerals (montmorillonite, illite, kaolinite), calcium carbonate and limonite were also employed as inorganic substrates. Kerogen (Type II) isolated from the Kimmeridge Blackstone band was heated in the presence of water and a 20-fold excess of mineral phase at two different temperatures (280 and 330°C) for 72 hr. Control experiments were also carried out using kerogen and water only and kerogen under anhydrous conditions. This preliminary study describes the bulk composition of the pyrolysates with detailed analyses of the aliphatic hydrocarbon distributions being provided by gas chromatography and combined gas chromatography-mass spectrometry.In the 280°C experiments, considerably more organic-soluble pyrolysate (15% by weight of original kerogen) was produced when calcium carbonate was the inorganic phase. At 330°C, all samples generated much greater amounts of organic-soluble products with calcium carbonate again producing a large yield (40% wt/wt). Biomarker epimerisation reactions have also proceeded further in the 330°C pyrolysate formed in the presence of calcium carbonate than with other inorganic phases. Implications of these and other observations are discussed.     

Groundwater recharge history and hydrogeochemical evolution in the Minqin Basin, North West China

The Minqin Basin is a type area for examining stress on groundwater resources in the Gobi Desert, and has been investigated here using a combination of isotopic, noble gas and chemical indicators. The basin is composed of clastic sediments of widely differing grain size and during the past half century over 10 000 boreholes have been drilled with a groundwater decline of around 1 m a⁻¹. Modern diffuse recharge is unlikely to exceed 3 mm a⁻¹, as determined using unsaturated zone profiles and Cl⁻ mass balance. A small component of modern (<50 a) groundwater is identified in parts of the basin from ³H–³He data, probably from irrigation returns. A clear distinction is found between modern waters with median δ¹⁸O values of 6.5 ± 0.5‰ and most groundwaters in the basin with more depleted isotopic signatures. Radiocarbon values as pmc range from 0.6% to 85% modern, but it is difficult to assign absolute ages to these, although a value of 20% modern C probably represents the late Pleistocene to Holocene transition. The δ¹³C compositions remain near-constant throughout the basin (median value of −8.1‰ δ¹³C) and indicate that carbonate reactions are unimportant and also that little reaction takes place. There is a smooth decrease in ¹⁴C activity accompanied by a parallel increase in ⁴He accumulations from S–N across the basin, which define the occurrence of a regional flow system. Noble gas temperatures indicate recharge temperatures of about 5.6 °C for late Pleistocene samples, which is some 2–3 °C cooler than the modern mean annual air temperature and the recharge temperature obtained from several Holocene samples. Groundwaters in the Minqin Basin have salinities generally below 1 g/L and are aerobic, containing low Fe but elevated concentrations of U, Cr and Se (mean values of 27.5, 5.8 and 5.3 μg L⁻¹, respectively). Nitrate is present at baseline concentrations of around 2 mg L⁻¹ but there is little evidence of impact of high NO₃ from irrigation returns. Strontium isotope and major ion ratios suggest that silicate reactions predominate in the aquifer. The results have important implications for groundwater management in the Minqin and other water-stressed basins in NW China – a region so far destined for rapid development. The large proportion of the water being used at present is in effect being mined and significant changes are urgently needed in water use strategy.     

In situ laboratory X-ray powder diffraction study of wollastonite carbonation using a high-pressure stage

A high-pressure gas stage, recently developed for in-situ X-ray powder diffraction studies of polymer crystallization under CO_2, has been used to observe the carbonation of wollastonite under various temperature/pressure conditions despite the fact that the stage was not designed for use with moisture-containing samples. The rate of carbonation of wollastonite at 60 °C was found to be pressure-independent. Additional experiments at 34.5 bar between 43 and 73 °C enabled an activation energy of 53 kJ mol⁻¹ to be determined for the rate-limiting step. This value agrees very well with a published value for the leaching of Ca from wollastonite in acidic conditions and suggests that Ca leaching is the rate-limiting step in wollastonite carbonation at these temperatures.     

Solubility of crude oil in methane as a function of pressure and temperature

The solubility of a 44° API (0.806 sp. gr.) whole crude oil has been measured in methane with water present at temperatures of 50 to 250°C and pressures of 740 to 14,852 psi, as have the solubilities of two high molecular weight petroleum distillation fractions at temperatures of 50 to 250°C and pressures of 4482 to 25,266 psi. Both increases in pressure and temperature increase the solubility of crude oil and petroleum distillation fractions in methane, the effect of pressure being greater than that of temperature. Unexpectedly high solubility levels (0.5–1.5 grams of oil per liter of methane—at laboratory temperature and pressure) were measured at moderate conditions (50–200°C and 5076–14504 psi). Similar results were found for the petroleum distillation fractions, one of which was the highest molecular weight material of petroleum (material boiling above 266°C at 6 microns pressure). Unexpectedly mild conditions (100°C and 15,200 psi; 200°C and 7513 psi) resulted in cosolubility of crude oil and methane. Under these conditions, samples of the gas-rich phase gave solubility values of 4 to 5 g/l, or greater.Qualitative analyses of the crude-oil solute samples showed that at low pressure and temperature equilibration conditions, the solute condensate would be enriched in C₅–C₁₅ range hydrocarbons and in saturated hydrocarbons in the C₁₅₊ fraction. With increases in temperature and especially pressure, these tendencies were reversed, and the solute condensate became identical to the starting crude oil.The data of this study, compared to that of previous studies, shows that methane, with water present, has a much greater carrying capacity for crude oil than in dry systems. The presence of water also drastically lowers the temperature and pressure conditions required for cosolubility.The data of this and/or previous studies demonstrate that the addition of carbon dioxide, ethane, propane, or butane to methane also has a strong positive effect on crude oil solubility, as does the presence of fine grained rocks.The n-paraffin distributions (as well as the overall composition) of the solute condensates are controlled by the temperature and pressure of solution and exsolution, as well as by the composition of the original starting material. It appears quite possible that primary migration by gaseous solution could ‘strip’ a source rock of crude-oil like components leaving behind a bitumen totally unlike the migrated crude oil. The data of this study demonstrate previous criticisms of primary petroleum migration by gas solution are invalid; that primary migration by gaseous solution cannot occur because methane cannot dissolve sufficient volumes of crude oil or cannot dissolve the highest molecular weight components of petroleum (tars and asphaltenes).     

Thermobarometric data from a fossil zircon partial annealing zone in high pressure–low temperature rocks of eastern and central Crete, Greece

A fossil partial annealing zone of fission tracks in zircon is described from high pressure–low temperature (HP–LT) rocks of the Phyllite–Quartzite Unit (PQ) on the island of Crete, Greece. Correlation of regional trends in fission track age populations with independent thermobarometric and microstructural data, and with new experimental annealing results, allows a calibration of this low temperature thermochronological method to a degree hitherto not available from other field examples.The zircon fission track (FT) ages of samples from the PQ across Crete range from original detrital signature through reduced to completely reset. The annealing is the result of a single heating period related to the HP–LT metamorphism with near-peak temperatures lasting for only a few million years some time between 24±1 and 20±1 Ma. In eastern Crete, where rocks have experienced temperatures of 300±50 °C and pressures of 0.8±0.3 GPa, zircon FT ages range from 414±24 to 145±10 Ma. Ages above 300 Ma occur mostly near the east coast of the island in rocks which have not been heated to above ca. 280 °C and probably represent a pre-Variscan source. Track lengths are already indicative of a substantial annealing at this temperature. Most of the zircon FT ages from eastern Crete scatter within error around the stratigraphic age. Samples with apparent zircon FT ages significantly younger than the depositional age are only observed in areas where temperatures exceeded ca. 320 °C. Towards the west, a sudden decrease to very young ages ranging from 17±2 to 18±1 Ma reflects a complete resetting at ca. 350 °C. Short tracks, however, are still observed. Throughout the central and western part of the island, ages are consistently below 22 Ma. Thermobarometric data for this area indicate maximum temperatures of 400±50 °C and pressures of 1±0.3 GPa. Only samples from western Crete, which have been exposed to 400±50 °C, show exclusively long tracks. Consequently, the high temperature limit of the zircon partial annealing zone (ZPAZ) appears to be between 350 and 400 °C.A significant influence of elevated confining pressure on the stability of fission tracks in zircon is ruled out by the results of annealing experiments at 0.5 GPa and at different temperatures, which fit the curves previously obtained by other authors at ambient pressure.     

Field experiments yield new insights into gas exchange and excess air formation in natural porous media

Gas exchange between seepage water and soil air within the unsaturated and quasi-saturated zones is fundamentally different from gas exchange between water and gas across a free boundary layer, e.g., in lakes or rivers. In addition to the atmospheric equilibrium fraction, most groundwater samples contain an excess of dissolved atmospheric gases which is called “excess air”. Excess air in groundwater is not only of crucial importance for the interpretation of gaseous environmental tracer data, but also for other aspects of groundwater hydrology, e.g., for oxygen availability in bio-remediation and in connection with changes in transport dynamics caused by the presence of entrapped air bubbles. Whereas atmospheric solubility equilibrium is controlled mainly by local soil temperature, the excess air component is characterized by the (hydrostatic) pressure acting on entrapped air bubbles within the quasi-saturated zone. Here we present the results of preliminary field experiments in which we investigated gas exchange and excess air formation in natural porous media. The experimental data suggest that the formation of excess air depends significantly on soil properties and on infiltration mechanisms. Excess air was produced by the partial dissolution of entrapped air bubbles during a sprinkling experiment in fine-grained sediments, whereas similar experiments conducted in coarse sand and gravel did not lead to the formation of excess air in the infiltrating water. Furthermore, the experiments revealed that the noble gas temperatures determined from noble gases dissolved in seepage water at different depths are identical to the corresponding in situ soil temperatures. This finding is important for all applications of noble gases as a paleotemperature indicator in groundwater since these applications are always based on the assumption that the noble gas temperature is identical to the (past) soil temperature.     

A 40 ka record of temperature and permafrost conditions in northwestern Europe from noble gases in the Ledo‐Paniselian Aquifer (Belgium)

The Ledo‐Paniselian Aquifer in Belgium offers unique opportunities to study periglacial groundwater recharge during the Last Glacial Maximum (LGM), as it was located close to the southern boundary of the ice sheets at that time. Groundwater residence times determined by ¹⁴C and ⁴He reveal a sequence of Holocene and Pleistocene groundwaters and a gap between about 14 and 21 ka, indicating permafrost conditions which inhibited groundwater recharge. In this paper, a dataset of noble gas measurements is used to study the climatic evolution of the region. The derived recharge temperatures indicate that soil temperatures in the periods just before and after the recharge gap were only slightly above freezing, supporting the hypothesis that permafrost caused the recharge gap. The inferred glacial cooling of 9.5°C is the largest found so far by the noble gas method. Yet, compared to other palaeoclimate reconstructions for the region, recharge temperatures deduced from noble gases for the cold periods tend to be rather high. Most likely, this is due to soil temperatures being several degrees higher than air temperatures during periods with extended snow cover. Thus the noble‐gas‐derived glacial cooling of 9.5°C is only a lower limit of the maximum cooling during the LGM. Some samples younger than the recharge gap are affected by degassing, possibly related to gas production during recharge in part of the recharge area, especially during times of melting permafrost. The findings of this study, such as the occurrence of a recharge gap and degassing related to permafrost and its melting, are significant for groundwater dynamics and geochemistry in periglacial areas. Copyright © 2010 John Wiley & Sons, Ltd.     

The effect of decomposition of hydrous minerals on the mechanical properties of rocks at high pressures and temperatures

Extensive experiments have been carried out in which specimens of gypsum, a partially serpentinized peridotite, a serpentinite and a chloritite have been subjected to pressures up to 0.662 GPa together with temperatures up to 780°C and have been deformed at a fixed strain rate of 10⁻⁵/s. The commencement of decomposition of the hydrous minerals is accompanied in sealed specimens by loss of strength, a reduction in sliding friction, and embrittlement of the rocks. Dilatancy-hardening effects are observed. Specimens which are drained to the atmosphere remain strong. In gypsum there is a ten-fold reduction in strength between temperatures of 50°C and 150°C. The partially serpentinized peridotite (40% forsterite, 60% antigorite) which contains 1% of brucite shows a reduction in strength 50% at 300°C, followed by a further ten-fold reduction between 300°C and 700°C. The serpentinite (90% lizardite and chrysotile) shows a ten-fold reduction in strength between 400°C and 600°C. The chloritite (85% ripidolite) shows a reduction of strength by about a half at 300°C; the strength remains approximately constant between 300°C and 600°C, and there is a further five-fold reduction in strength between 600°C and 700°C. The phase changes in the hydrous minerals have been studied by means of differential thermal analysis, X-ray diffraction and optical microscopy, and will be more fully described elsewhere. A detailed discussion is given of the deformation characteristics and mechanisms, with particular emphasis on the role of pore pressure and dilatancy. There is a range of temperature for each of these rocks in which the deformation of sealed samples is most stable, in the sense that brittle faulting accompanied by a stress-drop does not occur. At higher temperatures the rocks become unstable and very weak. Under conditions corresponding to geothermal gradients between 5 K km⁻¹ and 100 K km⁻¹ these rocks would be brittle and weak at shallow depths, and would again become brittle and weak at depths below some level which depends on the rock. Possible implications are discussed in connection with faulting and earthquakes, with syntectonic metamorphism, and with the emplacement of Alpine-type peridotites.     

Atomistic simulation of the mechanisms of noble gas incorporation in minerals

Atomistic simulations have been carried out to investigate the mechanisms of noble gas incorporation in minerals using both the traditional two-region approach and the “supercell” method. The traditional two-region approach has been used to calculate defect energies for Ne, Ar, Kr and Xe incorporation in MgO, CaO, diopside and forsterite in the static limit and at one atmosphere pressure. The possibilities of noble gas incorporation via both substitution and interstitial mechanisms are studied. The favored mechanism varies from mineral to mineral and from noble gas to noble gas. In all minerals studied, the variation of the solution energies of noble gas substitution with atomic radius appears approximately parabolic, analogous to those for 1⁺, 2⁺, 3⁺ and 4⁺ trace element incorporation on crystal lattice sites. Noble gas solution energies thus also fall on a curve, similar to those previously observed for cations with different charges, but with much lower curvature.The “supercell” method has been used to investigate the pressure dependence of noble gas incorporation in the same systems. Results indicate a large variation of the solubility of the larger noble gases, Kr and Xe with pressure. In addition, explicit simulation of incorporation at the (0 0 1) surface of MgO shows that the solubility of the heavier noble gases may be considerably enhanced by the presence of interfaces.     

Dissolved noble gases in the porewater of lacustrine sediments as palaeolimnological proxies

This paper presents results from the numerical modelling of the transport of atmospheric noble gases (He, Ne, Ar, Kr, Xe), tritiated water and ³He produced by radioactive decay of ³H, in unconsolidated lacustrine sediment. Two case studies are discussed: (1) the evolution of ³H and ³He concentrations in the sediment porewater of Lake Zug (Switzerland) from 1953 up to the present; and (2) the response of dissolved atmospheric noble gas concentrations in the sediment porewater of a subtropical lake to an abrupt climatic change that occurred some 10 kyr before the present. (1) Modelled ³H and ³He porewater concentrations are compared with recent data from Lake Zug. An estimate of the effective diffusion coefficients in the sediment porewater is derived using an original approach which is also applicable also to lakes for which the historical ³H and ³He concentrations in the water column are unknown. (2) The air/water partitioning of atmospheric noble gases is sensitive to water temperature and salinity, and thus provides a mechanism by which these environmental variables are recorded in the concentrations of atmospheric noble gases in lakes. We investigate the feasibility of using noble gas concentrations in the porewater of lacustrine sediments as a proxy for palaeoenvironmental conditions in lakes. Numerical modelling shows that heavy noble gases in sediment porewater, because of their comparatively small diffusion coefficients and the strong temperature sensitivity of their equilibrium concentrations, can preserve concentrations corresponding to past lake temperatures over times on the order of 10 kyr. Noble gas analysis of sediment porewaters therefore promises to yield valuable quantitative information on the past environmental states of lakes.     

Low solubility of He and Ar in carbonatitic liquids: Implications for decoupling noble gas and lithophile isotope systems

In order to asses the importance of carbonatitic liquids in transporting noble gases in the mantle, the solubilities of He and Ar in carbonatitic liquids were estimated from analyses of calcium-potassium carbonate glasses that had been synthesized at 1 bar and temperatures between 850 and 950 °C under He or Ar enriched atmospheres. Despite poor reproducibility related to difficulties synthesizing carbonatite glass, we have been able to estimate He and Ar solubilities in carbonatite liquids to be 1 × 10⁻⁸ and 2 × 10⁻⁹ mol g⁻¹ at 1 bar respectively (with ?50% uncertainty). Despite the significant uncertainties on these estimates, it is clear that the noble gases are not massively soluble in carbonatite liquids (within error, these solubilities are identical to their equivalent solubilities in tholeiitic melts). Assuming the results of these low pressure experiments can be applied to mantle conditions, it seems unlikely that carbonatite metasomatism per se transports noble gases within the mantle. It is nevertheless possible that partitioning of lithophile trace elements (including the important radioelements, U, K and Th) and noble gases between a carbonatitic melt and a silicate melt could effectively decouple lithophile and noble gas isotope systematics because the carbonatitic melt expressedly does not transport noble gases, yet is known to efficiently transport incompatible trace elements.     

应用Argus多接收稀有气体质谱仪准确测量空气的Ar同位素组成

稀有气体质谱仪准确测量氩同位素组成是Ar-Ar法高精度定年的前提,目前测量氩同位素主要应用单接收或多接收质谱仪,其中多接收稀有气体质谱仪在数据准确性和重现性等方面具备优势。本文研究了Argus多接收稀有气体质谱仪应用于测量Ar同位素过程中一些主要因素对测量结果准确度和重现性的影响情况。结果表明,整套系统在静态模式下不同时间段的本底值极低,不影响测定;仪器电子倍增器的接收效率优于99.67%,可显著提高Ar低含量样品测量精度,当⁴⁰Ar信号强度低于0.5 V时,用电子倍增器测量⁴⁰Ar/³⁶Ar组成的标准偏差仅为0.11%,而用法拉第杯测量⁴⁰Ar/³⁶Ar组成的标准偏差为0.53%;仪器的质量歧视效应可通过多次循环测量并采用指数定律获得稳定的质量歧视校正因子(此值相对标准偏差为0.0434%),实现对Ar同位素组成的准确校正。本文以测量空气中的氩同位素组成为例,证明了Argus多接收稀有气体质谱仪的测试效率比单个接收器跳峰方式的测试效率高,测试结果更精确,因此适合年轻样品或含钾量极低的样品的Ar-Ar高精度定年工作。     

Assessment of generation temperatures of crude oils

Biological marker maturity parameters were used to estimate the minimum HC generation temperatures of crude oils from Eastern Hungary. More than 50 oils and oil shows were analysed. Molecular- and homologous-ratios of biological marker compounds (triterpanes, steranes, mono- and triaromatic steroid hydrocarbons) were used as maturation parameters. The oils have at least five maturity stages, i.e. they have been generated under different thermal conditions. The highest reservoir temperature in each group was chosen as the best estimate of the groups' temperature just below the generation temperature, i.e. reservoirs of the group might be expected to be at shallower depths (lower temperatures) than those of the generation zone due to vertical migration into pools. For each maturation level, a threshold temperature range for genesis was inferred from reservoir temperatures; they are from 130–135°C for the least mature oils to 210–215°C for the most mature oils. In the least mature oils cracking was not observed, hence carbon–carbon cracking reactions had not taken place during their genesis. The most mature oils are intensively cracked oils; they are almost condensates. Two major genetic groups (families) of oils were found in the area. Both are present in each maturation level. The effects of migration were checked, and no influence on maturation was found. A number of the oils are in overpressured reservoirs within, or just above, the zone of the present-day active oil generation, hence the present-day temperatures of the pools must have been maximum temperatures. Contrary to the traditionally accepted temperature range for petroleum generation–maturation reactions (50–150°C), there is strong evidence from this study that the onset of oil generation requires temperatures higher than 130°C and is still proceeding above 215°C.     

Isotopic fractionation of noble gases by diffusion in liquid water: Molecular dynamics simulations and hydrologic applications

Despite their great importance in low-temperature geochemistry, diffusion coefficients of noble gas isotopes in liquid water (D) have been measured only for the major isotopes of helium, neon, krypton and xenon. Data on the diffusion coefficients of minor noble gas isotopes are essentially non-existent and so typically have been estimated by a kinetic-theory model in which D varies as the inverse square root of the isotopic mass (m): D ∝ m^−0.5. To examine the validity of the kinetic-theory model, we performed molecular dynamics (MD) simulations of the diffusion of noble gases in ambient liquid water. Our simulation results agree with available experimental data on the solvation structure and diffusion coefficients of the major noble gas isotopes and reveal for the first time that the isotopic mass-dependence of all noble gas self-diffusion coefficients has the power-law form D ∝ m^−β with 0 < β < 0.2. Thus our results call into serious question the widespread assumption that the ‘square-root’ model can be applied to estimate the kinetic fractionation of noble gas isotopes caused by diffusion in ambient liquid water. To illustrate the importance of this finding, we used the diffusion coefficients determined in our MD simulations to reconsider the geochemical modeling of ²⁰Ne/²²Ne and ³⁶Ar/⁴⁰Ar isotopic ratios in three representative hydrologic studies. Our new modeling results indicate that kinetic isotopic fractionation by diffusion may play a significant role in noble gas transport processes in groundwater.     

Noble gases in ultramafic xenoliths from San Carlos,Arizona

This work reports the results of noble gas (Ne, Ar, Kr, Xe) analyses of accidental mantle xenoliths from San Carlos, Arizona. Except for the addition of radiogenic ⁴⁰Ar and mass fractionation effects, the isotopic structures of these gases are indistinguishable from atmospheric composition. The absence of ¹²⁹Xe excesses in these rocks may reflect indirect mixing of atmospheric gases with the source region of the xenoliths. The dominant influence on the noble gas abundances in the San Carlos xenoliths appears to have been diffusive gas loss, which may have occurred in a mantle metamorphic event or during contact with the host basanite magma. Evidence is presented for the partitioning of significant amounts of the heavy noble gases into fluid inclusions in the xenolith minerals; the proportion of each gas in the inclusions increases with increasing atomic weight of the gas, possibly reflecting solubility effects. The noble gases are present in greater concentration in pyroxenes than in olivine, similar to the behavior of other incompatible elements.     

Experimental investigations on the formation of excess air in quasi-saturated porous media

The formation of an excess of dissolved gas (“excess air”) in quasi-saturated media was studied by analyzing and interpreting dissolved noble gas concentrations in laboratory column experiments. Using quartz sand filled columns of 1 m length, two different experimental designs were realized. In the first, groundwater recharge was simulated by a unidirectional vertical water flow through the columns. In the second, groundwater level fluctuations in an aquifer zone without active infiltration were reproduced by cyclic water level fluctuations in the columns. The reproducible generation of excess air under these defined, near natural conditions was successful. Partial or complete dissolution of air bubbles entrapped in the quartz sand could be identified as the mechanism responsible for the generation of excess air. Depending on the experimental design, supersaturation of the dissolved atmospheric noble gases ranging between 1.4% ΔNe and 16.2% ΔNe was found. The measured noble gas patterns were interpreted using inverse modeling and conceptual gas exchange models and were compared to results of numerical simulations of gas bubble dissolution in water filled soil columns. The gas composition in most of the samples resembles either unfractionated pure atmospheric excess air or is fractionated in accordance with closed-system equilibration between entrapped air and surrounding water. In addition to the amount of entrapped air, the hydrostatic pressure exerted on the entrapped air bubbles is the dominating parameter responsible for the total amount of dissolved air. The composition of the excess air component is controlled by the water flow regime, the bubble size distribution, the initially dissolved gas concentrations and the initially entrapped gas composition.     

微量陨石激光熔样稀有气体测定方法

微量陨石激光熔样稀有气体测定方法是一种可以在微米尺度上对几毫克陨石样品进行准确稀有气体同位素分析的方法,克服了传统全岩熔融法在测量时存在样品用量大、前处理过程复杂和样品稀有气体分布不均导致不同组分的宇宙射线暴露历史无法进一步区分等问题。但是由于该方法所用样品体积小和样品用量低,要求实验室具有超低本底的稀有气体提取系统,目前国内在微量陨石稀有气体分析技术方面尚处于起步阶段。本文采用金刚石激光样品窗成功研制了超低本底的气体提取系统,通过系统体积标定和天平称量误差、热本底、干扰元素、质量歧视及质谱灵敏度等参数的校正,在中国科学院地质与地球物理研究所建立了微量陨石激光熔样稀有气体测定方法,并对毫克级微量钙长辉长无球粒陨石Millbillillie粉末标样进行了稀有气体同位素含量和比值测定,计算获得准确一致的宇宙暴露年龄。该方法的建立,将为我国迅速发展的比较行星学和深空探测提供重要技术支撑。     

基于多接收稀有气体质谱Argus Ⅵ的激光40Ar-39Ar测年方法及其地质应用

单接收稀有气体质谱仪由于效率、测试精度相对较低,制约了高精度40Ar-39Ar测年的进一步发展.近年来,新一代多接收稀有气体质谱仪在高精度40Ar-39Ar测年中显示出巨大的优势和潜力,并得到了日益广泛的应用.简要介绍了基于多接收稀有气体质谱仪Argus Ⅵ的激光全熔/阶段加热40Ar-39Ar测年实验技术,并对空气氩同位素、标准样品FCs和YBCs以及东昆仑开木其花岗岩体钾长石样品开展了测试研究.结果显示,连续4个月326次循环测试得到的空气氩同位素比值及对应的质量歧视因子（MDF）十分一致,显示了仪器系统良好的稳定性;FCs与YBCs单颗粒全熔“模式年龄”结果表明,仪器在单颗粒、微量样品测试中具有良好的测试精度,“模式年龄”精度可以达到1‰以下（不含衰变常数及标准样品年龄误差）;FCs的单颗粒全熔测试获得的J值及F值（40Ar*/39Ar_K）与萨尔茨堡大学ARGONAUT实验室结果具有相同的变化趋势,均反映了捷克LVR-15反应堆中子通量的梯度变化;对YBCs单颗粒全熔测试获得YBCs与FCs之间的内部校正系数R_FCsYBCs=1.045 304±0.000 752（1σ）,YBCs单颗粒全熔年龄为29.280±0.086（1σ）,与前人结果在误差范围内一致.对东昆仑开木其花岗岩钾长石激光阶段加热测试,得到其坪年龄为229.9±0.2 Ma（1σ,MSWD=1.59）,反等时线年龄为229.8±0.4 Ma（1σ,MSWD=1.71）.综合区域内已有锆石U-Pb年代学及黑云母、钾长石40Ar-39Ar年代学研究成果,认为开木其岩体钾长石40Ar-39Ar年龄反映了东昆仑晚三叠世的一次快速冷却-剥露过程.      

Alternative kinetic models for the interpretation of amino acid enantiomeric ratios in Pleistocene mollusks: Examples from California, Washington, and Florida

Alternative kinetic models for amino acid racemization in Pleistocene molluscan samples are compared by examination of results for samples from marine Pleistocene deposits in California, Washington, and Florida. Linear kinetic models previously have been applied to the Florida samples [Mitterer, R.M. (1975). Earth and Planetary Science Letters 28, 275–282.] because these kinetics were observed in laboratory pyrolysis experiments with the particular genus involved (Mercenaria). Nonlinear kinetic models, extrapolated from deep-sea foraminifera racemization kinetics, are applied to samples of Protothaca and Saxidomus from California and Washington and seem more consistent with their local chronologic and stratigraphic control. Average or effective diagenetic temperatures can be estimated by each of these models if reliably dated samples are available. Linear models applied to such samples from California and Florida suggest average diagenetic temperatures that are cooler (by as much as 10°C) than would be inferred from available paleoclimatic records. Nonlinear kinetic models yield estimates of average diagenetic temperatures that are more consistent with these records: full-glacial (i.e., approximately 18,000 yr BP) temperature reductions of between 2 and 6°C are inferred for coastal California and southern Florida. The nonlinear kinetic model is used to expand (by a factor of 2.5 to 3.0) the time scale proposed by Mitterer (1975) for five marine Pleistocene units of Florida.