硫同位素在岩浆Cu-Ni-PGE硫化物矿床成因研究中的应用

岩浆Cu-Ni-PGE硫化物矿床形成的重要过程是硫化物熔体的熔离,而关键在于成矿岩浆中硫的过饱和。判断岩浆Cu-Ni-PGE硫化物矿床中硫来源最直接有效的方法就是研究其硫同位素特征。当矿床的硫同位素值超出了地幔硫同位素的组成范围,揭示了壳源硫的混入。如果矿床硫同位素值δ³⁴S落入地幔值的范围内,则需要结合围岩硫同位素组成、并考虑岩浆房中是否发生了硫同位素交换反应来进一步判断是否有围岩硫的加入。异常的Δ³³S值主要出现在太古宙沉积硫化物中,利用δ³⁴S与Δ³³S相结合可识别样品中是否存在太古宙岩石中来源的硫;然而,一些太古宙岩石中硫化物Δ³³S值也可以在0‰附近;在一些后太古宙岩石的硫化物中也发现了异常的Δ³³S值;因此在根据Δ³³S值来判断S是否来源于太古宙岩石时应谨慎。仔细测定围岩和潜在的混染源的硫同位素组成对于准确评价岩浆Cu-Ni-PGE硫化物矿床中S的来源是非常关键的。硫同位素和其他同位素如镍同位素、铜同位素、铁同位素相结合也许对于认识岩浆Cu-Ni-PGE硫化物矿床中成矿物质来源及成矿岩浆演化过程能够提供新的思路。     

一种改进的硫酸盐硫同位素制样方法

硫酸盐-氧化亚铜-石英砂直接热解法需要设置分离SO₂、H₂O和CO₂的冷阱。研究表明H₂O和CO₂主要来自试剂石英砂的气液包裹体。采取石英砂预处理措施能大大减少制样过程引入的H₂O和CO₂。改进后的制样系统简单、易操作,且与硫化物同位素样品制备兼容。     

东沟坝多金属矿床硫同位素交换动力学

本文详细研究东沟坝多金属矿床的硫同位素特征，并根据同位素资料评估硫在成矿溶液中的最短停留时间和成矿机理。根据硫化物和硫酸盐在化学及同位素交换反应的过程中同样都包含有分子结构中的硫键断开和硫原子的交换，提出了化学平衡是同位素平衡的先决条件。指出在不少成矿温度低于３５０℃的热液矿床中，共沉淀的硫化物矿物和硫酸盐矿物之间的硫同位素时常没有达到平衡     

基于共生金属硫化物硫同位素分馏程度约束热液活动温度：以川中下寒武统龙王庙组为例

硫循环及硫同位素(δ³⁴S)分馏研究对地表圈层的成岩作用具有重要意义,其中多种金属硫化物中硫同位素的分馏程度可以约束成矿热流体温度,进而作为地温计证据约束热液活动。四川盆地龙王庙组储集层内的热液改造影响着该储集层的非均质性,本研究着重讨论目的层中与热液成因白云石所伴生的黄铁矿(FeS₂)-黄铜矿(CuFeS₂)成矿现象：基于详尽的岩石学证据,应用纳米二次离子探针(NanoSIMS)对金属硫化物内部硫同位素分布进行测定,并基于热力学驱动下的硫化物间平衡分馏程度计算其成矿温度,进而约束层段内热液活动过程。研究发现：(1)微区硫同位素分布显示黄铁矿(FeS₂)与黄铜矿(CuFeS₂)沉淀过程中不仅存在热力学分馏,还存在动力学分馏现象,其中动力学分馏程度可以达到40.1‰,应用NanoSIMS微区测定手段可以有效剔除动力学分馏数据影响,获取热力学平衡分馏数据;(2)黄铁矿(FeS₂)与黄铜矿(CuFeS₂)成矿过程或利用不同的硫源,其中黄铁矿...     

由BaSO4直接热分解制备用于同位素分析的SO2

硫同位素地质研究工作中,经常遇到的研究对象是硫酸盐矿物。如何把这些硫酸盐矿物转化为适于质谱测定硫同位素组成的SO₂气体,是我国硫同位素地质研究中急待建立的实验手段之一。 经典的方法中,可溶于水的硫酸盐,通常是先把它沉淀为BaSO₄,然后通过一系列的化学反应转化为SO₂。 七十年代初期,B.D.Holt等人提出直接加热分解BaSO₄制备SO₂的方法。     

黔西北铅锌矿床硫同位素地球化学研究

位于扬子地块西南缘的川滇黔铅接壤区,是我国独具特色的铅锌银多金属矿集区,黔西北铅锌矿床是其重要的组成部分。黔西北铅锌成矿区内业已发现铅锌矿床(点)100余处,其赋矿围岩为泥盆至二叠系白云岩或白云质灰岩,而其分布严格受到三条区域性构造带的控制,其中大部分矿(化)体产于北西向褶皱+断裂构造体系中。在系统收集前人发表的有关矿床硫同位素数据基础上,对成矿流体中硫的来源及形成机制进行了详细的探讨。11个矿床的150件硫化物硫同位素组成介于+3.5‰⁺20.3‰,多数集中在+6‰+20.3‰,多数集中在+6‰⁺20‰分布,峰值处于+10‰+20‰分布,峰值处于+10‰⁺14‰,具有明显的塔式正态分布特征。可见硫化物明显富集重硫同位素,与在0‰附近的陨石硫不同。前人研究发现泥盆至二叠系沉积地层中,普遍发育膏盐层,其中硫酸盐硫同位素组成介于+12‰+14‰,具有明显的塔式正态分布特征。可见硫化物明显富集重硫同位素,与在0‰附近的陨石硫不同。前人研究发现泥盆至二叠系沉积地层中,普遍发育膏盐层,其中硫酸盐硫同位素组成介于+12‰⁺28‰,与泥盆至二叠纪海水硫酸盐硫同位素组成相似(+18‰+28‰,与泥盆至二叠纪海水硫酸盐硫同位素组成相似(+18‰⁺30‰)。硫酸盐热化学还原(TSR)可以使体系中的硫同位素组成降低15‰,因此,黔西北铅锌矿床成矿流体中的还原硫主要是TSR的产物,即蒸发岩是主要的硫源。     

环境同位素硫在大同南寒武-奥陶系地下水资源研究中的应用

对山西大同口泉沟南寒武-奥陶系碳酸盐岩地下水(岩溶水)资源的开发研究中,利用不同价态硫富集34S的不同以及硫同位素分馏,主要是硫酸盐和硫化物中δ34S(SO₄2-)、δ34S(HS-)的变化,分析了岩溶水的来源,区分出表征循环交替和补给条件的三种地下水类型和环境,识别出口泉南水文地质区内各个地下水子系统及其相互关系。对岩溶水开发中泉域划分问题,使用硫同位素之间的关系,并结合硫酸盐中氧同位素δ18O(SO₄2-)以及14C关系,表明本区与相邻的两泉域相互独立。岩溶水中δ34S(SO₄2-)、δ34S(HS-)和δ18O(SO₄2-)有很大变幅,神头泉Z1岩溶水有罕见的异常值。     

大西洋洋中脊TAG热液区硫化物铅和硫同位素研究

位于大西洋洋中脊26.08°N的 TAG 热液区是目前己知的赋存在无沉积物覆盖的洋中脊区的一个最大的海底热液硫化物矿床。新测得来自 ODP-158航次钻孔的9件热液硫化物的铅、硫同位素组成;2件铁锰氧化物和1件底盘玄武岩的铅同位素组成。结果表明,矿石硫化物的铅同位素组成~(206)Pb/~(204)Pb 为18.2343～18.3181,~(207)pb/~(204)Ph 为15.4717～15.5061,~(208)Pb/~(204)Pb 为37.7371～37.8417;它们位于该区底盘玄武岩(~(206)Pb/~(204)Pb=18.1454,~(207)Pb/~(204)Pb=15.4572,~(208)Pb/~(204)Pb=37.6534)和近洋底铁锰氧化物(~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb,~(208)Pb/~(204)Pb 分别为18.6907～18.9264,15.5615～15.6279,38.1164～38.3687)的铅同位素组成之间。三者呈线性相关关系,说明硫化物中铅来源于地幔(玄武岩)与海水(铁锰氧化物)的两端元混合。硫化物的硫同位素组成δ~(34)S 为6.2‰～9.5‰,它明显高于地幔玄武岩的硫同位素组成(δ~(34)S=±0‰),也高于东太平洋海隆 EPR21°N(δ~(34)S=0.9‰～4.0‰)和大西洋洋中脊 MAR23°N(δ~(34)S=1.2‰～2.8‰)等热液活动区硫化物的硫同位素组成,这一特征反映了 TAG 热液体系中硫来源于地幔玄武岩硫与海水硫酸盐无机还原作用产生的硫的两端元混合。此,铅硫同位素研究为现代大洋底热液硫化物矿床形成过程中矿质来源及流体混合作用提供了十分有益的信息。     

金川铜镍矿床硫同位素地球化学

本文利用硫同位素作为地球化学指示剂对金川硫化铜镍矿床的成矿作用和硫源进行分析,获得结论性的认识主要有:(1)交代型矿石中大多数黄铜矿与黄铁矿不属于同一成矿阶段的产物,且二者也没有在新的条件下建立硫同位素交换平衡;(2)在早期超基性岩型矿石到晚期贯入型矿石的漫长成矿作用过程中,硫同位素分馏不显著,表明成矿物质是均一化程度很高的高温浓硫化物熔融体;(3)硫来源于地幔。     

与火山岩容矿有关的海底热水沉积矿床硫同位素地球化学证据

对国内与火山岩容矿有关的海底热水沉积矿床新疆阿巴宫、铁-铅锌矿、甘肃桦树沟铁-铜矿床、新疆阿舍勒铜锌矿、新疆阿尔泰可可塔勒铅锌矿等矿床硫化物进行硫同位素测定,这些矿床硫化物和硫酸盐的硫同位素组成分别为-4.3‰~1‰(阿巴宫)、+8.1‰~+33.4‰(桦树沟)、-3.3‰~+8.2‰(阿舍勒矿床硫化物)、-20.6‰~5.1‰(阿尔泰可可塔勒)。硫化物的硫同位素变化范围较小,硫同位素可以达到平衡,也可以没有达到平衡,获得的δ34SΣS值有+18‰~29‰之间,δ34SΣS值高;表明与火山岩控矿有关的海底热水沉积矿床热液中硫的来源,不是直接来源岩浆去气的硫,而是岩浆去气硫与海水硫酸盐硫混合而成的硫。     

Primary fluids entrapped at blueschist to eclogite transition: evidence from the Tianshan meta-subduction complex in northwestern China

Orthopyroxene and olivine exposed along the rim of a harzburgite xenolith from La Palma (Canary Islands) show polycrystalline selvages and diffusion zones that result from contact with mafic, alkaline, silica-undersaturated melts during at least 10-100 years before eruption. The zoned selvages consist of a fine-grained reaction rim towards the xenolith and a coarser grained, cumulate-like layer towards the melt contact. The diffusion zones are characterized by decreasing magnesium number from about 89-91 in the xenolith interior to 79-85 at the rims, and clearly result from Fe-Mg exchange with surrounding mafic melt. The width of the diffusion zones is 80-200 µm in orthopyroxene and 1,020-1,730 µm in olivine. Orthopyroxene also shows decreasing Al₂O₃ and Cr₂O₃ and increasing MnO and TiO₂ towards the reaction rims. Textural relations and comparisons with dissolution experiments suggest that orthopyroxene dissolution by silica-undersaturated melt essentially ceased after days to weeks of melt contact, possibly because of decreasing temperature and formation of the reaction rims. The short dissolution phase was followed by prolonged growth of diffusion zones through cation exchange between xenolith minerals and melt across the reaction rims, and by the growth of cumulus crystals. The observations indicate that orthopyroxene xenocrysts and harzburgite xenoliths can survive in mafic, silica-undersaturated, subliquidus magmas at 1,050-1,200 °C and 200-800 MPa for tens of years. Modeling and comparison of the diffusion zones indicate that the average Fe-Mg interdiffusion coefficient D_FeMg in orthopyroxene is 2 log units lower than that in olivine; at 1,130 °C and QFM-buffered oxygen fugacity, D_FeMg^opx = 3 ×10 ^{- 19}  m²  s^{- 1}D_{FeMg}^{opx} = 3 \times 10^{ - 19} \,{\rm m}^2 \,{\rm s}^{{\rm - 1}} . The new data overlap well with recently published data for D_FeMg in diopside, and indicate that D_FeMg ^opxD_{FeMg\,}^{opx} (as predicted by previous authors) may be extrapolated to higher temperatures and oxygen fugacities. It is suggested that D_FeMg ^opx D_{FeMg\,}^{opx} and D_FeMg in Mn-poor ferromagnesian garnet are similar within 0.5 log units at temperatures between 1,050 and 1,200 °C.     

平衡热液体系中硫同位素演化的几个图解

根据含硫矿物的同位素组成推断热液矿床成因是很有意义的。 1968年首先由H.Sakai指出热液的温度和pH值可以影响硫化物的同位素组成。接着,1972年H.Ohmoto以及1979年他和R.O.Rye系统讨论了平衡条件下热液的物理化学条件对硫同位素分馏的影响,建立了高温热液系统和低温热液系统的热液流体以及含硫矿物与热液成分和物理化学条件(温度、压力、氧逸度和酸碱度等)之间的数学表达式。     

The effect of net-transfer reactions on the isotopic composition of minerals

To interpret correctly the isotopic composition of metmorphic rocks and minerals, the effect of nettransfer reactions must be quantitatively evaluated. Such evaluation requires a complete set of linearly independent, net-transfer reactions that fully describe the reacting system. The set of net-transfer reactions is then coupled with mass-balance equations for stable isotopes. Reaction spaces can be contoured with isopleths of °¹⁸O, °¹³C, and D of minerals which allows evaluation of the effect of different reactions and bulk compositions on the stable isotopic composition of minerals and rocks. Using this approach, we examined the effect of fractionation of isotopes due to net-transfer reactions at the biotite and second-sillimanite isograds in northern New England. Our analysis shows that the shift in °¹³C and °¹⁸O at an isograd depends strongly upon the overall net-transfer reaction at the isograd and the bulk composition of the rock. The use of model isograd reactions to determine isotopic shifts, therefore, can lead to serious errors in the interpretation of isotopic data. At the second-sillimanite isograd °¹⁸O _qtz (quartz), °¹⁸O _kspar (K feldsdpar), and °¹⁸O _wr (whole rock) decrease by 0.5, 1.0, and 0.8 per mil, respectively. Quantitative evaluation of the effect of fractionation of isotopes by net-transfer reactions shows that: (1) the relative changes in oxygen isotopes across the isograd could be caused by distillation of fluids during develatilization reactions; (2) the magnitude of the observed isotopic shifts often differs by a factor of 2 from the calculated shifts due to reaction progress alone. The difference between observed and calculated shifts is attributed to either, differences in bulk composition between individual rocks, or, to isotopic exchange between minerals after peak metamorphism. At the biotite isograd the shifts in carbon and oxygen isotope values are different from predicted shifts caused by net-transfer reactions alone. This discrepancy suggests that fluids infiltrated the rocks during the formation of the biotite isograd.     

Isotopic evidence of the origin of mineralized waters from the Central Carpathian Synclinorium,SE Poland

Stable isotopes of hydrogen and oxygen were determined in 45 samples of water (27 samples of oil-associated waters, 17 samples of mineral waters used by spas, 1 sample of surface river water) from the Central Carpathian Synclinorium, covering a stratigraphic range of flysch sediments from Upper Cretaceous to Oligocene. Moreover, oxygen isotope compositions of authigenic calcite (vein and cement) from core samples of four boreholes were made to evaluate isotopic equilibrium between waters and diagenetic carbonates as a function of temperature. The saline and brackish waters (TDS from1 g/l to 48.9 g/l) considered here, generally belong to four hydrogeochemical classes: Na-Cl, Cl-HCO₃-Na, HCO₃-Cl-Na and HCO₃-Na. Their isotopic composition causes them to fall to the right of Global Meteoric Water Line (GMWL) showing enrichment in ¹⁸O and ²H. On the other hand, relative to Standard Mean Ocean Water (SMOW) they are depleted in ²H and both depleted and enriched in ¹⁸O. The observed isotopic composition can be explained by the three-component mixing of surface water, diagenetically modified sea water (kind of connate water) and metamorphic water. The mixing is accompanied by an exchange of oxygen isotopes between water and carbonate cements causes ¹⁸O enrichment of interstitial waters. The contribution of isotopic exchange between water and clay minerals in shales was evaluated only theoretically basing of the literature.     

Experimental investigation of zoisite–clinozoisite phase equilibria in the system CaO–Fe2O3–Al2O3–SiO2–H2O

The system Ca₂Al₃Si₃O₁₁(O/OH)-Ca₂Al₂FeSi₃O₁₁(O/OH), with emphasis on the Al-rich portion, was investigated by synthesis experiments at 0.5 and 2.0 GPa, 500-800 °C, using the technique of producing overgrowths on natural seed crystals. Electron microprobe analyses of overgrowths up to >100 µm wide have located the phase transition from clinozoisite to zoisite as a function of P-T-X_ps and a miscibility gap in the clinozoisite solid solution. The experiments confirm a narrow, steep zoisite-clinozoisite two-phase loop in T-X_ps section. Maximum and minimum iron contents in coexisting zoisite and clinozoisite are given by X_ps^zo (max) = 1.9*10 ^{- 4} T+ 3.1*10 ^{- 2} P - 5.36*10 ^{- 2}{\rm X}_{{\rm ps}}^{{\rm zo}} {\rm (max) = 1}{\rm .9*10}^{ - 4} T{\rm + 3}{\rm .1*10}^{ - 2} P - {\rm 5}{\rm .36*10}^{ - 2} and X_ps^czo (min) = (4.6 * 10 ^{- 4} - 4 * 10 ^{- 5} P)T + 3.82 * 10 ^{- 2} P - 8.76 * 10 ^{- 2}{\rm X}_{{\rm ps}}^{{\rm czo}} {\rm (min)} = {\rm (4}{\rm .6} * {\rm 10}^{ - {\rm 4}} - 4 * {\rm 10}^{ - {\rm 5}} P{\rm )}T + {\rm 3}{\rm .82} * {\rm 10}^{ - {\rm 2}} P - {\rm 8}{\rm .76} * {\rm 10}^{ - {\rm 2}} (P in GPa, T in °C). The iron-free end member reaction clinozoisite = zoisite has equilibrium temperatures of 185ᇆ °C at 0.5 GPa and 0ᇆ °C at 2.0 GPa, with (H_r⁰=2.8ǃ.3 kJ/mol and (S_r⁰=4.5ǃ.4 J/mol2K. At 0.5 GPa, two clinozoisite modifications exist, which have compositions of clinozoisite I ~0.15 to 0.25 X_ps and clinozoisite II >0.55 X_ps. The upper thermal stability of clinozoisite I at 0.5 GPa lies slightly above 600 °C, whereas Fe-rich clinozoisite II is stable at 650 °C. The schematic phase relations between epidote minerals, grossular-andradite solid solutions and other phases in the system CaO-Al₂O₃-Fe₂O₃-SiO₂-H₂O are shown.     

A theoretical approach to understanding the isotopic heterogeneity of mid-ocean ridge basalt

We have developed an idealized mathematical model to understand the isotopic variability of the mantle and its relation to the observed variations in isotopic ratios ¹⁴³Nd/¹⁴⁴Nd, ⁸⁷Sr/⁸⁶Sr, ¹⁷⁶Hf/¹⁷⁷Hf, ²⁰⁸Pb/²⁰⁴Pb, ²⁰⁶Pb/²⁰⁴Pb, and ²⁰⁷Pb/²⁰⁴Pb measured on mid-ocean ridge basalt (MORB). We consider a simple box model of mantle processes. A single melt region produces a melt fraction F of melt, and the average time since a given parcel of mantle material last visited this region is given by the time scale τ_melt. The melt region fractionates the parent/daughter ratios. Over time this leads to variations in the mantle isotopic ratios as the parent decays to the daughter. Key assumptions are that the half-life of the parent isotope is large compared with τ_melt, that the flow is strongly stirring, and that the mantle has reached a statistical steady state. This enables us to neglect the specifics of the underlying flow. Sampling from our model mantle is dealt with by averaging over a large number N of samples to represent the mixing after melting.The model predicts a probability density for isotopic ratios in MORB which, with exception of the Pb isotopes, are consistent with measurements. Fitting the MORB data to this model gives estimates of the model parameters F, τ_melt, and N. Small melt fractions with F around 0.5% are essential for a good fit, whereas τ_melt and N are less well constrained. τ_melt is estimated at around 1.4 to 2.4 Ga, and N is of the order of hundreds. The model predicts a larger variability for the Pb isotopes than that observed. As has been stated by many previous authors, it appears that fundamental differences exist between the dynamics of Pb isotopes and those of Nd, Sr and Hf isotopes.     

Grain boundary diffusion of Si, Mg, and O in enstatite reaction rims: a SIMS study using isotopically doped reactants

Diffusion-controlled growth rates of polycrystalline enstatite reaction rims between forsterite and quartz were determined at 1,000 °C and 1 GPa in presence of traces of water. Iron-free, pure synthetic forsterite with normal oxygen and silicon isotopic compositions and quartz extremely enriched in ¹⁸O and ²⁹Si were used as reactants. The relative mobility of ¹⁸O and ²⁹Si in reactants and rims were determined by SIMS step scanning. The morphology of the rim shows that enstatite grows by a direct replacement of forsterite. Rim growth is modelled within a mass-conserving reference frame that implies advancement of reaction fronts from the initial forsterite-quartz interface in both directions. The isotopic compositions at the two reaction interfaces are controlled by the partial reactions Mg₂SiO₄=0.5 Mg₂Si₂O₆+MgO at the forsterite-enstatite, and MgO+SiO₂=0.5 Mg₂Si₂O₆ at the enstatite-quartz interface, implying that grain boundary diffusion of MgO is rate-controlling. Isotopic profiles show no silicon exchange across the propagating reaction interfaces. This propagation, controlled by MgO diffusion, is faster than the homogenisation of Si by self-diffusion behind the advancing fronts. From this, and using % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamiramaaDa % aaleaacaWGtbGaamyAaiaacYcacaWGfbGaamOBaaqaaiaadAfacaWG % VbGaamiBaaaaaaa!3DD2! D_Si,En^VolD_{Si,En}^{Vol} at dry conditions from the literature, results a % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGabmirayaafa % Waa0baaSqaaiaadofacaWGPbGaaiilaiaadweacaWGUbaabaaaaOGa % eqiTdqgaaa!3CCD! D￠_Si,En dD'_{Si,En}^{} \delta value of 3᎒^-24 m³ s^-1 at 1,000 °C. The isotopic profiles for oxygen are more complex. They are interpreted as an interplay between the propagation of the interfaces, the homogenisation of the isotope concentrations by grain boundary self-diffusion of O within the rim, and the isotope exchange across the enstatite-quartz interface, which was open to ¹⁸O influx from quartz. Because of overlapping diffusion processes, boundary conditions are unstable and D´_Ox,En' cannot be quantified. Using measured rim growth rates, the grain boundary diffusivity D´_MgO' of MgO in iron-free enstatite is 8᎒^-22 m³ s^-1 at 1,000 °C and 1 GPa. Experiments with San Carlos olivine (fo₉₂) as reactant reveal lower rates by a factor of about 4. Our results show that isotope tracers in rim growth experiments allow identification of the actual interface reactions, recognition of the rate-controlling component and further calculation of D´' values for specific components.     

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.     

Equilibrium H/H fractionations in organic molecules: I. Experimental calibration of ab initio calculations

Carbon-bound hydrogen in sedimentary organic matter can undergo exchange over geologic timescales, altering its isotopic composition. Studies investigating the natural abundance distribution of ¹H and ²H in such molecules must account for this exchange, which in turn requires quantitative knowledge regarding the endpoint of exchange, i.e., the equilibrium isotopic fractionation factor (α_eq). To date, relevant data have been lacking for molecules larger than methane. Here we describe an experimental method to measure α_eq for C-bound H positions adjacent to carbonyl group (H_α) in ketones. H at these positions equilibrates on a timescale of days as a result of keto-enol tautomerism, allowing equilibrium ²H/¹H distributions to be indirectly measured. Molecular vibrations for the same ketone molecules are then computed using Density Functional Theory at the B3LYP/6-311G** level and used to calculate α_eq values for H_α. Comparison of experimental and computational results for six different straight and branched ketones yields a temperature-dependent linear calibration curve with slope = 1.081−0.00376T and intercept = 8.404−0.387T, where T is temperature in degrees Celsius. Since the dominant systematic error in the calculation (omission of anharmonicity) is of the same size for ketones and C-bound H in most other linear compounds, we propose that this calibration can be applied to analogous calculations for a wide variety of organic molecules with linear carbon skeletons for temperatures below 100 °C. In a companion paper (Wang et al., 2009) we use this new calibration dataset to calculate the temperature-dependent equilibrium isotopic fractionation factors for a range of linear hydrocarbons, alcohols, ethers, ketones, esters and acids.     

The role of the grain boundary at chemical and isotopic fronts in marble during contact metamorphism

Carbon and oxygen isotopic profiles around a low pressure metasomatic wollastonite reaction front in a marble of the Hida metamorphic terrain, central Japan, display typical metamorphic fluid-enhanced isotopic zonations. Isotopic profiles obtained from detailed microscale analyses perpendicular to the chemical reaction front in calcite marble show that diffusion-enhanced isotopic exchange may control these profiles. Carbon and oxygen isotopic behaviour in grain boundaries is remarkably different. Oxygen isotopic troughs (¹⁸O depleted rims) around the calcite-grain boundaries are widely observed in this contact aureole, demonstrating that diffusion of oxygen in calcite grain boundary dominates over lattice diffusion in calcite. In contrast, no difference is observed in carbon isotopic profiles obtained from grain cores and rims. There is thus no specific role of the grain boundary for diffusion of carbonic species in the metamorphic fluid during transportation. Carbon chemical species such as CO₂ and CO₃ ions in metamorphic fluid migrate mainly through lattice diffusion. The carbon and oxygen isotope profiles may be modelled by diffusion into a semi-infinite medium. Empirically lattice diffusion of oxygen isotopes is almost six times faster than that of carbon isotopes, and oxygen grain-boundary diffusion is ten times faster than oxygen lattice diffusion. Oxygen isotopic results around the wollastonite vein indicate that migration of the metamorphic fluid into calcite marble was small and was parallel to the aquifer. From the stability of wollastonite and the attainment of oxygen isotopic equilibrium, we suggest that diffusion of oxygen occurred through an aqueous fluid phase. The timescale of formation of the oxygen isotopic profile around the wollastonite vein is calculated to be about 0.76 × 10⁶ years using the experimentally determined diffusion constant. Received: 14 January 1997 / Accepted: 23 April 1998