Hydrogen isotope exchange between clay minerals and sea water

The D/H ratios of separated size fractions of clay minerals in two deep sea sediments taken from depths of 30 and 1100cm in a North Pacific Ocean core were measured to investigate the extent of hydrogen isotope exchange between detrital clay minerals and sea water. The D/H ratio of each size fraction of the shallower sample was compared with that of the corresponding size fraction of the deeper sample. No differences were detected between D/H ratios of corresponding size fractions from the two levels in the core except for the <0.1μm size fraction, which makes up only 5% of the sample. Even in this size fraction only about 8–28% D/H exchange is apparent. This is interpreted as indicating that no significant hydrogen isotope exchange between clay minerals and sea water has occurred during the past 2–3 Myr. Therefore information concerning the provenance and mode of formation of detrital clay minerals can be obtained from the D/H ratios of deep sea sediments younger than 2–3 Myr.     

Hydrogen and oxygen isotope exchange reactions between clay minerals and water

The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100–350° for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100°. Exchange rates were 3–5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure.Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O¹⁸ exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O¹⁸ exchange.At 350° kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O¹⁸ exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor.     

The equilibration of clay minerals with sea water: exchange reactions

Studies of seawater-sediment and seawater-clay mineral exchange equilibria demonstrate that rinsing procedures employed in many previous studies have grossly shifted the exchange equilibria away from the true seawater conditions. Exchange complements have been determined here by measurement of compositional changes in seawater that result from reaction with clays, thereby avoiding rinsing. These data show that exchangeable Na⁺ is normally greater than or equal to exchangeable Mg²⁺ on clays and sediments in exchange equilibrium with seawater.On introduction to seawater, fluvial clays are shown to give up their exchangeable Ca²⁺ for Na⁺, a process of importance in the geochemical budget of Na⁺.     

碾子山晶洞碱性花岗岩矿物-水氧同位素交换反应动力学

对黑龙江碾子山碱性花岗岩的全岩及其主要单矿物进行了氧同位素分析，结果表明，全岩和单矿物不仅δ^18O 值变化范围较大（全岩－2．4－2．0‰，石英0．0－5．8‰，碱性长石－3．8－0．1‰，磁铁矿－8．5－1．0‰），而且强烈亏损^18O。共生矿物之间表现出明显不平衡的氧同位素分馏特征，指示在花岗岩侵位之后与水之间发生了同位素交换，根据锆石和现代大气降水的氧同位素组成，对岩石与外来流体的δ^18O值进行了估计，多维矿水－岩反应时限约为0．3－3Ma，水／岩比（氧摩尔比）介于0．11－1．02之间。水－岩反应温度较高（约400度）和反应时间较长是导致石英δ^18O值降低的主要原因。     

Kinetic theory of oxygen isotopic exchange between minerals and water

Kinetic and mass conservation equations are used to describe oxygen isotopic exchange between minerals and water in “closed” and open hydrothermal systems. In cases where n coexisting mineral phases having different reaction rates are present, the exchange process is described by a system of n + 1 simultaneous differential equations consisting of n pseudo first-order rate equations and a conservation of mass equation. The simultaneous solutions to these equations generate curved exchange trajectories on δ-δ plots. Families of such trajectories generated under conditions allowing for different fluid mole fractions, different fluid isotopic compositions, or different fluid flow rates are connected by positive-sloped isochronous lines. These isochrons reproduce the effects observed in hydrothermally exchanged mineral pairs including 1) steep positive slopes, 2) common reversals in the measured fractionation factors (δ), and 3) measured fractionations that are highly variable over short distances where no thermal gradient can be geologically demonstrated.     

The effect of fluid pressure on oxygen isotope exchange between feldspar and water

The rate of oxygen isotope exchange between adularia and 2 M KCl solution has been measured at 650°C at pressures from 125 to 4000 bar. Isotropie diffusion coefficients calculated from these data show a positive dependence on the fluid pressure. This dependence is opposite to the predicted effect of hydrostatic pressure and is attributed to the activity of ‘water’ (H₂O, H⁺ or OH^?) in the feldspar.     

Oxygen isotope fractionation between hydroxide minerals and water

The modified increment method has been applied to the calculation of oxygen isotope fractionation factors for hydroxide minerals. The results suggest the following sequence of ¹⁸O-enrichment in the common hydroxides: limonite > gibbsite > goethite > brucite > diaspore. The hydroxides are significantly enriched in ¹⁸O relative to the corresponding oxides. The sequence of ¹⁸O-enrichment in the hydroxides and oxides of trivalent cations is as follows: M(OH)₃ > MO(OH) > M₂O₃. There are also considerable fractionations within the polymorphos of Al(OH)₃. The internally consistent fractionation factors for hydroxide–water systems are obtained for the temperature range of 0 to 1200 °C, which are comparable with the data derived from synthesis experiments and natural samples at surficial temperatures. Temperature dependence of oxygen isotope fractionations between goethite, gibbsite, boehmite and diaspore and water are significant enough for the purpose of geothermometry. Thus the hydroxide–water pairs hold great promise of serving as reliable paleothermometers in surficial geological environments. Received: 22 January 1997 / Revised, accepted: 2 June 1997     

Hydrogen isotope fractionation between OH-bearing minerals and water

Hydrogen isotope fractionation factors between hydroxyl-bearing minerals and water were determined at temperatures ranging between 400 and 850°C. The hydrogen isotope exchange rates for the mineral-water pairs examined were very slow. In most cases it was necessary to use an interpolation method for the determination of the hydrogen isotope equilibrium fractionation factor, α_e.For the temperature range of 450–850°C the hydrogen isotope fractionation factors for the mica-water and amphibole-water systems are simply expressed as a function of temperature and the molar fractions of the six-fold coordinated cations in the crystal, regardless of mineral species, as follows: 10³ In α_{e(mineral-water)} = ? 22.4 (10⁶T^?2) + 28.2 + (2X_Al ? 4X_Mg ? 68X_Fe), where X is the molar fraction of the cations. As the equation indicates, for any specific composition of the OH-bearing minerals, the change of α_e with temperature, over the temperature range investigated, is the same for all minerals studied. Thus for any specified values of X_Al, X_Mg, and X_Fe for these minerals, the relationship between α_e and T is 10³ In α_e = αT^?2 + k. Consequently, hydrogen isotope fractionation among coexisting minerals is temperature independent and cannot be used as a hydrogen isotope geothermometer.Some exceptions to the above general observations exist for minerals such as boehmite and kaolinite. In these minerals hydrogen bonding modifies the equilibrium hydrogen isotopic fractionation between mineral and water.     

Prediction of high-temperature oxygen isotope fractionation factors between mantle minerals

The increment method is adopted to calculate oxygen isotope fractionation factors for mantle minerals, particularly for the polymorphic phases of MgSiO₃ and Mg₂SiO₄. The results predict the following sequence of ¹⁸O-enrichment: pyroxene (Mg,Fe,Ca)₂Si₂O₆>olivine (Mg,Fe)₂SiO₄>spinel (Mg,Fe)₂SiO₄>ilmenite (Mg,Fe, Ca)SiO₃>perovskite (Mg,Fe,Ca)SiO₃. The calculated fractionations for the calcite-perovskite (CaTiO₃) system are in excellent agreement with experimental calibrations. If there would be complete isotopic equilibration in the mantle, the spinel-structured silicates in the transition zone are predicted to be enriched in ¹⁸O relative to the perovskite-structured silicates in the lower mantle but depleted in ¹⁸O relative to olivines and pyroxenes in the upper mantle. The oxygen isotope layering of the mantle would essentially result from differences in the chemical composition and crystal structure of mineral phases at different mantle depths. Assuming isotopic equilibrium on a whole earth scale, the chemical structure of the Earth's interior can be described by the following sequence of ¹⁸O-enrichment: uppr crust>lower crust>upper mantle>transition zone>lower mantle >core.     

Experimentally-controlled carbon and oxygen isotope exchange between bioapatites and water under inorganic and microbially-mediated conditions

Modern bone and enamel powders have reacted at 301 K with ¹³C- and ¹⁸O-labelled waters under inorganic and microbial conditions. The aim of the study is to investigate the resistance of stable isotope compositions of bioapatite carbonate (δ¹³C, δ¹⁸Oc) and phosphate (δ¹⁸Op) to isotopic alteration during early diagenesis. Rapid and significant carbon and oxygen isotope changes were observed in the carbonate and phosphate fractions of bone apatite before any detectable change occurred in the crystallinity or organic matter content. These observations indicate that chemical alterations of bone apatite are likely to start within days of death. Enamel crystallites are much more resistant than bone crystallites, but are not exempt of alteration. Non removable carbon and oxygen isotope enrichments were measured in the carbonate phase of bone (50-90%) and enamel (40%) after the acetic acid treatment. This result indicates that a significant part of ¹³C and ¹⁸O-labelled coming from the aqueous fluid has been durably incorporated into the apatite structure, probably through isotopic exchange or secondary carbonate apatite precipitation. As a result, acetic acid pre-treatments that are currently used to remove exogenous material by selective dissolution, are not adequate to restore pristine δ¹³C and δ¹⁸Oc values of fossil apatites. Under inorganic conditions, kinetics of oxygen isotope exchange are 10 times faster in carbonate than in phosphate. On the opposite, during biologically-mediated reactions, the kinetics of oxygen isotope exchange between phosphate and water is, at least, from 2 to 15 times faster than between carbonate and water. Enamel is a more suitable material than bone for paleoenvironmental or paleoclimatical reconstructions, but interpretations of δ¹⁸Op or δ¹³C values must be restricted to specimens for which no or very limited trace of microbial activity can be detected.     

矿物氧同位素模式温度计算

根据对现遥氧扩散模型的解析分析,通过模拟矿物之间的氧同位素交换轨迹进行模式温度计算,改进了常规矿物对氧同位素地质温度计方法。将模式温度计算与矿物氧－扩散封闭次上结合,建立了一个系统独立的同位素温度计算方法,因此所得到的同位素温度能够更好地反映矿物在高温岩石冷却过程中,的氧同位素交换行为;模式温度计算有如下优点：（１）考虑到了矿物之间扩散引起的同位素交换;（２）遵循质量守恒原理,更严格地适用于有限封     

Oxygen isotope exchange between illite and water at 22°C

Oxygen isotope exchange experiments at 22°C have been made on a series of illites displaying a range of perfection of crystallinity and degree of interstratification. Structurally bound oxygen underwent significant non-equilibrium exchange in time periods ranging from 2 to 70 months. Exchange was found to be controlled by accessibility of water to the interlayer cation region.1000 In α appears to be in the general neighborhood of +23.4 at 22°C for the illite-water system; however, it was found that equilibrium fractionation cannot be represented by a single value for structurally and chemically distinct illites.     

Separation of Clay Minerals from Host Sediments Using Cation Exchange Resins

Classic physical and chemical treatments applied to separating clay minerals from the host sediments are often difficult or aggressive for clay minerals. A technique using cation exchange resins (amberlite IRC-50H and amberlite IR-120) is used to separate clay minerals from the host sediments. The technique is based on the exchange of cations in the minerals that may be associated clay minerals in sediments, such as Ca and Mg from dolomite; Ca from calcite, gypsum and francolite with cations carried by resin radicals. The associated minerals such as gypsum, calcite, dolomite and francolite are removed in descending order. Separation of clay minerals using cation exchange resins is less aggressive than that by other classic treatments. The efficiency of amberlite IRC-50H in the removal of associated minerals is greater than that of amberlite IR-120.     

Oxygen isotope exchange rate between dissolved sulfate and water at hydrothermal temperatures

Oxygen isotope exchange rate between dissolved sulfate and water was experimentally determined at 100, 200 and 300°C. The isotope exchange rate is strongly dependent on temperature and pH of the solution. Combining the temperature and pH dependence of the reaction rate, the exchange reaction was estimated to be first-order with respect to sulfate. The logarithm of apparent rate constant of exchange reaction at a given temperature is a function of the pH calculated at the experimental temperatures. From the pH dependence of the apparent rate constant, it was deduced that the isotope exchange reaction between dissolved sulfate and water proceeds through collision between H₂SO⁰₄ and H₂O at low pH, and between HSO^?₄ and H₂O at intermediate pH. The isotope exchange rate obtained indicates that oxygen isotope geothermometry utilizing the studied isotope exchange is suitable for temperature estimation of geothermal reservoirs. The extrapolated half-life of this reaction to oceanic temperature is about 10⁹ years, implying that exchange between oceanic sulfate and water cannot control the oxygen isotope ratio of oceanic sulfates.     

粘土矿物碱耗协同效应研究

选择蒙脱石,高岭石,伊利石等三种在储层中最党风的储层粘土矿物,两两分别按２Ｌ：０,１：１,０：２质量配比组成复配物系列;在３０℃、５０℃温度下按１：５,１：８,１：１０（ｇ／ｍｌ）固／液比分别与１．６％的Ｎａ２ＣＯ３深液反应８ｈ,３６０ｈ;监测反应前后碱液浓度的变化;计算了各条件下各自的绝对碱耗量。结果表明三种粘土矿物中蒙脱石耗碱最大,高蛉石的耗碱量与伊利石的接近;随着固／液比减小和温度升高,矿物     

Amino acid adsorption by clay minerals in distilled water

The adsorption of 15 protein amino acids from dilute (~ 10 μM) distilled water solutions onto organic-free kaolinite and montmorillonite clay minerals (1 wt% suspensions) was determined at room temperature over a 48 hour period. The systems came to steady state within 2 hours. Basic (positively charged) amino acids were strongly adsorbed (40–80% removal) by both clay minerals. Neutral (uncharged) amino acids were taken up appreciably (10–15%) by montmorillonite, but little if any (<5%) by kaolinite. Acidic (negatively charged) amino acids were adsorbed (20–35%) only by kaolinite. These adsorption patterns appear to be related in part to electrostatic interactions between the clay mineral surfaces and the different amino acid types. The measured extents and selectivities of adsorption onto these clay minerals are sufficiently great to potentially affect the distributions and reactions of free amino acids in natural environments.     

Isotopic exchange of Zn with stable Zn adsorbed on reference clay minerals

For reference clays of low organic content, Zn adsorbed on the clay minerals is in kinetic equilibrium with ⁶⁵Zn in solution. Thus the specific activity approach applied to the transport of ⁶⁵Zn(II) at the water-reference clay interface is intrinsically valid.     

Oxygen isotope fractionation between oxygen of different sites in illite minerals: a potential single-mineral thermometer

The experimental results of Hamza and Epstein mark internal oxygen isotope fractionations of hydrosilicates as potential single-mineral thermometers. In this study methodical investigations were made to determine the oxygen isotope ratios of hydroxyl groups in silicate minerals. As a reference material a commercial kaolinite was examined by vacuum extraction and by use of a modified partial fluorination technique first deseribed by Hamza and Epstein. The concordance of the results argue against oxygen isotope fractionation during dehydroxylation. Consequently, vacuum extraction can be used to determine the internal fractionation of minerals, which contain no ferrous iron. For calibration of the internal oxygen isotope fractionation, hydrothermally formed illites from the Lone Gull uranium deposit in Canada and from the Leuggern exploration drill site in Switzerland were investigated. Formation temperatures of the hydrothermal mineralization were estimated by mineral paragenesis, illite crystallinity and by oxygen isotope fractionations on coexisting mineral phases. the oxygen isotope fractionation between oxygen of different sites in several selected illites from both regions has been analysed. The results indicate a linear correlation between the illite-OH oxygen isotope fractionation and temperature. The fractionation can be expressed by the following equation:

Acidities of confined water in interlayer space of clay minerals

The acid chemistry of confined waters in smectite interlayers have been investigated with first principles molecular dynamics (FPMD) simulations. Aiming at a systematic picture, we establish the model systems to take account of the three possible controlling factors: layer charge densities (0 e, 0.5 e and 1.0 e per cell), layer charge locations (tetrahedral and octahedral) and interlayer counterions (Na⁺ and Mg²⁺). For all models, the interlayer structures are characterized in detail. Na⁺ and Mg²⁺ show significantly different hydration characteristics: Mg²⁺ forms a rigid octahedral hydration shell and resides around the midplane, whereas Na⁺ binds to a basal oxygen atom and forms a very flexible hydration shell, which consists of five waters on average and shows very fast water exchanges. The method of constraint is employed to enforce the water dissociation reactions and the thermodynamic integration approach is used to derive the free-energy values and the acidity constants. Based on the simulations, the following points have been gained. (1) The layer charge is found to be the direct origin of water acidity enhancement in smectites because the neutral pore almost does not have influences on water dissociations but all charged pores do. (2) With a moderate charge density of 0.5 e per cell, the interlayer water shows a pKa value around 11.5. While increasing layer charge density to 1.0 e, no obvious difference is found for the free water molecules. Since 1.0 e is at the upper limit of smectites’ layer charge, it is proposed that the calculated acidity of free water in octahedrally substituted Mg²⁺-smectite, 11.3, can be taken as the lower limit of acidities of free waters. (3) In octahedrally and tetrahedrally substituted models, the bound waters of Mg²⁺ show very low pKa values: 10.1 vs 10.4. This evidences that smectites can also promote the dissociations of the coordinated waters of metal cations. The comparison between the two Mg²⁺-smectites reveals that different layer charge locations do not lead to obvious differences for bound and free water acidities.