水体蒸发过程中稳定同位素分馏的模拟

通过对非平衡条件下水体蒸发中稳定同位素分馏机制的分析, 模拟了蒸发水体中稳定同位素比率的变化及与温度、大气湿度的关系. 在瑞利模式中, 剩余水中的稳定同位素随剩余水比例f的减小不断富集, 富集的速率与温度呈反比. 在动力蒸发条件下, 稳定同位素的分馏不仅与相变温度有关, 而且受大气湿度和液-气相之间物质交换的影响. 在动力蒸发过程中, 相对湿度越小, 剩余水中稳定同位素比率随 f的变化越快. 当相对湿度较大时, 在经历了一段时间蒸发后的剩余水中的δ将不随 f变化. 蒸发水体达到稳定状态的速率主要取决于大气的相对湿度. 当温度约20℃时, 在瑞利平衡条件下模拟的蒸发线与全球大气水线较接近. 在非平衡蒸发条件下, 蒸发线的梯度项和常数项与温度和相对湿度呈正比.     

咸化水体中DIC的同位素组成及环境过程分析

系统采集了天津地区地表水样品,对其溶解无机碳的稳定碳同位素比值(δ13CDIC)及相关化学组成进行了全面测定,以期对咸化并且受到污染水体中的溶解无机碳的来源和迁移转化特征进行探讨.研究结果显示,天津地表水中溶解无机碳的δ13CDIC值主要分布于0.27‰～ -14.9‰之间,显示了相对较宽的分布范围.同时,天津地表水体...     

华北平原典型区水体蒸发氢氧同位素分馏特征

为研究华北平原衡水地区水体蒸发氢氧同位素分馏特征,采集不同盐度的深层地下淡水(TDS 为0.61g/L)和浅层地下咸水(TDS为7.97g/L),现场开展室外器皿蒸发实验,获得了当地气象条件下氢氧同位素分馏参数.实验结果显示,淡水及咸水剩余表层水δ18O与剩余水比率f呈指数关系,与瑞利分馏模拟结果一致,δD和δ18O蒸发线斜率分别为4.78和4.69.整个蒸发过程中,淡水及咸水氢氧同位素值增量ΔδD分别为Δδ18O的4.82倍和4.76倍;剩余表层水相对于初始水δD和δ18O的变化量与累积蒸发量之比,淡水分别为2.68‰/cm和0.56‰/cm,咸水分别为2.78‰/cm和0.61‰/cm;而在不同的蒸发时段,剩余表层水δD和δ18O的变化量与蒸发量无明显相关性.受水分子扩散的影响,蒸发皿中氢氧同位素分馏在垂线上分层微弱.由于水体盐度较低,在当地气候条件下进行自由蒸发时,氢氧同位素分馏的盐效应可以忽略.     

氯化物单矿物溶液蒸发过程的氯同位素分馏

<正>1实验目的根据海水的等温蒸发实验,氯元素基本上参与了石膏析出阶段以后的全部成盐过程,形成了石盐、钾石盐、光卤石和水氯镁石等主要的氯化物矿物(陈郁华,1983)。卤水的演化过程是氯元素地球化学在地表储库的关键过程(Eastoe et al.,1999;Eastoe et al.,2001;Eastoe et al.,2007)。弄清稳定氯同位素组成在卤水演化过程中的变     

玄武岩及硫化物淋洗过程Cu同位素分馏实验

<正>作为重要的过渡族金属元素和营养元素,Cu的地球化学循环对海洋生命演化非常重要[1]。而海洋中的Cu大多来自大陆风化输入,因此研究风化过程的Cu同位素分馏行为至关重要。岩石风化过程会释放金属离子进入水体,进而影响金属离子在水圈和岩石圈的地球化学循环过程,研究风化过程Cu同位素分馏情况能够更好地应用Cu同位素解释自然环境中Cu同位素变化及其循环过程。前人主要集中研究酸性条件下的含Cu硫化物淋洗过程中Cu同位素变化[2-5],但含Cu硫化物中的Cu只占硅酸岩总Cu中的     

蒸发过程中水体稳定同位素富集与空气湿度的关系

通过同位素分馏模型的物理意义分析及实验模拟分析,探讨空气湿度对蒸发过程水体稳定同位素富集过程的影响机理,研究认为：①空气相对湿度决定了扩散系数和自由空气同位素组成对分馏系数的影响比例,空气相对湿度越小,分馏系数受扩散分馏系数影响越大,分馏系数受自由空气水汽同位素组成影响则越小,反之亦然;②空气相对湿度与蒸发残余水体氢氧稳定同位素富集程度具有负相关性,即空气湿度越大越不利于残余水体重同位素富集;③模拟残余水体同位素丰度对空气相对湿度的敏感性呈负指数关系。在无外界气态水介入的蒸发实验中,残余系数为0.194条件下,当相对湿度小于80%时,H、O稳定同位素模拟结果对湿度的敏感性均小于0.0002,即相对湿度变化对模拟残余水体同位素丰度影响很小;当湿度大于80%时,湿度变化对模拟结果的影响呈指数关系急剧增加,湿度大于80%的蒸发实验需要准确观测相对湿度值。     

氩同位素分馏的实验研究

尽管40Ar和36Ar之间质量相差达1/10,但是受放射性成因40Ar的影响,一般认为难以进行氩同位素分馏研究.本文通过自行设计的一套氩扩散迁移实验分析系统,对比研究了氩在不同的扩散介质条件下扩散迁移前后氩同位素组成变化情况,证实氩在致密的扩散介质条件下以分子流形式从一个储库向另一个储库的迁移过程中,由于36Ar和40Ar的迁移速率不同,扩散后的40Ar/36Ar值比扩散前的值要小,也即发生了氩同位素分馏.氩同位素分馏的特征表现为最初的一段时间内分馏程度逐步增强,在一定时间后,由于储库之间压力逐渐达到平衡,分馏程度逐步减小.研究自然界中存在的氩同位素分馏,不仅可以判别油气田中油气运移的方向、增强油气远景评价和地球化学勘探,而且对深源岩浆的起源、迁移等研究也可提供新的研究思路和途径.     

海水蒸发时的硼同位素分馏

采用立式亚沸石英蒸馏器，在非流动条件下进行了海水蒸发实验，以研究海水一空气界面硼同位素的行为。将具有不同pH值的天然海水在不同温度下平静地蒸发，采用冷水收集海水蒸汽，实现了无流动空气的真实的蒸发过程，共进行了3种类型的实验。 实验1 将不同pH值（(7.71-8.49)的海水在27℃，33℃和40℃下蒸发，蒸发时连续地补充高纯水以维持蒸发液体的体积恒定。收集海水蒸汽，进行蒸汽的硼同位素组成、硼和氯浓度的测定。 实验2将天然海水在33℃下蒸发，蒸发时不补加高纯水．搏派承药蒸干。分捌收集海水蒸汽和蒸干后的固体盐，进行蒸汽和固体盐的硼同位素组成测定。并同时测定不同蒸发阶段海水的pH值。 实验3 将加人不同硼量的天然海水在40℃下蒸发.蒸发时连续地补充高纯水以维持蒸发液体的体积恒定，收集海水蒸汽，进行硼同位素和硼浓度的测定。 硼浓度的结果表明：①在实验1中，蒸汽的硼浓度变化范围是1.51-10.7 μg/L，平均值为5.16 μg/L，随海水pH值升高而降低，但与蒸发温度无关；②在实验2和3中蒸汽硼的浓度要远远高于实验1，而且蒸汽硼浓度与海水硼浓度具有线性的正相关关系；③蒸汽相的Cl/B比（摩尔比值：平均23.4)远远低于海水的Cl/B比（摩尔比值：1485)，这表明蒸发时没有将海水喷雾的细珠引人蒸汽中。 硼同位素结果表明： (1)在实验1中，蒸汽的δ11B值除一个以外均低于海水B(OH)3的δ11B值，而高于海水B(OH)4-的δ11B值，而且都比海水的δ11B值高，蒸汽与海水间的平均硼同位素分馏系数为1.0019，这表明在海水蒸发时，11B富集在蒸汽相中。此结果与以前所进行的硼溶液蒸发实验结果一致，但与以前所进行的海水蒸发实验结果完全相反。以前的海水蒸发实验结果表明，10B在蒸汽相富集。这种截然相反的结果要归结于蒸发条件的差异，以前蒸发的海水蒸汽是由流动空气带出，此时非平衡的动力因素将起到重要作用，造成质量轻的10B优先进人蒸汽相。而本次实验在非空气流动条件下进行，B(OH)3和B(OH)-4间的同位素平衡将起主导作用。显然，燕汽的δ11B值与海水的pH值没有明显的关系。 (2)在实验2中，蒸汽与海水间的硼同位素分馏系数要远远高于实验1，特别当海水蒸干前的500 mL蒸汽，分馏系数高达1.0182。而蒸干后的固体盐的δ11B值明显低于原始海水，分馏系数为0.9973。这充分表明，在海水蒸发时，11B优先被蒸发而进人燕汽相。海水蒸发时蒸汽相的δ11B值随蒸发程度呈平方指数形式增加，这与蒸发时残留海水的δ11B值急剧升高有关。 (3）实验3中，蒸汽的δ11B值随海水硼浓度的增加而升高，当硼浓度为19.7 μg/mL和63.5 μg/mL时，硼同位素分馏系数分别为1.0072和1.0107。 海水蒸发时的硼同位素分馏可用于对大气降雨硼来源的研究。在不同时期采集的西宁雨水的δ11B值为12.1‰和9.0‰，受风向的影响甚微，表明西宁地区的大气环境受海洋影响较小，大气中的硼主要来源于陆地。但南海西江石油平台大气降雨的δ11B值明显受风向所控制，高δ11B值（33.2‰）表明其海洋来源，而低δ11B值（8.4‰）表明其陆地来源。以往文献所报道的陆地及其沿海大气降雨的δ11B值变化范围很宽(0.8‰~35‰)，但是它们都低于海水的δ11B值，这表明陆地及其沿海大气中的硼主要来源于陆地。 海水中的硼将因洋壳低温蚀变、沉积物吸附以及生物碳酸盐共沉淀从海洋中迁出，这些过程均造成海水10B的贫化。惟独海水蒸发时会造成海水10B的富集，但由于此时硼同位素分馏小，而且与其他因素相比，被海水蒸汽迁出的硼量低，根据计算，海水燕发对古海洋硼同位素组成的影响完全可以忽略不计。     

方解石晶体生长过程中钙同位素分馏

钙同位素分馏及微量元素(Sr、Mn、Mg等)分异可以作为重要的指标来研究大气圈和海洋的化学演化(Jacobson和Holmden,2008)。作为钙同位素的重要载体,方解石成为众多学者研究的焦点,包括生物成因方解石和无机方解石。在方解石的形成过程中,诸多因素例如温度、晶     

蒸发皿中水面蒸发氢氧同位素分馏的实验研究

气象要素与蒸发密切相关,通过室内外不同气象条件下的器皿水蒸发实验,获得了水面蒸发氢氧稳定同位素分馏因子与气象要素的关系。实验结果表明,随着蒸发的进行,剩余水体中逐渐富集重同位素;自由水体蒸发同位素分馏在垂线上有分层现象,表层水体同位素值比垂线平均的同位素值略富集;不同温度条件下的室内蒸发实验中,温度越高,液-气间分馏系数越小,相应于同一剩余水体体积比,剩余水体稳定同位素值则越低。室外器皿水自由蒸发实验中得出的蒸发线方程斜率较大地偏离了当地降水线,表明实验期间水体蒸发分馏作用较明显。该研究为进一步揭示水体蒸发分馏规律提供了可靠的实验依据。     

Experimental study of evaporation and isotopic mass fractionation of potassium in silicate melts

The behavior of Na and K during evaporation from chondrule composition melts was studied using a vacuum furnace. Though Na is the less volatile of the two as an element, it is lost more rapidly than K from silicate melts. Mass fractionation of K isotopes was measured by ion microprobe and Rayleigh fractionation is observed for vacuum evaporation (10⁻⁵ atm). With higher pressures of air, the K loss rate decreases but with increasing hydrogen pressure, K is lost more rapidly. δ⁴¹K decreases with higher pressures, because of back reaction between melt and K in the gas. With long heating duration, the release of light K condensed within the furnace leads to interaction with the K-depleted melt and a further reduction of δ⁴¹K. Natural chondrules differ in some ways from our experimental residues. Some (especially type IIA) have superchondritic Na and K, despite their assumed formation in nebular hydrogen, which enhances volatile loss, and chondrules do not show K isotopic fractionation. Type I chondrules in Semarkona (LL3.0) either plot on our evaporation trend, or are depleted in K but slightly enriched in Na, relative to K. In Bishunpur (LL3.1), type I chondrules are mostly K-depleted but moderately to strongly enriched in Na. In petrologic type 3.2 to 3.4 chondrites they are enriched in both K and Na, like type II chondrules. The alkali contents suggest type I chondrules experienced evaporation and subsequent metasomatism. Their normal δ⁴¹K values suggest closed-system evaporation of a chondritic precursor in a gas with relatively high K pressures due to vaporization of dust accompanying chondrule precursor aggregates. Type II chondrules are volatile-rich, as well as unfractionated in K isotopes. They probably formed in a gas with higher pK than in the case of type I chondrules, due to heating of a more dust-rich parcel of gas.     

Silicon isotopic fractionation of CAI-like vacuum evaporation residues

Calcium-, aluminum-rich inclusions (CAIs) are often enriched in the heavy isotopes of magnesium and silicon relative to bulk solar system materials. It is likely that these isotopic enrichments resulted from evaporative mass loss of magnesium and silicon from early solar system condensates while they were molten during one or more high-temperature reheating events. Quantitative interpretation of these enrichments requires laboratory determinations of the evaporation kinetics and associated isotopic fractionation effects for these elements. The experimental data for the kinetics of evaporation of magnesium and silicon and the evaporative isotopic fractionation of magnesium is reasonably complete for Type B CAI liquids (Richter F. M., Davis A. M., Ebel D. S., and Hashimoto A. (2002) Elemental and isotopic fractionation of Type B CAIs: experiments, theoretical considerations, and constraints on their thermal evolution. Geochim. Cosmochim. Acta66, 521-540; Richter F. M., Janney P. E., Mendybaev R. A., Davis A. M., and Wadhwa M. (2007a) Elemental and isotopic fractionation of Type B CAI-like liquids by evaporation. Geochim. Cosmochim. Acta71, 5544-5564.). However, the isotopic fractionation factor for silicon evaporating from such liquids has not been as extensively studied. Here we report new ion microprobe silicon isotopic measurements of residual glass from partial evaporation of Type B CAI liquids into vacuum. The silicon isotopic fractionation is reported as a kinetic fractionation factor, α_Si, corresponding to the ratio of the silicon isotopic composition of the evaporation flux to that of the residual silicate liquid. For CAI-like melts, we find that α_Si = 0.98985 ± 0.00044 (2σ) for ²⁹Si/²⁸Si with no resolvable variation with temperature over the temperature range of the experiments, 1600-1900 °C. This value is different from what has been reported for evaporation of liquid Mg₂SiO₄ (Davis A. M., Hashimoto A., Clayton R. N., and Mayeda T. K. (1990) Isotope mass fractionation during evaporation of Mg₂SiO₄. Nature347, 655-658.) and of a melt with CI chondritic proportions of the major elements (Wang J., Davis A. M., Clayton R. N., Mayeda T. K., and Hashimoto A. (2001) Chemical and isotopic fractionation during the evaporation of the FeO-MgO-SiO₂-CaO-Al₂O₃-TiO₂-REE melt system. Geochim. Cosmochim. Acta65, 479-494.). There appears to be some compositional control on α_Si, whereas no compositional effects have been reported for α_Mg. We use the values of α_Si and α_Mg, to calculate the chemical compositions of the unevaporated precursors of a number of isotopically fractionated CAIs from CV chondrites whose chemical compositions and magnesium and silicon isotopic compositions have been previously measured.     

Elemental and isotopic fractionation of Type B CAI-like liquids by evaporation

Vacuum evaporation experiments with Type B CAI-like starting compositions were carried out at temperatures of 1600, 1700, 1800, and 1900 °C to determine the evaporation kinetics and evaporation coefficients of silicon and magnesium as a function of temperature as well as the kinetic isotope fractionation factor for magnesium. The vacuum evaporation kinetics of silicon and magnesium are well characterized by a relation of the form J = J_oe^−E/RT with J_o = 4.17 × 10⁷ mol cm⁻² s⁻¹, E = 576 ± 36 kJ mol⁻¹ for magnesium, J_o = 3.81 × 10⁶ mol cm⁻² s⁻¹, E = 551 ± 63 kJ mol⁻¹ for silicon. These rates only apply to evaporation into vacuum whereas the actual Type B CAIs were almost certainly surrounded by a finite pressure of a hydrogen-dominated gas. A more general formulation for the evaporation kinetics of silicon and magnesium from a Type B CAI-like liquid that applies equally to vacuum and conditions of finite hydrogen pressure involves combining our determinations of the evaporation coefficients for these elements as a function of temperature (γ = γ₀e^−E/RT with γ₀ = 25.3, E = 92 ± 37 kJ mol⁻¹ for γ_Si; γ₀ = 143, E = 121 ± 53 kJ mol⁻¹ for γ_Mg) with a thermodynamic model for the saturation vapor pressures of Mg and SiO over the condensed phase. High-precision determinations of the magnesium isotopic composition of the evaporation residues from samples of different size and different evaporation temperature were made using a multicollector inductively coupled plasma mass spectrometer. The kinetic isotopic fractionation factors derived from this data set show that there is a distinct temperature effect, such that the isotopic fractionation for a given amount of magnesium evaporated is smaller at lower temperature. We did not find any significant change in the isotope fractionation factor related to sample size, which we interpret to mean that recondensation and finite chemical diffusion in the melt did not affect the isotopic fractionations. Extrapolating the magnesium kinetic isotope fractionations factors from the temperature range of our experiments to temperatures corresponding to partially molten Type B CAI compositions (1250-1400 °C) results in a value of α_Mg ≈ 0.991, which is significantly different from the commonly used value of .     

Experimental study of D/H isotopic fractionation factor of water adsorbed on porous silica tubes

This paper presents D/H isotopic fractionation factor measurements of water adsorbed on porous silica tubes in isotopic equilibrium with water vapor. The fractionation factor is measured as a function of vapor pressure ranging from 10% to 80% RH (relative humidity) at room temperature. It is shown that the fractionation factor between the adsorption film or nanometrically confined water and vapor is smaller than that between bulk liquid water and vapor. A qualitative analysis relates this deuterium depletion to a modification of the zero-point energy of the water isomers in the adsorbed/confined state. Furthermore, the behavior of the fractionation factor with RH shows two different linear trends. The transition between the two (at 60% RH) may indicate the transition from a two-dimensional adsorbed water to a three-dimensional water network.     

海洋天然气水合物氢氧同位素分馏初探

天然气水合物的形成会造成氢、氧同位素的分馏.在实验室合成研究中,利用天然海水 [(含 0.03%十二烷基硫酸钠 (SDS)]与甲烷气体反应,通过对水合物生成前后溶液中的 Cl-的质量浓度和氢、氧同位素组成的测定,研究了天然气水合物生成过程中氢、氧同位素的分馏情况.实验证明氢、氧的重同位素易于富集在水合物中,其在天然海水-甲烷体系中的分馏系数分别为 1.018～ 1.036和 1.003 4～ 1.006 3,这一分馏系数稍大于前人在纯水和 NaCl溶液中所测得的分馏系数.     

Kinetic isotopic fractionation during diffusion of ionic species in water

Experiments specifically designed to measure the ratio of the diffusivities of ions dissolved in water were used to determine . The measured ratio of the diffusion coefficients for Li and K in water (D_Li/D_K = 0.6) is in good agreement with published data, providing evidence that the experimental design being used resolves the relative mobility of ions with adequate precision to also be used for determining the fractionation of isotopes by diffusion in water. In the case of Li, we found measurable isotopic fractionation associated with the diffusion of dissolved LiCl (D_⁷Li/D_⁶Li=0.99772±0.00026). This difference in the diffusion coefficient of ⁷Li compared to ⁶Li is significantly less than that reported in an earlier study, a difference we attribute to the fact that in the earlier study Li diffused through a membrane separating the water reservoirs. Our experiments involving Mg diffusing in water found no measurable isotopic fractionation (D_²⁵Mg/D_²⁴Mg=1.00003±0.00006). Cl isotopes were fractionated during diffusion in water (D_³⁷Cl/D_³⁵Cl=0.99857±0.00080) whether or not the co-diffuser (Li or Mg) was isotopically fractionated. The isotopic fractionation associated with the diffusion of ions in water is much smaller than values we found previously for the isotopic fractionation of Li and Ca isotopes by diffusion in molten silicate liquids. A major distinction between water and silicate liquids is that water surrounds dissolved ions with hydration shells, which very likely play an important but still poorly understood role in limiting the isotopic fractionation associated with diffusion.     

First-principles calculation of H/D isotopic fractionation between hydrous minerals and water

Hydrogen fractionation laws between selected hydrous minerals (brucite, kaolinite, lizardite, and gibbsite) and perfect water gas have been computed from first-principles quantum-mechanical calculations. The β-factor of each phase was calculated using the harmonic phonon dispersion curves obtained within density functional theory. All the fractionation laws show the same shape, with a minimum between 200 °C (brucite) and 500 °C (gibbsite). At low temperatures, the mineral/liquid water fractionation laws have been obtained using the experimental gas/liquid water fractionation laws. The resulting fractionation laws systematically overestimate measurements by 15‰ at low temperatures to 8‰ at ≈400 °C. Based on this general agreement, all calculated laws were empirically corrected with reference to brucite/water data. These considerations suggest that the experimental or natural calibrations by Xu and Zheng (1999) and Horita et al. (2002) (brucite/water), Gilg and Sheppard (1996) (kaolinite/water), Wenner and Taylor (1973) (lizardite/water), and in some extents Vitali et al. (2001) (gibbsite/water) are representative of equilibrium fractionations. Besides, internal isotopic fractionation of hydrogen between inner-surface and inner hydroxyl groups has been computed for kaolinite and lizardite. The obtained fractionation is large, of opposite sign for the two systems (respectively, −23‰ and +63‰ at 25 °C) and is linear in T^-2. Internal fractionation of hydrogen in TO phyllosilicates might thus be used in geothermometry.     

枫丹白露砂土的环境箱蒸发试验

为研究土壤水分的蒸发机理,自主开发了大型环境箱试验装置,并以枫丹白露砂土为研究对象,室内模拟土壤水分的蒸发过程。该试验在控制大气参数和保持土壤底部水位稳定的条件下,对蒸发过程中大气参数（空气温度、相对湿度和流量）和土壤参数（土壤温度、基质吸力和体积含水量）的变化,特别是土壤表面基质吸力的变化进行了研究。同时根据试验结果对蒸发速率及累积蒸发量进行了计算分析。研究结果表明:蒸发主要限制在土壤浅层区域,浅层土壤的体积含水量和温度的变化均较大;空气温度和土壤蒸发过程对土壤温度的变化具有较大的影响;土壤表面空气相对湿度与蒸发过程具有相关性;土壤基质吸力随着蒸发的进行逐渐增大; 实际蒸发速率呈现3个阶段。