Lithium isotope fractionation in the southern Cascadia subduction zone

We present lithium (Li) abundances and isotope compositions for a suite of anhydrous olivine tholeiites (HAOTs) and hydrous basalt-andesitic (BA) lavas from the Mt. Shasta and Medicine Lake regions, California. The values of δ⁷Li vary from + 0.9‰ to + 6.4‰ and correlate inversely with distance from the trench. These data are consistent with continuous isotope fractionation of Li during dehydration of the subducted oceanic lithosphere, an interpretation corroborated by uniformly high pre-eruptive H₂O contents in basaltic andesites accompanied by high Li, Rb, Sr, Ba and Pb abundances. The subduction-derived component that was added to these hydrous magmas is shown to be very similar beneath both Mt. Shasta and Medicine Lake volcanoes despite characteristically distinct Li isotope compositions in the magmas themselves. More evolved andesites and dacites from Mt. Shasta have δ⁷Li from + 2.8 to + 6.9‰ which is identical with the range obtained for HAOTs and BA lavas from Mt. Shasta. Therefore, Li isotopes do not provide evidence for any other crustal component admixed to Mt. Shasta andesites or dacites during magmatic differentiation and magma mixing in the crust.     

Element diffusion ability in metasomatic agents and its effect on chemical characteristics of metasomatized peridotites

The partial melting and metasomatism are two most important geological processes of changing chemical compositions of mantle. Extracting partial melt from primitive mantle leads residual mantle to deplete in- compatible elements, whereas the metasomatism …     

微生物降解有机物的碳氢同位素分馏研究进展

微生物降解使有机化合物的稳定碳、氢同位素发生不同程度分馏的研究在有机污染物来源和微生物环境修复等领域取得了长足进展,并对原油和天然气微生物降解研究有借鉴意义。微生物作用下的同位素分馏为动力同位素分馏,导致重同位素在残余物中富集。影响微生物降解有机物同位素分馏的主要因素有微生物的降解代谢途径、辅酶作用、降解类型与程度、同位素质量差异和有机物碳数等。不同的微生物代谢途径代表不同的生物化学反应,造成了同位素分馏的显著差异;辅酶对反应的催化作用使微生物作用造成的同位素分馏更加复杂。低碳数正构烷烃遭受微生物降解程度越高,碳、氢同位素的分馏也越大,同位素变重与降解程度之间有明显的相关性。但对于复杂化合物,由于降解的多级反应,同位素分馏与降解程度间的相关性并不明显。在同样降解程度下,氢同位素分馏大于碳同位素分馏,低碳数正构烷烃的同位素分馏大于高碳数正构烷烃的同位素分馏。     

氢氧化物族矿物的氧同位素分馏

应用增量方法计算了氢氧化物族矿物的氧同位素分馏,得到常见氢氧化物的18O富集顺序为：褐铁矿＞三水铝石＞针铁矿＞水镁石＞硬水铝石。氢氧化物与其对应的氧化物相比显著地富集18O。三价阳离子的氢氧化物和氧化物的18O富集顺序为：M（OH）3＞MO（OH）＞M2O3。Al（OH）3同质多象变体之间也存在一定的分馏。对于石英-氢氧化物、方解石-氢氧化物和氢氧化物-水体系,本文计算提供了在0-1200℃温度范围内三组内部一致的分馏系数方程。这些理论校准与合成实验结果和／或地表温度下的天然样品相吻合,特别针铁矿、勃姆石和硬水铝石与水之间的氧同位素分馏关系能够满足地质测温的要求。因此,对氢氧化物-水体系的氧同位素分析可望提供表生环境下可靠的地质温度计。     

Oxygen isotope fractionation in 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 of¹⁸O-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 the 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 in¹⁸O relative to the perovskite-structured silicates in the lower mantle but depleted in¹⁸O relative to olivines and pyroxenes in the upper mantle. The oxygen isotope layering of the mantle might 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 of¹⁸O-enrichment:upper crust>lower crust>upper mantle>transition zone>lower mantle>core. Project supported by the National Natural Science Foundation of China and the Chinese Academy of Sciences.     

A Coupled Riverine-Marine Fractionation Model for Dissolved Rare Earths and Yttrium

Fractionation of yttrium (Y) and the rare earth elements (REEs) begins in riverine systems and continues in estuaries and the ocean. Models of yttrium and rare earth (YREE) distributions in seawater must therefore consider the fractionation of these elements in both marine and riverine systems. In this work we develop a coupled riverine/marine fractionation model for dissolved rare earths and yttrium, and apply this model to calculations of marine YREE fractionation for a simple two-box (riverine/marine) geochemical system. Shale-normalized YREE concentrations in seawater can be expressed in terms of fractionation factors ( _ij ) appropriate to riverine environments ( ) and seawater ( ):

Behavior of REE Fractionation during Weathering of Dolomite Regolith Profile in Southwest China

<正>REE fractionation during the weathering of dolomite has been recognized for decades.A regolith profile on dolomite in southwest Yunnan of China was selected to investigate the behaviors of REE during weathering.The weathering of dolomite is divided into two stages:the pedogenesis stage and soil evolution stage,corresponding to the saprolites and soils respectively in the regolith profile. SiO_2,TiO_2,P_2O_5,Zr,Hf,Nb and Ta were immobile components during the weathering by and large, while Al_2O_3,K_2O and Fe_2O_3 were lost during the soil evolution stage in the physical form(clay minerals probably).REE were fractionated during the whole weathering of dolomite.The field weathering profile and the lab acid-leaching experiments on dolomite indicate that MREE were enriched clearly relative to other REE during the pedogenesis stage in a "capillary ascending-adsorption" mechanism, but they did not fractionate clearly in the soil evolution stage.REE were lost and accumulated in the weathering front of dolomite during the soil evolution stage in a "physical-chemical leaching" mechanism.     

强烈气洗作用导致原油成分变化的定量计算:以库车坳陷天然气藏为例

库车坳陷以产天然气为主,同时产出少量原油和凝析油,油气充注不同步,普遍具有"油早气晚"的特点,晚期大量天然气的侵入,必然对早期聚集的油藏发生改造作用。对气藏中原油成分变化的定量计算和讨论,可为天然气的注入强度定量评价提供直接证据。未遭受气洗的原油,正构烷烃摩尔浓度的对数与相应的碳数呈线性关系,而气洗作用可使轻组分的正构烷烃最先溶解于干气中,并随着天然气继续向前运移,原始油藏中的轻组分正构烷烃大大减少。以此为理论基础,建立了正构烷烃损失的定量计算模型。结果表明克拉2构造原油正构烷烃损失程度最高,平均可达70%左右,大北构造带原油正构烷烃损失程度差异较大,与该地区断块发育有关。气洗作用导致原油正构烷烃减少,而金刚烷、多环芳烃等在天然气中溶解度较低的化合物得以浓缩富集,相对含量大大增加。轻芳烃含量也会随之而增加,原油芳香度增加,石蜡度降低。在模拟实验基础上对气洗程度进行了定量评价,初步估算表明,克拉2构造原油遭受的气洗作用最强,是其他构造带的2～5倍。     

样品前处理过程中多环芳烃的稳定碳同位素分馏

利用多环芳烃标准样品连续和穿插进样相结合的方式,检验了气相色谱-燃烧-同位素比质谱仪(GC-C-IRMS)测定多环芳烃单体碳同位素比值(δ13C)的稳定性和准确性,观察了测定过程中色谱柱的分离效果。结果表明,出峰面积和分离程度是影响化合物δ13C平行性的主要原因。通过多次实验,分析了样品前处理过程中多环芳烃各个化合物稳定碳同位素的分馏情况,包括凝胶渗透色谱(GPC)和硅胶柱等净化过程,以及旋转蒸发和氮气吹扫等浓缩过程。实验表明,各前处理过程中样品内多环芳烃的稳定碳同位素分馏均不明显,其中硅胶柱净化过程相比GPC过程对样品中多环芳烃的δ13C影响较大,但总体上仍未超过未处理标样δ13C值的2倍标准偏差范围。旋转蒸发和氮吹过程对样品中多环芳烃的δ13C影响程度相当,都位于未处理标样δ13C值1倍标准偏差以内的水平。     

13X分子筛活化及其对氧气转移时吸附/解吸过程中氧同位素分馏效应的研究

在激光BrF5法分析硅酸盐和氧化物矿物的真空提取流程中,通常采用氧气作为工作气体来测定样品的氧同位素组成。这需要使用分子筛吸附并转移氧气到质谱进样系统,而分子筛的活化对于有效吸附和解吸氧气至关重要,否则会引起分析过程中的氧同位素分馏。通过采用13X分子筛进行多组实验分析,笔者发现用不同活化程度或中毒失活分子筛沸石转移时可能存在氧同位素分馏。在低温下分子筛是不能够活化的(或活化不完全),吸附能力很低,所测定的δ18O值是波动的。在200℃马弗炉中预加热24h,然后迅速转移到温度为100℃、真空度为10-3Pa系统中加热12h的分子筛,对氧气吸附能力很强,氧同位素分析的绝对误差为±0.05‰(1σ),能够满足地球化学氧同位素分析的要求。如果分子筛受BrF5污染,其吸附能力大为降低,测定的δ18O值呈下降趋势,氧同位素分馏高达0.7‰。如果分子筛受水汽污染,质谱接受电压不断地降低,存在解吸温度下的再吸附过程,测定δ18O值呈上升趋势。因此,分子筛在使用前要在适当条件下的活化,在发现污染或测量值发生波动变化时要及时更换,否则难以保证氧同位素分析数据的可靠性。