Equilibrium thallium isotope fractionation and its constraint on Earth’s late veneer

Equilibrium isotope fractionation of thallium(Tl) includes the traditional mass-dependent isotope fractionation effect and the nuclear volume effect(NVE). The NVE dominates the overall isotope fractionation, especially at high temperatures. Heavy Tl isotopes tend to be enriched in oxidized Tl^3+-bearing species. Our NVE fractionation results of oxidizing Tl^+ to Tl^3+ can explain the positive enrichments observed in ferromanganese sediments. Experimental results indicate that there could be0.2–0.3 e-unit fractionation between sulfides and silicates at 1650 ℃. It is consistent with our calculation results,which are in the range of 0.17–0.38 e-unit. Importantly,Tl’s concentration in the bulk silicate Earth(BSE) can be used to constrain the amount of materials delivered to Earth during the late veneer accretion stage. Because the Tl concentration in BSE is very low and its Tl isotope composition is similar with that of chondrites, suggesting either no Tl isotope fractionation occurred during numerous evaporation events, or the Tl in current BSE was totally delivered by late veneer. If it is the latter, the Tl-contentbased estimation could challenge the magnitude of late veneer which had been constrained by the amount of highly siderophile elements in BSE. Our results show that the lateaccreted mass is at least five-times larger than the previously suggested magnitude, i.e., 0.5 wt% of current Earth’s mass. The slightly lighter 205 Tl composition of BSE relative to chondrites is probable a sign of occurrence of Tlbearing sulfides, which probably were removed from the mantle in the last accretion stage of the Earth.     

Hydrous pyrolysis of a Type III source: fractionation effects during primary migration in natural and artificially matured samples

A core from the Cambay Shale Formation of the Cambay Basin, containing immature Type III organic matter, was pyrolysed at 300°C for different durations of time to different maturation levels. Fractionation effects were studied employing a three-step extraction technique after removal of the expelled pyrolysate. The extractable organic matter (EOM) obtained on extraction of the whole core is assumed to be that present in open pores, while that obtained on finely crushing the sample is assumed to be that present in closed pores. The EOM obtained from 1 cm chips is termed EOM from semi-open pores. The gross composition of the pyrolysates expelled during pyrolysis is not similar to the oils reservoired in the area, and there is no significant fractionation observed between expelled pyrolysates and unexpelled EOM. Our study indicates movement of fluids between closed, semi-open and open pores. In both systems, there is a higher concentration of EOM in open pores than in semi-open and closed pores, and the fraction of EOM in open pores is much greater in the artificial system than in the natural system. Fractionation effects on n-alkane and isoprenoid hydrocarbon-based parameters were also studied. n-Alkenes are present in semi-open and closed pores of the immature core and in the core after it was pyrolysed to 300°C for 6 and 48 h, but are absent in the open pores. n-Alkenes are present in closed pores in the naturally matured core. Presence of n-alkenes in the pyrolysates expelled during the 6 and 48 h experiments, but their absence in the open pores of the core, indicates that expulsion also occurs through temporary microfractures during laboratory pyrolysis, whereas in the natural system expulsion from closed pores seems to be only via semi-open and open pores.     

苏北盐城凹陷天然气与凝析油的成因机制

盐城凹陷天然气中甲烷含量高,碳同位素具有正分布系列,主体具有高成熟腐泥型气特征,伴随产出的凝析油则体现出与本区湖相原油和海相原油既相似又相区别的特征。不同组分间存在成熟度差异,轻质组分反映高成熟,中等组分体现出未熟低熟,重质组分表现出成熟特征。母源分析对比表明天然气与凝析油主要源自古生界海相腐泥型源岩,混有泰州组少许贡献,造成组分差异和成熟度变化的重要原因是大量气体注入配以长期发育断裂引起的运移分馏和不同成熟度油气混合所致。     

空间因子分析与沉积地球化学旋回元素组合的确定

１９９５年５月,引用地矿部“七五”东北太平洋ＣＣＡ１２１柱状沉积物的８个元素地球化学分析数据,利用空间因子分析方法确定两种周期度（Ｄ１＝６５ｃｍ,Ｄ２＝１０５ｃｍ）内的沉积地球化学旋回元素组合,并据此探讨多金属结核成矿与物源环境的关系,研究表明,与小尺度周期（Ｄ１＝６５ｃｍ）对应的元素组合：Ｕｄ１（Ｍｎ,Ｃｏ,Ｃｕ,Ａｌ２Ｏ３,ＳｉＯ２和Ｕｄ２（Ｆｅ,Ｃａ,Ｃｏ,Ｃｕ）与大尺度周期对应的元素组合为     

用离散单元法评价采煤巷道地面建筑适宜性

根据建筑物下部采煤巷道的断面尺寸、位置及埋深等地质条件,针对地面拟建建筑物的特点,分别应用二维及三维离散单元方法,对工程场地的地面变形进行了定量评价,得出了地面建筑物在巷道影响下的水平位移量及竖向位移量。结果分析认为,地下巷道的存在不会对上部建筑物造成威胁,仅会产生微小沉降变形。同时提出了一些工程安全措施,为工程建设的顺利实施提供了必要依据。     

哈拉湖岩芯XRF扫描元素统计分析及其环境意义

青藏高原东北缘高山湖泊哈拉湖是位于季风与西风影响的交汇带的封闭深水湖泊,是区域环境和气候变化的良好记录载体。目前对该湖的研究还较少,缺乏对沉积物中元素环境意义的系统认识。通过高分辨率XRF岩芯扫描,用相关、聚类和因子分析的方法对哈拉湖沉积岩芯地球化学元素进行分析。结果显示Ti、K、Si、Al、Fe、Mn等元素变化一致,相关性高,归为同一类,即径流输入的陆源碎屑组分,反映了流域水文状况如径流量的变化。Sr、Zr元素相关性高,为赋存在粗颗粒沉积物中的元素,根据哈拉湖实际,应为冬季湖泊冰面风力搬运,反映了湖区冬季风力强度的变化。Ca元素既与径流输入元素总体变化一致,也与Sr、Zr元素显著相关,且在第一和第二主成分(径流和风力)上的载荷相当,表明哈拉湖沉积物中的碳酸盐既有粗颗粒的外源碎屑,也有湖泊自生的组分,这在利用碳酸盐进行地球化学研究时应重视,注意去除外源碎屑碳酸盐的影响。可溶元素S和Cl可能反映了入湖水量与蒸发对比情况,与湖泊盐度有关。     

Fractionation mechanism of stable isotope in evaporating water body

Under Rayleigh equilibrium condition, stable isotopic ratio in residual water increases with the decrease of the residual water proportion f exponentially, and the fractionation rate of stable isotopes is inversely proportional to temperature. However, under kinetic evaporation condition, the fractionation of stable isotopes is not only related to the phase temperature but also influenced by the atmospheric humidity and the mass exchange between liquid and vapor phases. The ratio δ in residual water will not change with f after undergoing evaporation of a long time for great relative humidity. The rate that the evaporating water body reaches isotopic steady state is mainly dependent on the relative humidity in atmosphere. The analysis shows that the actual mean linear variety rates, about -30.0, of the δ18O in residual water versus the residual water proportion at Nagqu and Amdo stations are consistent with the simulated process under temperature of 20 oC and relative humidity of 50%. The distillation line simulated under Rayleigh equilibrium condition is analogous to the global meteoric water line (MWL) as the temperature is about 20 oC. Under non-equilibrium condition, the slope and constant values of distillation line are directly proportional to temperature and relative humidity. According to the basic data, the simulated distillation line is very consistent with the actual distillation line of Qinghai Lake.     

On the origin of bleaching phenomena in red bed sediments of Triassic Buntsandstein deposits in Central Germany

The Lower Triassic Buntsandstein in Central Germany comprises one of the major clastic, lithified hydrocarbon reservoirs, it is a major groundwater aquifer and it is considered as a potential underground gas storage lithology. Thus, sandstones of the Buntsandstein from Thuringia and NE Hesse were used to analyse their geochemical composition combined with mineralogical data in order to investigate the origin of several bleaching phenomena in primary red beds, since these give a hint for mineral alteration, mineral formation and mineral reactivity in the course of fluid-rock-interactions. This is relevant for e.g. recent Carbon Capture and Storage (CCS) efforts. The origin of the observed bleaching phenomena is diverse and it is linked to certain stages of diagenesis and different episodes of fluid flow: (1) eodiagenetic bleaching coupled with palaeosoil formation and iron mobilisation, (2) mesodiagenetic bleaching as a result of hydrocarbon migration, (3) Tertiary bleaching due to CO₂ degassing from Miocene volcanism, (4) Tertiary telodiagenetic bleaching due to weathering under humid climate conditions, and (5) weathering processes related to recent telodiagenesis/pedogenesis. This study emphasizes the multiple nature of fluids, which can induce iron mobilisation and bleaching of red beds.     

滇东北富乐铅锌矿床微量元素和S-Pb同位素地球化学研究

富乐铅锌矿床位于我国西南川滇黔铅锌多金属矿集区的东南部,矿体呈层状、透镜状赋存于中二叠统阳新组白云岩中,受层间破碎带控制。该矿床铅锌金属资源量超过50万吨,铅锌平均品位大于15. 6%。碳酸盐岩围岩溶蚀、重结晶和热液角砾岩化是该矿床普遍发育的热液蚀变类型,是酸性热液流体与碳酸盐岩围岩化学反应的结果。热液白云岩在成矿期前、成矿期和成矿期后都可形成,晚期形成的热液白云岩往往会部分替换早期形成的白云石,热液沿裂隙充填过程中,会引起围岩重结晶作用,形成明显的蚀变晕。矿石中主要硫化物包括闪锌矿、方铅矿和黄铁矿,伴有少量的黄铜矿和黝铜矿,白云石和方解石是主要脉石矿物。矿石的主要构造有致密块状、浸染状、脉状和角砾状。本次工作在富乐矿床厘定出三种颜色闪锌矿,即黑色、红色和棕色。LA-ICPMS研究表明,三种颜色闪锌矿中Cd、Cu、Ga和Ge等元素不同程度富集,而Fe、Mn和In等元素有不同程度亏损。在LA-ICPMS时间分辨率剖面图中,上述元素均呈水平直线出现,与Zn和S等主要元素的含量曲线平行,表明它们可能以类质同象形式赋存于闪锌矿中。而Sb、Pb和Ag等元素在LA-ICPMS时间分辨率剖面图中,呈较大波动趋势,暗示这些元素可能以微细粒包体存在,这与显微观测发现闪锌矿中有方铅矿微小矿物颗粒相吻合。本研究初步认为富乐闪锌矿颜色可能是Ni、Cu、Tl、Ga、Hg、Fe和Cr等多种元素共同引起的,其中Ni、Cu和Ga使闪锌矿呈紫色,Cu使闪锌矿呈红色,Ga使闪锌矿呈黄色。三种颜色闪锌矿样品的硫同位素组成变化较小,其δ~(34)S值变化范围为12. 2‰～14. 6‰,具有富集34S特征,与二叠系海相硫酸盐的δ~(34)S值相似,暗示热化学硫酸盐还原作用(TSR)可能是该矿床HS~-或S~(2-)离子形成的主要机制。不同颜色闪锌矿的~(207)Pb/~(204)Pb、~(206)Pb/~(204)Pb和~(208)Pb/~(204)Pb值分别为15. 604～15. 737、18. 570～18. 732和38. 532～38. 667。大部分闪锌矿的Pb同位素组成与基底昆阳群浅变质岩石的Pb同位素组成相似,少量闪锌矿具有与峨眉山玄武岩和赋矿沉积岩相似的Pb同位素组成,表明富乐铅锌矿床的成矿金属主要来源于基底岩石,并可能受到沉积岩和玄武岩的影响。综上所述,本文认为富乐铅锌矿床是一个形成于挤压背景下、受层间构造控制的高品位、富分散元素后生碳酸盐岩容矿型铅锌矿床。