Natural fractionation of U/U

The isotopic composition of U in nature is generally assumed to be invariant. Here, we report variations of the ²³⁸U/²³⁵U isotope ratio in natural samples (basalts, granites, seawater, corals, black shales, suboxic sediments, ferromanganese crusts/nodules and BIFs) of ∼1.3‰, exceeding by far the analytical precision of our method (≈0.06‰, 2SD). U isotopes were analyzed with MC-ICP-MS using a mixed ²³⁶U-²³³U isotopic tracer (double spike) to correct for isotope fractionation during sample purification and instrumental mass bias. The largest isotope variations found in our survey are between oxidized and reduced depositional environments, with seawater and suboxic sediments falling in between. Light U isotope compositions (relative to SRM-950a) were observed for manganese crusts from the Atlantic and Pacific oceans, which display δ²³⁸U of −0.54‰ to −0.62‰ and for three of four analyzed Banded Iron Formations, which have δ²³⁸U of −0.89‰, −0.72‰ and −0.70‰, respectively. High δ²³⁸U values are observed for black shales from the Black Sea (unit-I and unit-II) and three Kupferschiefer samples (Germany), which display δ²³⁸U of −0.06‰ to +0.43‰. Also, suboxic sediments have slightly elevated δ²³⁸U (−0.41‰ to −0.16‰) compared to seawater, which has δ²³⁸U of −0.41 ± 0.03‰. Granites define a range of δ²³⁸U between −0.20‰ and −0.46‰, but all analyzed basalts are identical within uncertainties and slightly lighter than seawater (δ²³⁸U = −0.29‰).Our findings imply that U isotope fractionation occurs in both oxic (manganese crusts) and suboxic to euxinic environments with opposite directions. In the first case, we hypothesize that this fractionation results from adsorption of U to ferromanganese oxides, as is the case for Mo and possibly Tl isotopes. In the second case, reduction of soluble U^VI to insoluble U^IV probably results in fractionation toward heavy U isotope compositions relative to seawater. These findings imply that variable ocean redox conditions through geological time should result in variations of the seawater U isotope compositions, which may be recorded in sediments or fossils. Thus, U isotopes might be a promising novel geochemical tracer for paleo-redox conditions and the redox evolution on Earth. The discovery that ²³⁸U/²³⁵U varies in nature also has implications for the precision and accuracy of U-Pb dating. The total observed range in U isotope compositions would produce variations in ²⁰⁷Pb/²⁰⁶Pb ages of young U-bearing minerals of up to 3 Ma, and up to 2 Ma for minerals that are 3 billion years old.     

Zinc stable isotopes in seafloor hydrothermal vent fluids and chimneys

Many of the heaviest and lightest natural zinc (Zn) isotope ratios have been discovered in hydrothermal ore deposits. However, the processes responsible for fractionating Zn isotopes in hydrothermal systems are poorly understood. In order to better assess the total range of Zn isotopes in hydrothermal systems and to understand the factors which are responsible for this isotopic fractionation, we have measured Zn isotopes in seafloor hydrothermal fluids from numerous vents at 9–10°N and 21°N on the East Pacific Rise (EPR), the TAG hydrothermal field on the Mid-Atlantic Ridge, and in the Guaymas Basin. Fluid δ⁶⁶Zn values measured at these sites range from + 0.00‰ to + 1.04‰. Of the many physical and chemical parameters examined, only temperature was found to correlate with fluid δ⁶⁶Zn values. Lower temperature fluids (< 250 °C) had both heavier and more variable δ⁶⁶Zn values compared to higher temperature fluids from the same hydrothermal fields. We suggest that subsurface cooling of hydrothermal fluids leads to precipitation of isotopically light sphalerite (Zn sulfide), and that this process is a primary cause of Zn isotope variation in hydrothermal fluids. Thermodynamic calculations carried out to determine saturation state of sphalerite in the vent fluids support this hypothesis with isotopically heaviest Zn found in fluids that were calculated to be saturated with respect to sphalerite. We have also measured Zn isotopes in chimney sulfides recovered from a high-temperature (383 °C) and a low-temperature (203 °C) vent at 9–10°N on the EPR and, in both cases, found that the δ⁶⁶Zn of chimney minerals was lighter or similar to the fluid δ⁶⁶Zn. The first measurements of Zn isotopes in hydrothermal fluids have revealed large variations in hydrothermal fluid δ⁶⁶Zn, and suggest that subsurface Zn sulfide precipitation is a primary factor in causing variations in fluid δ⁶⁶Zn. By understanding how chemical processes that occur beneath the seafloor affect hydrothermal fluid δ⁶⁶Zn, Zn isotopes may be used as a tracer for studying hydrothermal processes.     

八达岭基性岩和高Ba—Sr花岗岩地球化学特征及成因探讨：华北和大别—苏鲁造山带中生代岩浆岩的对比

八达岭杂岩侵位于华北北部，由辉长闪长岩岩、石英闪长岩、石英二长岩、二长闪长岩、二长花岗岩、碱长花岗岩和石英正长岩等组成，主要属高钾钙碱性系列。除了含V-Ti磁铁矿的堆晶辉长闪长岩，整套岩石的主量元素变化范围较大，SiO2=46.5%-75.3%,MgO=5.6%-0.2%，中酸性岩石的K2O/NaO为0.59-1.09。碱长花岗岩和少数石英二长岩Ba和Sr含量较低，且具有明显（Eu）负异常。大多数中酸性岩石（高Ba-Sr花岗岩）具有如下显著的微量元素地球化学特征：Ba,Sr和轻稀土（LREE）富集，Y和重稀土（HREE）亏损，LREE/HREE强烈分离，Sr/Y和La/Yb比值较高；在原始地幔标准化的蛛网图中具有显著的Nb,Ta和Ti亏损，不具明显的Sr和Eu亏损。在Harker图解中，基性岩石和高Ba-Sr花岗岩的主量元素相关性明显，两者还具有相似的微量元素和稀土（REE）分配特征，并且，REE,Y,Sr,P和Ti含量从基性到酸性逐渐降低。辉长闪长岩和高Ba-Sr花岗岩的Sr-Nd同位素初始值呈EMI特征（Isr=0.7051-0.7068,εNdi=-8.2-20.2），大致呈负相关。地球化学特征表明基性岩浆为富集的大陆岩石圈地幔部分熔融形成，而高Ba-Sr花岗岩则为基性岩浆通过陆壳混染和结晶分离形成；富P和Ti的副矿物（如磷灰石和的榍石）的分离结晶导致了REE,P和Ti丰度的逐渐降低。另外，华北板块内部和大别-苏鲁造山带基性岩和高Ba-Sr花岗岩分别具有相似的地球化学特征，这表明，上述地区燕山期大规模岩浆活动具有相似的地球动力学机制，大别-苏鲁造山带岩浆岩的地球化学特征并不反映其地幔源区一定受到过来自深俯冲的扬子板块的流体的富集作用。岩石圈的拆沉和减簿作用可能导致了华北板块和大别-苏鲁造山带下古老岩石圈地幔的部分熔融，岩石圈地幔的富集作用可能主要性发生于元古代。