Paleoclimate reconstruction based on the timing of speleothem growth and oxygen and carbon isotope composition in a cave located in the rain shadow in Israel

High-resolution ²³⁰Th/²³⁴U ages and δ¹⁸O and δ¹³C compositions of speleothems in Ma’ale Efrayim Cave located to the east of the central mountain ridge of Israel enable us to examine the nature of the rain shadow aridity during glacial and interglacial intervals. Speleothem growth occurred during marine glacial isotopic periods, with no growth during the two last marine isotope interglacial intervals and during the peak of the Last Glacial Maximum. This contrasts with speleothem growth in caves located on the western flank of the central mountain ridge, in the Eastern Mediterranean semiarid climatic zone, which continued throughout the last 240,000 yr. Thus, during glacial periods water reached both sides of the central mountain ridge. A comparison of the present-day rain and cave water isotopic compositions and amounts at the Ma’ale Efrayim Cave site with those on the western flank shows that evaporation and higher temperatures on the eastern flank are major influences on isotopic composition and the lack of rainfall. The δ¹⁸O and δ¹³C profiles of the speleothems deposited between 67,000 and 25,000 yr B.P. match the general trends of the isotopic profiles of Soreq Cave speleothems, suggesting a similar source (eastern Mediterranean Sea) and similar climatic conditions. Thus, during glacial periods the desert boundary effectively migrated further south or east from its present-day location on the eastern flank, whereas interglacial periods appear to have been similar to the present, with the desert boundary at the same position. The decrease in overall temperature and a consequent reduction in the evaporation to precipitation ratios on the eastern flank are viewed as the major factors controlling the decay of the rain shadow effect during glacial periods.     

地球化学样品中硒的循序提取技术

研究开发了一种硒的循序偏提取步骤，将地球化学样品中的硒选择性地循序提取到六个“操作上”定义的相态中：水溶性硒（水提取）；吸附在氧化矿物和粘土矿物上配位可交换的亚硒酸根离子（０．１ｍｏｌ／ＬＫＨ２ＰＯ４提取）；与有机质结合的硒（０．１ｍｏｌ／ＬＮａ４Ｐ２Ｏ７提取）；与铁锰铝氧化物和碳酸盐结合的硒（４．０ｍｏｌ／ＬＨＣｌ提取）；硫化物中的硒（ＫＣｌＯ３＋浓ＨＣｌ提取）；硅酸盐残渣中以副矿物和被硅质包裹的硒微粒存在的硒（ＨＦ＋ＨＮＯ３＋ＨＣｌＯ４强混合酸溶解）。对提取步骤的可行性和实用性作了详细的讨论。     

Polymetallic Mineralization at the Suttsu Vein-type Deposit, Southwestern Hokkaido, Japan

Abstract. The Suttsu polymetallic vein-type deposit, hosted by tuff, tuff breccia and shale of the Miocene Kunnui Formation and propylitized hornblende-augite andesite, is located in southwestern Hokkaido, Japan. It has been exploited and explored for Cu, Pb, Zn and Ag until 1962.
In this study, we examined K-Ar ages, ore mineralogical characteristics and fluid inclusions to obtain new data for the deposit.
The K-Ar ages on sericite indicate that the polymetallic mineralization occurred in Late Miocene (8.1–5.7 Ma). The polymetallic banded ore from the Ohkubo vein is characterized by an abundance of Au, Ag, Sn, Bi, in, Se and Te. These metals are mainly ascribed to electrum (30.3–37.8 atom% Ag), Se-bearing pavonite (8.5–9.5 wt% Se), gustavite-lillianite solid solution, Se-bearing bismuthinite (5.0–5.3 wt% Se), kawazulite, cassiterite, Sn-bearing chalcopyrite (3.3–4.2 wt% Sn), In-bearing stannite, stannite-chalcopyrite solid solution, and In- and Sn-bearing sphalerite (2.6–8.4 wt% In and 1.8–4.3 wt% Sn), occurring in narrow bands of the ore. The In- and Sn-bearing sphalerite likely forms a sphalerite-roquesite-stannite solid solution with the contents of roquesite and stannite being about 2–9 and 2-A mole%, respectively. Temperatures and salinities (in wt% NaCl equiv.) of the ore fluids are estimated to be 180-250C and 3–4 wt%, respectively. The Sn-bearing chalcopyrite therefore probably precipitated metastably. The geologic and mineralogical features suggest that pre-Tertiary basement rocks rich in organic material underlie the Miocene Kunnui Formation nearby the deposit and that they contributed to local and temporary reduction of magnetite-series magmas favorable for the early stage tin-polymetallic mineralization.     

硒对华贵栉孔扇贝碱性磷酸酶的酶动力学及理化性质研究

探讨了微量硒(Se~(4+))对华贵栉孔扇贝(Chlamys nobilis(Reeve))碱性磷酸酶(AKP)的作用。以催化动力学原理研究了不同缓冲系统中微量硒时AKP的影响。结果表明,Se~(4+)对谈酶的作用与酶所处的环境有关。在0.05 mol/L Na_2CO_3-NaHCO_3(pH 9.0)缓冲溶液中Se~(4+)浓度小于12.5 mmol/L时呈现出激活作用;Se~(4+)浓度大于12.5 mmol/L时呈现出非竞争性的抑制作用,其抑制常数为6.81×10~(-2)mol/L。在0.05 mol/L Tris-HCl缓冲系统(pH 9.0)中,微量Se~(4+)对AKP具有强烈竞争性抑制作用,其抑制常数为3.79×10~(-1)mol/L。经紫外吸收光谱、荧光发射光谱和圆二色谱的实验表明,微量Se~(4+)与AKP作用后,该酶的构象已发生了变化。研究发现海水环境中若含有微量Se~(4+)(SeO_3~(2-)),可以促进扇贝AKP的水解。利于贝类的生长发育和外壳的形成,并有益于贝类的繁殖。     

无机地球化学参数与有效烃源岩发育环境的相关研究

探索海相有效烃源岩判识指标仍是我国油气勘探中尚待解决的重要科研任务之一。古生产力及氧化还原条件是研究全球变化和海洋环境的重要内容,也是重塑有效烃源岩发育环境的主要参数。Si、Ba是古生产力的替代指标,Cd对古营养盐的反演具良好前景。过渡金属及其相关比值是缺氧环境的有效判识指标,可用其推断有机质保存条件。δ13Ccarb正偏移指示有机质埋藏量增加,是底部水体缺氧的响应。过渡金属同位素（δ65Cu、δ66Zn、δ97Mo）受生物活动及氧化还原条件的影响发生较大分馏,示踪环境变化具灵敏、高效性。将这些无机参数对古环境的示踪意义引入油气地质研究,从环境角度分析某一套地层能否发育有效烃源岩,进而探讨高演化海相有效烃源岩的判识,就更具特殊意义。     

对壤中钒、硒、钼测量方法的观察与思考

本文简要介绍了钒、硒、钼的地球化学性质。根据我国西北业已查实的3个层间氧化带砂岩型铀矿床中钒、硒、钼与铀的展布特征,认为,按已知铀矿床中铀与钒、硒、钼的存在及相互关系,试图用壤中钒、硒、钼测量对层间氧化带砂岩型铀矿实施伴生元素找矿或进行“空间定位”的依据尚不足。     

思茅坳陷油气地质特征与勘探前景

思茅坳陷存在古生界和中一新生界两套沉积盖层,具有多套生储盖组合。以二叠系、三叠系为主力烃源岩,储层低孔低渗,侏罗系一白垩系“红层”组成区域盖层。思茅坳陷气水同喷、原油显示表明,该区海相地层仍有油气勘探前景,以存在K3-N区域盖层、断裂改造较弱、源岩成熟度较低、构造发育的英德一景谷、勐腊一勐满含油气保存单元为首选靶区,具有一定勘探前景。     

高硒环境样品中硒的形态分析方法

在恩施富硒碳质岩和土壤样品中硒矿物学研究的基础上,提出了硒连续化学提取的改进方案。化学操作上定义为7个连续步骤:水溶态(MQ水提取)、可交换态(0.1 mol/L的K2HPO4 KH2PO4,pH=7.0)、有机结合态(0.1 mol/L NaOH)、元素态(1 mol/L Na2SO3溶液)、酸溶性提取态(15%CH3CO2H溶液)、硫化物/硒化物态(1 mol/L CrCl2 HCl溶液)和残渣态硒(HNO3 HF H2O2混合消化液)。使用HG-AFS法检测了各结合态中的硒形态和总硒,上述流程提取硒加和与总硒间显著一致,平均回收率为99.2%,符合平行样品间变异系数低于10%的精度要求。该方法简单易行,能够准确地揭示富硒地质样品中硒的形态信息。     

硒在干酪根中的两种不同赋存状态:TEM证据

对拉尔玛Se—Au矿床和渔塘坝硒矿床中干酪根的高分辨透射电镜(TEM)研究表明，两个矿床的Se在干酪根中的赋存状态是截然不同的。前者Se在干酪根中的富集可能主要以有机结合态的形式存在，主要是取代干酪根中的硫；而后者Se在干酪根中的富集主要以超微包体Se的形式吸附在干酪根中。两种不同的赋存状态可能主要取决于干酪根中硫含量的多少以及成矿时氧化还原条件的变化。研究表明，TEM是研究元素在干酪根中赋存状态的有效手段。     

海南岛农田土壤Se的地球化学特征

Se是人和动物必需的微量元素之一,具有广阔的开发应用前景,研究土壤中Se的地球化学分布规律和生物有效性控制因素意义重大。系统总结了海南岛27 426 km2范围内土壤Se的含量特征和影响因素。结果表明,研究区69.98%土地面积为足硒和富硒土壤,表层土壤Se含量在一定程度上继承了成土母岩(或深层土壤)Se含量,但不同成土母岩形成的表层土壤Se含量富集贫化趋势不同。进一步研究显示,土壤中Se含量与有机碳、Al2O3、TFe2O3、Mn和CIA等具有显著的正相关关系,说明土壤中粘土矿物、有机碳、铁锰氧化物及风化淋溶程度对Se的地球化学行为有重要影响,同时这些指标又是影响土壤Se生物有效性的重要参数。土壤有机碳、粘粒、CEC等含量或指标越高,Se的生物有效性越低。研究区土壤pH6.5时,土壤Se含量较低;土壤pH6.5时,土壤Se含量随pH下降而增加;当土壤pH为5.5～7.5时,土壤Se生物有效性相对较高。因此,开发富硒农产品不但要依据土壤总Se含量,还必须考虑土壤pH、TOC、CEC、粘粒等指标含量。