土壤样品镉同位素分析中Cd与Sn有效分离方法的改进

保证Cd的高回收率以及彻底的Sn干扰去除是获得精确镉同位素组成的前提,目前报道的多种Cd分离与纯化方法获得的Cd回收率有较大差异(42.6%~99.8%),且去除Sn干扰的效果也不同(去除率在87.8%~97.4%之间),Cd回收率和Sn去除率均不理想。本文对前人报道的分离方法进行对比实验,发现0.1 mol/L氢溴酸-0.5 mol/L硝酸是分离Cd和Sn的有效试剂,增加该组混合酸的用量可淋洗出样品中更多的Sn且不会损失Cd,当混合酸的淋洗用量增加至30 mL时,Sn的淋洗率达到99.8%以上,Cd的回收率亦达到99.0%±0.5%,可满足土壤样品镉同位素的测定要求。本工作为获得高精度的镉同位素组成奠定了基础,为研究土壤环境中镉的污染来源提供了技术手段。     

滇西芦子园远程矽卡岩Pb-Zn-Fe(Cu)多金属矿床流体包裹体初探及矿床成因探讨

滇西镇康芦子园是"三江"成矿带保山地块内迄今发现的唯一超大型Pb-Zn-Fe(Cu)多金属矿床,是区内系列同类层控热液铅锌矿床的典型代表。矿体呈似层状、脉状及透镜状产于寒武系碳酸盐岩建造的矽卡岩和大理岩层间破碎带,矿石构造以条带状、浸染状和脉状-网脉状为主要特征;围岩蚀变复杂、分带明显,由下至上依次为石榴子石-透辉石-透闪石-阳起石化带→绿泥石-绿帘石-阳起石-蔷薇辉石化带→碳酸盐-大理岩化带。矿床成矿流体从早期到晚期经历了多个矿化阶段。本文选取了该矿床早矽卡岩阶段、晚矽卡岩阶段、石英硫化物阶段和石英碳酸盐阶段的多种脉石矿物及闪锌矿进行了系统的流体包裹体研究。结果显示,早矽卡岩阶段发育微溶CO_2富液相和纯液相水溶液包裹体,并含大量K~+、Na~+、Ca~(2+)、F~-和Cl~-和少量SO_4~(2-),气相成分主要为H_2O、CO_2及少量CH_4和N_2,包裹体均一温度为233.6~315.6℃,盐度为10.6%~17.6%NaCleqv;晚矽卡岩阶段发育含CO_2和子矿物三相包裹体,均一温度214.9~388.0℃,盐度5.9%~16.4%NaCleqv;石英硫化物阶段发育含CO_2的水溶液包裹体,气相成分为CH_4、H_2O和少量CO_2,均一温度150.0~285.0℃,盐度为2.5%~13.8%NaCleqv;石英碳酸盐阶段为单一成分的水溶液包裹体,均一温度为105.0~187.5℃,盐度为0.5%~12.3%NaCleqv。结合H-O同位素研究表明,成矿流体最初来源于具中高温、中高盐度、高K、Na,富CO_2、Cl、F等特征的深部岩浆热液,在石英硫化物阶段开始有大气降水混入,演化为中阶段中低温、低盐度、贫CO_2的热液流体,至成矿晚阶段转化为以大气降水占主导。该矿床成矿环境的改变、流体混合以及流体的沸腾作用可能是导致成矿物质富集沉淀的重要机制。综合矿床地质特征、成矿流体包裹体和HO同位素研究认为,该矿床为与陆陆碰撞造山和深部隐伏岩体有关的远程矽卡岩成矿系统。     

A Common Reference Material for Cadmium Isotope Studies – NIST SRM 3108

Research into natural mass‐dependent stable isotope fractionation of cadmium has rapidly expanded in the past few years. Methodologies are diverse with MC‐ICP‐MS favoured by all but one laboratory, which uses thermal ionisation mass spectrometry (TIMS). To quantify the isotope fractionation and correct for instrumental mass bias, double‐spike techniques, sample‐calibrator bracketing or element doping has been used. However, easy comparison between data sets has been hampered by the multitude of in‐house Cd solutions used as zero‐delta reference in different laboratories. The lack of a suitable isotopic reference material for Cd is detrimental for progress in the long term. We have conducted a comprehensive round‐robin assay of NIST SRM 3108 and the Cd isotope offsets to commonly used in‐house reference materials. Here, we advocate NIST SRM 3108 both as an isotope standard and the isotopic reference point for Cd and encourage its use as ‘zero‐delta’ in future studies. The purity of NIST SRM 3108 was evaluated regarding isobaric and polyatomic molecular interferences, and the levels of Zn, Pd and Sn found were not significant. The isotope ratio ¹¹⁴Cd/¹¹⁰Cd for NIST SRM 3108 lies within ～ 10 ppm Da^?1 of best estimates for the Bulk Silicate Earth and is validated for all measurement technologies currently in use.     

吉林蛟河地幔橄榄岩捕虏体的Sr-Nd-Hf-Os同位素特征与岩石圈地幔时代

吉林省蛟河市境内大石河新生代玄武岩中含有丰富的地幔橄榄岩包体,详细的岩石学与矿物学研究显示,这些包体的主要岩石类型为尖晶石二辉橄榄岩-方辉橄榄岩,未发现石榴石橄榄岩.岩相学及地球化学资料显示它们都是经历过熔体抽取而形成的岩石圈地幔残留.矿物平衡温度计算发现,本区的这些地幔橄榄岩包体来自地下40～60km深度,且下部以二辉橄榄岩为主,而上部以贫单斜辉石的二辉橄榄岩和方辉橄榄岩为主,显示明显的岩石圈地幔分层现象.Sr-Nd-Hf同位素资料反映这些地幔包体均表现为亏损性质,而Re-Os同位素资料确定上述岩石圈地幔形成于中元古代,明显老于上覆地壳的新元古宙时代,反映壳幔年龄上的解耦.因此我们推测,该区曾经历过华北克拉通类似的早期岩石圈地幔的整体丢失事件,然后形成于其它地区的中元古宙岩石圈地幔在本区增生.     

粤西大降坪黄铁矿床硫、铅同位素组成初步研究

大降坪黄铁矿床是产于云开隆起中段偏北震旦系海相碎屑岩-细碎屑岩中的层状硫化物矿床,矿床成因和海底喷气热水沉积作用有关,局部经受了后期热液的叠加改造。黄铁矿的δ~(34)S值在-25.55‰—+21.07‰之间,与矿石及黄铁矿中的有机碳含量呈反比。从条带状细粒黄铁矿到块状粗粒黄铁矿,亦即从南到北,硫同位素组成从富轻硫变为富重硫。条带状矿石的铅同位素组成与矿体围岩一致,为富放射成因上地壳源铅,块状矿石铅同位素组成较均一,三组铅同位素比值较条带状矿石略低,为原始沉积的矿石铅与热液带来基底混合岩铅的混合铅。     

招远金矿区水体中硫同位素特征及其对污染来源的指示

稳定同位素因其指纹效应已成为分析矿区污染来源的重要技术手段。文章以招远金矿区为例,应用硫同位素联合水化学分析、聚类分析及氢氧同位素分析招远金矿区水污染特征和成因。通过分析可知,矿区内地表水和地下水主要接受大气降水补给,水力联系密切。水化学类型以SO4—Ca和SO4—Na型为主,阴离子以SO42-为主,地表水和地下水的NO3-和Cl-在空间上变异性较大。地表水硫酸盐含量普遍偏高,硫酸盐污染较为严重,高值区出现在玲珑金矿、金翅岭金矿和张星镇附近;而地下水高值区都出现在玲珑金矿附近,且SO42-浓度沿着径流方向逐渐降低。地表水中硫酸盐δ34S值介于1.8‰~9.8‰,地下水中硫酸盐δ34S值介于2.7‰~9.6‰,地表水和地下水硫酸盐含量受玲珑金矿硫化、玲珑花岗岩和胶东岩群影响明显。在地下水径流途中,有地表水入渗污染地下水的现象。另外,工业废水的排放也是硫酸盐含量升高的主要原因。研究表明：硫同位素在金矿区硫酸盐污染的来源和特征方面有很好的指示作用,是评价矿山开采对地下水污染的有效工具。     

距今14亿年低生物量的碳同位素证据

北京十三陵和天津蓟县两剖面中距今十四亿年海相碳酸盐岩的碳同位素表明,十三陵—蓟县地区当时具有较低的δ¹³C 值(共分析了152个样品),平均占δ¹³C=-0.7‰(PDB)。这种较低的δ¹³C 值很可能具有全球性。原始的海相碳酸盐岩较低的碳同位素组或反映较低的有机碳埋藏速率。有机碳的埋藏速率与当时全球生物量的大小有着密切的关系。磷酸盐岩较低的δ¹³C 值进一步反映当时较小的全球生物量的存在。每年8.11×10⁸吨有机碳推测是距今十四亿年全球生物量的最小值。     

湘南芙蓉锡矿田成矿地质特征及成矿模式

通过对湘南芙蓉锡矿田地质特征的研究,认为芙蓉锡矿田与东坡和香花岭两大锡多金属矿田具有相同的成矿特征和相同的成矿时代,所不同的是芙蓉锡矿田的矿体主要位于大岩基中,其矿体的展布和矿脉(体)的形态及其产状等严格受断裂构造控制.铅同位素组成显示其成矿以壳源物质为主,锡多金属成矿与燕山早期晚阶段侵入的细粒花岗岩有关.     

中国大陆科学钻探工程主孔（734～933m）榴辉岩和片麻岩元素及Sr-Nd同位素地球化学研究

对中国大陆科学钻探工程主孔两段榴辉岩与片麻岩互层的岩芯样品(Ⅰ:734.21-737.16m和Ⅱ:929.67-932.86m)分别进行了主要元素和微量元素以及Sr-Nd同位素分析。结果表明:(1)榴辉岩具有较大的成分变化范围(SiO2含量为46.8%-59.8%),表现出平坦或轻稀土(LREE)富集的分布模式和大离子亲石元素(LILE)富集或亏损以及Nb、Ta负异常特征。部分榴辉岩样品具有明显低的活动性元素(Rb、Ba和K)含量,指示了板块俯冲过程中的脱水变质效应;(2)两段岩芯中的片麻岩具有明显不同的主量和微量元素组成,其中第Ⅰ段具有相对较低的SiO2含量(61.3%～66.2%)和高的重稀土(HREE)含量,而第Ⅱ段具有明显偏高的SiO2含量(73.8%～74.1%)和低的HREE含量。但两段均表现出LREE富集和Eu负异常以及LILE富集和高场强元素(Nb、Ta、Ti)负异常特征;(3)榴辉岩和第Ⅰ段岩芯中的片麻岩具有相近的且偏高的εNd(750Ma)值(-3.6- 0.5),而第Ⅱ段岩芯中的片麻岩具有明显偏低的εNd(750Ma)值(-8.7)。部分片麻岩样品表现出较高的87Sr/86Sr比值(0.7070)和非常低的Rb/Sr比值(0.008),指示岩石Rb-Sr同位素体系受到了变质扰动。非活动性元素如Zr、Hf、Nb、Ta、Ti、Y、REE和Ti在脱水变质过程中没有受到明显扰动,因此可用于恢复榴辉岩和片麻岩的原岩性质及其形成的大地构造背景。根据分析样品的元素和Nd同位素特点,推测榴辉岩原岩具有板内玄武岩性质,第Ⅰ段岩芯中的片麻岩原岩为玄武质岩浆上升过程中同化地壳物质形成的中性岩,而第Ⅱ段岩芯中的片麻岩原岩为地壳物质重熔形成的酸性岩。因此,深钻榴辉岩和片麻岩原岩为新元古代华南陆块北缘裂谷构造带双峰式岩浆活动的产物,在岩浆侵位过程中经历了高温大气降水热液蚀变。     

Origin and quantitative source assessment of deep oils in the Tazhong Uplift,Tarim Basin

A large amount of deep oil has been discovered in the Tazhong Uplift, Tarim Basin whereas the oil source is still controversial. An integrated geochemical approach was utilized to unravel the characteristics, origin and alteration of the deep oils. This study showed that the Lower Cambrian oil from well ZS1C (

_1x) was featured by small or trace amounts of biomarkers, unusually high concentration of dibenzothiophenes (DBTs), high δ³⁴S of DBTs and high δ¹³C value of n-alkanes. These suggest a close genetic relationship with the Cambrian source rocks and TSR alteration. On the contrary, the Middle Cambrian oils from well ZS1 (

_2a) were characterized by low δ¹³C of n-alkanes and relatively high δ³⁴S of individual sulfur compounds and a general “V” shape of steranes, indicating a good genetic affinity with the Middle–Upper Ordovician source rocks. The middle Cambrian salt rock separating the oils was suggested to be one of the factors responsible for the differentiation. It was suggested that most of the deep oils in the Tazhong Uplift were mixed source based on biomarkers and carbon isotope, which contain TSR altered oil in varied degree. The percentage of the oils contributed by the Cambrian–Lower Ordovician was in the range of 19–100% (average 57%) controlled by several geological and geochemical events. Significant variations in the δ³⁴S values for individual compounds in the oils were observed suggesting a combination of different extent of TSR and thermal maturation alterations. The unusually high DBTs concentrations in the Tazhong-4 oilfield suggested as a result of mixing with the ZS1C oil (

_1x) and Lower Ordovician oils based on δ³⁴S values of DBT. This study will enhance our understanding of both deep and shallow oil sources in the Tazhong Uplift and clarify the formation mechanisms of the unusually high DBTs oils in the region.