电感耦合等离子体质谱(ICP-MS)技术在地学研究中的应用

简单介绍ICP MS技术应用最新进展。着重对该技术在中国地学研究和多目标地质调查中的应用作一回顾 ,包括ICP MS技术简介和地质样品分析需求 ,稀土稀散等痕量、超痕量多元素分析 ,铂族元素分析 ,卤素等非金属元素分析 ,同位素比值分析等内容。着重对最近几年国内地质样品分析的一些新方法加以介绍。     

咸化湖盆白云岩碳氧同位素特征及古环境意义:以柴西地区始新统下干柴沟组为例

近年来,柴西地区始新统致密碳酸盐岩中的油气勘探获得了重要进展,其中白云岩为最优质的储集岩。系统的岩石学、矿物学和地球化学特征研究表明,该套白云岩主要为泥晶结构,白云石晶间孔广泛发育,孔径多小于1μm。泥晶白云岩的δ13CPDB值变化范围为-4.5‰~0.2‰,平均值为-2.4‰,相对于典型湖相碳酸盐岩偏负,反映了周缘辫状三角洲供给富含轻碳的地表水在一定程度上改变了白云岩的碳同位素组成,且湖水中的溶解碳部分来源于有机质氧化解体产生的CO2,通过改变湖水中溶解碳的碳同位素组成从而间接影响了湖相白云岩的碳同位素组成。泥晶白云岩的δ18OPDB值变化范围为-6.1‰~0.4‰,平均值为-2.6‰,相对于典型湖相碳酸盐岩偏正,明显受咸化湖沉积环境影响。碳氧同位素相关关系投点图及其计算出的盐度、温度数据反映了泥晶白云岩是在准同生阶段、半开放-半封闭的咸化环境下、于水/沉积物界面附近由方解石交代而成的低温白云岩,这类准同生交代成因白云岩在区域上分布较广,且孔径极小的白云石晶间孔抗压实能力强,这一重要发现无论是平面展布上还是纵向深度上均开拓了柴达木盆地致密油勘探的新领域。     

Characteristics of Triassic epithermal Au mineralization at the Q prospect,Chatree mining area,Central Thailand

The Chatree deposit is located in the Loei‐Phetchabun‐Nakhon Nayok volcanic belt that extends from Laos in the north through central and eastern Thailand into Cambodia. Gold‐bearing quartz veins at the Q prospect of the Chatree deposit are hosted within polymictic andesitic breccia and volcanic sedimentary breccia. The orebodies of the Chatree deposit consist of veins, veinlets and stockwork. Gold‐bearing quartz veins are composed mainly of quartz, calcite and illite with small amounts of adularia, chlorite and sulfide minerals. The gold‐bearing quartz veins were divided into five stages based on the cross‐cutting relationship and mineral assemblage. Intense gold mineralization occurred in Stages I and IV. The mineral assemblage of Stages I and IV is characterized by quartz–calcite–illite–laumontite–adularia–chlorite–sulfide minerals and electrum. Quartz textures of Stages I and IV are also characterized by microcrystalline and flamboyant textures, respectively. Coexistence of laumontite, illite and chlorite in the gold‐bearing quartz vein of Stage IV suggests that the gold‐bearing quartz veins were formed at approximately 200°C. The flamboyant and brecciated textures of the gold‐bearing quartz vein of Stage IV suggest that gold precipitated with silica minerals from a hydrothermal solution that was supersaturated by boiling. The δ¹⁸O values of quartz in Stages I to V range from +10.4 to +11.6‰ except for the δ¹⁸O value of quartz in Stage IV (+15.0‰). The increase in δ¹⁸O values of quartz at Stage IV is explained by boiling. P_H2O is estimated to be 16 bars at 200°C. The f_CO2 value is estimated to be 1 bar based on the presence of calcite in the mineral assemblage of Stage IV. The total pressure of the hydrothermal solution is approximately 20 bars at 200°C, suggesting that the gold‐bearing quartz veins of the Q prospect formed about 200 m below the paleosurface.     

云南兰坪-思茅盆地脉状铜矿床铅、硫同位素地球化学与成矿物质来源研究

云南兰坪-思茅盆地中一新生代砂页岩中赋存有许多脉状铜矿床。本文对盆地内从北至南三个典型脉状铜矿床(金满、水泄和白龙厂)进行了详细的铅、硫同位素研究，探讨了该类型矿床的成矿物质来源。分析表明。该类型矿床的铅同位素组成总体变化较小，且均位于上地壳铅演化线附近，说明成矿流体中铅具有稳定的上地壳来源。各矿床由于赋矿层位不同，矿石铅同位素组成表现出一定差异，如由兰坪盆地侏罗纪地层中的金满矿床到思茅盆地二叠纪地层中的白龙厂矿床，铅同位素比值(^207Pb/^204Pb)呈增高趋势，这表明这类矿床的铅主要来源于围岩地层，且地层越老，提供的铅就相对富含放射成因铅。矿床中脉石矿物重晶石、铁白云石等的锶同位素组成也表明，金满矿床成矿流体的^87Sr／^86Sr比值较高(0．70874—0．71232)，而白龙厂矿床的^87Sr／^86Sr比值较低(0．70829—0．70938)，接近于围岩灰岩的值(0．70755)。硫同位素研究表明，金满矿床中硫化物的δ^34S值变化最大，为-20．5‰- 7．0‰。水泄矿床中硫化物的δ^34S值变化最小，为-0．1‰- 4．2‰。而白龙厂矿床中硫化物的δ^34S值为-14．3‰--3．6‰。水泄和白龙厂矿床中重晶石的δ^34S值分别为 12．3‰- 19．0‰和 13．1‰，它们与盆地中蒸发岩层中石膏的δ^34S值( 10．8‰- 15．7‰)相近。分析表明，兰坪-思茅盆地中脉状铜矿的硫源主要来源于盆地热卤水萃取的地层中蒸发岩硫酸盐，它们通过有机质的热分解反应还原为沉淀硫化物所必需的低价硫。各矿床独特的硫同位素组成还表明它们的硫源受局部地层硫源和成矿流体物理化学性质所控制。本文提出大气降水起源的盆地热卤水通过对围岩中新生代地层的淋滤和萃取，获得了成矿所需的金属和硫，并在构造薄弱部位沉淀形成了本区的脉状铜矿床。     

塔里木盆地柯坪地区上寒武统表生溶蚀型藻格架白云岩的地球化学特征及意义*

采用野外观察、室内薄片鉴定及多项地球化学分析技术方法,对塔里木盆地柯坪地区上寒武统表生溶蚀型藻格架白云岩的特征及成因进行了研究。宏观上,藻格架白云岩呈丘状、透镜状夹于潮坪相白云岩层间,由于差异性溶蚀,发育了大量表生溶蚀孔。微观上,藻格架由富藻的泥粉晶白云石组成,而架间孔由浅色的亮晶白云石充填。藻格架泥粉晶白云石呈他形—半自形,镶嵌结构,具有暗红色—橙红色的阴极发光,较高的Na、K含量,较低的Fe含量;δ¹³C为-0.572‰～0.124‰、平均值-0.116‰,δ¹⁸O为-5.391‰～-4.983‰、平均值-5.240‰,表明其形成于准同生阶段盐度较高的相对氧化环境中。架间充填的亮晶白云石胶结物,呈半自形—自形中细晶,具有昏暗的阴极发光或者不发光,较低的Na、K含量,较高的Fe含量,δ¹³C值为-0.662‰～-0.251‰、平均值为-0.460‰;δ¹⁸O值为-6.639‰～-5.939‰、平均值-6.267‰,表明其形成于相对还原的埋藏环境。稀土元素分析结果表明,二者均具有LREE轻微富集、HREE亏损、Eu负异常特征,与海相泥晶灰岩稀土元素配分模式相似,揭示了其白云化流体均来自于原始的海水。在溶蚀作用方面,亮晶白云石胶结物相对泥粉晶白云石藻格架更易于溶蚀。前者在大气水表生溶蚀过程中,主量元素Ca、Mg丢失显著,Mg/Ca值由0.955降至0.007,微量元素Na、K丢失相对明显,Na/Ca值由原来的3.8×10^-4降为1.9×10^-4,K/Ca值由1.1×10^-3降至检测限以下,而不改变稀土元素的配分模式。这些特征表明,表生溶蚀过程在元素特征上是一个去白云化的盐度降低过程,而这一过程中基本无稀土元素的带入带出。     

微细浸染型金矿床的稳定同位素特征与成因探讨

对我国众多沉积岩系中的微细当染型金矿床开展了较为系统的稳定同位素地球化学研究,非常分散复杂的氢氧同位素组成被认为是沉积盆地流体的一个典型特征,这是因为盆地流体中水的两个主要来源－海水和大气降水,经不同程度的水－岩反应同位素交换后又以不同比例相互混合,再加上有机物和粘土矿物的相变水在不同阶段以不同比例加入。     

U-Pb Age and Hf Isotope Study of Detrital Zircons from the Wanzi Supracrustals： Constraints on the Tectonic Setting and Evolution of the Fuping Complex, Trans-North China Orogen

Located in the middle segment of the Trans-North China Orogen, the Fuping Complex is considered as a critical area in understanding the evolution history of the North China Craton （NCC）. The complex is composed of various high-grade and multiply deformed rocks, including gray gneiss, basic granulite, amphibolite, fine-grained gneiss and marble, metamorphosed to upper amphibolite or granulite facies. It can be divided into four rock units： the Fuping TTG gneisses, Longquanguan augen gneisses, Wanzi supracrustals, and Nanying granitic gneisses. U-Pb age and Hf isotope compositions of about 200 detrital zircons from the Wanzi supracrustals of the Fuping Complex have been analyzed. The data on metamorphic zircon rims give ages of 1.82-1.84 Ga, corresponding to the final amalgamation event of the NCC, whereas the data for igneous zircon cores yield two age populations at -2.10 and -2.51 Ga, with some inherited ages scattering between 2.5 and 2.9 Ga. These results suggest that the Wanzi supracrustals were derived from the Fuping TTG gneisses （-2.5 Ga） and the Nanying granitic gneisses （2.0-2.1 Ga） and deposited between 2.10 and 1.84 Ga. All zircons with -2.51 Ga age have positive initial εHf values from ＋1.4 to ＋10.9, suggesting an important crustal growth event at -2.5 Ga through the addition of juvenile materials from the mantle. The Hf isotope data for the detrital zircons further imply that the 2.8 Ga rocks are important components in the lower crust, which is consistent with a suggestion from Nd isotope data for the Eastern Block. The zircons of 2.10 Ga population have initial εHf values of-4.9 to ＋6.1, interpreted as mixing of crustal re-melt with minor juvenile material contribution at 2.1 Ga. These results are distinct from that for the Western Block, supporting that the Fuping Complex was emplaced in a tectonic active environment at the western margin of the Eastern Block.     

微量水δ(~(17)O)和δ(~(18)O)CoF_3法线外同时测试新技术

三氧同位素(16O、17O、18O)组成特征可有效示踪天然水循环及其环境效应,微量水δ(17O)和δ(18O)CoF3法同时测试新技术的建立,可为三氧同位素定量研究提供有效的分析手段,特别是能够捕捉到像光合作用、呼吸作用等生物过程中发生的同位素分馏现象。在国内首次建立了微量水δ(17O)和δ(18O)CoF3法线外同时测试新技术,样品量仅需2μL,整个制样时间约40min。采用在质谱测试前对待测样品在100℃下预热10 min,待O2完全解吸后再进行质谱测试的方法,避免了制样和测试过程中的记忆效应及分馏效应,δ(17O)和δ(18O)的分析精度分别达到±0.07‰和±0.14‰。该法使用固体试剂CoF3替代了剧毒的气态氟化物BrF5,使得制样流程更加安全可靠且样品量少,适用性强,具有很大的推广应用价值。     

多接收器等离子体质谱(MC-ICPMS)高精度测定Nd同位素方法

多接收器等离子体质谱是近年发展起来的高精度同位素分析手段之一,通过用等离子体质谱测量Nd国际标准材料La Jolla和JMC Nd203以及实际样品GBW04419,研究MC-ICPMS测量Nd的质量分馏特点,解决MC-ICPMS测量的关键所在质量分馏校正.通过修正分馏系数,可以实现理想的分馏校正.结果显示出所得到的分析精度达到热电离质谱的测量水平.具有实际地质样品代表性的实验室内部标准CAGS-Nd-1重现性长期分析结果为:143Nd/144Nd=0.512072±0.000008(2σ,n=140).     

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.