Sulfur Concentration in Geochemical Reference Materials by Solution Inductively Coupled Plasma‐Mass Spectrometry

With implications for the origin of ore deposits, redox state of the atmosphere, and effects of volcanic outgassing, understanding the sulfur cycle is vital to our investigation of Earth processes. However, the paucity of sulfur concentration measurements in silicate rocks and the lack of well‐calibrated reference materials with concentrations relevant to the rocks of interest have hindered such investigations. To aid in this endeavour, this study details a new method to determine sulfur concentration via high mass resolution solution inductively coupled plasma‐mass spectrometry (ICP‐MS). The method is based on an aqua regia leach, involving relatively rapid sample preparation and analysis, and uses small test portion masses (< 50 mg). We utilised two independently prepared standard solutions to calibrate the analyses, resulting in 4% accuracy, and applied the method to eight geochemical reference materials. Measurements were reproducible to within ~ 10%. Sulfur concentrations and isotopes of six reference materials were measured additionally by elemental analyser‐combustion‐isotope ratio mass spectrometry to independently evaluate the accuracy of the ICP‐MS method. Reference materials that yielded reproducible measurements identical to published values from other laboratories (JGb‐1, JGb‐2 and MAG‐1) are considered useful materials for the measurement of sulfur. Reference materials that varied between studies but were reproducible for a given test portion perhaps suffer from sample heterogeneity and are not recommended as sulfur reference materials.     

辽宁西丰一带侵入岩形成环境和成因探讨

西丰一带侵入岩即以前所说的西丰大岩体,是布列亚-张广才岭巨型花岗岩带组成部分.该巨型花岗岩带记录了造山带从古亚洲洋板块开始俯冲、洋盆闭合到增生造山演化过程的基本信息.现在已经将规模宏大的西丰大岩体进行了详细解体,重新归并成4个侵入期次,划分为11个侵入序次,统称辽宁省西丰一带侵入岩.在详细解体、重新归并和划分的基础上,进一步探讨了各序次侵入岩形成的温压条件、构造环境、物质来源与成因.早二叠世第一序次、第二序次侵入岩以及中侏罗世第一序次侵入岩为I型花岗岩,晚白垩世第三序次(闪长玢岩)也为I型,主要物质来源是地壳中岩浆岩重熔的成分.其余各序次侵入岩均为S型花岗岩,主要物质来源是地壳中沉积岩重熔的成分.西丰一带,早二叠世第一个序次侵入岩为火山弧型深成岩,早二叠世第二个序次侵入岩为火山弧型与同碰撞型的过渡类型.早二叠世第三序次至中侏罗世第各序次侵入岩和晚白垩世各序次侵入岩为同碰撞型和碰撞后型花岗岩.这些特征与古亚洲洋晚期的消减、闭合和增生造山演化序列基本吻合.     

西秦岭舒家坝地区泥盆纪舒家坝群碎屑锆石LA-ICP-MS U-Pb年龄：源区特征与形成时代

以西秦岭舒家坝地区泥盆纪舒家坝群碎屑岩为研究对象,进行碎屑锆石LA-ICP-MS U-Pb年龄研究,探讨其形成时代、物源组成和构造背景。所测样品最小锆石年龄组的年龄加权平均值为413Ma,代表了舒家坝群的沉积下限,结合前人研究的古生物资料将其形成时代限定为中泥盆世。所获碎屑锆石年龄可划分为4个谱段：震旦纪—古生代年龄谱段619~409Ma,峰值为445Ma;新元古代年龄谱段930~735Ma,峰值为849Ma;中元古代年龄谱段1760~1033Ma;新太古代—古元古代年龄谱段3095~2478Ma。综合研究认为,舒家坝群的物源具多元性,包括西秦岭北缘构造带、北祁连造山带东段和华北板块基底,其中北祁连造山带东段和西秦岭北缘构造带是舒家坝群沉积的主要物源区,且后者占主导地位。结合区域地质资料,根据其物源组成特征判断,舒家坝群形成于陆—陆或弧—陆碰撞后由挤压转换为伸展环境的局部裂陷盆地。     

熔融制样波长色散X射线荧光光谱法测定白云石中钙镁硅铁铝

白云石属碳酸盐矿物,应用熔融制样X射线荧光光谱法测定其中主次量组分钙、镁、硅、铁、铝时,由于白云石灼烧减量大,在试料片制备过程中,如果以干基试料制备试料片,除灼烧减量外还有少量其他组分被分解出的大量CO₂带走,导致试料损失,测定结果偏低;如果以灼烧基试料制备试料片,由于灼烧后的试料极易吸收空气中的水分和CO₂,同样使测定结果偏低。基于质量守恒原理,本文直接以灼烧减量测量后的灼烧基试料质量作为试料量(即灼烧减量测定所称量的干基试料量扣除灼烧减量的量),以四硼酸锂为熔剂,5%碘化铵溶液为脱模剂,试料与熔剂的稀释比为1:10,于1050℃熔融15 min以上制备的试料片透彻、玻璃化程度高。以白云石标准物质和标准样品作为标准试料,制作各组分的标准曲线的相关系数在0.9940~0.9994之间;方法检出限为0.011%~0.48%;标准物质和标准样品的测定值与认定值基本一致,各组分的相对标准偏差(RSD,n=11)在0.5%~1.7%之间,方法具有较好的重现性。本方法以1050℃灼烧后的试样作为试料制备XRF分析样片,最大限度地降低了灼烧减量因素(空气中的水分和CO₂)对测定结果的影响,适用于白云石及其煅烧物中钙、镁、硅、铁、铝等组分的同时测定。     

云南建水水草冲铜矿矿床地质特征及成矿物质来源

本文通过研究云南建水水草冲铜矿地质特征、围岩玄武岩和矿石矿物的微量元素、S、C、O同位素的组成,示踪了该矿床的成矿物质来源和性质。研究结果表明,云南建水水草冲铜矿位于滇东南哀牢山变质体北侧,容矿围岩为峨眉山玄武岩,矿体受北东向逆断层及其次级断裂控制,延深大于延长,形状不规则,矿体内多夹灰岩角砾及矿化玄武岩角砾,矿石矿物主要为黄铜矿,矿化蚀变以硅化、碳酸盐化、绿泥石化为主。水草冲铜矿黄铜矿与黄铁矿稀土元素具有相同的稀土元素组成与含量,ΣREE平均为1.901×l0-6,富集轻稀土元素,轻重稀土元素比(LREE/HREE)平均为8.188,（La/Yb）N值平均为10.259;δEu值平均为0.977;Ce呈现弱负异常,δCe值平均为0.808。黄铁矿中的Co/Ni比值为0.835,显示水草冲铜矿床为中温热液矿床;黄铁矿的Y/Ho比值平均为38.23,表明水草冲铜矿床的成矿流体为混合来源。结合黄铁矿的稀土微量元素特征,推断水草冲铜矿床的成矿流体是Cl多于F的流体。S的来源复杂,黄铁矿δ34SCDT（‰）的变化范围（18.3~29.4）与海水硫酸盐(海相蒸发岩)的δ34S值接近或略低;黄铜矿δ34SCDT（‰）变化范围是-0.5~10.1,表明有深部硫的参与。δ13C V-PDB（0.9‰~2.6‰）,δ18O V-SMOW（14.3‰~15.9‰）反映了方解石流体可能为热液循环萃取沉积岩地层混合形成。综上,推测成矿物质为后期构造热液萃取围岩（玄武岩和灰岩等）所得,其中铜主要来自于玄武岩本身,而硫的来源以地层硫为主。     

微波消解—冷原子荧光光谱法测定植物样品中的汞

为了简化测量植物中汞含量的方法,提高灵敏度及结果的可信度,实验采用微波消解植物样品的办法,使样品经氯化亚锡还原,再用冷原子荧光测定出植物样品中汞的含量。确定了消解样品的方法和微波消解样品的条件,优化了仪器的最佳工作参数。方法检出限0.30×10-9(稀释因子100倍),精密度(n=12)在2.09%~6.05%,加标回收率94.1%~105.5%,方法经生物国家一级标准物质验证方法准确可靠。     

Genesis study of high abundant 17a（H）-diahopanes in Lower Cretaceous lacustrine source rocks of the Lishu Fault Depression,Songliao Basin,Northeast China

Relatively abundant 17α（H）-diahopanes have been detected in the lower cretaceous lacustrine source rocks from the Lishu Fault Depression in the Songliao Basin Northeast China. Rich long chain tricyclic terpanes （carbon number up to C35） and gammacerane have been observed in those source rocks with relatively abundant 17α（H）-diahopanes, which is rarely seen in previous reports. In this paper, the formation of 17α（H）-diahopanes has been discussed from three aspects including maturity, oxidation-reduction nature of depositional environment and parent material composition by the GC/MS analyses. The results reveal that maturity and oxidation-reduction nature of depositional environment have little effect on the formation of 1 7α（H）-diahopanes in the investigated area. How- ever, the positive correlation between long-chain tricyclic terpanes and 17α（H）-diahopanes argues strongly for a common origin, and the origin is related to the algaes in saline water environment. The algaes in saline water envi- ronment may be a kind of origin of 1 7α（H）-diahopanes.     

基于VBA实现设计点位编号和坐标提取

针对实际生产需要,探讨利用计算机实现化探设计点位坐标提取和填写样品编号,重点介绍用VBA编程填写样品编号。这里还介绍了VBA语言及主要函数功能、程序流程及主要程序编码。通过实际应用表明,该程序流程合理、过程简单、运行速度快,有效改善了野外生产的精度及效率。     

An enhanced constitutive model for crushable granular materials

Studies in the past have tried to reproduce the mechanical behaviour of granular materials by proposing constitutive relations based on a common assumption that model parameters and parameters describing the properties, including gradation of individual grains are inevitably linked. However successful these models have proved to be, they cannot account for the changes in granular assembly behaviour if the grains start to break during mechanical loading. This paper proposes to analyse the relation between grading change and the mechanical behaviour of granular assembly. A way to model the influence of grain breakage is to use a critical state‐based model. The influence of the amount of grain breakage during loading, depending on the individual grain strength and size distribution, can be introduced into constitutive relations by means of a new parameter that controls the evolution of critical state with changes in grain size distribution. Experimental data from a calcareous sand, a quartz sand, and a rockfill material were compared with numerical results and good‐quality simulations were obtained. The main consequences of grain breakage are increased compressibility and a gradual dilatancy disappearance in the granular material. The critical state concept is also enriched by considering its overall relation to the evolution of the granular material. Copyright © 2009 John Wiley & Sons, Ltd.     

Determination of the constriction size distribution of granular filters by filtration tests

This paper presents the calibration of an experiment based on filtration tests, able to provide the cumulative constriction size distribution of granular materials. Here, simulations of these tests are performed using a discrete element method. Filters of same density but different thicknesses are created with a poly‐sized spherical material. Lateral periodic boundaries for the samples are used, and their size is calibrated so that a representative elementary volume is obtained. Fine particles are released on the created samples, and the particle size distribution of the collected material that successfully crossed the filters is computed. These particle size distributions are related to the underlying cumulative constriction size distribution (CSD) of the granular material involved in the samples. The CSD is derived using a probabilistic approach for the path length of individual particles through a granular material. We settle all the requisites related to the technique and to the fine particles that are released to allow reaching a correct CSD for the filter. The reference CSD used for the calibration of the experiment is obtained after a radical partition of the void space into Delaunay tetrahedra and a geometrical characterisation of constrictions on each tetrahedron face. Copyright © 2012 John Wiley & Sons, Ltd.