Improved Inter‐calibration of Faraday Cup and Ion Counting for In Situ Pb Isotope Measurements Using LA‐MC‐ICP‐MS: Application to the Study of the Origin of the Fangshan Pluton,North China

A laser ablation multi‐collector inductively coupled plasma‐mass spectrometry (LA‐MC‐ICP‐MS) method was developed to obtain precise and accurate Pb isotopic ratio measurements in low‐Pb materials (< 10 μg g^?1) using a combination of Faraday cups and ion counters (FC–IC). The low abundance ²⁰⁴Pb (~ 1.4%) was collected using an IC. A NBS 981 standard solution was used to cross‐calculate the FC–IC gain and to investigate the signal response characteristics of the IC. A significant, continuous and linear decrease in the FC–IC gain was observed within 1 hr, but this drift could be corrected using the calibrator‐sample‐calibrator bracketing method. In addition, a non‐linear response of the IC used in this study was observed and corrected by a non‐linear correction algorithm, which was established by measuring a series of gravimetrically prepared NBS 981 standard solutions (NIST SRM 981). Compared with the conventional arrangement, the use of the newly designed X skimmer cone and Jet sample cone improved the signal intensities from Pb isotopes by a factor of 1.9. Compared with only Faraday cups, using a combination FC–IC array was found to enhance the measurement repeatability (RSD) of ^20xPb/²⁰⁴Pb by approximately one order of magnitude when the ²⁰⁴Pb intensity was < 8 mV. Eight natural glasses and the NIST SRM 612 reference material glass (as a calibration material) were measured to evaluate the new protocol for Pb isotope determination. The analytical results were in agreement with the reference values within 2s measurement uncertainties. For MPI‐DING ATHO‐G (5.67 μg g^?1 total Pb), KL2‐G (2.07 μg g^?1 total Pb) and ML3B‐G (1.38 μg g^?1 total Pb), the typical accuracies of ^20xPb/²⁰⁴Pb were 0.09% of preferred values with precisions of < 0.33% (2RSD). The Pb isotope ratios in feldspars from granodiorite and within mafic microgranular enclaves (MMEs) from the Fangshan pluton, North China, were measured using the present method. The Pb isotopic compositions of feldspars from the whole host granodiorite show that that are radiogenic in the margin zone and gradually become less radiogenic. For the MMEs, the Pb isotopic compositions of feldspars are highly variable and overlap with those of the whole host granodiorite. For single‐grain feldspar, the strong rim‐core‐rim variations of the Pb isotopic compositions and trace elements are interpreted to have been generated via magma mixing. These results suggest that the Fangshan pluton underwent magma mixing of mantle‐derived mafic magmas with felsic magmas, and the proportion of the mafic magma influx decreased over time.     

一种改进的点云数据配准方法

针对利用最近点迭代（ICP）算法进行点云数据配准时费时较多的问题,提出结合Butterworth高通滤波器和Sobel边缘检测算子首先对点云数据进行预处理,然后再用ICP算法进行点云配准,有效解决这一问题,加快配准速度,并在Matlab中编程实现该方法,具体实验结果证明该方法的有效性。     

Distribution Study of U,V, Mo,and Zr in Different Sites of Lakes Van and Hazar,River and Seawater Samples by ICP‐MS

The aim of this study is to investigate the concentrations of U, Th, V, Mo, and Zr in natural waters taken from Turkey. Among these water species, Lake Van is the largest soda lake and the fourth largest closed basin on Earth. The water samples were collected from 51 locations between 2008 and 2009. The inductively coupled plasma‐MS was used for determinations. The obtained U and Zr concentrations are in the range of 37–110 µg L^?1 and 17–78 µg L^?1 in Lake Van and 0.53–0.81 µg L^?1 and 0.15–0.19 µg L^?1 in Lake Hazar, respectively. The concentration of uranium in other studied waters varies from the lowest 0.09 µg L^?1 in Tigris (Dicle) river to the highest 4.0 µg L^?1 in Mediterranean Sea water. Mean Mo and V concentrations in the studied water samples were found to be in ranges of 0.1–17 and 2.7–113 µg L^?1, respectively. The obtained highest U concentration in Lake Van correlates with the highest Mo and Zr levels compared to the Lake Hazar and river waters. These results imply that there is a young occurrence of uranium minerals around Lake Van. It is concluded that there is about 50.000 ton of uranium in Lake Van water.     

全谱直读ICP发射光谱测定低冰镍中砷

对低冰镍样品中的砷进行了试验,采用硝酸分解试样,在ICP发射光谱上测定砷元素。本法采用冶标准样品进行实验,结果与标准值基本相符,其精确度与准确度均能满足低冰镍分析的要求。     

Speeding Up the Analytical Workflow for Coltan Fingerprinting by an Integrated Mineral Liberation Analysis/LA‐ICP‐MS Approach

Coltan (the African trade name for columbite‐tantalite, a tantalum ore) is one of several raw materials that finance the civil wars in the eastern provinces of the Democratic Republic of the Congo. To improve the transparency along the tantalum trade chain, a ‘certificate of origin’ for so‐called ‘conflict minerals’ has been recommended by the United Nations. Accordingly, the German Federal Institute for Geosciences and Natural Resources (BGR) has developed an analytical fingerprint procedure for coltan. Mineral formation age, modal mineralogy and chemical composition are important fingerprint parameters. The original workflow to obtain these parameters was streamlined and is now based on mineral liberation analysis and LA‐ICP‐MS. The use of an ICP‐MS instrument with a detector system covering an extended linear dynamic range and the application of an internal standard‐independent calibration strategy allowed data for major and trace element determination and mineral formation age estimates to be obtained simultaneously. The analytical results of this new approach were compared with analytical techniques of the original workflow and showed excellent agreement in terms of mineralogical and chemical characterisation and mineral formation age of coltan samples. Within a test, samples of different origin were allocated correctly and simple, binary mixtures were also identified successfully.     

Simultaneous Determination of Cd,In, Tl and Bi by Isotope Dilution‐Internal Standardisation ICP‐QMS with Corrections Using Externally Measured MoO+/Mo+ Ratios

A method for the simultaneous determination of Cd with In, Tl and Bi by isotope dilution‐internal standardisation (ID‐IS) ICP‐QMS using the same aliquot for rare earth element and other trace element determinations was developed. Samples mixed with an enriched ¹⁴⁹Sm spike were decomposed using a HF‐HClO₄ mixture, which was evaporated and then diluted with HNO₃. After determination of Sm by ID‐ICP‐QMS and Cd, In, Tl and Bi concentrations were determined using the ¹⁴⁹Sm intensity as an internal standard. The interference of MoO⁺ on Cd⁺ was corrected using the MoO⁺/Mo⁺ ratio separately measured using a Mo standard solution, and the validity of the externally determined oxide‐forming ratio correction was evaluated. The MoO⁺/Mo⁺ ratios measured using the standard solution and samples were ～ 0.0002 and < 0.002, respectively. Detection limits for Cd, In, Tl and Bi in silicate samples were at levels of < 1 ng g^?1 with a total uncertainty of < 7%. Cadmium in the carbonaceous chondrites, Orgueil (CI1), Murchison (CM2) and Allende (CV3) as well as Cd, In, Tl and Bi in the reference materials, JB‐2, JB‐3, JA‐1, JA‐2, JA‐3, JP‐1 (GSJ), BHVO‐1, AGV‐1, PCC‐1 and DTS‐1 (USGS) and NIST SRM 610, 612, 614 and 616 were determined to show the applicability of this method.     

Determination of Bromine and Iodine Speciation in Drinking Water Using High Performance Liquid Chromatography‐Inductively Coupled Plasma‐Mass Spectrometry

A specific method for the determination of bromine and iodine species in drinking water was developed by using high performance liquid chromatography‐ICP‐MS. An ICS‐A23 ion chromatography column was chosen for the separation of species, with the mobile phase being 0.03 mol l^?1 ammonium carbonate at a flow rate of 0.8 ml min^?1. The detection limits for BrO₃^?, Br^?, IO₃^? and I^? were 0.032, 0.063, 0.008 and 0.012 μg l^?1, respectively. Spectroscopic interferences were only observed in blank samples and mainly resulted from the argon‐potassium polyatomic ion (⁴⁰Ar³⁹K⁺). However, this interference was negligible because of the elution and complete separation from that of iodinate under optimised conditions. The method developed was successfully applied to twenty‐two samples of drinking water obtained from a supermarket. Results indicated that 36.4% of the samples had BrO₃^? concentrations exceeding the Chinese national limit for drinking water of 10 μg l^?1.     

U–Pb ages of zircons from metamorphic rocks in the upper sequence of the Hidaka Metamorphic Belt,Hokkaido, Japan: Identification of two metamorphic events and implications for regional tectonics

The Hidaka Metamorphic Belt is a well-known example of island-arc crustal section, in which metamorphic grade increases westwards from unmetamorphosed sediment up to granulite facies. It is divided into lower (granulite to amphibolite facies) and upper (amphibolite to greenschist facies) metamorphic sequences. The metamorphic age of the belt was considered to be ~55 Ma, based on Rb – Sr whole-rock isochron ages for granulites and related S-type tonalities. However, zircons from the granulites in the lower sequence yield U – Pb ages of ~21 – 19 Ma, and a preliminary report on zircons from pelitic gneiss in the upper sequence gives a U – Pb age of ~40 Ma. In this paper we provide new zircon U – Pb ages from two pelitic gneisses in the upper sequence to assess the metamorphic age and also the maximum depositional age of the sedimentary protolith. The weighted mean ²⁰⁶Pb/²³⁸U ages from a biotite gneiss in the central area of the belt yield 39.6 ± 0.9 Ma for newly grown metamorphic rims and 53.1 ± 0.9 Ma for the youngest detrital cores. The ages of zircons from a cordierite–biotite gneiss in the southern area are 35.9 ± 0.7 Ma for metamorphic rims and 46.5 ± 2.8 Ma for the youngest detrital cores. These results indicate that metamorphism of the upper sequence took place at ~40 – 36 Ma, and that the sedimentary protolith was deposited after ~53 – 47 Ma. These metamorphic ages are consistent with the reported ages of ~37–36 Ma plutonic rocks in the upper sequence, but contrast with the ~21–19 Ma ages of metamorphic and plutonic rocks in the lower sequence. Therefore, we conclude that the upper and lower metamorphic sequences developed independently but coupled with each other before ~19 Ma as a result of dextral reverse tectonic movement.     

三门峡高庙石英闪长玢岩的…特征、LA-ICP-MS锆石U-Pb年龄及…

三门峡市高庙石英闪长玢岩的激光探针等离子质谱(LA-ICP-MS)锆石U-Pb同位素年代测定获得了135Ma的年龄,与华北地块南缘早白垩世岩石圈伸展和减薄事件的时间一致.高庙岩体中继承锆石的形成年龄为2768Ma,该年龄和模式年龄均与华北克拉通早期地壳演化的峰期时间一致.石英闪长玢岩的SiO2含量为62.93％～65.54％,铝指数A/CNK=0.90 ～ 1.03,属于准铝质-弱过铝质系列.富钠(Na2O/K2O=1.29～1.46)、镁指数偏低(Mg#=33.5～42.4＜ 45),属于高钾钙碱性岩系.岩石稀土含量∑REE=197.09×10-6 ～234.41×10-6(平均216.00×10-6),轻重稀土明显分异[(La/Yb)N=15.86～20.55],基本不显示铕异常(δEu =0.96～1.02).岩石富集大离子亲石元素Rb、Ba、Sr、K等和轻稀土,高Sr/Y值(Sr/Y =41.99 ～56.71),亏损高场强元素Nb、Ta、Ti、重稀土和Y等.该石英闪长玢岩具有较低的n(143Nd)/n(144Nd) (t)值(0.5116)和较高的n(87Sr)/n86Sr) (t)值(0.7080),εNd(t)=-19.08,εsr(t) =49.89,TDM =2.15Ga.岩石的地球化学特点反映岩体由下地壳部分熔融形成.综合分析认为,高庙石英闪长玢岩源自加厚的基性下地壳的部分熔融作用,是华北克拉通的岩石圈在早白垩世减薄和破坏作用的产物,华北克拉通早白垩世期间的岩石圈减薄和破坏作用影响到了华北克拉通中-南部一带.     

U‐Pb Detrital Zircon Analysis – Results of an Inter‐laboratory Comparison

Inter‐laboratory comparison of laser ablation ICP‐MS and SIMS U‐Pb dating of synthetic detrital zircon samples provides an insight into the state‐of‐the art of sedimentary provenance studies. Here, we report results obtained from ten laboratories that routinely perform this type of work. The achieved level of bias was mostly within ± 2% relative to the ID‐TIMS U‐Pb ages of zircons in the detrital sample, and the variation is likely to be attributed to variable Pb/U elemental fractionation due to zircon matrix differences between the samples and the reference materials used for standardisation. It has been determined that ~ 5% age difference between adjacent age peaks is currently at the limit of what can be routinely resolved by the in situ dating of detrital zircon samples. Precision of individual zircon age determination mostly reflects the data reduction and procedures of measurement uncertainty propagation, and it is largely independent of the instrumentation, analytical technique and reference samples used for standardisation. All laboratories showed a bias towards selection of larger zircon grains for analysis. The experiment confirms the previously published estimates of the minimum number of grains that have to be analysed in order to detect minor zircon age populations in detrital samples.