Trace Element Analysis of NIST SRM 614 and 616 Glass Reference Materials by Laser Ablation Microprobe-Inductively Coupled Plasma-Mass Spectrometry

Fifty elements in NIST SRM 614 and 616 glass reference materials were determined by laser ablation microprobe-inductively coupled plasma-mass spectrometry (LAM-ICP-MS). The values determined for NIST SRM 614 agreed well with the NIST-certified and information values (mean relative difference ± 3.6%), except for B, Sc and Sb. The values determined for NIST SRM 616 agreed with the NIST-certified and information values within a mean relative difference of ± 1.5%, except for B, Sc and Ga. In addition, at an 80 μm sampling scale, NIST SRM 614 and 616 glass discs were homogeneous for trace elements within the observed precisions of 5 and 15% (mean), respectively. Detection limits were in the range 0.01 - 0.3 μg g⁻¹ for elements of lower mass numbers (amu < 80) and 1 - 10 ng g⁻¹ for heavy elements (amu > 80). Detection at the sub ng g⁻¹ level is possible for most of the heavy elements by using an ablation pit size larger than 10 0 μm.     

Determination of Lithium, Beryllium and Boron at Trace Levels by Laser Ablation-Inductively Coupled Plasma-Sector Field Mass Spectrometry

The analytical capabilities of laser ablation (LA)-ICP-MS in determining Li, Be and B at trace levels in geological samples have been tested on a series of glass reference materials and natural samples. The LA-ICP-MS instrument used consisted of a sector-field ICP-MS coupled with a laser ablation microprobe operating at either 266 or 213 nm wavelength. Reference glasses from NIST (SRM 612, 614 and 616) and MPI-DING (KL2-G, ML3B-G, StHs6/80-G, GOR128-G, GOR132-G, T1-G and ATHO-G) were selected to develop the analytical method and to assess the best instrumental configuration. A series of calcic amphiboles with different Li, Be and B concentrations were also analysed using both LA-ICP-MS and SIMS to test the applicability of the method to natural minerals. Results indicated that with a spot size of 40 μm the agreement between measured and reference values of Li, Be and B is generally better than 10% for NIST SRM 612 and 20% for NIST SRM 614. Average reproducibility at the 2s level was 10% for Li, 20% for Be and 15% for B. Limits of detection were approximately 100 ng g^-1 for Be and B and 200 ng g^-1 for Li. These results were confirmed by analyses carried out on natural amphiboles and compared well in terms of precision and accuracy with those commonly achieved by SIMS.     

Study on snowmelt runoff simulation in the Kaidu River basin

Alpine snowmelt is an important generation mode for runoff in the source region of the Tarim River basin, which covers four subbasins characterized by large area, sparse gauge stations, mixed runoff supplied by snowmelt and rainfall, and remarkably spatially heterogeneous precipitation. Taking the Kaidu River basin as a research area, this study analyzes the influence of these characteristics on the variables and parameters of the Snow Runoff Model and discusses the corresponding determination strategy to improve the accuracy of snowmelt simulation and forecast. The results show that: (i) The temperature controls the overall tendency of simulated runoff and is dominant to simulation accuracy, as the measured daily mean temperature cannot represent the average level of the same elevation in the basin and that directly inputting it to model leads to inaccurate simulations. Based on the analysis of remote sensing snow maps and simulation results, it is reasonable to approximate the mean temperature with 0.5 time daily maximum temperature. (ii) For the conflict between the limited gauge sta-tion and remarkably spatial heterogeneity of rainfall, it is not realistic to compute rainfall for each elevation zone. After the measured rainfall is multiplied by a proper coefficient and adjusted with runoff coefficient for rainfall, the measured rainfall data can satisfy the model demands. (iii) Adjusting time lag according to the variation of snowmelt and rainfall position can improve the simulation precision of the flood peak process. (iv) Along with temperature, the rainfall increases but cannot be completely monitored by limited gauge stations, which results in precision deterioration.     

基于流量监测的西藏东南部然乌湖水量平衡季节变化及其补给过程分析

青藏高原分布着亚洲大陆最大的湖泊群,其湖泊变化对气候变化响应敏感。基于遥感数据的湖泊面积变化不足以反映外流湖对气候变化的响应,需借助湖泊水量平衡过程分析来进一步研究各补给要素的变化。本文利用2015年4月-11月然乌湖水文气象监测数据,通过建立流量—水位关系,依据连续的水位数据重建了观测期内然乌湖主要径流的水文过程线,并结合SRM模型分析了然乌湖的水量平衡过程及季节变化。结果表明,观测期内然乌湖入湖水量约为18.49×10⁸ m³,其中冰川融水约为10.06×10⁸ m³,冰川融水占然乌湖补给的54%以上,湖面降水、湖面蒸发对湖泊水量平衡过程影响微弱。流域降水对湖泊的补给具有明显的季节特征。春季受西风南支扰动影响,然乌湖地区降水量大,降水是春季然乌湖的主要补给源。夏季和早秋由于气温升高,冰川消融量大,冰川融水是湖泊补给的主控因素。在未来气候变暖的条件下,冰川融水将会在湖泊补给中占据更大比例,并可能使得流域内的冰湖水量增加,产生潜在灾害风险。     

Effect of climatic change on snowmelt runoffs in mountainous regions of inland rivers in Northwestern China

Snow is one of the most active natural elements of snow cover through its high albedo, variation of the the cryosphere on the earth surface. Its unique proper- snow cover distribution and frozen soils in regional ties, such as areal extent, surface albedo, and snow scales not only affect local climate and environments, depth are important parameters in global energy bal- but also feedback to large-scale, or even global cli- ance models. On global and terrestrial scales, a large matic change th…     

Determination of Trace Elements in BCS CRM 313/1 (BAS) and NIST SRM 1830 by Inductively Coupled Plasma-Mass Spectrometry and Instrumental Neutron Activation Analysis

In the past, there has been little interest in the trace element characteristics of quartz, and in consequence little activity in the trace element characteristics of reference materials with high silicon content. The main purpose of this paper is to contribute to the characterisation of two international certified reference materials, BCS 313/1 from the Bureau of Analysed Samples, (BAS), UK and SRM 1830 from the National Institute of Standards and Technology (NIST), USA. BCS 313/1 was analysed by laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS), solution ICP-MS and instrumental neutron activation analysis (INAA). NIST SRM 1830 was analysed by LA-ICP-MS and INAA. Analytical results are reported for more than forty elements, most of them for the first time. For most elements, the results obtained by the different methods agree within 15 % relative. The recent, heightened interest in quartz and in particular the precise determination of trace0element contents in natural quartz samples requires the use of well characterised reference materials such as BCS 313/1 and SRM 1830, to which this study is designed to contribute.     

Isotope Dilution MC-ICP-MS Rare Earth Element Analysis of Geochemical Reference Materials NIST SRM 610, NIST SRM 612, NIST SRM 614, BHVO-2G, BHVO-2, BCR-2G, JB-2, WS-E, W-2, AGV-1 and AGV-2

We present data for the concentrations of eleven rare earth elements (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Lu) in eleven international geochemical reference materials obtained by isotope dilution multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). We have analysed both rock powders and synthetic silicate glasses, and the latter provide precise data to support the use of these as reference materials for in situ trace element determination techniques. Our data also provide precise measurements of the abundance of mono-isotopic Pr in both glasses and powders, which allows more accurate constraints on the anomalous redox-related behaviour of Ce during geochemical processes. All materials were analysed in replicate providing data that typically reproduce to better than one percent. Sm/Nd ratios in all these materials also reproduce to better than 0.2% and are accurate to < 0.2% and can thus be used as calibrants for Sm-Nd geochronology. Our analyses agree well with existing data on these reference materials. In particular, for NIST SRM 610, USGS BHVO-2, AGV-1 and AGV-2, our measured REE abundances are typically within < 2% (and mostly 1%) of REE concentrations previously determined by isotope dilution analysis and thermal ionisation mass spectrometry, consistent with the higher degree of precision and accuracy obtained from isotope dilution techniques. Close agreement of results between basaltic glass reference materials USGS BHVO-2G and BCR-2G and the BHVO-2 and BCR-2 powders from which they were created suggests that little fractionation, concentration or dilution of REE contents occurred during glass manufacture.     

天山托木尔峰南坡科其喀尔冰川流域径流模拟

天山冰雪融水是塔里木河的重要补给水源。利用融雪径流模型(SRM)对天山南坡科其喀尔冰川流域冰雪径流进行模拟研究。基于流域的气象梯度观测,确定了不同高度带降水梯度和月气温直减率。基于2007和2008年的实测径流值优化确定了各月的积雪、裸冰以及表碛覆盖冰的度日因子值。模拟结果表明,融雪和融冰径流过程都得到了比较好的模拟。流域径流对气候变化的响应研究表明,气温是敏感因子。气温分别升高1℃、2℃和4℃时,以融雪径流为主的3—5月径流分别增加48%、155%和224%,以冰川径流为主的5—10月径流分别增加30%、77%和104%。气候变化也会影响流域径流过程,气温升高4℃、降水增加20%时,春季径流峰值出现时间由5月中旬提前到4月20日左右。流量由6 m3/s增大到17 m3/s。     

Automated Analyte Separation by Ion Chromatography Using a Cobot Applied to Geological Reference Materials for Li Isotope Composition

The demand for large and reliable data sets on isotopic composition has increased in geochemistry and environmental sciences over recent years. We present an automated ion chromatographic separation method using a robotic pipetting arm, termed ‘ChemCobOne’, to reduce sample separation time. Its performance was tested for lithium isotope separation in geological reference materials using a single‐step separation with HCl (0.2 mol l^?1) and a 2 ml resin volume. This refined lithium purification method does not forfeit precision, accuracy or purity compared with manual sample processing. In addition, a δ⁷Li value for NASS‐6 of 30.99 ± 0.50‰ (2s) (95% CI = 0.14‰, n = 44) was determined and the first δ⁷Li values for the granite rock reference material GS‐N (?0.57 ± 0.25‰ (2s), 95% CI = 0.15‰, n = 15), and for the soil reference material NIST SRM 2709a (?0.37 ± 0.67‰ (2s), 95% CI = 0.15‰, n = 63) are proposed.     

Determination of Reference Values for NIST SRM 610–617 Glasses Following ISO Guidelines

We present new reference values for the NIST SRM 610–617 glasses following ISO guidelines and the International Association of Geoanalysts’ protocol. Uncertainties at the 95% confidence level (CL) have been determined for bulk‐ and micro‐analytical purposes. In contrast to former compilation procedures, this approach delivers data that consider present‐day requirements of data quality. New analytical data and the nearly complete data set of the GeoReM database were used for this study. Data quality was checked by the application of the Horwitz function and by a careful investigation of analytical procedures. We have determined quantitatively possible element inhomogeneities using different test portion masses of 1, 0.1 and 0.02 μg. Although avoiding the rim region of the glass wafers, we found moderate inhomogeneities of several chalcophile/siderophile elements and gross inhomogeneities of Ni, Se, Pd and Pt at small test portion masses. The extent of inhomogeneity was included in the determination of uncertainties. While the new reference values agree with the NIST certified values with the one exception of Mn in SRM 610, they typically differ by as much as 10% from the Pearce et al. (1997) values in current use. In a few cases (P, S, Cl, Ta, Re) the discrepancies are even higher.