Determination of Mercury in Thirty‐three International Stream Sediment and Soil Reference Samples by Direct Mercury Analyser

Mercury was determined in thirty‐three international stream sediment and soil reference samples (eleven Chinese soils, GSS‐1 to GSS‐11; twelve Chinese stream sediments, GSD‐1A to GSD‐12; four Canadian stream sediments STSD‐1 to STSD‐4; South African stream sediments, SARM‐42, SARM‐46 and SARM‐47; Japanese stream sediments, JSd‐1 to JSd‐3) by direct mercury analyser. Samples were taken in 500 μl quartz boats, placed in an auto sampler and processed (drying time 60 s at 300 °C; decomposition time 120 s at 850 °C; waiting time 45 s). The instrument was calibrated in the low (0‐50 ng) and high ranges (50‐500 ng) with two reference materials GSS‐5 and GXR‐2 (USGS). Using the calibration line, reference samples were analysed for Hg. The results of the determinations agreed with the recommended values of RMs in all cases except JSd‐1. The RSD calculated for the RMs was found to be within 20%. The detection limit was 1 ng g^?1.     

Determination of Precise and Accurate 51V/50V Isotope Ratios by Multi‐Collector ICP‐MS,Part 2: Isotopic Composition of Six Reference Materials plus the Allende Chondrite and Verification Tests

We present the first measurements of vanadium (V) stable isotopes for six reference materials – USGS PCC‐1, BHVO‐2, BCR‐2, BIR‐1a, GSP‐2 and AGV‐2 – plus the widely available carbonaceous chondrite Allende. We present standard addition and matrix spiking tests to assess the robustness and reproducibility of our data. Standard addition utilised an enriched ⁵⁰V solution designated VISSOX (Vanadium Isotope Standard Solution OXford). We further assessed the veracity of the method by spiking collected sample matrices with the same amount of a V standard solution, whose isotopic composition was defined as 0‰. Standard addition and matrix spiking tests recorded no appreciable artificial isotope fractionation. We estimate that the best currently attainable long‐term reproducibility of stable ⁵¹V/⁵⁰V isotope measurements in complex matrices is 0.15‰, which is in the same order as the reproducibility achievable with standard solutions. Finally, a large range of ～ 1.2‰ in stable V isotopic composition was documented, with ～ 0.5‰ of that variation in high temperature igneous materials alone. The range and resolving power of V stable isotopes, with respect to igneous material, compared favourably with the magnitude of fractionation reported for other non‐traditional stable isotope systems, which bodes well for the utility of this new system.     

Suitability of Mn‐ and Fe‐Rich Reference Materials for Microanalytical Research

Manganese‐ and iron‐rich materials are of major geoscientific and economic interest, many of which contain microscopic features that provide valuable information. To obtain accurate results, a homogeneous microanalytical reference material for calibration is needed. Several researchers have used the Mn‐ and Fe‐rich RMs, JMn‐1, NOD‐A‐1, NOD‐P‐1 and FeMn‐1, for this purpose; therefore, they were tested in this study to determine their suitability for microanalysis. Their homogeneity was investigated by laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) with two different types of lasers (nano‐ and femtosecond), with spot and line scan analyses and with different operating parameters, such as spot size, pulse repetition rate and fluence. As the established manganese nodule RMs revealed inhomogeneities for picogram to microgram test portions, we also investigated the new synthetic Fe‐ and Mn‐rich RM, FeMnOx‐1. FeMnOx‐1 was found to be homogeneous for large (ø 40 μm: 2% RSD repeatability) and small (ø 8–10 μm: 10% RSD repeatability) spot sizes. This homogeneity is in the range of the homogeneous NIST SRM 610 and GSE‐1G reference glasses. Furthermore, FeMnOx‐1 revealed a large‐scale homogeneity within uncertainties of a few per cent, using test portions in the ng range, when measuring four individual mounts of this material.     

新疆可支塔格蛇绿混杂岩的特征及其成因

新疆可支塔格蛇绿混杂岩位于青藏高原北缘东昆仑西段,属于木孜塔格-鲸鱼湖大断裂的西延部分。主要由辉橄岩、辉长岩、闪长岩、斜长花岗岩、辉绿岩、玄武岩及硅质岩等组成,形成时代为早石炭世。其中辉橄岩具有高Mg,贫Al,Ca,低硅、低碱的特点,富集相容元素Cr,Ni,Co。稀土总量低,接近于球粒陨石稀土元素总量,以LREE略富集为特征。闪长岩SiO2,K2O含量较低,MsO,CaO,Na2O较高,稀土总量高,∑REE为90．95×10^-6,LREE富集。斜长花岗岩SiO2 69．8％,Na2O〉K2O,K2O／Na2O为0．78,A／CNK为1．68,具有大洋斜长花岗岩的岩石化学特征。闪长岩、斜长花岗岩的微量元素特征相似,表现为大离子亲石元素K,Sr,Rb,Ba相对富集,高场强元素Nb,Ta,Zr,Hf相对亏损。研究表明,辉橄岩来源于亏损的地幔岩,接近于强烈亏损的方辉橄榄岩,而明显不同于结晶分异作用成因的超镁铁质岩石。闪长岩、斜长花岗岩为蛇绿混杂岩的浅色岩组分,是地幔岩浆结晶分异的产物,但可能受到了围岩的混染和后期热液交代影响。     

Flux‐Free Fusion of Silicate Rock Preceding Acid Digestion for ICP‐MS Bulk Analysis

We present a new method for the decomposition of silicate rocks by flux‐free fusion in preparation for whole‐rock trace element determination (Sc, Rb, Sr, Y, Zr, Nb, Cs, Ba, rare earth elements and Hf) that is especially applicable to zircon‐bearing felsic rocks. The method was verified by analyses of RMs of mafic (JB‐1a, JB‐2, JGb‐1) and felsic rocks (JG‐3, JR‐3, JSd‐1, GSP‐2, G‐2). Pellets of powdered sample (up to 500 mg) without flux were weighed and placed in a clean platinum crucible. The samples were then fused in a Siliconit® tube furnace and quenched to room temperature. The optimum condition for the fusion of granitic rock was determined to be heating for 2–3 min at 1600 °C. The fused glass in the platinum crucible after heating was decomposed using HF and HClO₄ in a Teflon® beaker. Decomposed and diluted sample solutions were analysed using a quadrupole inductively coupled plasma‐mass spectrometer. Replicate analyses (n = 4 or 5) of the RMs revealed that analytical uncertainties were generally < 3% for all elements except Zr and Hf (～ 6%) in JG‐3. These higher uncertainties may be attributed to sample heterogeneity. Our analytical results for the RMs agreed well with recommended concentrations and recently published concentrations, indicating complete decomposition of our rock samples during fusion.     

Precise Determination of Sm and Nd Concentrations and Nd Isotopic Compositions in Highly Depleted Ultramafic Reference Materials

In this study, a high‐precision method for the determination of Sm and Nd concentrations and Nd isotopic composition in highly depleted ultramafic rocks without a preconcentration step is presented. The samples were first digested using the conventional HF + HNO₃ + HClO₄ method, followed by the complete digestion of chromite in the samples using HClO₄ at 190–200 °C and then complete dissolution of fluoride formed during the HF decomposition step using H₃BO₃. These steps ensured the complete digestion of the ultramafic rocks. The rare earth elements (REEs) were separated from the sample matrix using conventional cation‐exchange chromatography; subsequently, Sm and Nd were separated using the LN columns. Neodymium isotopes were determined as NdO⁺, whereas Sm isotopes were measured as Sm⁺, both with very high sensitivity using single W filaments with TaF₅ as an ion emitter. Several highly depleted ultramafic rock reference materials including USGS DTS‐1, DTS‐2, DTS‐2b, PCC‐1 and GSJ JP‐1, which contain extremely low amounts of Sm and Nd (down to sub ng g^?1 level), were analysed, and high‐precision Sm and Nd concentration and Nd isotope data were obtained. This is the first report of the Sm‐Nd isotopic compositions of these ultramafic rock reference materials except for PCC‐1.     

Episodic porphyroblast growth in the Fleur de Lys Supergroup, Newfoundland: timing relative to the sequential development of multiple crenulation cleavages

Inclusion trails in garnet and albite porphyroblasts in the Fleur de Lys Supergroup preserve successive generations of microstructures, some of which correlate with equivalent microstructures in the matrix. Microstructure–porphyroblast relationships provide timing constraints on a succession of seven crenulation cleavages (S1–S7) and five stages of porphyroblast growth. Significant destruction and alteration of early fabrics has occurred during the microstructural development of the rock mass. Garnet porphyroblasts grew episodically through four growth stages (G1–G4) and preserve a succession of five fabrics (S1–S5) as inclusion trails. Garnet growth during each of the four growth phases did not occur on all pre-existing porphyroblasts, resulting in contrasting growth histories between individual garnet porphyroblasts from the same outcrop. Albite porphyroblasts grew during a single stage of growth and have overgrown microstructures continuous with the matrix. The garnet and albite porphyroblast inclusion trails record a succession of crenulation cleavages without any rotation of the porphyroblasts relative to other porphyroblasts in the population.
Complex microstructural histories are best resolved by preparing multiple oriented thin sections from a large number of samples of different rock types within the area of study. The succession of matrix foliations must be understood, as it provides the most useful time-frame against which to measure the relative timing of phases of porphyroblast growth. Comparable microstructures must be identified in different porphyroblasts and in the rock matrix.     

Use of Hydrofluoric Acid Desilicification in the Determination of Highly Siderophile Element Abundances and Re‐Pt‐Os Isotope Systematics in Mafic‐Ultramafic Rocks

Properly combining highly siderophile element (HSE: Re, Pd, Pt, Ru, Ir, Os) abundance data, obtained by isotope dilution, with corresponding ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁶Os/¹⁸⁸Os measurements of rocks requires efficient digestion of finely‐ground powders and complete spike‐sample equilibration. Yet, because of the nature of commonly used methods for separating Os from a rock matrix, hydrofluoric acid (HF) is typically not used in such digestions. Consequently, some silicates are not completely dissolved, and HSE residing within these silicates may not be fully accessed. Consistent with this, some recent studies of basaltic reference materials (RMs) have concluded that an HF‐desilicification procedure is required to fully access the HSE (Ishikawa et al. (2014) Chemical Geology, 384, 27–46; Li et al. (2015) Geostandards and Geoanalytical Research, 39, 17–30). Highly siderophile element abundance and Os isotope studies of intraplate basalts typically target samples with a range of MgO contents (< 8 to > 18% m/m, or as mass fractions, < 8 to > 18 g per 100 g), in contrast to the lower MgO mass fractions (< 10 g per 100 g) of basalt and diabase RMs (i.e., BIR‐1, BHVO‐2, TDB‐1). To investigate the effect of HF‐desilicification on intraplate basalts, experiments were performed on finely ground Azores basalts (8.1–17 g per 100 g MgO) using a ‘standard acid digestion’ (2:1 mixture of concentrated HNO₃ and HCl), and a standard acid digestion, followed by HF‐desilicification. No systematic trends in HSE abundances were observed between data obtained by standard acid digestion and HF‐desilicification. Desilicification procedures using HF do not improve liberation of the HSE from Azores basalts, or some RMs (e.g., WPR‐1). We conclude that HF‐desilicification procedures are useful for obtaining total HSE contents of some young lavas, but this type of procedure is not recommended for studies where Re‐Pt‐Os chronological information is desired. The collateral effect of a standard acid digestion to liberate Os, followed by HF‐desilicification to obtain Re and Pt abundances in samples, is that the measured Re/Os and Pt/Os may not correspond with measured ¹⁸⁷Os/¹⁸⁸Os or ¹⁸⁶Os/¹⁸⁸Os.     

新疆萨尔托海石英菱镁岩中发育的韧性剪切带及其对金矿的控制

萨尔托海金矿产在达拉布特蛇绿混杂岩带中。本文首次在该金矿区厘定出韧性剪切带,糜棱岩或者糜棱岩化石英菱镁岩中构成糜棱面理的矿物(铬云母、石英)形成于韧性剪切变形过程中,而切割糜棱面理的方解石-石英-黄铜矿-白云母脉代表脆性变形阶段的流体活动。根据矿物组合相互切割关系,识别出三期构造变形:早期NE向韧性变形(形成铬云母-石英组合)之后,发生了应力方向显著不同的破裂,形成NNW向分布的方解石-石英-黄铜矿-白云母脉;再晚期,应力方向又恢复到NE向,发育了浅层次的脆性构造破坏,形成了白云母-石英细脉。韧性剪切变形向脆性变形转换期间形成了石英-碳酸盐脉,其中往往含硫化物和自然金,此阶段是萨尔托海金矿的主要成矿时期。韧性剪切带控制着萨尔托海地区的金矿分布,成矿作用主要受沿剪切带迁移流体的控制,穿切糜棱面理的方解石-石英-黄铜矿-白云母脉是主要的找矿标志。韧性剪切带对金矿的显著控制表明,韧脆性转换期间形成的含硫化物石英碳酸盐脉以及相伴生的热液蚀变使金富集成矿,矿体一般赋存在断裂构造复杂的膨胀部位。萨尔托海金矿的成因与蛇绿岩的形成和演化没有关系。对韧性剪切带的系统研究是在该地区取得找矿勘探突破的关键。     

Determination of Cr,Cu, Ni,Sn, Sr and Zn Mass Fractions in Geochemical Reference Materials by Isotope Dilution ICP‐MS

Isotope dilution (ID) mass spectrometry is a primary method of analysis suited for the accurate and precise measurement of several trace elements in geological matrices. Here we present mass fractions and respective uncertainties for Cr, Cu, Ni, Sn, Sr and Zn in 10 silicate rock reference materials (BCR‐2, BRP‐1, BIR‐1, OU‐6, GSP‐2, GSR‐1, AGV‐1, RGM‐1, RGM‐2 and G‐3) obtained by the double ID technique and measuring the isotope ratios with an inductively coupled plasma‐mass spectrometer equipped with collision cell. Test portions of the samples were dissolved by validated procedures, and no further matrix separation was applied. Addition of spikes was designed to achieve isotope ratios close to unity to minimise error magnification factors, according to the ID theory. Radiogenic ingrowth of ⁸⁷Sr from the decay of ⁸⁷Rb was considered in the calculation of Sr mass fractions. The mean values of our results mostly agree with reference values, considering both uncertainties at the 95% confidence level, and also with ID data published for AGV‐1. Considering all results, the means of the combined uncertainties were < 1% for Sr, approximately 2% for Sn and Cu, 4% for Cr and Ni and almost 6% for Zn.