Trace Element Data for Gold, Iridium and Silver in Seventy Geochemical Reference Materials

New concentrations for Au, Ir and Ag obtained by instrumental neutron activation analysis are presented for seventy geochemical reference materials. Results in agreement with literature values for Au and Ir down to concentrations of a few ng g⁻¹ were obtained. For Au and Ir concentrations above 10 ng g⁻¹, the repeatability of replicate analyses of reference materials was mostly better than 10%. For concentrations between 1 and 10 ng g⁻¹ the RSD for Ir was 10–30%, whereas for Au it was higher and more variable (20–50%). In addition, concentrations for Cd and Hg are presented for some of the same reference materials. The high RSD at relatively high concentrations seen in gold for some RMs (e.g., WMG-1, WMS-1) did not exist for Ir and suggests homogeneity for this platinum-group element at the sub-sample size used in this study. For the following eight RMs, mostly ultramafic rocks (CHR-Pt+, OREAS-13P, OREAS-14P, PCC-1, UMT-1, WMG-1, WMS-1, WPR-1), Ir measurements agreed within ± 10% of mostly certified or recommended concentrations, which ranged from 2 ng g⁻¹ to 6 μg g⁻¹. For the reference material UB-N, iridium concentration compared favourably to published results obtained by isotope dilution ICP-MS methods and a previously unrecognised heterogeneity is inferred for Au, Hg and Sb, but not for the other measured elements.     

中国大陆科学钻探主孔100～2000m岩石热导率及其各向异性：对研究俯冲带热结构的启示

系统研究了中国大陆科学钻探工程主孔100～2000米岩石的热导率和生热率特征。初步研究了岩石热导率随矿物组成的变化关系、岩石热导率的各向异性及其影响因素。主孔2000米的岩心热导率介于1．873～4．062Wm^-1K^-1之间，平均热导率2．967Wm^-1K^-1。整体上热导率出现的频率主峰分布在2．8～3.0Wm^-1K^-1。榴辉岩热导率随着其退变质程度的增加而降低，新鲜榴辉岩热导率集中分布于3．6～3．7Wm^-1K^-1，角闪石化榴辉岩的热导率分布在3．1～3.2Wm^-1K^-1，强退变的榴辉岩热导率分布于2．4～2．5Wm^-1K^-1。片麻岩热导率主要分布于2．8～3.0Wm^-1K^-1。从垂向上看，主孔100～735米主要由榴辉岩组成，热导率整体比较大，平均3.265Wm^-1K^-1；1200～1600米主要以花岗质片麻岩为主，热导率比其它层位偏低，平均2．755Wm^-1K^-1。通过对面理发育的样品进行测试，东海地区各类岩石的热导率具有较明显的各向异性。榴辉岩和片麻岩热导率的各向异性平均值分别为4、66％和22．99％，超基性岩的热导率平均值为3．322Wm^-1K^-1，各向异性16．08％。岩石热导率在垂直于面理的方向上具有最小值，在平行于面理的方向上具有最大值。上述资料对超高压地体热结构特征的研究提供了重要数据基础。     

Gold in BHVO-1, BIR-1, DNC-1 and BCR-1 by Fire-Assay Preconcentration Neutron Activation Analysis: Sample Size vs. Accuracy

Four mafic USGS rock standards (BHVO-1, BIR-1, DNC-1, BCR-1) were analyzed at three sample sizes (1, 5, and 10 g) for gold by neutron activation analysis subsequent to fire-assay concentration. The results indicate that large samples, in the order of 10 g, are required to produce consistent results, although analyses of variance indicate that sample sizes of 5 g may be used effectively. The analysis of 1 g samples resulted in a large range of values and high standard deviations. BCR-1 was found to be the most homogeneous of the four standards for gold, followed in decreasing order by BIR-1, DNC-1, and BHVO-1. Data for Ir in BIR-1 and DNC-1 are also presented.     

Two New Polish Geological-Environmental Reference Materials: Apatite Concentrate (CTA-AC-1) and Fine Fly Ash (CTA-FFA-1)

World-wide intercomparison runs has made possible the certification of two new Polish geological-environmental reference materials for multi-element trace analysis: Apatite Concentrate (CTA-AC-1) and Fine Fly Ash (CTA-FFA-1). "Recommended values' are established for 25 (CTA-AC-1) and 40 (CTA-FFA-1) elements respectively. In addition, "information values' are assigned for 12 elements in CTA-AC-1 and 10 elements in CTA-FFA-1. Our method of data evaluation has been further improved and a modified version of criteria for assigning recommended and information values is proposed.     

Trace metals (Cd,Cu, Ni,and Zn) and nutrients in coastal waters adjacent to San Francisco Bay,California

Samples collected in December 1990 and July 1991 show that dissolved Cd, Cu, Ni, and Zn distributions in the Gulf of the Farallones are dominated by mixing of two end-members: (1) metal-enriched San Francisco Bay water and (2) offshore California Current water. The range of dissolved metal concentrations observed is 0.2–0.9 nmol kg^?1 for Cd, 1–20 nmol kg^?1 for Cu, 4–16 nmol kg^?1 for Ni, and 0.2–20 nmol kg^?1 for Zn. Effective concentrations in fresh water discharged into San Francisco Bay during 1990–1991 (estimated by extrapolation to zero salinity) are 740–860 μmol kg^?1 for silicate, 21–44 μmol kg^?1 for phosphate, 10–15 nmol kg^?1 for Cd, 210–450 nmol kg^?1 for Cu, 210–270 nmol kg^?1 for Ni, and 190–390 nmol kg^?1 for Zn. Comparison with effective trace metal and nutrient concentrations for freshwater discharge reported by Flegal et al. (1991) shows that input of these constituents to the northern reaches of San Francisco Bay accounts for only a fraction of the input to Gulf of the Farallones from the estuary system as a whole. The nutrient and trace metal composition of shelf water outside a 30-km radius from the mouth of the estuary closely resembles that of California Current water further offshore. In contrast to coastal waters elsewhere, there is little evidence of Cd, Cu, Ni, and Zn input by sediment diagenesis in continental shelf waters of California.     

江苏基础地质工作程度概述

江苏基础地质工作开展较早，研究程度较高，从区域地质调查，地球物理勘探，地球化学勘探三方面对江苏的基础地质工作情况进行了概述。     

Suppression of Matrix Effects in ICP-MS by High Power Operation of ICP: Application to Precise Determination of Rb, Sr, Y, Cs, Ba, REE, Pb, Th and U at ng g-1 Levels in Milligram Silicate Samples

We found that the suppression of signals for ⁸⁸Sr, ¹⁴⁰Ce and ²³⁸U in rock solution caused by rock matrix in ICP-MS (matrix effects) was reduced at high power operation (1.7 kW) of the ICP. To make the signal suppression by the matrix negligible, minimum dilution factors (DF) of the rock solution for Sr, Ce and U were 600, 400 and 113 at 1.1, 1.4 and 1.7 kW, respectively. Based on these findings, a rapid and precise determination method for Rb, Sr, Y, Cs, Ba, REE, Pb, Th and U using FI (flow injection)-ICP-MS was developed. The amount of the sample solution required for FI-ICP-MS was 0.2 ml, so that 1.8 mg sample was sufficient for analysis with a detection limit of several ng g^-1. Using this method, we determined the trace element concentrations in the USGS rock reference materials, DTS-1, PCC-1, BCR-1 and AGV-1, and the GSJ rock reference materials, JP-1, JB-1, -2, -3, JA-1, -2 and -3. The reproducibilities (RSD %) in replicate analyses (n=5) of BCR-1, AGV-1, JB-1, -2, -3, JA-1, -2, and -3 were < 6 %, and typically 2.5%. The difference between the average concentrations of this study for BCR-1 and those of the reference values were < 2%. Therefore, it was concluded that the method can give reliable data for trace elements in silicate rocks.     

乌尔逊凹陷南二段油气成藏与分布主控因素及有利区预测

通过对乌尔逊凹陷南二段油气成藏各种条件与油气藏的叠合研究证明,鸟尔逊凹陷南二段油气成藏与分布的主控因素主要有盖源时空匹配关系、储层岩性、断层和圈闭.盖源时空匹配关系控制着油气聚集数量和空间分布;粉砂岩和泥质粉砂岩是油气储集的有利岩性;断裂活动时期与源岩大量排烃期的匹配关系控制着油气聚集数量,较好的断层垂向封闭性有利于油气聚集,断裂活动和封闭控制着不同类型圈闭的形成.反向高断块和断背斜有利于油气运聚成藏.在此基础上得到乌尔逊凹陷南二段油气成藏与分布的有利勘探区主要分布在苏仁诺尔构造带和黄旗庙构造带南部;较有利区主要分布在铜钵庙构造带、乌东斜坡带、乌西断裂带、乌中构造带和巴彦塔拉构造带的部分地区.     

Determination of the REE in Geological Reference Materials DTS-1 (Dunite) and PCC-1 (Peridotite) by Ultrasonic and Microconcentric Desolvating Nebulisation ICP-MS

Inductively coupled plasma-mass spectrometry is well suited for the precise, accurate and rapid determination of rare earth elements in most geological samples. However, determination of rare earth elements in certain mantle-derived materials, without applying preconcentration techniques, remains problematical due to low natural concentrations (generally < 1 ng g⁻¹). Consequently, USGS reference materials DTS-1 (a dunite) and PCC-1 (a partially serpentinized harzburgite) have only suggested rather than recommended values for the rare earth elements in reference material compilations. We compared results obtained using two ICP-MS instruments: a U-5000AT ultrasonic nebuliser coupled to a PQ2+ quadrupole ICP-MS and an ELEMENT sector field ICP-MS equipped with a MCN-6000 microconcentric desolvating nebuliser, with the suggested literature values for these two reference materials. Precision and accuracy of analytical methods employed by both instruments were demonstrated by excellent relative standard deviations (< 2%) and inter-laboratory agreement (< 5%) for numerous analyses of BHVO-1 and BIR-1, which are well established with rare earth elements contents at the μg g⁻¹ level. Repeat analyses of DTS-1 and PCC-1 at each laboratory indicate that each method is generally precise to better than 5% at sub-g g⁻¹ levels. Furthermore, values from both instruments generally agree to within 10%. Our DTS-1 and PCC-1 values agree reasonably well with selected data reported in the literature (except for Ce and Sm in DTS-1) but exhibit poorer agreement with reported compilation values. With the demonstrated level of precision and accuracy, we contend that these new values for DTS-1 and PCC-1, generated by two different instruments, are the best estimates of the true whole-rock composition of these samples reported to date.     

Simultaneous Determination of Fluorine,Chlorine, Bromine and Iodine in Six Geochemical Reference Materials Using Pyrohydrolysis,Ion Chromatography and Inductively Coupled Plasma‐Mass Spectrometry

Concentrations of halogens (fluorine, chlorine, bromine and iodine) were determined in six geochemical reference materials (BHVO‐2, GS‐N, JG‐1, JR‐1, JB‐1b, JB‐2). Halogens were first extracted from powdered samples using a pyrohydrolysis technique, then hydrolysis solutions were analysed by ion chromatography for F and Cl and inductively coupled plasma‐mass spectrometry for Br and I. The detection limits in solutions were 100 μg l^?1 for both F and Cl and 10 ng l^?1 for Br and I. Considering the extraction procedure, performed on a maximum of 500 mg of sample and producing 100 ml of pyrohydrolysis solution, detection limits in rock samples were 20 mg kg^?1 for F and Cl and 2 μg kg^?1 for Br and I. The mean analytical errors on the studied composition ranges were estimated at 10 mg kg^?1 for F and Cl, 100 μg kg^?1 for Br and 25 μg kg^?1 for I. The concentration values, based on repeated (generally > 10) sample analysis, were in good agreement generally with published values and narrowed the mean dispersion around mean values. Large dispersions are discussed in terms of samples heterogeneity and contaminations during sample preparation. Basaltic RMs were found to be more suitable for studies of halogen compositions than differentiated rock material, especially granites – the powders of which were heterogeneous in halogens at the 500 mg level.     

Determination of REE, Y, Nb, Zr, Hf, Ta, Th and U in Geological Reference Materials LSHC-1 and Amf-1 by Solution and Laser Ablation ICP-MS

This paper presents data on REE and Y, Nb, Zr, Hf, Ta, Th and U abundances for two candidate reference materials (RMs), spinel lherzolite LSHC-1 and amphibole Amf-1, being currently developed at the Institute of Geochemistry SB RAS, Irkutsk. To determine the contents of these elements inductively coupled plasma-mass spectrometry was applied with: (i) solution nebulisation (solution ICP-MS) and (ii) laser ablation (LA-ICP-MS) of fused glass disks. The precision of results obtained by both techniques was better than 6% RSD for most elements. Accuracy was assessed by using the geochemical RMs JB-2, JGb-1 (GSJ) and MAG-1 (USGS). The trace element results by solution ICP-MS for JGb-1 and JB-2 agree with reference values presented by Imai et al. (1995, this Journal) within 1–10%. Significant differences were found for Nb and Ta determinations. The accuracy of LA-ICP-MS results evaluated by RM MAG-1 was within 4%, except for Eu (about 10%). The analytical results obtained for LSHC-1 and Amf-1 by solution ICP-MS and LA-ICP-MS were in good agreement with each other and with INAA and XRF data presented for the certification of these RMs. They can be considered as the indicative values for assigning certified values to the above-mentioned RMs.     

B货翡翠的红外光谱特征及鉴定意义

在对9个B货翡翠样品进行常规宝石学特征描述的基础上，进行了红外光谱测试。结果表明B货翡翠最主要的吸收峰是2959（或2966），2931（或2924）和2895cm^-1这一组，而1510，1581，1609cm^-1和3040，3060cm^-1这两组谱带可作为鉴定B货翡翠的辅助谱带，但不是必要的谱带。研究结果可为准确鉴定B货翡翠提供进一步的资料。     

Local and regional minimum 1D models for earthquake location and data quality assessment in complex tectonic regions: application to Switzerland

One-dimensional (1D) velocity models are still widely used for computing earthquake locations at seismological centers or in regions where three-dimensional (3D) velocity models are not available due to the lack of data of sufficiently high quality. The concept of the minimum 1D model with appropriate station corrections provides a framework to compute initial hypocenter locations and seismic velocities for local earthquake tomography. Since a minimum 1D model represents a solution to the coupled hypocenter-velocity problem it also represents a suitable velocity model for earthquake location and data quality assessment, such as evaluating the consistency in assigning pre-defined weighting classes and average picking error. Nevertheless, the use of a simple 1D velocity structure in combination with station delays raises the question of how appropriate the minimum 1D model concept is when applied to complex tectonic regions with significant three-dimensional (3D) variations in seismic velocities. In this study we compute one regional minimum 1D model and three local minimum 1D models for selected subregions of the Swiss Alpine region, which exhibits a strongly varying Moho topography. We compare the regional and local minimum 1D models in terms of earthquake locations and data quality assessment to measure their performance. Our results show that the local minimum 1D models provide more realistic hypocenter locations and better data fits than a single model for the Alpine region. We attribute this to the fact that in a local minimum 1D model local and regional effects of the velocity structure can be better separated. Consequently, in tectonically complex regions, minimum 1D models should be computed in sub-regions defined by similar structure, if they are used for earthquake location and data quality assessment.     

页岩剪切摩擦与非稳态滑移特性实验

龙一₁亚段页岩是川南页岩气开发的主要目的层,实践表明水平井单井产气量对井轨迹所在小层较为敏感.龙一₁亚段页岩各层脆性矿物组分、弹性模量变化幅度小,采用常规页岩脆性评价方法和模型不能有效评价川南龙一₁亚段各小层页岩的可压性,借鉴地震学地震成核原因研究思路,提出利用稳态-非稳态破坏特征来表征各小层可压性.优化设计一种页岩剪切摩擦、稳态-非稳态特性实验方法,利用川南页岩地面露头进行线切割制样开展相关实验测试,分析研究页岩摩擦系数受层理性构造、矿物组分、法向应力大小的影响,表征量化不同矿物组分下的页岩稳态-非稳态特征,确定了速度弱化向速度强化转换的粘土矿物含量临界值.以川南昭通YS108井区龙一₁亚段页岩储层为例,对各小层可压性进行整体评价,得到:龙一₁1~2层较易开启剪切滑移,且易形成网状裂纹,储层整体可压性好;龙一₁3层较难开启剪切滑移,但裂纹为单一裂纹、网状裂纹过渡状态,储层整体可压性较差;龙一₁4层较易开启剪切滑移,但裂纹则呈现单一状态,储层整体可压性较差.      

FWG1幂指数递减开发模型

本文提出了ＦＷＧ１幂指数递减开发模型,提出了开发速度,采出程度等开发指标的数学关系式。分析了参数对ＦＷＧ１幂指数递减开发模型的影响。当ｃ＾１／２ｔ＝１时,ＶＤ＝ｅ＾－１为不动点。提出了开发初期ＦＷＧ１幂指数递减开发模型的确定方法,便于开发初期决策。     

The F,Cl, Br and I Contents of Reference Glasses BHVO‐2G,BIR‐1G,BCR‐2G,GSD‐1G,GSE‐1G,NIST SRM 610 and NIST SRM 612

Halogen contents for the widely distributed reference glasses BHVO‐2G, BIR‐1G, BCR‐2G, GSD‐1G, GSE‐1G, NIST SRM 610 and NIST SRM 612 were investigated by pyrohydrolysis combined with ion chromatography, total reflection X‐ray fluorescence analysis, instrumental neutron activation analysis, the noble gas method, electron probe microanalysis and laser ablation‐inductively coupled plasma‐mass spectrometry. Glasses BHVO‐2G, GSD‐1G and GSE‐1G have halogen contents that can be reproduced at the 15% level by all bulk techniques and cover a significant range in halogen mass fractions for F (~ 20–300 μg g^?1), Cl (~ 70–1220 μg g^?1) and Br (~ 0.2–285 μg g^?1) and I (~ 9–3560 ng g^?1). The BIR‐1G glass has low F (< 15 μg g^?1), Cl (~ 20 μg g^?1), Br (15 ng g^?1) and I (3 ng g^?1). The halogen contents for the silica‐rich NIST SRM 610 and 612 glasses were poorly reproduced by the different techniques. The relatively high Cl, Br and I abundances in glasses GSD‐1G and GSE‐1G mean that these glasses are well suited for calibrating spatially resolved micro‐analytical studies on silicate glasses, melt and fluid inclusions. Combined EPMA and laser ablation‐inductively coupled plasma‐mass spectrometry data for glass GSE‐1G demonstrate homogeneity at the 10% level for Cl and Br.     

沥青质傅里叶变换红外光谱 (FT IR)分析及其在有机地球化学研究中的应用

沥青质傅里叶变换红外光谱（FT－IR）分析可以反映出其分子结构上的特征，红外吸收因子Z[I(1380cm^-1)/I(720cm^-1）]能指示不同来源沥青质的母质类型；吸收因子Y[I(1600cm^-1)/I(1450cm^-1)]可以较好地讨论沥青质的成熟度演化状况；沥青质的红外研究认为，所有的沥青质都具有较好的再生烃潜力，其中Ⅲ型母质来源的沥青质具有较好的再生气潜力。而Ⅰ和Ⅱ型母质来源的沥青质具有高的再生油潜力。     

Determination of High Field Strength Elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g−1 Levels in Geological Reference Materials by Magnetic Sector ICP-MS after HF/HClO4 High Pressure Digestion

Six low abundance rock reference materials (basalt BIR-1, dunite DTS-1, dolerite DNC-1, peridotite PCC-1, serpentine UB-N and basalt TAFAHI) have been analysed for high field strength elements (Zr, Nb, Hf, Ta, Th and U), Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g⁻¹ levels (in rock) by magnetic sector inductively coupled plasma-mass spectrometry after HF/HClO₄ high pressure decomposition. The adopted method uses only indium as an internal standard. Detection limits were found to be in the range of 0.08 to 16.2 pg ml⁻¹ in solution (equivalent to 0.08 to 16.2 ng g⁻¹ in rock). Our data for high field strength elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi for the six selected low abundance geological reference materials show general agreement with previously published data. Our Ta values in DTS-1 and PCC-1 (1.3 and 0.5 ng g⁻¹) are lower than in previously published studies, providing smooth primitive mantle distribution patterns. Lower values were also found for Tl in BIR-1, DTS-1 and PCC-1 (2, 0.4 and 0.8 ng g⁻¹). Compared with quadrupole ICP-MS studies, the proposed magnetic sector ICP-MS method can generally provide better detection limits, so that the measurement of high field strength elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g⁻¹ levels can be achieved without pre-concentration, ion exchange separation or other specialised techniques.     

Determination of Zirconium, Niobium, Hafnium and Tantalum at ng g-1 Levels in Geological Materials by Direct Nebulisation of Sample HF Solution into FI-ICP-MS

We have developed a rapid and accurate method to determine Zr, Nb, Hf and Ta (denoted as HFSE) in geological samples by inductively coupled plasma-mass spectrometry fitted with a flow injection system (FI-ICP-MS). The method involves sample decomposition by HF followed by HF dissolution of HFSE coprecipitated with insoluble M and Ca fluoride residues formed during the initial HF attack. This HF solution was directly nebulized into an ICP mass spectrometer. An external calibration curve method and an isotope dilution method (ID) were applied for the determination of Nb and Ta, and of Zr and Hf, respectively. Recovery yields of HFSE were > 96% for peridotite, basalt and andesite compositions, apart from Zr and Hf for peridotite (> 85%). No matrix effects for either signal intensities of HFSE or isotope ratios of Zr and Hf were observed in basalt, andesite and peridotite solutions down to a dilution factor of 100. Detection limits in silicate rocks were 40, 2, 1 and 0.1 ng g-1 for Zr, Nb, Hf and Ta, respectively. This technique required only 0.1 ml of sample solution, and thus is suitable for analysing small and/or precious samples such as meteorites, mantle peridotites and their mineral separates. We also present newly determined data for the Zr, Nb, Hf and Ta concentrations in USGS silicate reference materials DTS-1, PCC-1, BCR-1, BHVO-1 and AGV-1, GSJ reference materials JB-1, -2, -3, JA-1, -2 and -3, and the Smithsonian reference Allende powder.     

Characterisation of Two New Reference Materials: STL-1, the Stewart Lepidolite and ZA-1, the Zapot Amazonite

The analysis of granitic pegmatites still remains a challenge because suitable natural reference materials are scarce or not available. Two new reference materials were prepared at the Smithsonian Institution, to provide an avenue to pursue the geochemical analysis of micas and feldspars in granitic pegmatites: STL-1, the Stewart lepidolite (NMNH 174041) and ZA-1, the Zapot amazonite (NMNH 174042). STL-1 was prepared from lepidolite collected from the lithium-rich Stewart pegmatite, San Diego County, California (33°22'52'N, 117°03'41'W). ZA-1 was prepared from an amazonite from the topaz-bearing Zapot pegmatite, Mineral County, Nevada, (38° 41'N, 118 °33'W). The results of this study indicated that STL-1 and ZA-1 are homogeneous and could be used as reference materials that would allow the expansion of calibration curves in XRF analysis up to 16000 μg g⁻¹ for Rb, 2000 μg g⁻¹ for Cs and 100 μg g⁻¹ for Tl. STL-1 and ZA-1 also contain unusually high concentrations of Ga and Tl, and STL-1 of Nb.