熔融制样-波长色散和能量色散X射线荧光光谱仪应用于硅酸盐类矿物及疑难样品分析

目前硅酸盐类样品中主量元素一般采用熔融制样X射线荧光光谱法（XRF）测定，不仅单元素测定结果不能超差，而且百分数加和也要满足要求。但对于矿化样品，由于微量元素较高，往往造成不能满足加和质量要求。充分利用波长色散（WD）和能量色散（ED）复合式X射线荧光光谱仪同时波谱、能谱测定的优势，可使分析人员快速掌握样品组成信息，对评估矿化样品数据质量具有重要意义。本文利用波长-能量色散X射线荧光光谱仪，可在测定主量元素的同时加入更多的微量元素进行测定，而分析时间不延长。主量元素采用波长色散定量，次量元素主要采用能量色散测定，在保证主量元素准确度的情况下，合理设置测量条件，延长能谱测量时间，实现在波长色散12min左右测定主量元素的同时，能够提供14个微量元素如Rb、Sr、Y、Zr、Ba、Cu、Zn的测定结果和10个线性范围较窄或含量较低元素如Co、Ge、Pr、Ta的参考结果，24个微量元素最大检出限为16.76μg/g。通过准确度考核，主量元素测定结果与认定值基本一致，高含量微量元素测定结果亦满足定量分析要求。该方法可使分析人员快速掌握样品组成信息，为提供更加准确、可靠的数据奠定基础，有效地解决矿化疑难样品主量元素测定问题。     

熔融制样-X射线荧光光谱法测定稀土矿石中的主量元素和稀土元素

应用熔融制样-X射线荧光光谱法(XRF)分析矿石样品具有定量准确、试剂用量少、重现性好等优点,但由于目前稀土标准物质较少,不能满足复杂稀土矿石类样品的准确定量要求。本文采用配置人工标准样品,解决了现有稀土标准物质较少的问题,加入高纯稀土氧化物La2O3、Ce O2、Y2O3扩展了La、Ce、Y的线性范围,利用人工标准样品和现有稀土标准物质、碳酸盐标准物质制作工作曲线,建立了XRF测定稀土矿石、矿化样品中25种主量元素和稀土元素的分析方法。针对主量元素采用理论α系数法校准,稀土元素采用经验系数法校准,对有谱线重叠的元素进行干扰校正,使绝大多数主量元素的相对标准偏差(RSD,n=13)小于1.5%,稀土元素含量在300"g/g以上时RSD(n=13)在0.69%~6.94%之间。通过未知样品考核,主量元素、稀土元素和烧失量的加和结果为99.41%~100.63%,满足《地质矿产实验室测试质量管理规范》的一级标准。     

利用ICP-AES快速检测碳酸盐金属元素的方法研究

本实验采用湿法消解碳酸盐岩矿石样品,利用电感耦合等离子体发射光谱仪(ICP-AES),采用内标法和基体匹配法相结合测定了碳酸盐岩标准物质(GBW10035a)中高达54%的氧化钙主量元素含量及其它常微量元素的含量;对实际样品中微量元素进行样品加标回收率实验,对主量和常量元素采用稀释法验证。实验结果表明,样品加标回收率在94%~108%之间,稀释比率在99.4%~100.2%,标准物质测定值与标准值吻合,6次平行样测定的稳定性4%;该方法一次溶样,径向测定主量和常量元素,轴向测定微量元素含量,操作简单,快速,该方法适用于盐湖碳酸盐样品,以及其他含有碳酸盐的各类样品的分析测试。     

熔融制样X射线荧光光谱法测定含硫量高的石膏矿物中主次量元素

X射线荧光光谱法(XRF)已经应用于石膏等非金属矿物的测定,但由于石膏标准物质匮乏、硫含量较高且在高温易挥发损失,给测定带来了一定困难。本文采用石膏标准物质、高纯硫酸钙和其他国家一级标准物质(土壤、水系沉积物、碳酸盐)配制人工标准物质拟合校准曲线,优化稀释比、熔矿温度等熔融制样条件,用理论α系数校正基体效应,建立了采用XRF同时测定石膏矿中10个主次量元素(硅铝铁钙镁钾钠钛硫锶)的分析方法。样品与四硼酸锂-偏硼酸锂熔剂的稀释比为1∶9,在1050℃温度下样品熔融完全。方法检出限为4~135μg/g,精密度(RSD,n=12)小于3.0%。本方法配制的人工校准样品加强了样品基体的适应性,使用的四硼酸锂-偏硼酸锂熔剂在样品熔融过程中可有效地结合硫,抑制了硫的挥发损失,适用于批量分析硫含量高达12.60%~51.91%的实际石膏矿物。     

华北燕山东段下马岭组黑色岩系元素地球化学组成——对其沉积作用的约束

华北地区燕山东段下马岭组地层中发育一套黑色岩系,本文测定了该岩系代表性岩石的地球化学组成。主微量元素分析结果显示,样品主量元素含量变化较大(如SiO2=53.00%~78.83%,Al2O3=1.20%~17.57%);PAAS标准化稀土配分型式为重稀土富集型,具Ce负异常,与现代海水配分型式一致。样品具有较高的Al2O3+TiO2含量(1.31%~18.48%),其U含量(平均3.95×10-6)、Th/Sc值(0.97~1.26)、Th/U值(平均3.50)、球粒陨石标准化稀土配分型式及大陆地壳标准化微量元素蛛网图表明黑色岩系沉积过程中有较多陆源碎屑物质的加入。黑色岩系Ba/Sr值(9.28~22.79)、Co/Zn值(0.01~0.29)及相关图解显示其沉积过程明显受到海底热液作用的影响,但原始溶液中热液组分含量不足0.1%。主微量元素比值、Ce/Ce*PAAS值(0.82~0.93)及构造背景判别图解表明黑色岩系可能沉积于大陆岛弧背景下的深水缺氧环境。     

X射线荧光光谱法测定高氟地质样品中氟、钙等元素

采用X射线荧光光谱法测定高氟地质样品中氟、钙等元素,对样品进行熔融制样前处理,理论α系数和经验系数法校正基体效应。应用此方法分析国家一级标准物质和代表性样品,所测元素的精密度(RSD)均小于5%(除含量较低元素);分析不参加回归的标准物质和人工配制的标准样品,测量结果与标准值基本一致。通过实验数据可知,该方法可以满足高氟硅酸盐样品、萤石、萤石型铀矿、磷矿石等样品的测定要求。     

“壳-幔”混合成因高Ba-Sr花岗质岩浆演化——以华北克拉通中部带老山和狐偃山岩体为例

锆石U-Pb年龄显示华北克拉通中部带西缘老山杂岩体和狐偃山正长岩形成时间接近(128.7～125.4Ma),代表华北克拉通中部带早白垩世岩浆活动。系统的地球化学研究显示两岩体具有如下特征:(1)SiO_2含量中等(57.3%～69.8%),高K_2O(3.0%～8.2%)和Na_2O(4.3%～6.4%)含量,低MgO(0.2%～1.4%)、CaO、TiO_2和P_2O_5含量;(2)富集大离子亲石元素(Ba、Sr、K)和LREEs,亏损高场强元素(Nb、Ta、Zr、Hf)和HREEs。全岩地球化学特征(如高Ba、Sr含量和K/Rb比值,低Rb、Y含量)与高Ba-Sr花岗岩相符;(3)根据主量元素,相容元素(Cr、Co、Ni、V)和微量元素(Ba、Sr)特征,研究样品可分为2组:组1具有高Ba特征,Sr(~(87)Sr/~(86)Sr(t)=0.7049～0.7053)和Nd(ε_(Nd)(t)=-11.5～-9.7)同位素组成均一,经历了以黑云母为主的分离结晶作用;组2具有低Ba特征,Sr(~(87)Sr/~(86)Sr(t)=0.7051～0.7070)和Nd(ε_(Nd)(t)=-18.7～-14.8)同位素组成更加富集且分散,经历了角闪石,斜长石及磷灰石、磁铁矿和榍石等矿物分离结晶。2组样品不同的源区组分和分离结晶组合会显著改变岩浆中特征微量元素(Ba、Sr、Rb)含量和比值(Sr/Y、Nb/Ta、Dy/Yb)。本文研究表明华北克拉通中部带岩石圈地幔富集机制主要与元古代东、西陆块向中部带碰撞拼合时俯冲板块派生流体交代作用有关,该区中生代破坏机制为古太平洋板块俯冲所引起的碰撞后伸展背景下富集岩石圈地幔减压熔融、底侵至下地壳并引起"壳-幔"岩浆相互作用所形成的大规模深部岩浆抽取。     

川东南—黔中及其周边地区下组合烃源岩元素地球化学特征及沉积环境意义

笔者采用ICP-MS测试分析技术,对川东南-黔中及其周边地区震旦-志留纪地层28件样品进行了B、V、Ni、Sr、Ba、Th、U等指示沉积环境的敏感微量元素做了系统测试分析,采用GB/T14506.28-93硅酸盐岩石化学分析方法和X射线荧光光谱法测定主要元素和微量元素含量,并探讨了Sr/Ba、V/Ni、V/(V+Ni)、Sr/Ca、Ca/Mg、Th/U比值与沉积环境的对应关系.分析结果表明,本区下组合沉积环境主要为半深海、深海及浅海滞流环境.元素空间分布的差异性反映了沉积环境的区域性变化.     

LA-ICP-MS微区原位准确分析含水硅酸盐矿物主量和微量元素

通过描述一种利用LA-ICP-MS准确测定含水硅酸盐矿物主量元素和微量元素含量的多外标、无内标分析方法.总结出该方法基于矿物化学计量式计算含水硅酸盐矿物中挥发分的相对含量,再将全部分析元素归一化到总金属氧化物含量(100%减含水量)的原理,利用多种天然成分的岩石标准玻璃(如MPI-DING玻璃和USGS玻璃)作为外标进行校正计算.利用该方法对角闪石、绿帘石、电气石和透闪石等含水硅酸盐矿物进行了分析,并与利用电子探针和微钻(直径300 μm)取样溶液-ICP-MS分析的结果进行了对比研究.研究结果表明:对于组成均一的主量元素的分析结果与电子探针分析数据一致,相对偏差集中在5%以内.除了那些分布异常不均一的元素(在300 μm尺度上),对微量元素的分析结果与溶液-ICP-MS分析结果具有很好的一致性,二者之间的相对偏差大部分集中在10%以内.研究结论为采用归一化校正策略,选择MPI-DING和USGS玻璃作为外标,利用LA-ICP-MS微区分析方法可以准确测定含水硅酸盐矿物中的主、微量元素含量.      

单道扫描电感耦合等离子体发射光谱法测定珊瑚礁中主量和微量元素

建立了用单道扫描电感耦合等离子体发射光谱法测定珊瑚礁中主量和微量元素的方法。珊瑚礁样品经酸溶解后,直接进行Ca、Mg、K、Na、V、Sr、Ba、Co、Ni、Pb、Li、Rb的测定,方法检出限为0.0004～0.1mg/L,精密度RSD<5%(n=6),样品的加标回收率为97%～105%。测定w(CaO)为50%的样品,结果与传统的EDTA容量法相符。方法经碳酸盐岩石国家一级标准物质验证可行,已用于大批量的珊瑚礁样品的测定。     

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.     

A Flux‐Free Fusion Technique for Rapid Determination of Major and Trace Elements in Silicate Rocks by LA‐ICP‐MS

A simple flux‐free fusion technique was developed to analyse major and trace element compositions of silicate rocks. The sample powders were melted in a molybdenum capsule sealed in a graphite tube to make a homogenous glass in a temperature‐controlled one‐atmosphere furnace. The glass was then measured for both major and trace element concentrations by LA‐ICP‐MS using a calibration strategy of total metal‐oxide normalisation. The optimum conditions (i.e., temperature and duration) to make homogeneous glasses were obtained by performing melting experiments using a series of USGS reference materials including BCR‐2, BIR‐1, BHVO‐2, AGV‐1, AGV‐2, RGM‐1, W‐2 and GSP‐2 with SiO₂ contents from 47 to 73% m/m. Analytical results of the USGS reference materials using our method were generally consistent with the recommended values within a discrepancy of 5–10% for most elements. The routine precision of our method was generally better than 5–10% RSD. Compared with previous methods of LA‐ICP‐MS whole‐rock analyses, our flux‐free fusion method is convenient and efficient in making silicate powder into homogeneous glass. Furthermore, it limits contamination and loss of volatile elements during heating. Therefore, our new method has great potential to provide reliable and rapid determinations of major and trace element compositions for silicate rocks.     

Major and Trace Element Analysis of Silicate Rocks by XRF and Laser Ablation ICP-MS Using Lithium Borate Fused Glasses: Matrix Effects, Instrument Response and Results for International Reference Materials

Major and trace element compositions of fifteen silicate rock reference materials have been determined by a combined XRF and laser ablation ICP‐MS (LA‐ICP‐MS) technique on glasses prepared by fusing the sample with a lithium borate flux (sample:flux = 1:3). Advantages of this technique include the ability to measure major and trace element abundances on a single sample using a quick and simple preparation that attacks resistant phases such as zircon without the need for acid dissolution. The method is suitable for a wide variety of bulk compositions including mafic, intermediate and silicic rocks. Abundance‐normalized mass response patterns (the ratio of signal intensity to element concentration) of the LA‐ICP‐MS analyses vary systematically with major element composition, demonstrating the presence of a matrix effect that cannot be compensated by normalisation to a single internal standard element. Increasing the sampling distance between the ICP‐MS cone and the torch reduces the magnitude of this effect, suggesting that a mechanism related to residence time of ablated particles in the plasma may be at least partially responsible for the observed variations in mass response patterns. When using a matrix‐matched calibration, agreement of the LA‐ICP‐MS results with published reference values or those obtained by solution ICP‐MS is 10% relative. Analytical precision based on replicate analyses is typically 5% RSD. Procedural detection limits that include contributions from gas background and flux are 0.01‐0.1 μg g‐¹ for the heavy mass trace elements (Rb‐U). Major element analyses by XRF show excellent agreement with results obtained using a conventional heavy element absorbing flux. High quality major and trace element data for silicate rocks can be achieved by a combined XRF and LA‐ICP‐MS analysis of Li₂B₄O₇/LiBO₂ fused glasses provided an appropriate matrix‐matched calibration is adopted.     

Determination of Trace Elements in Calcite Using Solution and Laser Ablation ICP-MS: Calibration to NIST SRM Glass and USGS MACS Carbonate, and Application to Real Landfill Calcite

We report new data on the trace element concentrations of Mg, Cr, Mn, Co, Ni, Cu, Zn, Sr, Cd, Ba, La, Ce, Nd, Pb and U in USGS carbonate reference materials (MACS-1 and MACS-2) and compare solution ICP-MS and LA-ICP-MS trace element determinations on landfill calcites using calibration to different reference materials (MACS-1 and MACS-2 carbonate and NIST SRM 612 glass). Very good agreement (differences below 10% relative) was found between laser ablation and solution ICP-MS data for MACS-1 with higher concentrations of trace elements (values between 100 and 150 μg g⁻¹), with the exception of Cu and Zn. Similarly good agreement was found for MACS-2 with lower trace element concentrations (units to tens of μg g⁻¹), with the exception of Cr, Co and Zn. The MACS-1 reference material for calibration of LA-ICP-MS was found to be extremely useful for in situ determination of trace elements in real-world carbonate samples (landfill calcites), especially those present in calcite in higher concentrations (Mn, Sr, Ba; < 5% RSD). Less accurate determinations were generally obtained for trace elements present at low concentrations (∼ units of μg g⁻¹). In addition, good agreement was observed between the instrument calibration to MACS and NIST SRM 612 glass for in situ measurements of trace elements in landfill calcites K-2, K-3 and K-4 (differences below 15% relative for most elements). Thus, the application of MACS carbonate reference materials is promising and points to the need for the development of new carbonate reference materials for laser ablation ICP-MS.     

南堡凹陷沉积岩化学元素分布特征及多元统计方法研究

对南堡凹陷Ed₁亚段、Ng_下、Ng_上、Nm_底地层的75个沉积岩样品进行了主量、微量元素分析,结果表明粒度效应造成砂岩和泥岩元素丰度明显不同,砂岩除富集K、Na、Sr、Ba、Si外,其余元素均较泥岩亏损.根据地层垂向上元素丰度由高—低—高的变化规律,可将这4个亚段分为Ed₁、Ng_下和Ng_上、Nm_底3个阶段,与凹陷构造演化特征响应.因子分析、聚类分析等多元统计方法表明,表生环境中元素具有不同的迁移富集规律,Ca、Na、Sr等具有较强的活动性,Zr、Hf等少数元素则在粗粒级中含量较高,而其余元素则多在黏土粒级中富集.元素在表生环境中地球化学行为的不同主要受化学结构特征控制,沉积环境对其也有影响.     

The determination of minor and trace element associations in coal using a sequential microwave digestion procedure

A sequential extraction procedure, using acid digestion in a CEM MDS-81D® microwave system, is reported for the investigation of trace and minor element associations in coal in (1) mineral phases other than pyrite, (2) pyrite and (3) the organic matrix. The concentrations of sulphate, pyrite and organic sulphur can also be determined by this method. The extract solutions from each stage are rapidly analysed by ICP-AES. The association of major, minor and trace elements with mineral and organic phases is suggested for a suite of certified reference coal samples. In stage 1, a significant percentage of the total Ba, Co, Cr, Cu, Mn, Ni, Pb and Sr was extracted suggesting an association with silicate, carbonate, sulphate and phosphate minerals for these elements. In stage 2, a proportion of the Cu, Mn, Ni, Pb and Zn was dissolved implying the occurrence of these elements in pyrite. An association with the organic matrix is suggested for Cr and also for Ba and Sr in lower rank coals.     

Temporal transport of major and trace elements in the upper reaches of the Xijiang River,SW China

This study investigated the temporal variations of major and trace element contents and controlling factors in the upper reaches of the Xijiang River, SW China. The results showed the major ions principally derived from the weathering of carbonate and silicate rocks, with a seasonal variation impacted by the monsoonal climate. The contents of dissolved trace elements also varied seasonally in the two main tributaries: the Nanpan and Beipan rivers. Most dissolved trace elements such as Mn, Zn and Pb being affected by anthropogenic contributions displayed a large seasonal variability, from onefold to hundred-fold, while V, Rb and U show a relative stable trend uncorrelated with the different seasons, suggesting a natural origin by rock weathering. Suspended particle matter in the Nanpan and Beipan rivers was depleted in Ca, Mg, Na, K and Sr, but enriched in Al, Fe and Sb compared to the upper crust (UC) values. A binary mixture of silicate-rich and carbonate-rich sources dominates the behavior of elements such as Ca and Sr in riverine sediments, while a third end-member with an anthropogenic signature influenced the content of trace elements like Mn, Sb, Pb, Zn, Cd, Cr and Cu. The enrichments of Sb relative to the UC would be related to the mining activity in the studied area. The study highlights the importance of investigating temporal variations of major and trace element contents of rivers controlled by the monsoon climate and impacted by human activity.     

Laser Ablation ICP-MS Analysis of Geological Materials Prepared as Lithium Borate Glasses

A simple, rapid and precise method is described for determining trace elements by laser ablation (LA)-ICP-MS analysis in bulk geological materials that have been prepared as lithium borate glasses following standard procedures for XRF analysis. This approach reliably achieves complete sample digestion and provides for complementary XRF and LA-ICP-MS analysis of a full suite of major and trace elements from a single sample preparation. Highly precise analysis is enabled by rastering an ArF excimer laser (λ= 193nm) across fused samples to deliver a constant sample yield to the mass spectrometer without inter-element fractionation effects during each analysis. Capabilities of the method are demonstrated by determination of twenty five trace elements (Sc, Ti, V, Ga, Rb, Sr, Y, Zr, Nb, Cs, Ba, REE, Hf, Ta, Pb, Th and U) in a diverse range of geological reference materials that includes peridotites, basalts, granites, metamorphic rocks and sediments. More than 90% of determinations are indistinguishable from published reference values at the 95% confidence level. Systematic bias greater than 5% is observed for only a handful of elements (Zr, Nb and U) and may be attributed in part to inaccurate calibration values used for the NIST SRM 612 glass in the case of Zr and Nb. Detection limits for several elements, most notably La, are compromised at ultra-trace levels by impurities in the lithium borate flux but can be corrected for by subtracting appropriate procedural blanks. Reliable Pb analysis has proved problematic due to variable degrees of contamination introduced during sample polishing prior to analysis and from Pt-crucibles previously used to fuse Pb-rich samples. Scope exists for extending the method to include internal standard element/isotope spiking, particularly where integrated XRF analysis is not available to characterise major and trace elements in the fused lithium borate glasses prior to LA-ICP-MS analysis.