Rapid Determination of Trace Impurity Elements in Pure Molybdenum by Inductively Coupled Plasma-Mass Spectrometry Based on the Online-Standard-Addition Method
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摘要:
纯钼的纯度或杂质含量对材料性能有重要的影响，痕量杂质的准确测量是产品质量控制的关键。电感耦合等离子体质谱法(ICP-MS)由于具有高灵敏、多元素同时测量的优势，是测量痕量杂质的最有效方法之一；但在测量高浓度纯钼基体中的痕量杂质时，会产生较强的基体抑制效应，严重影响测量结果准确性。基体匹配法、标准加入法以及基于同位素丰度比值测量的同位素稀释质谱法(IDMS)可以有效地补偿复杂的基体效应，获得准确的测量结果；但步骤繁琐、分析效率低、分析成本高使其难以满足高通量的测量需求。本万工作集成了标准加入法的准确性及在线自动分析的高效性，基于标准加入法的原理，通过双路进样，将样品溶液与标准溶液(系列标准溶液依次自动进样)同时引入三通进行混合，然后经过雾化进入ICP-MS进行检测，从而建立了基于在线加标的ICP-MS法。该方法有效地补偿了高浓度试样的基体效应，通过样品-标准进样流量差异的校正，提高了测量结果的准确性，实现了纯钼中29种痕量杂质元素的快速准确测量，满足了纯钼中痕量杂质标准物质的准确定值要求。经考察，本工作建立的方法对29种元素的方法检出限(MDL)在0.004～0.90μg/g之间，标准加入法标准曲线的线性相关系数r基本大于0.999，除Ca、Zn由于沾污问题导致的测量准确性较差外(Ca、Zn相对偏差分别为32%、13%)，27种元素的测量相对偏差在−6.8%～5.1%之间。将Cr、K测量结果与IDMS法比较，进一步验证了该方法的可靠性。结果表明，两种方法测量结果偏差在1%以内，且具有相当的精密度(本方法对于Cr、K的RSD为1.8%～3.2%，IDMS法的RSD为0.9%～1.4%)，但本方法分析效率与分析成本具有明显的优势，经评估15min可完成29种元素的测量，分析效率比IDMS法可提高上百倍，能够满足高通量的样品测试需求。
Abstract:BACKGROUNDMolybdenum (Mo) is widely used in aerospace, nuclear industry, integrated circuits, flat display and photovoltaic solar energy and other fields[2-4]. The purity or impurity content of high purity molybdenum has an important effect on material properties, so the accurate measurement of trace impurities is the key to quality control. In the China national standard “Molybdenum Powder” (GB/T 3461—2016), the limits of impurities such as Pb and Bi which are commonly in the range of 5 to 50mg/kg, are specified. Rapid and accurate analysis of trace or ultra-trace impurities is necessary with the development of high purity Mo requirements of high throughput analysis. The ICP-MS method has become the most powerful method for trace impurities analysis in high purity Mo, but the tedious and time-consuming matrix effect calibration strategies makes it a big challenge to achieve rapid and accurate analysis. ICP-MS has the advantages of high sensitivity, good accuracy and the possibility of simultaneous measurement of multiple elements, compared with AAS, ICP-OES, and GD-MS methods. However, the matrix effect is heavy in the analysis of high purity Mo, which seriously affects the accuracy of the measurement results. Matrix matching method, standard addition method and isotope dilution mass spectrometry (IDMS) based on isotope abundance ratio measurement can effectively compensate for the complex matrix effect, and accurate analytical results can be obtained, but the analysis processes are complicated, the efficiency is low, and the cost is high, making it difficult to meet the measurement requirements of high throughput. To meet the requirements of rapid analysis, on-line analysis based on flow injection[28] and tandem calibration[29] was used. The online matrix separation and pre-concentration process for flow injection not only eliminates the matrix effect and reduces the detection limits, but also improves the automation level, and achieves high throughput measurement[31-33]. Wang et al.[32] measured a variety of trace metal elements in seawater samples within 28.5min based on online ion exchange. An online calibration process through a new analytical methodology called tandem calibration could be achieved based on a dual sample introduction system with two nebulizers working in parallel[29] or a multiple-channel nebulizer[34], for which the special design of the nebulizer is necessary.
OBJECTIVESTo develop a rapid and accurate method for the analysis of trace impurities in high purity molybdenum to meet the requirements of high throughput sample tests.
METHODSA dual-channel simultaneous sampling ICP-MS measurement method based on online-standard-addition was established by calibrating the difference in sample-standard injection flow rate. The in-house online platform was set up based on an auto-sampler and two peristatic pumps. The pure Mo reference material candidates containing homogeneous impurities with mass fraction of 0.1-200μg/g were used as samples. About 0.1g sample was digested based on the China national standard GB/T 4325.26—2013 and diluted about 1000-fold for analysis. The digested sample solution was introduced from a tube (designated as A) continuously by using a peristaltic to a T-joint in which the sample solution and a series of standard solutions from another tube (B) using an auto-sampler were mixed thoroughly. The mixed solutions were introduced through a nebulizer and rotary spray chamber, ionized in the plasma, and then introduced to mass spectrometry for analysis. For more accurate results, the difference flow rate between the sample and standard tube (the internal diameter of the sampling tube was 0.25mm and 0.38mm for the sample and standard, respectively) was calibrated by using the 20ng/mL standard solution. The ratio (R1) of intensity using A tube injection to the intensity using B tube injection was 1.54±0.06 for each element, indicating the difference of injection flow for A and B tube. The ratio of intensities for simultaneous sample injection to the sum intensities of A and B injection respectively was about 1.
RESULTSMethodological parameters for ICP-MS method based on online-standard-addition were evaluated in terms of method detection limit (MDL), linearly dependent coefficient, precision and accuracy. The limits of detection of this method based on the 3-σ criterion ranged from 0.004μg/g to 0.90μg/g for 29 elements, which meets the requirements of trace impurities analysis. The linear correlation coefficient r of the standard curve was mostly more than 0.999 at the concentration range of 0-500ng/g. The precision was evaluated by introducing the Mo digested solutions from A tube and 5ng/mL standard solution from B tube simultaneously, and the relative standard deviations (RSDs) of 6 repeated measurements were low, ranging from 0.8%-3.9% for 28 elements, in spite of the relative high RSD for Nb (6.1%). The multi-elements standard solution of GBW(E)082429, GBW(E)082430, GBW(E)082431were used for accuracy evaluation. After flow rate calibration, the relative deviation (RDs) between measured values and certified values ranged from −6.8% to 5.1% for 27 elements. For Ca and Zn, the RDs were relatively large (32% for Ca and 13% for Zn), which was probably due to the contamination. To further evaluate the method reliability, the analytical results of K and Cr were compared with those by using the IDMS method. Relative deviation of less than 1% between the two methods was found. Calibration of the difference for flow rate between the sample and standard injection. When the sample and standard is introduced from different tubes or nebulizers, the efficiency should be calibrated. The mathematical correction used was first introduced by Salin et al.[36] A dual sample introduction system based on two nebulizers working in parallel was set up by Canals et al.[29] The transport efficiencies for online standard addition were calibrated and the deviations of less than 3% for Na, K, Ba and Rb elements analysis in different matrixes were obtained. Different from the reported systems which needed to be specially designed[29,34], the online platform in this work was simple and easy to apply, because it only used a T-joint for the mixing of the sample and standard. This similar setup was found elsewhere[37-38]. In this setup, the same nebulizer was used for the sample and standard solution, and thus the same nebulization efficiency was obtained. The difference of signals between using A tube injection and B tube injection only resulted from the flow rates. In the flow process, fractionation could not occur. Therefore, the very consistent R1 factors were found for different elements, which indicated that it was not needed for the measurement of R1 factors for all elements. The merits of online-standard-addition ICP-MS method.Satisfactory limits of detection were obtained for 29 elements ranging from 0.004μg/g to 0.90μg/g, which was better than the MDL derived from the China national standard GB/T 4325.26—2013(1μg/g) and was comparable with the reported method based on ICP-MS/MS[6]. In fact, compared with the traditional standard addition method, the online method would attenuate the MDL due to the dilution of sample solution, although Schwartz et al.[37] deemed that there was no obvious difference between online and traditional methods in terms of SNR (Signal to Noise Ratio) and precision. The good precision 0.8%-3.9% for 28 elements was better than literature[37-38]. Apart from Ca and Zn, the satisfactory accuracy for 27 elements (relative deviation ranged from −6.8% to 5.1%) was obtained, which was better than the online internal standard method[39] because of the calibration of matrix effect for the standard-addition method. The comparative results of Cr and K by using the online-standard-addition method (this work) and the IDMS method showed good agreement of ±1%, which further validates the reliability of this work. It can be concluded that the accuracy and precision of this established method were comparable with the IDMS method. However, the analysis efficiency and cost showed obvious advantages, because the measurement of 29 elements could be completed in 15min, and thus the analysis efficiency was hundreds of times higher than that of the IDMS method.
CONCLUSIONSThe method combined the properties of high accuracy and high throughput, and thus can achieve rapid and accurate trace impurities analysis in pure Mo.
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Keywords:
- standard addition method /
- online sample introduction /
- high purity molybdenum /
- trace impurity analysis /
- matrix effect /
- inductively coupled plasma-mass spectrometry
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植硅石，又名植物硅酸体，是植物在生长过程中，通过根系从土壤中吸收的水溶性硅(单硅酸)并在细胞内或细胞间沉淀，形成各种形态的固体非晶质含水二氧化硅颗粒，植硅石主要成分为：SiO2含量约70%～95%，水分3%～12%，有机碳0.1%～6%及微量元素［1］。在植硅石形成过程中，通常会封存部分有机碳及微量元素，其中封闭的有机碳受硅质外壳的保护避免了与外界的污染，因此成为较好的测年材料。
植硅石的14C放射性测年研究，在考古遗址、湖泊沉积、深海沉积和陆相沉积物中得到广泛运用［2］。此外，与有机质密切相关的定年研究中，全岩同位素中Re-Os同位素定年近年来越发受到学者关注。Re、Os同位素的亲有机性、富集过程与岩石沉积过程的同时性以及Re-Os同位素体系较好的封闭性等特点促使Re-Os同位素定年在富有机质沉积岩研究中的应用较为广泛［3-4］，定年对象已从黑色页岩、泥岩、片岩、板岩等拓展至原油、沥青、焦沥青、油砂以及油页岩等地质样品，并取得一系列重要进展［5-9］。
作为植硅石的主要测年方法，当前14C放射性测年研究仍具有一定局限性，主要是受测试技术所限，其测试年代极限约为0.04Ma［10］，年代学研究严格受限于第四纪。而Re-Os同位素体系的测试年代虽覆盖较广，但研究对象多集中为富有机质的海相沉积岩样品，而湖相沉积岩样品的定年研究少见成功报道。李欣尉等［9］认为，相较于海相沉积物，湖相沉积物形成过程受物质来源、经历的地质作用以及更多的陆源碎屑物等诸多复杂因素的影响，这会造成Re-Os同位素体系在湖相沉积物测年研究中面临挑战。
江西省丰城石炉坑天然微纳米硅碳矿为全球首例由植硅石沉积形成的矿床，矿石主要由微米至纳米级石英和碳组成［11］，硅碳矿与常规石英、石墨等矿种相比，在分布范围、成因类型、资源类型等方面均具有自身特点，当前正作为新矿种开展研究，极具研究价值。矿石经简单加工后可制备高纯石英、纳米硅微粉、介孔硅、介孔碳等，在信息技术、新能源、新材料、高端制造等战略性新兴产业中可以发挥关键作用［12］，对解决新一轮找矿突破战略行动中关于战略性矿产资源开发利用的问题亦可提供有力支撑。当前，石炉坑硅碳矿床研究工作尚处初期，仅开展了矿区地质特征、矿石特征以及工艺矿物学等方面的研究［11，13］。对于沉积型矿床的研究，成岩成矿年代的精确厘定具有重要意义，不仅可为矿床成矿规律及找矿方向研究提供年代学依据，也可为邻区地层对比提供新的参考，并有望推动相似层位取得找矿突破。植硅石岩作为湖相沉积岩，考虑到区域地质特征、矿石含有机质以及Re-Os同位素的亲有机性等特点，本文尝试利用Re-Os同位素分析测试法开展年代学研究。
1. 地质背景
丰城地区位于萍乐坳陷中段，清江盆地北东缘(图1)。萍乐坳陷位于江西中北部，在大地构造位置上北接江南造山带，南接华夏板块，南北两侧分别受宜丰—景德镇断裂和萍乡—鹰潭断裂两条长期发育的深大断裂所限(图1a)。萍乐坳陷自晚古生代以来主要发育海相、海陆交互相及陆相地层：泥盆纪至二叠纪早期，主要发育以浅海、滨海相碎屑岩及碳酸盐岩为主的海相沉积岩；二叠纪中晚期，受东吴运动影响，区内海水退出，转为海陆交互相沉积环境，主要发育海陆交互相的含煤碎屑岩和海相碳酸盐岩；三叠纪早中期的印支运动进一步结束了区内大规模的海侵，主要发育以陆相碎屑岩为主的陆相地层［14-17］。自白垩纪始，受赣江断裂带活动影响［18］，在萍乐坳陷海相地层上开始发育以清江盆地、鄱阳盆地等为主(图1b)的中、新生代陆相断陷盆地［19］。
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图 1 江西石炉坑矿床(a)大地构造位置图(据胡正华等［20］)和(b)矿区地质图1—第四系进贤组； 2—古近系石炉坑组； 3—二叠系中统茅口组； 4—石炭系下统梓山组； 5—泥盆系上统—石炭系下统华山岭组； 6—取样位置； 7—断层;； 8—地层界线； 9—勘探线； 10—矿区边界。Figure 1. (a) Geotectonic location (Modified after Hu, et al［20］); (b) Mining geology map of the Shilukeng deposit in Jiangxi Province.1—Quaternary Jinxian Formation; 2—Neogene Shilukeng Formation; 3—Maokou Formation of middle Permian; 4—The lower Carboniferous Zishan Formation; 5—Devonian—Carboniferous Huashanling Formatimon; 6—Sample position; 7—Fault; 8—Formation boundary; 9—Exploration line; 10—Mining area boundary.矿区总体为一断坳盆地，出露地层有：华山岭组(D3-C1h)、梓山组(C1z)、茅口组(P2m)、石炉坑组(E2s)和第四系进贤组(Qp2j)(图1b)。区内地表无岩浆岩出露，经少数钻孔揭示存在隐伏玄武岩，呈似层状产出。矿体产状与石炉坑组地层基本一致，走向NEE，倾向NW，倾角5°～10°，矿体厚1.09～52.03m，平均21.5m。石炉坑组(E2s)为主要的赋矿地层，上段由紫红色-土黄色黏土岩、泥岩组成，为不含矿层位，与上覆第四系进贤组(Qp2j)不整合接触；下段岩性为灰黑色、深灰色植硅石岩，间夹硅质黏土岩或含矿黏土岩与浅灰色-灰白色黏土岩(图2a)，是硅碳矿的主要赋矿层位，岩性特征显示其为较平静的湖相沉积环境，并与下部茅口组(P2m)深灰色、灰色钙质泥砂岩呈不整合接触。矿石特征主要为：深灰至灰黑色，块状、粉末状构造，微细层状。具有较多孔隙，质轻且自然状态下可浮于水，断口呈参差状，染手，含炭质和黏土矿物(图2b)。矿石经分析测试后［13］，主要成分、含量为：81.28% SiO2、10.77% C、4.56% Al2O3以及2.01% Fe2S。主要矿物为石英，在镜下多为异形，颗粒表面锐角偏多(图2c)，经电镜扫描多见植硅体结构(图2d)。
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图 2 (a)石炉坑天然微纳米硅碳矿柱状简图及样品特征；(b)植硅石岩照片；(c)矿物电镜扫描图；(d)电镜扫描下植硅体形状Figure 2. (a) Stratigraphic column of Shilukeng natural micro/nano silicon-carbon deposit and sample characteristics; (b) Phytolith rock sample; (c) SEM image of ore sample; (d) SEM image of phytolith.2. 实验部分
2.1 样品处理
本次样品主要来自矿区ZK8-13、ZK14-9中的两个钻孔(图1b)，共采集了7件植硅石岩样品用于Re-Os同位素测年，所采集样品主要来自于石炉坑组下段地层(E2s2)15.41～41.5m处，从而保证样品的同时性、同源性。此外，需控制适量取样间距及取样量，防止样品可能存在Re-Os失耦问题影响定年结果［21］。Re-Os同位素样品制备、溶样和测试分析工作均是在国家地质实验测试中心(中国地质调查局铼-锇同位素地球化学重点实验室)完成。
2.2 样品测试
整个实验流程如下：准确称取岩石样品2g，通过细颈漏斗加入Carius管内，缓慢将液氮加到有半杯乙醇的保温杯中，使成黏稠状(−50～80℃)。将装好样品的Carius管置于该保温杯中。用3mL 10mol/L盐酸通过细颈漏斗将准确称取的185Re和190Os混合稀释剂转入Carius管底部。再依次加入5mL 16mol/L硝酸和1mL 30%过氧化氢分解样品。
当Carius管底溶液冻实后，用液化石油气和氧气火焰加热封好Carius管的细颈部分。擦净表面残存的乙醇，放入不锈钢套管内。轻轻放套管入鼓风烘箱内，待回到室温后，逐渐升温到230℃(岩石样品)保温24h。取出，冷却后在底部冻实的情况下，先用细强火焰烧熔Carius管细管部分一点，使内部压力得以释放。再用玻璃刀划痕，并用烧热的玻璃棒烫裂划痕部分。对样品溶液采用直接蒸馏法分离Re，微蒸馏法提纯Os以及丙酮溶液萃取分离Re。
实验中采用Triton-plus热表面电离质谱仪(美国ThermoFisher公司)测定同位素比值［22］。对于Re，采用静态法拉第杯模式同时测定185ReO4、187ReO4；对于Os，采用法拉第杯多接收模式测定186OsO3、187OsO3、188OsO3、189OsO3、190OsO3、192OsO3。对测量数据利用氧同位素自然丰度和统计学中的等概率模型，采用逐级剥谱法进行氧同位素干扰扣除。采用普通Re的185Re/187Re=0.59738作为外标对Re同位素进行质量分馏校正，采用迭代法以192Os/188Os=3.0827作为内标对Os元素进行质量分馏校正。
2.3 数据处理和质量控制
本次实验使用的国家一级标准物质GBW04477(JCBY)是采自甘肃省金川铜镍硫化物矿二矿区的网状硫化物矿石，经球磨粉碎后，再进行人工混匀，然后直接分装于棕色玻璃瓶中，采用负离子热电离质谱(N-TIMS)、高分辨电感耦合等离子体质谱(HR-ICP-MS)、多接收电感耦合等离子体质谱(MC-ICP-MS)和ICP-MS标定。本次样品全流程空白Re含量为3.8pg，Os含量为0.48±0.01pg，均远远小于植硅石岩样品Re、Os含量，可忽略不计。标准物质GBW04477(JCBY)的测定结果Re含量为37.99±0.28ng/g，Os含量为15.59±0.12ng/g，187Os/188Os值为0.3369±0.0008，与该标准物质相应的标准值(Re含量38.61±0.54ng/g，Os含量16.23±0.17ng/g，187Os/188Os值0.3363±0.0029)在误差范围内一致，表明本次测试数据真实可靠。
3. 分析测试结果
3.1 Re-Os同位素测试结果
石炉坑硅碳矿植硅石岩的Re-Os同位素测试结果列于表1。其中7件植硅石岩样品的Re含量范围为22.72～299.20ng/g，普通Os含量为0.789～2.544ng/g，187Os含量为0.1873～0.7056ng/g，187Re/188Os值为139.1～813.8，187Os/188Os值为1.824～2.301(表1)，采用剩余7件样品的Re-Os数据获得等时线年龄为43.1±3.7Ma(MSWD=6.2)(图3)，187Os/188Os初始值等于1.713±0.0036。上述特征表明，石炉坑硅碳矿中植硅石岩沉积成岩的时代为古近纪始新世。
表 1 江西丰城石炉坑植硅石岩Re-Os同位素数据Table 1. Re-Os isotope data of phytolith rock from Shilukeng deposit in Fengcheng area, Jiangxi Province.样品编号 取样
深度
(m)Re含量(ng/g) 普通Os含量(ng/g) 187Os含量(ng/g) 187Re/188Os 187Os/188Os 测定值 不确定度 测定值 不确定度 测定值 不确定度 测定值 不确定度 测定值 不确定度 ZK8-13-H6 15.41 108.6 0.8 1.227 0.012 0.3242 0.0029 406.5 4.4 1.991 0.004 ZK14-9-Y1 26.0 292.8 2.5 2.544 0.031 0.7056 0.0073 556.0 8.3 2.131 0.034 ZK14-9-Y2 26.2 270.4 2.0 1.996 0.016 0.5658 0.0043 654.4 6.8 2.177 0.005 ZK14-9-Y3 26.4 229.9 1.7 2.168 0.018 0.5894 0.0045 512.1 5.5 2.091 0.006 ZK14-9-Y4 26.6 226.7 2.1 1.844 0.020 0.5123 0.0044 593.8 8.4 2.135 0.029 ZK14-9-Y11 36.4 22.72 0.20 0.789 0.0068 0.1873 0.0018 139.1 1.7 1.824 0.023 ZK14-9-H16 41.5 299.2 2.2 1.727 0.015 0.5214 0.0043 813.8 8.8 2.301 0.004 ![]()
图 3 江西丰城石炉坑矿床植硅石岩Re-Os等时线年龄Figure 3. Re-Os isochron ages of phytolith in Shilukeng deposit of Fengcheng area, Jiangxi Province.3.2 Re-Os同位素数据分析
本文以植硅石岩为研究对象，得到了较好的Re-Os同位素等时线，说明样品具备以下条件：①同源性。187Os/188Os初始值相同，成矿物质的来源保持一致；②同时性。矿物矿石形成年龄大致相同；③封闭性。矿物矿石形成后，Re-Os同位素体系较为封闭，后期成岩作用很难使其发生同位素分馏［23］，能很好地保持成岩过程中的原始信息，即Re-Os等时线年龄可以代表岩石的沉积年龄。研究结果表明Re-Os同位素定年对植硅石岩这类陆相沉积岩具有适用性。
从187Os/188Os值(表2)可以看出，灰岩、黑色页岩以及碳质泥岩等富有机质样品的比值一般小于1，而石墨、沥青等富有机质地质样品的187Os/188Os值虽大于1，却被认为只是其变质过程中Re-Os同位素体系发生重置重新计时的结果［24-25］。与石墨、沥青不同，植硅石岩的岩性特征显示其主要为生物沉积成岩，区内偶见的玄武岩对植硅石岩影响甚微，未发生明显的热变质作用，因此Re-Os同位素等时线年龄可以代表植硅石岩成岩年代。
表 2 富有机质地质样品及各种不同储库中的187Os/188Os初始值Table 2. Data of initial 187Os/188Os of various organic-enriched geological samples and geochemical reservoirs.4. 讨论
4.1 Re-Os同位素年龄与沉积时代的对比
始新世中晚期是全球气候条件从温室向初始冰室过渡的重要时期(约33～49Ma)，在此期间出现如中始新世气候适宜期(MECO)［31-32］这样突然而短暂的变暖事件。同时受东亚季风的影响，更多的湿气自太平洋输送至中国东部，东部地区变得温暖而湿润［33］。而前人对清江盆地的孢子花粉研究发现，与古新世地层中出现大量麻黄粉［34］所反映的干旱古气候环境不同，始新世中晚期地层中出现的亚热带、热带植物的孢子、花粉指示古气候开始变得温暖而湿润［35-36］，这种温暖、湿润的气候为区内单子叶植物生长提供了有利条件，繁茂的单子叶植物年复更替的生长与死亡则为植硅石的形成提供了物质来源。在晚白垩世至古近纪，东亚地区发生了太平洋板块俯冲和华南板内构造变形［37-38］，华夏系主干断裂的活动造成丰城地区自古新世开始抬升，该构造事件致使连为一体的清江盆地、鄱阳盆地分隔开，造成了清江盆地逐渐发展为封闭的闭流盆地［34］。梁兴等［39］将清江盆地、鄱阳盆地发育的古近纪地层划分为清江组(E1q)、新余组(E2x)或临江组(E2-3l)。
植硅石可以在地层中保存数百万年之久，研究表明目前植硅石多出现在古近纪及更晚时代的地层中［2］，最早则出现在晚白垩世地层［40］。通过比对清江盆地、鄱阳盆地相似层位的岩石组合以及沉积环境，本文认为石炉坑组(E2s)与区内同属湖相沉积的临江组(E2-3l)具有相似之处，应与临江组(E2-3l)下部并齐。而临江组(E2-3l)地层的沉积年代学研究中，在岩层中发现的包括Taxodiaceae pollenites(杉粉)以及非海相腹足类化石的组合［41］均指示其沉积时代应为古近纪始新世。综合区域地质环境、相似层位沉积时代以及植硅石岩的Re-Os年龄的讨论结果，可以认为石炉坑硅碳矿床的成岩成矿时代应为古近纪始新世。
4.2 海相沉积岩中Os来源及沉积环境
海相沉积岩中的Os主要来自于海水，影响海水Os组成的端元组分主要有(表2)：河水带入的陆源Os(187Os/188Os值约为1.4)、海底热液输入的幔源Os(187Os/188Os值约为0.127)以及宇宙尘埃带来的Os(187Os/188Os值约为0.12)。不同来源的Os共同影响海相沉积岩中Os的组成，通过分析比对187Os/188Os值，可以有效地示踪沉积时的物源，并进一步为古环境研究等方面提供证据。
本文对石炉坑硅碳矿的植硅石岩开展Re-Os同位素示踪研究显示，植硅石岩样品的187Re/188Os值较高，7件样品的187Re/188Os平均值为525.1。较高的Re/Os分异不仅与沉积环境有关，也可能与沉积地层生物的类型具有相关性。李超等［5］认为Re受风化作用影响明显比Os大，更多的Re会丢失随雨水进入河流。Danish等［42］研究了印度吉尔卡湖(泻湖)的沉积物中Re含量的影响因素，发现Re含量与Mg、Al元素及TN(总氮)含量具有正相关性，并认为其中60%的Re通过黏土吸附；其余40%的Re通过生物活动作用吸附，且主要在植物的细胞膜形成过程中通过氨基酸吸附。植硅石岩的沉积环境及生物沉积成因则进一步解释了岩石具有Re/Os高分异的原因。
植硅石岩的187Os/188Os初始值(1.713±0.0036)远高于海底热液、宇宙尘埃的Os同位素比值，也高于现代海水的187Os/188Os值(约1.06)以及河流的Os同位素比值(约1.4)。Georgiev等［43］研究认为黑色页岩中的Os高含量和较高的迁移率可以显著提升海水的187Os/188Os高值，特别是上二叠纪至始新世早期页岩具有较高的187Os/188Os值(＞10)，该时期岩石的侵蚀可以显著提升海水的187Os/188Os值。Lúcio等［44］研究了Araripe盆地的Ipubi地层黑色页岩，认为其较高的187Os/188Os初始值(1.75～2.054)可能与该盆地为一个高度受限的水团有关。而区内石炉坑组(E2S)与下部茅口组(P2m)不整合接触，并缺失中生代的海相地层(图2)，缺失地层岩石可能具有较高的187Os/188Os值。因此，前文所述区内的构造运动不仅导致岩石风化作用增强，也造成了封闭的闭流盆地环境，共同推动了陆源Os输入，并进一步提高植硅石岩的187Os/188Os值。
4.3 Re-Os同位素赋存机制及适用性原因
Re、Os同位素体系应用于富有机质样品的主要原理是［5］：在氧化条件下，海水中的Re、Os分别以$\mathrm{ReO}_4^{-} $、$\mathrm{HOsO}_5^{-} $形式存在并易于迁移。在还原条件下，$\mathrm{ReO}_4^{-} $会被还原成较难溶解的组分被有机物吸附，高价态的Os则被还原为活动性很弱的低价形式富集。不同学者在Re、Os同位素的富集机制研究中认为，Re、Os同位素的富集主要与还原环境、富有机质等条件紧密相关［3，28，45-46］。植硅石岩中Re、Os同位素平均含量较地壳丰度高出两个数量级［47-48］，指示植硅石岩在成岩成矿过程中对Re、Os同位素存在明显富集作用。而植硅石岩主要是由生长在温暖湿润环境下的单子叶草本植物，年复更替地生长、死亡并在原地堆积，植物细胞内腔或细胞之间沉淀堆积的难容的硅酸以及炭质被保存在原地，经压实作用形成［11］，同期较平静的湖相沉积环境也提供了较好的还原条件。据此，本项目组认为矿区植硅石岩中Re、Os同位素赋存富集机制是：湖水中大量植物死亡后形成的沉积物，在微生物作用下产生大量有机质。在此富有机质的还原沉积环境下，$\mathrm{ReO}_4^{-} $被还原成较难溶解的组分，$\mathrm{HOsO}_5^{-} $也被还原发生富集作用，被有机质吸附并随着植物细胞内腔或细胞之间沉淀堆积的难溶硅酸一起淀积。
关于Re、Os同位素在植硅石岩中的适用性原因，主要有两点：一是体系的封闭性问题。Re-Os同位素体系的封闭性与稳定性是能否得到成功应用的决定性因素［49］。植硅石具备稳定的硅氧结构，具有耐高温、耐腐蚀的特性，在形成过程中会包裹C、H、O、N等多种元素。受特殊结构的保护，这些包裹的元素才得以长期封存［50］。其中，植硅石中的有机碳主要赋存于植硅石的微小空腔中［51］，而有机碳因封存其中未与外界发生交换，进而为测年提供了有利条件。因此，植硅石岩的Re、Os同位素在赋存富集过程中，随有机碳吸附并封存在植硅石中，进而有效地避免了Re、Os的流失并保障了体系的封闭性与稳定性；二是Re、Os在主要矿物中的富集含量问题。刘桂建等［52］通过分析测定淮北煤田中煤的Re、Os含量，因含量低于检出限未能成功获取年龄数据。在以往植硅石的测年研究中，植硅石含量和提取也制约了相关的测年研究，前人认为因考古地层中含量高、较易提取，自然地层中的钻孔样品难以满足其需要，导致植硅石作为非常规的测年材料在考古方面运用多于自然地层的主要原因［2］。植硅石岩为植硅石沉积而成，在植硅石含量和提取中具有得天独厚的条件，样品中植硅石的数量优势扩大了植硅石中的有机碳及吸附Re、Os同位素的含量，进而被分析仪器成功检出。
5. 结论
在前人研究的基础上，结合区内地质背景、矿区(床)地质特征等方面研究，通过对丰城石炉坑硅碳矿床植硅石岩样品采样并进行Re-Os同位素测试，获得Re-Os同位素年龄为43.1±3.7Ma，认为该矿床的成岩成矿时代为古近纪始新世。本研究成功获取了植硅石岩的Re-Os等时线年龄，为该矿成矿年代学研究提供了直接、准确的年代学依据，对于Re-Os同位素体系在湖相沉积岩中的成功运用，不仅增加了植硅石的有效测年方法，也拓展了Re-Os同位素定年体系在沉积岩中的运用范围。
植硅石岩的Re、Os同位素研究有待深入，特别是亟需加强对Re、Os同位素来源、富集机制以及对测试结果的影响因素等方面的研究，从而扩大植硅石的测年范围并进一步推动Re、Os同位素定年体系的发展。
致谢：感谢江西省地质局能源地质大队石晓燕工程师、朱强工程师，江西理工大学王平教授在论文资料等方面提供的帮助。
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图 1 在线加标ICP-MS测量方法平台示意图(实验室搭建)
Figure 1. Schematic diagram of the ICP-MS measurement method platform based on online-standard-addition. The platform was in-house set up based on an auto-sampler and two peristaltic pumps. The digested sample solution (③) was introduced from B tube continuously by using a peristaltic (④) to a T-joint (⑤) in which the sample solution from B and a series of standard solutions (②) from A tube using an auto-sampler (①) were mixed thoroughly. After that, the mixed solutions were introduced through nebulizer (⑥)and rotary spray chamber (⑦), ionized in the plasma (⑧), and then introduced to mass spectrometry (⑨) for analysis.
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图 2 不同管路进样的元素(按质量数排序)离子强度比较：(a)离子强度值；(b)离子强度比值
Figure 2. Comparison of signal intensities of elements or ratios of signal intensities by using different pipelines for sample injections. The elements shown were in order of mass numbers shown in Section 2.1. The intensities of elements for sample injection from A (or B) tube represent the intensities that the standard solution with nominal mass fraction of 20ng/mL was introduced from A (or B) tube，and at the same time the blank solution (2% HNO3) was introduced from B (or A) tube，shown in Fig.2(a). For the simultaneous sample injection means that the 20ng/mL standard solution was introduced from A and B tube at the same time. The intensities of elements for simultaneous sample injection were compared with the sum of the intensities using A tube and B tube sample injection, respectively, shown in Fig.2(a). The ratio of intensity using A tube injection to the intensity using B tube injection was about 1.5 for each element, indicating the difference of injection flow for A and B tube, shown in Fig.2(b). The ratio of intensities for simultaneous sample injection to the sum intensities of A and B injection respectively was about 1, shown in Fig.2(b).
表 1 在线加标ICP-MS法检出限、精密度、标准曲线线性方法学参数
Table 1 Methodological parameters for ICP-MS method based on online-standard-addition. The method detection limit (MDL) was evaluated based on the 3σ criterion. The precision was represented by the relative standard deviation (RSD) of 6 repeated measurements. The linearly dependent coefficient r was evaluated based on the concentration range of 0-500ng/g.
元素 检出限
(μg/g)RSD
(%，n=6)线性相关系数
r元素 检出限
(μg/g)RSD
(%，n=6)线性相关系数
rB 0.44 3.3 0.9566 Zn 0.10 2.2 0.9999 Na 0.19 1.7 0.9998 Ga 0.004 3.3 0.9998 Mg 0.17 3.9 0.9995 As 0.10 3.5 0.9997 Al 0.25 0.8 0.9999 Sr 0.013 2.0 0.9997 Si / / 0.7839 Zr 0.075 2.0 1.0000 P 0.32 1.3 0.9986 Nb 0.057 6.1 0.9999 K 0.90 3.9 0.9998 Cd # # −0.3704 Ca 0.16 3.2 0.9998 Sn 0.018 1.8 0.9986 Ti 0.12 1.1 1.0000 Sb 0.054 1.1 0.9905 V 0.018 2.6 0.9999 Ba 0.071 3.9 0.9998 Cr 0.033 2.0 0.9997 Hf 0.023 3.8 0.9990 Mn 0.046 1.7 0.9999 Ta 0.059 2.9 0.9985 Fe 0.18 1.4 0.9999 W 0.12 2.0 0.9999 Co 0.014 1.6 0.9999 Pb 0.021 3.4 0.9997 Ni 0.080 1.0 0.9998 Bi 0.012 2.7 0.9997 Cu 0.10 3.0 0.9995 注：“/”表示对于Si元素，由于空白值较高，故未列出检出限及RSD数据；“#”表示对于Cd元素，由于MoO及MoN的干扰在非基体分离条件下无法去除，故未列出检出限及RSD数据。 
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表 2 在线加标ICP-MS法方法验证
Table 2 Method validation for ICP-MS method based on online-standard-addition. The calibrated values were calculated based on the measured values multiplied by the intensity ratio R1. For the certified values (or nominal values), the calculated values were used based on the certified values of standard solutions and the dilution factors. The relative deviations (RDs) between the calibrated values and certified values were used to evaluate the method reliability and accuracy and calculated by using the equation: RD=(calibrate values-certified values)/certified values×100%.
元素 测量值
(ng/g)强度比值
R1*校正值
(ng/g)理论值**
(ng/g)相对偏差##
(%)B 14.1 1.48 20.9 20.6 1.8 Na 13.2 1.60 21.0 21.6 −2.5 Mg 14.4 1.52 21.9 21.6 1.3 Al 13.8 1.54 21.3 21.6 −1.5 Si 79.5 1.12 88.8 20.6 /＆ P 13.3 1.59 21.1 20.6 2.8 K 13.5 1.54# 20.8 21.6 −3.5 Ca 18.2 1.57 28.6 21.6 32.0 Ti 12.9 1.60 20.7 20.6 0.5 V 13.8 1.58 21.7 21.6 0.6 Cr 13.6 1.56 21.2 21.6 −1.7 Mn 13.5 1.63 22.0 21.6 2.1 Fe 13.2 1.62 21.4 21.6 −0.9 Co 12.8 1.67 21.4 21.6 −0.8 Ni 14.4 1.58 22.7 21.6 5.1 Cu 13.0 1.66 21.5 21.6 −0.4 Zn 15.2 1.60 24.3 21.6 13.0 Ga 13.5 1.61 21.8 21.6 0.9 As 14.1 1.55 21.7 21.6 0.8 Sr 13.9 1.53 21.2 21.6 −1.8 Zr 13.4 1.52 20.4 20.6 −0.9 Nb 12.9 1.52 19.6 20.6 −4.6 Cd 17.6 1.51 26.5 21.6 /＆ Sn 16.1 1.50 24.1 24.3 −0.7 Sb 15.7 1.59 25.0 24.3 2.8 Ba 14.0 1.50 21.0 21.6 −2.5 Hf 16.8 1.50 25.3 24.3 4.2 Ta 13.5 1.53 20.5 20.6 −0.1 W 13.3 1.50 19.9 20.6 −3.4 Pb 13.8 1.46 20.1 21.6 −6.8 Bi 14.3 1.48 21.1 21.6 −2.1 注：“*”表示R1为标准进样管(A管)与样品进样管(B管)相同浓度溶液信号强度比，为流量差异校正因子； “**”表示理论值为标准溶液稀释(500倍)后计算得出的浓度值，标准物质原浓度为10mg/kg，扩展不确定度为3(k=2)； “#”表示采用其他元素的比值平均值；“＆”表示对于111Cd，由于受到95Mo16O的干扰，因此采用简单酸基体溶液难以评估其可靠性，故未列出相对偏差；对于Si，由于使用氢氟酸导致测量空白严重偏高，故未列出相对偏差；“##”通过公式计算：(校正值-理论值)/理论值×100%。
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表 3 在线加标-ICP-MS法与同位素稀释质谱法的测量结果比较
Table 3 Comparison of the measurement results by using ICP-MS method based on online-standard-addition and using isotope dilution mass spectrometry, respectively. The relative standard deviations (RSDs) and standard deviations (SDs) of 4 repeated measurements were listed for each element.
元素 含量测定值(μg/g) 在线加标ICP-MS法* RSD
(%)同位素稀释质谱法* RSD
(%)Si / / 24.8±1.5 6.0 K 87.4±2.8 3.2 87.7±0.8 0.9 Cr 50.1±0.9 1.8 50.4±0.7 1.4 注：“*”表示平均值±SD(n=4)；“/”表示由于采用氢氟酸消解，Si空白较高，故未列出测量结果及RSD数据。
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表 4 纯钼粉标准物质候选物样品中杂质元素测量结果
Table 4 Measurement results of impurity elements in high purity molybdenum powder reference material candidate sample by using ICP-MS method based on online-standard-addition. The relative standard deviations (RSDs) of 4 repeated measurements were listed.
元素 含量测定值
(μg/g)RSD
(%，n=4)元素 含量测定值
(μg/g)RSD
(%，n=4)B ＜1.5 / Zn ＜0.3 / Na 73.4 5.7 Ga 0.4 46 Mg 85.1 1.8 As 1.2 24 Al 18.1 1.3 Sr 17.8 3.4 Si / / Zr 16.4 3.0 P 83.3 1.9 Nb ＜0.2 / K 87.4 3.2 Cd / / Ca 18.6 7.0 Sn 171.2 2.6 Ti 99.6 2.2 Sb 150.1 2.9 V 17.7 3.4 Ba 18.2 3.0 Cr 50.1 1.8 Hf 16.7 1.4 Mn 178.4 1.5 Ta 19.4 1.7 Fe 122.5 2.8 W 18.7 5.1 Co 20.2 0.9 Pb 1.5 9.4 Ni 31.6 0.6 Bi 1.5 10 Cu 199.2 1.5 / / /
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