铂矿标准物质的核分析方法研究

针对铂矿标样基体中高铜、高镍、高硫等特点．对常规的镍锍试金预处理中子活化分析流程作了适当改进，包括铂矿样品的灼烧、调节试金配方、改变酸溶条件和仪器测试条件。流程中铂族元素的回收率均在86％以上。用南非的铂矿标准物质SARM7和我国的铜镍硫化物铂族元素标准物质975作了对照分析,结果与标准值相符。表明改进后的流程适用于同类含铂铜镍矿样品中铂族元素的测试。     

锍镍试金技术制备含铂族元素硫化物微区分析标准样品的可行性

激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)适合于直接分析硫化物矿物中痕量元素的含量及空间分布,但硫化物矿物的激光剥蚀特性与硅酸盐及氧化物不同,受到的干扰也更严重,且由于硫化物标准物质(尤其是含铂族元素、Au、Ag等贵金属元素标准物质)极度缺乏,限制了LA-ICP-MS技术在硫化物微区分析中的广泛应用。本文以贵金属标准样品GPT-9和矿石标准物质为原料合成锍镍试金扣,并封入真空管中重熔,利用背散射电子图像和LA-ICP-MS分析元素分布的均匀性,探讨真空重熔锍镍试金扣制备硫化物原位微区分析标准样品的可行性。背散射电子图像(BSE)显示真空重熔后锍镍试金扣由单相S、Ni化合物组成。LA-ICP-MS线扫描和点扫描分析表明,锍镍试金扣中S、Ni、Cr、Co、Cu、Pb、Sb、Cd、Bi等主量及微量元素分析精密度(RSD)均小于10%,均匀分布;在镍扣制备过程中Zn相对于Cu、Pb、Sb更难进入硫化物相;贵金属元素Au、Ag、Pt均一性较好,其余贵金属元素由于含量低、仪器波动及质谱干扰等影响因素造成分析数据的RSD相对较大,但可通过提高原料中贵金属元素含量、降低熔融样品淬火温度等方法进一步提高其均匀性。锍镍试金扣的组成元素对铂族元素分析的质谱干扰研究表明,重铂族元素(Os、Ir、Pt)和Au受到的干扰可忽略不计;轻铂族元素(Ru、Rh、Pd)受金属氩化物干扰较为严重,需进行干扰校正。研究认为,真空重熔技术可有效提高锍镍试金扣中各元素(包括贵金属)的均一性,达到硫化物原位微区分析标准样品的要求,利用真空重熔锍镍试金扣制备LA-ICP-MS原位微区痕量及贵金属硫化物分析标准样品具可行性。     

铂族元素中子活化分析的微型镍锍试金预富集方法研究

建立了适用于小样品(≤1g)中铂族元素分离富集的微型镍锍试金流程。讨论了试金熔剂、捕集剂的用量和比例,以及熔炼条件。化学回收实验显示铂族元素全流程回收率≥90%,分析精密度(RSD,n=6)为4.3%~7.7%。标准参考物质分析显示分析值与标准值基本吻合,表明所建立的微型镍锍试金流程是可靠的。     

中子活化分析大洋多金属结核标准物质的研究

采用中子活化分析相对＿Ｋ０法对研制的两个深海多金属结核标准物质ＧＳＰＮ＿２和ＧＳＰＮ＿３中的２６种主量和微量元素进行了定值测定，所得结果与初定值符合；对中子辐照自屏蔽效应进行了实验测定和理论计算，结果显示了很好的一致性；同时还对这两个多金属结核标准物中的Ａｓ、Ｂａ、Ｃｅ、Ｃｏ、Ｅｕ、Ｆｅ、Ｌａ、Ｌｕ、Ｍｎ、Ｍｏ、Ｎａ、Ｓｂ、Ｓｍ、Ｓｃ、Ｔｈ、Ｙｂ和Ｚｎ的取样量与取样误差关系进行了研究。结果表明，在ＧＳＰＮ＿２和ＧＳＰＮ＿３试样中分别有８种和１１种元素，在取样量１０ｍｇ时其取样误差小于１％。     

深海沉积物及多金属结核中微量元素的光谱测定

用全燃烧法一次曝光发射光谱同时测定了大洋深海沉积物和多金属结核中多个微量元素；重点考察了缓冲剂和分析条件的优化，解决了大洋试样吸湿性强、光谱相互干扰多及激发时易喷溅等问题。所测项目有Ｂ、Ｂａ、Ｂｅ、Ｃｏ、Ｃｒ、Ｃｕ、Ｇａ、Ｌａ、Ｍｏ、Ｎｂ、Ｎｉ、Ｐｂ、Ｓｃ、Ｓｒ、Ｔｌ、Ｖ、Ｙ、Ｙｂ、Ｚｎ和Ｚｒ共２０项。用国家一级深海标准物质对方法进行检验，所得结果与标准值相符，相对标准偏差（ｎ＝３０）大多在１０％左右。方法用于新研制的大洋标准物质ＧＳＭＳ＿２，３和ＧＳＰＮ＿２，３定值分析，结果与初定值符合。     

原子吸收法测定大洋沉积物中多种金属元素

应用火焰原子吸收法对大洋沉积物中的Ｆｅ、Ｍｎ、Ｃｕ、Ｃｏ、Ｎｉ、Ｐｂ、Ｚｎ、Ｃａ、Ｍｇ、Ｋ、Ｎａ、Ｃｒ和Ｒｂ１３个元素进行直接测定，对测试工作条件、介质、酸度和共存元素干扰等方面进行了综合考察。各元素测定的ＲＳＤ（ｎ＝１０）≤１２％，经标准物质分析验证，结果与标准值相符，应用此法为待定值大洋沉积物标样ＧＳＭＳ＿２和ＧＳＭＳ＿３提供了定值数据，结果与初定值相符     

微型核反应堆中子活化分析测定地质样品中铂族元素

采用镍铳试金预富集微型核反应堆中子活化分析测定地质样品中铂族元素，方法检出限低，ＲＳＤ〈１０％。     

四川盐边冷水箐岩体铂族元素的中子活化分析

四川盐边冷水箐岩体铂族元素的中子活化分析李晓林，汪云亮，肖庆帘（成都理工学院，成都６１００５９）关键词铂族元素，中子活化分析，镍锍试金为在川西地区寻找超大型硫化Ｃｕ－Ｎｉ－Ｐｔ矿床，需要对比剖析一些有关岩体。冷水箐岩体是研究对象之一。准确测定其铂族元...     

锍镍试金-等离子体质谱法测定地球化学勘探样品中的铂族元素和金Ⅰ．分析流程的简化

报道了一个改进的锍镍试金一等离子体质谱测定铂族元素和金的分析流程，用封闭溶解贵金属硫化物滤渣与同位素稀释法测锇相结合，解决了包括锇在内的全部铂族元素和金的测定，避免了锇的蒸馏分离和（或）单独测定，简化了分析流程，以适应大批量化探样品的要求，用所拟方法分析了标准物质中铂族元素和金，其结果与参考值相符。     

锍镍试金富集-等离子体质谱法测定西太平洋富钴结壳中的铂族元素

根据西太平洋麦哲伦海山富钴板状结壳样品的成分特征，对常规的锍镍试金配方作了改进；酌情减少捕集剂羰基镍的加入量，可显著降低铂族元素的空白值。富集后的样品，采用电感耦合等离子体质谱测定铂族元素（PGE）。其中，Ru、Rh、Pd、Ir和Pt用常规外标法测定，^175Lu作内标；Os用同位素稀释法测定。用国家一级标准物质GBW07290和GBW07291作监控分析质量的参考样，结果满足要求。     

Improved Platinum-Group Element Extraction by NiS Fire Assay from Chromitite Ore Samples Using a Flux Containing Sodium Metaphosphate

Many chromite-rich rocks contain relatively high concentrations of the platinum-group elements (PGE). In many cases, the phases carrying PGE occur as either platinum-group minerals (PGM) or as base metal sulfides in solid solution in sulfides. In some cases, such as the UG-2 unit of the Bushveld Complex, the PGM are occluded inside chromite grains. Chromites are notably difficult to dissolve in most fluxes and if the chromite contains some PGM the possibility exists that not all the PGE will be recovered during fusion. In this work, shortcomings in published methods of analysis based on the nickel sulfide fire assay procedure were investigated and a new procedure developed based on the addition of sodium metaphosphate to the fusion mixture. Optimum composition of the fusion mixture was found to be 10 g sodium metaphosphate and 9 g silica to 10 g sample, 15 g sodium carbonate, 30 g lithium tetraborate, 7.5 g nickel and 4.5 g sulfur to achieve complete dissolution of chromite grains. The new flux mixture was evaluated by the analysis of reference material CHR-Pt+ (which is known to contain PGM inside chromite grains) and no undissolved chromite grains were found in the glassy slag. Analysis of the nickel sulfide beads from this fire assay using neutron activation analysis showed similar results for Rh and Ru when compared with published conventional true (or accepted) values, while Au, Ir, Os, Pd and Pt values determined here were 10 to 30% higher than the corresponding published conventional true values. It was concluded that the addition of sodium metaphosphate improved chromite dissolution in the flux and appears to improve PGE recovery.     

Determination of the Platinum-Group Elements and Gold in Twenty Rock Reference Materials by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) after Pre-Concentration by Nickel Sulfide Fire Assay

The platinum-group elements (PGE) and gold have been determined in twenty international rock reference materials by inductively coupled plasma-mass spectrometry (ICP-MS) after pre-concentration by a nickel sulfide fire assay. It was possible to achieve determination limits for a 50 g sample that ranged from 1 pg g^-1 (Rh) to 23 pg g^-1 (Au). Compared to published certified and recommended values for rock reference materials, the trueness of the method was found to be good. However, in some cases we observed large deviations for all elements in the sub 10 ng g^-1 range within individual reference sample splits. Our results show that the PGE and Au are inhomogeneously distributed in the reference materials analysed here, where they are present in low concentrations, using 50 g test portions.     

New Progress on Certified Reference Materials for Platinum-Group Elements: IGGE GPt-8, GPt-9 and GPt-10

Three new certified reference materials (CRM), certified for the platinum-group elements (PGE), GPt-8, GPt-9 and GPt-10 were developed based on the previous CRMs IGGE GPt-1 to GPt-7. The PGE concentration of GPt-8 is about 1 ng g^-1. GPt-9 and GPt-10 are ore samples with PGE concentrations of more than 1 μg g^-1. A multi-laboratory collaborative analysis scheme was adopted in the certification procedure, in which nine highly-experienced institutes and laboratories participated. The samples were analysed for the six platinum-group elements by nickel sulfide mini fire assay, with Te coprecipitation, and were determined by ICP-MS. Osmium was determined by isotope dilution.     

北大别白垩纪镁铁－超镁铁岩的铂族元素地球化学研究

采用镍锍火试金法结合ICP-MS分析了12个北大别白垩纪镁铁-超镁铁岩样品的Ir,Ru,Rh,Pt和Pd的含量,结果显示铂族元素（PGE）的含量较低,原始地幔标准化后的PGE分布模式呈正斜率型,PPGE相对原始地幔略微亏损,而IPGE强烈亏损,Pd/Ir值远高于相应的地幔比值。这些镁铁-超镁铁岩中PGE的强烈分异是地幔低程度的部分熔融过程中,PPGE主要受硫化物控制,而Ir则存在于非硫化物相如尖晶石,可能还有合金之中造成的。同时,铂族元素的分布特征表明这些镁铁-超镁铁岩是岩浆结晶分异的产物。     

Comparison of Recoveries by Lead Fire Assay and Nickel Sulfide Fire Assay in the Determination of Gold/ Platinum/ Palladium and Rhenium in Sulfide Ore Samples

We compared the recovery of gold, palladium and platinum by two fire assaying procedures, using nickel sulfide and lead as collectors. The presence of appreciable amounts of sulfide minerals in the sample caused interferences in both procedures. An in-house reference sample, a reference sample of high-grade sulfide ore and samples of high sulfide content from the Recsk porphyry copper ore in Hungary were analysed by both methods. The elements were determined by inductively coupled plasma-atomic emission (ICP-AES) and/or inductively coupled plasma-mass spectrometry (ICP-MS). It was found that for the sulfide ore samples, the recoveries of Au and Pd are sometimes lower by nickel sulfide fire assay than by lead fire assay. Recovery of Re by nickel sulfide fire assay was found to be low: the average recovery of five repeated analyses of the reference sample NIST SRM 330 was 9% with a relative standard deviation of 48%. Increasing the amount of S in the fusion flux gave better recovery.     

陕西太白金矿含金角砾岩中铂族元素特征

采用硫镍火法试金(NiS-FA)结合电感耦合等离子质谱(ICP-MS)分析了太白金矿硫化物和含金角砾岩中铂族元素的含量,结果显示,与秦岭地区八卦庙相比铂族元素含量较高,而低于原始地幔,其中铂(Pt)、钯(Pd)、钌(Ru)富集,并结合前人研究资料对铂族元素的来源和迁移机制进行探讨。铂族元素可能受深源的影响,IPGE(Ir、Os、Ru)可能主要以硫化物形式存在而PPGE(Rh、Pt、Pd)可能主要以单质存在。     

COMPARISON BETWEEN THE USE OF SODIUM AND LITHIUM TETRABORATEIN PLATINUM-GROUP ELEMENT DETERMINATION BY NICKEL SULPHIDE FIRE-ASSAY

The alternative use of lithium tetraborate and/or sodium tetraborate as flux constituents in the quantitative determination of platinum group elements (PGE) in standard reference materials SARM-7, CHR-Pt+ and CHR-Bkg by graphite furnace atomic absorption spectrometry after preconcentration by nickel sulphide fire assay was reinvestigated. Results showed that lithium tetraborate has a lower recovery rate than sodium tetraborate, except for chromitites with PGE abundances in the ppm-range. Best results for chromitites were obtained by using a mixture (1:1) of the two tetraborates. Examination of the NiS-reguli by an electron microprobe revealed finer grain-sizes of PGE-phases for lithium tetraborate and coarser ones for sodium tetraborate, the finer grains being a possible reason for greater losses during analysis filtration.