锍镍试金-电感耦合等离子体质谱法测定硫铁矿中铂族元素

锍镍试金常用于富集常规地质样品中的铂族元素(PGEs);而用于富集硫铁矿中的PGEs鲜有报道。硫铁矿中硫和铁的含量较高,采用常规的试金配方不能得到较好的锍扣,影响下一步样品的溶解和过滤。本文对锍镍试金-电感耦合等离子体质谱法测定硫铁矿中PGEs的流程进行改进。针对硫铁矿中硫和铁含量高的特点,在不减少称样量的情况下,调整常规锍镍试金中的试剂配方,获得了理想的锍扣和熔渣,使锍扣富集PGEs的能力达到最佳,且避免了由于反应时间过长而造成PGEs损失。同时利用硫化铁易剥落和粉化的特点,省去了锍扣的机械粉碎工序,简化了流程,避免了碎扣时的机械损失和样品间可能的交叉污染。结果表明,高含量的铁对PGEs的测定无显著影响。加标回收试验显示PGEs全流程回收率大于94%。按10 g取样量计算,方法检出限分别为Ru 0.018 ng/g,Rh 0.017ng/g,Pd 0.18 ng/g,Os 0.019 ng/g,Ir 0.013 ng/g,Pt 0.11 ng/g。实际样品分析和加标回收试验表明,改进后的锍镍试金-电感耦合等离子体质谱测定流程可以满足大多数硫铁矿中PGEs的测定要求。     

锍镍试金富集-等离子体质谱法测定煌斑岩中铂族元素

试金配料中适量加入铁粉,控制硫化铁在锍扣中的含量在20%~40%,获得的锍扣直接用水浸泡粉化后加盐酸分解,分解结束后趁热过滤,沉淀用1mL王水溶解,定容后上机测定,Cs作内标。改进后的方法空白水平进一步降低,检出限得到显著改善,分析流程简化。采用改进后的锍镍试金富集-等离子体质谱法测定了云南哀牢山金矿带煌斑岩和国家一级标准物质GBW 07288(GPt-1)、GBW 07290(GPt-3)中的铂族元素(PGEs)含量,方法检出限为0.001~0.01ng/g,精密度(RSD,n=5)为7.49%~16.6%。     

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。     

锍镍试金富集—等离子质谱法测定地质样品中的金铂钯铑铱钌

建立了锍镍试金富集—电感耦合等离子质谱法测定地质样品中金铂钯铑铱钌的方法。研究了富集时各种实验因素的影响,样品用琉试金富集,盐酸处理锍镍扣,碲共沉淀富集,过滤,沉淀用王水溶解,ICP-M S测定。方法检出限:A u为0.11、P t为0.050、Pd为0.028、R h为0.018、Ir为0.013、R u为0.02,相对标准偏差(n=12),A u为8.25%、P t为4.76%、P t为4.97%、R h为5.63%、Ir为5.38%、R u为6.81%。经国家一级地球化学标准物质验证,铂族元素和金的测定值与标准质相吻合。     

锍镍试金富集-电感耦合等离子体质谱法测定铜阳极泥中微量元素铱铑

铜阳极泥富集了矿石、精矿或熔剂中绝大部分贵金属(如铱和铑),具有很高的综合回收价值。目前尚无铜阳极泥中铱和铑检测标准,而对其中铱和铑检测方法的开发是铱铑回收提取工作的重要前提。本文建立了锍镍试金富集结合电感耦合等离子体质谱法(ICP-MS)测定铜阳极泥中铱铑的检测技术。实验中通过锍镍试金捕集试样中的贵金属铱和铑,用50%盐酸溶解锍镍扣,使得含铱和铑的沉淀物与银及其他杂质元素有效分离,趁热过滤,铱铑沉淀物和滤膜转入封闭消解罐中以50%王水为介质溶解。试液采用ICP-MS直接测定铱和铑含量。实验优化了样品预处理条件,镍硫比为4∶1,时,熔渣为酸性,熔渣流动性和渣扣分离效果好且能有效捕集试样中铱和铑;锍镍扣溶解酸度为50%盐酸时,锍镍扣溶解反应合适且溶解完全,趁热过滤,其中银、镍、铜等杂质元素大部分被盐酸除去,达到了分离含铱和铑沉淀物与银及其他杂质元素的效果;密封消解温度和时间分别为160℃、2～3h时,铱和铑消解完全;选择合适的测定同位素可以消除可能存在的质谱干扰,以¹⁹³Ir和¹⁰³Rh为测定同位素、²⁰³Tl和^...     

大洋多金属结核和深海沉积物标准物质中铂族元素的中子活化分析

采用镍锍试金预富集中子活化分析方法,测定了大洋多金属结核标准物质ＧＳＰＮ２、ＧＳＰＮ３和深海沉积物标准物质ＧＳＭＳ２、ＧＳＭＳ３中的铂族元素;根据大洋样品成分特征,对常规的镍锍试金配方和熔炼条件作了改善;计算了活化分析中的铂族元素干扰核反应,校正了Ａｕ对Ｐｔ的二级干扰;选用羰基化镍粉配料,降低了铂族元素空白值。用国家一级标准物质ＧＢＷ０７１０２作了对照分析,结果与标准值相符。     

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。     

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-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Ⅱ．分析流程空白的降低

对锍镍试金富集－等离子体质谱法测定贵金属流程中的试剂空白进行了检查，并对空白主要来源－捕集剂镍的各种纯化方法作了对比，提出了回收试金流程中溶扣后滤液中的镍循环使用。在有效降低空白的基础上，满足了化探样品所要求的0.0x ng/g级检出限，对超痕量贵金属标样分析结果与标准值符合。     

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。     

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。     

黑色页岩样品中痕量级铂族元素地球化学成分标准物质研制

介绍了黑色页岩样品中6个铂族元素铂、钯、钌、锇、铑、铱的标准物质研制过程。黑色页岩样品采自贵州黄家湾,为一次采集、一次混样的原始样品,随机抽取包装好后的样品进行检验与定值。均匀性、稳定性符合要求后,按照国际标准化组织(ISO)34、35指南的基本要求和我国一级标准物质的技术规范,采用多个实验室协同测试的定值方式,利用不同原理的分析方法对此样品的6个铂族元素进行定值。以各实验室组数据作为最小统计单元,用Grubbs准则、Dixon法检验剔除离群数据,Shapiro-Wilk法检验各元素数据分布的正态性。检验结果100%的元素呈正态或近似正态分布。定值的6个元素均符合标准值水平。     

吉林省油页岩中铂族元素的化学牲及分配规律研究

采用电感耦合等离子体发射质谱仪(ICP-MS)测定了吉林省油页岩中铂族元素的含量,并对油页岩中铂族元素的化学特征、与无机组分的相关性及其分布模式等进行了分析和阐述.通过油页岩中铂族元素的含量与地壳和中国东部出露地壳中铂族元素丰度的比较表明,Rh、Ru、Ir等元素相对富集,其中松原油页岩中Rh、Ir的含量约为地壳平均值的10倍.研究区油页岩中铂族元素以Pt-Pd分配模式为典型特征,一般Pt的丰度大于Pd.油页岩中铂族元素与无机组成相关分析的结果表明,油页岩中铂族元素可能呈吸附态存在于高岭石、伊利石等粘土矿物中.     

吉林省油页岩中铂族元素的化学特征及分配规律研究

采用电感耦合等离子体发射质谱仪(ICP MS)测定了吉林省油页岩中铂族元素的含量,并对油页岩中铂族元素的化学特征、与无机组分的相关性及其分布模式等进行了分析和阐述。通过油页岩中铂族元素的含量与地壳和中国东部出露地壳中铂族元素丰度的比较表明,Rh、RuI、r等元素相对富集,其中松原油页岩中RhI、r的含量约为地壳平均值的10倍。研究区油页岩中铂族元素以Pt Pd分配模式为典型特征,一般Pt的丰度大于Pd。油页岩中铂族元素与无机组成相关分析的结果表明,油页岩中铂族元素可能呈吸附态存在于高岭石、伊利石等粘土矿物中。     

Simulating experiment on the enrichment of precious metals in Lower Cambrian black shale series of Hunan and Guizhou provinces

Adsorption experiments were made at room temperature and neutral pH value on different types of min-erals associated with the Lower Cambrian black shale series polymetallic layers in Hunan and Guizhou provinces on nanometer-sized Pt colloids and PtCl42--bearing ionic solutions with an attempt to constrain the relationship between the different types of minerals in the polymetallic layers and the enrichment of platinum group elements (PGEs). Experimental results showed that the different types of minerals show strong selectivity to the adsorption of nano-meter-sized Pt colloids and PtCl42--bearing ionic solutions. Metallic sulfides, organic matter and clay minerals are the strong adsorbents of PGEs, while quartz, albite, muscovite and other silicate minerals show a week adsorbility to both of them. This phenomenon is well consistent with the geological fact that metallic sulfides, organic matter and clay minerals in the polymetallic layers of the black shale series are the major carrier minerals of PGEs, giving a thorough explanation to the mechanism of enrichment of previous metal elements. Adsorption may be a principal mechanism of enrichment of precious metal elements under lower temperature conditions. The presence of the aforementioned strong adsorbents is the good geochemical barriers for the enrichment of PGEs.     

Weathering characteristics of the Lower Paleozoic black shale in northwestern Guizhou Province,south China

The northwestern Guizhou in the Yangtze Craton of south China has a tremendous potential of shale gas resource. In this paper, we present results from major and trace elements, total organic carbon, mineralogical composition analysis and petrophysical parameters to characterise shale weathering features. Further, the differences of black shale between underground and outcrops have also been presented to examine the changes of black shale after weathering. Our results show that the trace elements of shale have varying degrees of loss in the weathering leaching process, both in Niutitang shale and Longmaxi shale, the loss of B, V, Ni, Cu, Zn and Ba is obvious, but the element migration quantity in the former is greater than in the latter. Decomposition of minerals such as pyrite, feldspar and calcite result in the leaching of Na, Ca, Mg and Fe. The loss rate of total organic carbon (TOC) in black shales ranges from 18% to 70% with an average of 43%; moreover, the loss of organic carbon in samples with high TOC content is larger than in those samples with low TOC content. Results following the testing of porosity and permeability show that porosity increases significantly after weathering but permeability changes little. Furthermore, the increment of porosity is greater in the Niutitang shale (with more sulphide minerals) than in the Longmaxi shale, suggesting that the oxidation of sulphide minerals may have led to the formation of an acidic environment, causing the other minerals in the black shale to weather more quickly, thus resulting in increased porosity. The content of clay minerals in the core samples is slightly lesser than the outcrop samples, but the TOC content in the core samples is greater and has a larger specific surface area. This suggest that the TOC content played a decisive role on the specific surface area of shale. In addition, changes in the black shale caused by the weathering process mainly depend on the mineral composition and the TOC content in shale. In this study, we try to establish relations between outcrop samples and core samples, in order to better understand the underground characteristics of shale reservoir.     

The geochemistry of platinum group elements in marine oil shale—A case study from the Bilong Co oil shale,northern Tibet,China

The Bilong Co oil shale zone is located in the South Qiangtang depression. This zone, together with the Shengli River-Changshe Mountain oil shale zone in the North Qiangtang depression, northern Tibet plateau, represents the potentially largest marine oil shale resource in China. Seventeen samples including oil shale and micritic limestone were collected from the Bilong Co oil shale area to determine the concentrations, distribution patterns, occurrences and origins of platinum group elements (PGEs) in marine oil shale. The oil shale samples from the Bilong Co area exhibit very low total PGE contents ranging from 1.04 to 2.96 ng/g with a weighted mean value of 1.686 ng/g, while the micritic limestone samples from the Bilong Co area exhibit a little lower PGE value ranging from 0.413 to 1.11 ng/g. PGEs in oil shale samples are characterized by high contents in Pd (average 0.79 ng/g), Os (average 0.123 ng/g) and Pt (average 0.644 ng/g) compared with Ru (average 0.068 ng/g), Rh (average 0.033 ng/g) and Ir (average 0.026 ng/g). The highest values for individual PGEs are not uniformly distributed in the section. Clearly, the PGEs are generally enriched in the oil shale samples near the boundary between micritic limestone and oil shale.The individual PGEs in oil shale samples from the Bilong Co area exhibit various modes of occurrence. Ruthenium and Pt occur mainly in pyrite, while Pd is associated mainly with organic matter and Mg-minerals. Rhodium and Os are controlled mainly by pyrite and organic matter. Iridium is present mainly in other Fe-bearing minerals, rather than pyrite. The PGEs in the Bilong Co oil shale are mainly of seawater origin and possibly influenced by terrigenous supply.     

贵州省开阳县钼镍钒矿的基本特征

本文从已有资料入手,以典型矿点为例子,结合系统的采样工作,分析了开阳县境内牛蹄塘组含矿岩系及矿床基本特征,认为开阳县境内的牛蹄塘组有两个岩石组合类型,即硅质磷块岩、炭质页岩、黄铁矿、白云岩组合和硅质磷块岩、炭质页岩组合;牛蹄塘组黑色岩系内的钼镍钒富集有一定的规律性,硅质磷块岩、炭质页岩组合中的钼镍钒含量普遍较高,钼镍矿层厚度较稳定,品位较高;并认为今后在开阳找寻钼镍钒矿的主要靶区是翁昭背斜及龙水的牛蹄塘组。