ICP-MS法测定化探样品中痕量金铂钯的富集分离方法研究

本方法用HCl和H_2O_2分解试样,以泡沫塑料富集Au、Pt和Pd,在酸性介质中解脱,用电感耦合等离子体质谱法测定化探样品中痕量金铂钯,研究了富集解脱介质及浓度。结果表明,在0.5%NaI+0.5%KBr+20%HCl介质中泡沫塑料对Au、Pt、Pd的吸附率大于95%;在1%硫脲+2%KSCN+2%HCl解脱介质中Au、Pt、Pd的回收率高于90%。方法检出限为Au 0.072 ng/g,Pt 0.17 ng/g,Pd 0.096 ng/g,标准物质的测定值与标准值基本一致,准确度和精密度满足相关规范要求,因此该方法对化探样品中痕量金铂钯的测定有一定实用性。     

混合吸附剂分离富集-电感耦合等离子体质谱法测定地质样品中铂钯金

贵金属分析应用火试金法分离富集时,试金配料复杂、耗时较长,分析成本相对较高,空白较难控制.本文建立了采用过氧化氢-盐酸湿法分解样品,电感耦合等离子体质谱同时测定地质样品中Pt、Pd、Au的分析方法.在10％的盐酸介质中,以LSC-400巯基树脂和活性炭为混合吸附剂,采用动态吸附方式对样品中的Pt、Pd、Au分离富集,用Lu作内标元素,195 Pt、197 Au、108 Pd为待测同位素消除了非谱线干扰和谱线干扰,三元素的回收率均大于96.4％.方法检出限(3σ):Pt为0.06 ng/g,Pd为0.08 ng/g,Au为0.12 ng/g,优于火试金等其他分离富集方法的检出限.应用于测定国家标准物质,Pt、Pd、Au的测定结果与标准值相符,12次测定的相对标准偏差均小于16.1％,满足区域地球化学调查样品的分析要求.该方法操作简便、成本低廉,提高了分析速度,有效地降低了测试过程的空白值.     

泡沫塑料富集-电感耦合等离子体质谱法测定土壤中超痕量金铂钯

样品采用王水溶解,二氯化锡还原,泡沫塑料富集,用Re作内标,电感耦合等离子体质谱法同时测定土壤中超痕量金、铂、钯。在盐酸-二氯化锡体系中,盐酸酸度为15%,二氯化锡浓度为45 g/L,吸附时间30 min时吸附效果明显,吸附温度为25℃时吸附率相对稳定。方法检出限Au为0.21 ng/g,Pt为0.18 ng/g,Pd为0.16ng/g,方法加标回收率Au为91.3%~97.8%,Pt为92.0%~96.7%,Pd为96.0%~101.6%。该方法用于测定国家一级标准物质,线性范围宽、重现性好,结果准确可靠,样品处理简便、快速。     

铂-钯区域地球化学勘查

以Pt、Pd作为直接指示元素，利用1：20万全国区域化探扫面水系沉积物测量副样和全国超低密度泛滥平原沉积物测量样品，采用化学光谱法测定Pt、Pd和Au三种元素，进行了中国大陆超低密度Pt、Pd地球化学填图，在川滇等地球化学省开展了1：20万Pt、Pd区域化探，发现中国大陆存在几个重要的Pt、Pd地球化学省和一些区域异常。中国大陆Pt、Pd丰度低：Pt0.42ng/g,Pd0.35ng/g，呈不均匀分布。在活动带Pt、Pd有显著富集。川滇是一个重要的铂族元素成矿省，除镁铁-超镁铁岩及在关的铂族元素矿化外，在黑色岩系以及西南暗色岩系等岩层中Pt、Pd等显著富集，并且发现了非传统类型的铂族矿化。     

DT—1016型阴离子交换树脂分离富集金铂钯

研究了DT－1016型阴离子交换树脂对超痕量Au,Pt,Pd的吸附性能及条件。在0.025mol/L HCl介质中，流出速度为0.5-1.0mL/min时，Au,Pt和Pd的富集效果最佳，吸附率分别为99.72％，99.06％和97.95％，共存离子无显著性影响。用等离子体质谱测定标准物质中Au，Pt和Pd，其结果与标准值基本相符。检出限Au为0.27μg/L，Pt为0.40μg/L，Pd为0.19μg／L。对GBW 07294铂族元素国家标准物质进行精密度试验，RSD（n=8）Au为19．2％，Pt为28.1％，Pd为15.6％。     

阴离子交换树脂-活性炭动态吸附无火焰原子吸收法测定矿石中的微量金铂钯

采用717阴离子交换树脂-活性炭分离富集矿石中的微量Au、Pt、Pd。40μg待测元素富集结果表明,Au、Pt、Pd的回收率分别为100%、95.3%和96.3%。以HC l为介质在无火焰原子吸收仪上测定。方法经对国家一级标准物质GBW 07291、GBW 07292分析检验,结果与标准值相符。对GBW 07291国家一级标准物质测定7次,其精密度(RSD)分别为:Au 9.4%、Pt 11.2%、Pd 3.0%。方法适用于矿石中10-6~10-9量级Au、Pt、Pd的测定。     

中国地质调查局郑州矿产综合利用研究所贵金属元素分析技术迈向国际

正自然资源部中国地质调查局郑州矿产综合利用研究所贵金属分析团队在学科带头人倪文山高级工程师的带领下,建立了铅试金分离富集与激光剥蚀-电感耦合等离子体质谱(LA-ICP-MS)联用技术测定地球化学样品中痕量、超痕量金(Au)、铂(Pt)、钯(Pd)的新方法,实现了固体样品前处理和直接进样技术的有效联合。该方法较传统铅试金分析方法节省了样品前处理时间,降低了Au、Pt和Pd的空白值,避免了溶液进样时大量O、     

亚硝基R盐负载树脂分离富集测定样品中的金铂钯

以亚硝基R盐作为螯合剂制备了负载树脂,研究了用该树脂分离富集Au(Ⅲ)、Pt(Ⅳ)和Pd(Ⅱ)的最佳条件。当pH为2.0时,溶液中Au(Ⅲ)、Pt(Ⅳ)和Pd(Ⅱ)的氯络阴离子被吸附富集在树脂上,吸附率94%～96%,而大部分常见的贱金属离子在上负载树脂柱前上阳离子交换柱得以分离。用0.1mol/LHCl-30g/L硫脲溶液以0.5mL/min的流速对被吸附的Au(Ⅲ)、Pt(Ⅳ)和Pd(Ⅱ)进行洗脱,洗脱率96%,最后用原子吸收光谱法进行测定。方法经标样分析验证,结果与标准值相符,对含量为10-6水平的Au(Ⅲ)、Pt(Ⅳ)和Pd(Ⅱ),6次测定的RSD分别为5.2%、8.4%和6.9%。     

离子交换分离富集无火焰原子吸收法测定岩石中痕量铂,钯,金

在10％的王水介质中,采用717阴离子交换树脂交换富集Pt、Pd和Au,与大部分阳离子分离,被吸附的Pt、Pd和Au用硫脲解脱后以无火焰石墨炉原子吸收法进行测定。方法简便、快速,检测限低。各元素的特征量分别为Pt5.8γ×10~(-11)g,Pd8.9×10~(-12)g,Au7.72×10~(-12)g。方法已成功地用于岩石矿物中痕量Pt、Pd、Au的测定。     

铜试金预富集-辉光放电质谱法测定贵金属矿样中痕量铂钯铱金

对利用铜试金预富集后辉光放电质谱法(GDMS)测定贵金属矿样中痕量Pt、Pd、Ir、Au的方法进行了探索性研究。着重考察了铜试金条件的选择和辉光放电电极的匹配、质谱的测定条件和测定方法等。分析结果表明,痕量(μg级)贵金属元素Pt的含量在1.99~15.0μg,回收率为92.0%~111.9%;Pd的含量在3.15~29.78μg,回收率为88.4%~113.3%;Ir的含量在0.12~0.60μg,回收率为68.3%~100.0%;Au的含量在10.43~24.08μg,回收率为98.9%~127.0%。方法可应用于矿石、矿物及其他物料中痕量贵金属的分析。     

阴离子树脂-活性炭分离富集等离子体发射光谱法测定富钴锰结壳中的痕量金银铂钯

采用717阴离子树脂活性炭联合交换分离富集技术,电感耦合等离子体发射光谱法同时测定富钴锰结壳中痕量金、银、铂、钯。方法检出限四元素分别为:Au1. 3、Ag0. 4、Pd0. 6、Pt4. 8ng/g。样品加标回收率在89. 0% ~110. 3%,相对标准偏差3. 5% ~7. 8% (n=4)。方法已用于富钴锰结壳中痕量金银铂钯的测定。     

NK8310螯合树脂分离富集地质样品中痕量金银铂钯及其测定

研究了硫脲螯合树脂（NK8310）分类富集地质样品中痕量Au、Ag、Pt和Pd的实验条件。在φ=10％的王水介质中，[AuCI4]^-、[AgCI2]^-、[PtCI6]^2-和[PdCI4]^2-定量吸附于树脂上并与大量贱金属分离；用5g/L硫脲－0.12mol/L HCI溶液洗脱Au、Ag、Pt和Pd，回收率为97％－104％。用硫镍矿管理样以及国家一级标准物质进行分析验证，分析结果与推荐值及标准值吻合，表明NK8310螯合树脂适用于地质样品中Au、Ag、Pt和Pd的分离富集。     

Observations on New Approaches for the Determination of Platinum-Group Elements, Gold and Silver in Different Geochemical Samples from Siberia and the Far East

Some recent experiments on the determination of Au and the platinum-group elements (PGE) in geochemical samples are reviewed. Emphasis is given to the determination of ultra-low levels of PGE concentrations in resistant matrices, including chromites, molybdenites and ultrabasic ores. The problems and features of PGE determination in samples of various chemical composition are considered. For each sample type studied, a series of sample preparation techniques are proposed. These techniques included acid digestion, fusion with sodium peroxide, cold sintering with an oxidizing mixture of Na₂O₂+ Na₂CO₃ and also oxidizing fluorination with bromine trifluoride. A new approach for preparing geochemical material prior to digestion, based on mechano-chemical activation with simultaneous hyperfine grinding, is proposed and studied. The instrumental determination of PGE contents was carried out directly by AAS from extracted organic phases. It was found that a combination of digestion processes was required to achieve geochemical background levels of Au and PGE concentrations with the following detection limits: Pd, Rh - 1 ng g⁻¹, Pt, Ru - 10 ng g⁻¹, Au - 0.2 ng g⁻¹, Ag - 0.1 ng g^−1. The uncertainty in PGE and Au determination in geochemical samples is dependent on metal concentration, and also on their distribution in samples. The total analytical uncertainty of the proposed method is between 15-30%.     

沉淀基体分离-电感耦合等离子体质谱法测定高纯硝酸银中痕量杂质元素

高纯硝酸银中痕量杂质元素的存在会影响其性能和质量,为提高现代测试技术分析痕量杂质元素的准确度,需要解决的首要问题是通过加入沉淀剂或还原剂将银除去,克服基体元素的基体效应。本文提出采用10 mL 10 g/L柠檬酸-5 g/L乙醇酸作络合保护剂,12 mL 100 g/L氯化铵作沉淀剂,建立了沉淀基体分离-电感耦合等离子体质谱同时测定高纯硝酸银中15种痕量杂质元素的分析方法。探讨了络合剂和沉淀剂浓度及用量、质谱干扰及同位素选择、非质谱干扰及内标选择、实验空白值等因素对测定结果的影响。在最佳的实验条件下,Cu、Pb、Ni、Mn、Au、Pd、Pt、Rh、Ru、Ir元素在0~100 ng/mL,Fe、Hg、Bi、Cr、Sn元素在0~250ng/mL浓度范围内呈良好的线性关系。方法检出限(3σ)为0.005~0.062 ng/g,方法精密度(RSD,n=11)为0.6%~2.6%,加标回收率为94.1%~103.1%。与现行的分析方法相比,本方法采用的络合剂和沉淀剂能将基体元素与杂质元素完全分离而不影响测定结果;实验流程简单快速,检出限低,准确度和精密度均满足了实际样品的分析要求。     

硫脲介质-石墨炉原子吸收光谱法测定化探样品中微量银

样品经王水分解,硫脲提取,石墨炉原子吸收光谱法测定化探样品中的微量银。方法检出限为0.058 ng/mL;精密度(RSD,n=6)为0.8%～5.4%;回收率为94%～105%。方法经国家一级标准物质验证,测定结果与标准值相符。     

The characteristics of automobile catalyst-derived platinum group elements in road dusts and roadside soils: a case study in the Pearl River Delta region,South China

The emission of platinum group elements (PGE) from automobile catalytic converters has led to enrichment of PGE in road dusts and roadside soils in urban areas that are well above the natural background levels. This paper evaluates the source of contamination of all the PGE and Au in road dusts and roadside soils in the Pearl River Delta region, including three major cities, Shenzhen, Guangzhou and Hong Kong, South China. Samples were digested using Carius tube and analyzed by isotope dilution ICP-MS; Os was separated by distillation and other PGE by Te-coprecipitation. All samples have elevated PGE concentrations above the background values of uncontaminated soils and contain higher Pt, Pd and Rh than other PGE. The maximum values are 181 ng/g Pt, 514 ng/g Pd, 53 ng/g Rh and 1345 ng/g Au. There are clear positive correlations between Pt and Pd, Pt and Rh, and Pd and Rh, indicating that the main emitted of PGE from automobile catalyst are Pt, Pd and Rh. High concentrations of Au were also found in road dust samples from Hong Kong and Shenzhen. Dust samples with higher Os contents have lower ¹⁸⁷Os/¹⁸⁸Os ratios. Samples from Hong Kong show relatively high Pt/Rh ratios. Positive correlations between Pt and Ru, and Pt and Ir were found in Shenzhen and Hong Kong, but only positive correlations between Pt and Ir were found in Guangzhou. These different characteristics reflect different automobile catalytic systems used in Hong Kong and mainland China.     

Comprehensive Analysis of Precious Metals in some Geological Standards by Flameless A.A. Spectroscopy

Precious metals (Ag, Au, Pt, Pd, Rh) were determined by flameless absorption atomic spectrornetry. Aqua regia sample decomposition followed by Te coprecipitation was employed to preconcentrate the precious metals in geological materials. With 5 g sample take-up, the limits of determination were 1-2 ppb for Au, Pd and Rh, 5 ppb for Ag and 10-20 ppb for Pt. These elements were determined in some geochemical standards.