首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 453 毫秒
1.
王瑞敏 《岩矿测试》2011,30(3):295-298
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。  相似文献   

2.
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。  相似文献   

3.
辉钼矿的铼-锇同位素地质年龄测定方法研究   总被引：234，自引：27，他引：234  
本研究在国内首次将同位素稀释等离子体质谱法应用于铼-锇同位素系统地质年龄测定。建立的化学分离方法包括碱熔分解样品、丙酮萃取分离铼、 蒸馏法分离锇。全流程化学回收率在90％以上。铼和~(187)Os的空白值分别为0.07ng和0.01ng。用本法测定了我国4个钼矿床的辉钼矿矿化年龄,其年龄测定精度(2σ)在3％以内。测定结果与地质背景的符合情况令人满意。直接测定金属矿床年龄的铼-锇法较之间接测定围岩时代来推断矿化年龄的其它定年方法更能反映真实年龄。鉴于许多热液硫化物矿床常含有辉钼矿,该法有较广泛的应用前景。  相似文献   

4.
Carius管直接蒸馏快速分离锇方法研究   总被引：18，自引：10，他引：8  
建立了Carius管直接蒸馏快速分离锇的方法。采用一次性的常规硅胶管和细聚四氟乙烯管来封闭Carius管及作为通气管,将常规的把样品溶液转入蒸馏瓶中进行蒸馏的方法改进为从Carius管内直接蒸馏分离锇,简化了实验流程,缩短了锇的分离时间,同时节省了大量清洗蒸馏器皿的时间及清洗试剂。用电感耦合等离子体质谱法测定铼-锇同位素的模式年龄,结果表明,通气流量为30~80 mL/min时,蒸馏30 min,对铼-锇定年标准物质GBW04435(HLP)的7次测定平均值为(221.3±0.4)Ma,标准物质GBW04436(JDC)的2次测定平均值为(139.7±0.2)Ma,分别与模式年龄的标准值(221.4±5.6)Ma、(139.6±3.8)Ma在不确定度范围内一致。方法具有批量分析样品铼-锇同位素的应用前景。  相似文献   

5.
沥青样品铼-锇同位素分析溶解实验研究   总被引：4，自引：1，他引：3  
沥青样品中Re、Os含量较低,且组成复杂,因含有大量有机质,在溶样过程中会释放大量CO2,需要大量氧化剂。控制样品称样量和氧化剂比例、用量对保证Os的回收率以及测量信号的稳定性非常重要。本文根据沥青样品组成特点改进了Re-Os同位素分析技术方法,称样量由原来的0.2 g增加到0.4 g,氧化剂由原来的3 mLHCl、6 mL HNO3改为3 mL HCl、4 mL HNO3、3 mL H2O2,改进的方法所得到Os的信号强度提高了大约2倍。考察了改变溶剂组成对不同称样量沥青的氧化效果,研究了氧化剂中加入H2O2对不同称样量沥青样品溶解效果,以及对Os的回收率和仪器测量信号强度的影响程度。采用2 mL HCl、5 mL HNO3、2 mL H2O2作为氧化剂,Carius管高温密闭溶样,直接蒸馏法或传统蒸馏法分离富集Os,丙酮萃取法分离纯化Re,用电感耦合等离子体质谱法(ICP-MS)对采自云南某铅锌矿床的沥青样品Re-Os同位素进行分析测定。沥青的Re-Os同位素等时线年龄为(60±2)Ma(MSWD=2.5,n=7),初始187Os/188Os值为4.36±0.14,表明该沥青样品中Re-Os同位素体系的封闭性较好,而且物质来源为典型的壳源性质。建立的方法能够用于沥青年龄厘定与来源示踪方面的研究。  相似文献   

6.
高艳  李大伟  常洲 《甘肃地质》2017,26(4):82-86
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。  相似文献   

7.
目前测定地质样品痕量、超痕量金常用的三种方法是活性炭吸附富集-发射光谱法、泡塑吸附富集-石墨炉原子吸收光谱法、活性炭吸附富集-电感耦合等离子体质谱法,这三种方法的检出限在0.1~0.3ng/g之间,由于矿石矿物的组成非常复杂,因此在有效富集和分离的基础上,采用合适的分析手段,能够对地质样品提供满意的分析结果。为保证试样要求的灵敏度和准确性,分析方法的选择需求应根据具体试样情况和实验室条件而定。根据田口玄一博士在测量工程学中提出的信噪比(S/N)能测量系统抗干扰能力,评价测量系统的稳健性和可靠性这一观点,本文利用田口测量质量控制理论,评价地质样品中痕量、超痕量金常用的上述三种分析测试方法,对这三种分析方法三个金标准物质的测试数据进行分类处理,计算S/N值和相对标准不确定度,通过比较三者的S/N值和相对标准不确定度值,确定更为可靠的测试体系。分析结果表明,对于地质样品中痕量金(含量大于1 ng/g)的测试,三种分析方法均能够满足要求;对于超痕量金(含量小于1 ng/g)的测试,活性炭吸附富集-电感耦合等离子体质谱法是较好的测试方案。  相似文献   

8.
砂岩型铀矿中铀的平均含量为635μg/g,而铼的含量仅为0.3~1.9μg/g,由于铼的含量低,准确测定高含量铀矿样中的低含量铼仍是分析化学的一个难题。本文建立了电感耦合等离子体质谱法测定砂岩型铀矿中痕量铼的方法。样品经过氧化镁烧结,热水浸提以及采用103Rh作内标元素等方式消除了铀、钼及其他基体元素对测定铼的干扰。在最佳条件下,痕量铼的检出限可低至0.12 ng/g,回收率达99.8%。本方法通过多种标准样品验证,铼的测定值与标准值吻合,对铼含量在0.06~180.57μg/g范围内的实际样品进行测定,相对标准偏差均小于1.5%,能够满足砂岩型铀矿等高含量铀矿中痕量铼的测定需求。  相似文献   

9.
邵坤  赵朝辉  刘卫 《岩矿测试》2014,33(1):29-33
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。  相似文献   

10.
电感耦合等离子体质谱法测定井间示踪剂中稀土元素   总被引：5，自引：3，他引：2  
以甲醇为稀释剂,用电感耦合等离子体质谱法快速测定稀土示踪剂中17个稀土元素。研究表明,在优化的稀释剂甲醇浓度为2%(体积分数)、pH<2.47的条件下测定稀土元素,方法精密度(RSD)为1.23%~2.83%,日间6次测定的精密度为2.25%~4.76%,各稀土元素线性关系良好,检出限为2.0~9.0 ng/L;17个稀土元素的加标回收率为85%~108%,满足痕量元素分析要求。  相似文献   

11.
A method was developed for the determination of platinum‐group elements (PGE) in geological samples by isotope dilution‐inductively coupled plasma‐mass spectrometry combined with sulfide fire assay preconcentration. Samples were fused and PGE analytes were concentrated in sulfide buttons. The buttons were dissolved using HCl leaving PGE analytes in insoluble residues, which were digested in HNO3 and simultaneously processed for the distillation of Os. The remaining solutions were further prepared for the purification of Ru, Rh, Pd, Ir and Pt using a tandem assembly of cation and Ln resin columns. The eluents were directly analysed by membrane desolvation‐ICP‐MS. Ruthenium, Pd, Os, Ir and Pt were determined by isotope dilution, whereas Rh was determined by conventional reference material calibration combined with 193Ir as the internal standard element. The method was validated using a series of PGE reference materials, and the measurement data were consistent with the recommended and the literature values. The measurement precision was better than 10% RSD. The procedural blanks were 0.121 ng for Ru, 0.204 for Rh, 0.960 ng for Pd, 0.111 ng for Os, 0.045 ng for Ir and 0.661 ng for Pt, and the limits of detection (3s) were 0.011 ng g?1 for Ru, 0.008 ng g?1 for Rh, 0.045 ng g?1 for Pd, 0.009 ng g?1 for Os, 0.006 ng g?1 for Ir and 0.016 ng g?1 for Pt when a test portion mass of 10 g was used. This indicates that the proposed method can be used for the determination of trace amounts of PGE in geological samples.  相似文献   

12.
In recent years, the 187Re–187Os isotope system has been increasingly used to study samples containing very small quantities of Os. For such samples, optimisation of measurement procedures is essential to minimise the loss of Os before mass spectrometric measurements. Micro‐distillation is a necessary purification step that is applied after the main Os chemical separation procedure, prior to Os isotope ratio measurements by negative‐thermal ionisation mass spectrometry (N‐TIMS). However, unlike the other separation steps, this procedure has not yet been optimised for small samples. In this study, we present a refined micro‐distillation method that achieved higher yields and allowed high‐precision R(187Os/188Os) expressed as 187Os/188Os measurements for small‐sized geological samples that contain only a few pg Os. The Os recovery in the micro‐distillation step was tested by changing the operating conditions including heating time and temperature, and amounts of oxidant and reductant. Recoveries were measured by the isotope dilution ICP‐MS method after the addition of 190Os‐enriched spike solution. We found that the most critical factor controlling the chemical yield of Os during micro‐distillation is the extent of dilution of the reductant (HBr) by H2O evaporated from the oxidant. A refined micro‐distillation method, in which the amount of oxidant solution is reduced from the conventional method, achieved an improved chemical yield of Os (~ 90%). This refined method was applied to the measurement of 187Os/188Os by N‐TIMS of varying test portions of the geological reference material BIR‐1a. The resulting 187Os/188Os ratios of BIR‐1a matched the literature data, with propagated uncertainties of 0.2, 1.1 and 11% digested sample quantities containing 150, 10 and 1 pg of Os, respectively.  相似文献   

13.
A comprehensive method for the precise determination of Re, Os, Ir, Ru, Pt and Pd concentrations as well as Os isotopic compositions in geological samples is presented. Samples were digested by the Carius tube method, and the Os was extracted by conventional CCl4 method. The Re, Ir, Ru, Pt and Pd were first subgroup separated from the matrix elements into Re‐Ru, Ir‐Pt and Pd by a 2‐ml anion exchange column. Subsequently, the Re‐Ru was further purified by a secondary 0.25 ml anion exchange column or by microdistillation of Ru using CrO3‐H2SO4 as an oxidant followed by a secondary 0.25 ml anion exchange separation of Re. The Pd and Ir‐Pt were further successively purified by an Eichrom‐LN column to completely remove Zr and Hf, respectively. Rhenium, Ir, Ru, Pt and Pd were individually measured by multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS), except for Ru after microdistillation purification was analysed by negative‐thermal ionisation mass spectrometry (N‐TIMS). The analytical results for peridotite reference material WPR‐1 agree well with the previously published data. Finally, several mafic rock reference materials including TDB‐1, WGB‐1, BHVO‐2, BCR‐2, BIR‐1a and DNC‐1a were analysed for Re‐Os isotopes and platinum‐group element concentrations to test their suitability for certification.  相似文献   

14.
Voluminous platinum-group mineral(PGM) inclusions including erlichmanite(Os,Ru)S_2, laurite(Ru,Os)S_2, and irarsite(Ir,Os,Ru,Rh)As S, as well as native osmium Os(Ir) and inclusions of base metal sulphides(BMS), including millerite(NiS), heazlewoodite(Ni_3S_2), covellite(CuS) and digenite(Cu_3S_2), accompanied by native iron, have been identified in chromitites of the Zedang ophiolite, Tibet. The PGMs occur as both inclusions in magnesiochromite grains and as small interstitial granules between them; most are less than 10 μm in size and vary in shape from euhedral to anhedral. They occur either as single or composite(biphase or polyphase) grains composed solely of PGM, or PGM associated with silicate grains. Os-, Ir-, and Ru-rich PGMs are the common species and Pt-, Pd-, and Rh-rich varieties have not been identified. Sulfur fugacity and temperature appear to be the main factors that controlled the PGE mineralogy during crystallization of the host chromitite in the upper mantle. If the activity of chalcogenides(such as S, and As) is low, PGE clusters will remain suspended in the silicate melt until they can coalesce to form alloys. Under appropriate conditions of ?S_2 and ?O_2, PGE alloys might react with the melt to form sulfides-sulfarsenides. Thus, we suggest that the Os, Ir and Ru metallic clusters and alloys in the Zedang chromitites crystallized first under high temperature and low ?S_2, followed by crystallization of sulphides of the laurite-erlichmanite, solid-solution series as the magma cooled and ?S_2 increased. The abundance of primary BMS in the chromitites suggests that ?S_2 reached relatively high values during the final stages of magnesiochromite crystallization. The diversity of the PGE minerals, in combination with differences in the petrological characteristics of the magnesiochromites, suggest different degrees of partial melting, perhaps at different depths in the mantle. The estimated parental magma composition suggests formation in a suprasubduction zone environment, perhaps in a forearc.  相似文献   

15.
The analytical performance of a method for Os isotope ratio measurement by double‐focusing, sector field ICP‐MS (ICP‐SFMS) was evaluated. The method is based on several optimised, concurrent processes: Os extraction from samples in hot concentrated nitric acid; separation of Os from the digest solution by the formation of volatile osmium tetroxide accelerated by continuous hydrogen peroxide addition; transport of analyte vapour by an oxygen flow into the ICP; and isotopic determination by ICP‐SFMS. Due to the very efficient utilisation of analyte (approaching 0.5‰), Os isotope ratio measurement could be performed at low pg levels. Combined with an ability to process sample sizes up to 2 g (up to 50 g if the organic matrix of biological or botanical samples is eliminated by ashing), materials with Os concentrations in the low, or even sub pg g?1 range could be determined by this method. Given that two complete digestion/distillation systems were available for interchangeable use, throughputs of up to fifteen samples per 8 hour shift could be achieved. The method precision, evaluated as the long‐term reproducibility of 187 Os/188Os ratio measurements in a commercial Os reference sample containing 0.5 ng Os, was 0.16% relative standard deviation (RSD, 1s). The method has been applied to perform replicate 187 Os/188 Os ratio measurements on a suite of fifty reference materials of various origins and matrix compositions, with Os concentrations varying from < 0.1 pg g?1 to > 100 ng g?1, yielding an average precision of 3% RSD. Though none of the materials tested are certified for Os content or Os isotope composition, comparison of the obtained data with published Os isotope information for similar sample types revealed close agreement between the two. The method can also be used for the simultaneous, semi‐quantitative determination of Os concentrations.  相似文献   

16.
Mineralogical studies of the heavy fraction from a Holocene pyrope-rich garnet placer deposit at Vestřev (Krkonoše Piedmont Basin, Bohemian Massif) have identified the presence of very rare grains of platinum group minerals (PGM). Pt–Fe alloy grains are accompanied by Os–Ir–Ru minerals (native osmium, iridium, and ruthenium) with inclusions of Pt–Fe alloy and hongshiite (PtCu). This mineral assemblage is typical for several mantle settings including ophiolites. The chemistry of the Os–Ir–Ru minerals shows an enrichment of the PGM in Ru, which is typical of ophiolites. The grain morphology of PGM and pyrope-rich garnet (mostly rounded with numerous euhedral/subhedral grains) does not exclude a common source. In-situ laser-ablation MC-ICP-MS was used to measure the Re–Os isotopic compositions of single Os-rich grains, which show heterogeneous subchondritic Os isotopic compositions (187Os/188Os = 0.12082–0.12505 ± 0.00003). This precludes their low-temperature origin and indicates derivation of platinum-group elements (PGEs) essentially from mantle-derived rocks without a significant contribution of crustal Os. The mantle model age (TMA) and Re-depletion model age (TRD) model ages range from ~ 0.4 to ~ 1.0 Ga and most likely reflect a long history of melt depletion that affected the mantle sources of PGM.  相似文献   

17.
For two decades, the nature of Fe‐rich, oxygen‐bearing, Ru–Os compounds found in the supergene environment has been debated. Ru–Os–Fe‐oxides and nano‐intergrowths of ruthenium with magnetite have been proposed. We applied FE‐SEM, EMPA, μ‐Raman spectroscopy and synchrotron tts‐μXRD to Ru–Os–Fe compounds recovered from Ni‐laterites from the Dominican Republic. The results demonstrate that a significant portion of Fe exists in a common structure with the Ru–Os alloy, that is, ruthenian hexaferrum. This mineral occurs both as nanoparticles and as micrometric patches within a matrix of Fe‐oxide(s). Our data suggest that supergene ruthenian hexaferrum with a (Ru0.4(Os,Ir)0.1Fe0.5)?1.0 stoichiometry represents the most advanced weathering product of primary laurite within Ni‐laterites from the Dominican Republic.  相似文献   

18.
湖南尖峰岭矿床是一个典型的花岗岩型Li、Nb和Ta稀有金属矿床,为研究花岗岩成矿作用以及指导湘南地区稀有金属找矿工作,采用XRF、ICP-MS和ISE法分析了与成矿有关的黑云母花岗岩、钠长石花岗岩及云英岩的中主量、微量元素和挥发分。结果表明:钠长石花岗岩和云英岩中的SiO_2(70.6%~84.85%)和挥发分F(2.43%~3.74%)质量分数高,富Al_2O_3(9.36%~22.99%),且A/CNK1.0,为过铝质岩石,全碱(w(Na_2O+K_2O)=1.51%~7.52%)和w(CaO)(0.1%~3.44%)变化大,w(Fe_2O_3)、w(MgO)、w(TiO_2)、w(MnO)、w(P_2O_5)较低;稀土元素组成具显著的Eu负异常和"M"型四分组效应,强烈富集Rb、Th、U、Nb、Ta元素,亏损Ba、Sr、Ti元素。花岗岩地球化学特征显示在演化过程中经历了高程度分异演化作用和岩浆不混溶作用,其挥发分F对稀有元素有明显的富集作用,并制约着熔体/流体体系的地球化学行为及其成矿效应。钠长石花岗岩和云英岩的稀有金属富集成矿受到岩浆不混溶作用、水岩反应、风化淋滤作用的共同控制。  相似文献   

19.
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.  相似文献   

20.
利用电感耦合等离子体质谱法(ICP-MS)测定植物样品中微量元素的关键技术是消除植物样品的有机基体效应,本文通过预处理方法中的酸消解体系、称样量和消解方式消除其影响。以国家标准物质灌木枝叶组合样(GBW07603)为材料进行研究,对比分析了硝酸-过氧化氢、硝酸-氢氟酸、硝酸-氢氟酸-过氧化氢3种酸溶体系的消解效果,以确定最佳酸溶体系,进而定量研究2种称样量(50 mg和100 mg)和3种消解方式(密封高压二次消解、密封高压一次消解、微波消解)的消解效果,并以In作为内标采用ICP-MS测定微量元素含量。结果表明:硝酸-氢氟酸-过氧化氢酸溶体系的消解效果最好;50 mg的测定值更接近于参考值;微波消解法的测定值明显偏低,而密封高压二次消解法是灌木枝叶样品预处理的有效方法。  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号