能量色散X射线荧光光谱法测定卤水中痕量溴铷砷

用模拟卤水建立了能量色散X射线荧光光谱法测定卤水中溴、铷、砷痕量元素含量的方法.实验表明,方法可以直接取样测定,适用于大批量样品的测试分析.方法的精密度RSD(n＝15)小于1%,加标回收率为86.8%～101.6%.卤水中溴、铷、砷的测定结果与比色法、原子吸收和原子荧光法结果相符.     

发射光谱载体蒸馏法测定地质样品中微量硼铍锡银

选择了适合的缓冲剂,利用载体蒸馏法将被测元素与基体元素分离,使Be转变为易挥发的氟化物与B、Sn、Ag同时蒸发;降低了谱线背景及元素检出限;加入内标元素Au、Bi,提高了方法的准确度和精密度;采用普通 3mm×3mm×0.7mm杯型电极,装样量少,操作简单。方法检出限(wB/10-6)分别可达B1.5、Be0.3、Sn0.8、Ag0.02;准确度(Δlog C)基本在-0.05～0.05,精密度(RSD,n=8)为2.9%～17%。     

高倍稀释熔融制样X射线荧光光谱测定钨砂和铬铁矿中主含量

用X射线荧光光谱测定钨砂中WO3和铬铁矿中Cr2O3,通过高倍稀释熔融玻璃片制样法,采用高纯WO3或Cr2O3作单一标准样测量X射线荧光强度计数,然后同未知样品测量所得X射线荧光强度计数相比,即可计算出WO3和Cr2O3的测量值.方法用于钨砂矿和铬铁矿中WO3和Cr2O3的测定,结果与标准值相符.     

大兴安岭地区浅覆盖层对地面伽马能谱测量的影响

讨论在大兴安岭地区进行地质填图中浅覆盖层对伽马能谱测量的影响问题。通过放射性元素的取样分析、岩石—土壤的矿物分析以及实测剖面分析,得知了伽马能谱测量的影响因素,从而为应用伽马能谱测量解决地质填图中的问题提供了依据。     

Holocene calcrete crust deposits on the moraine of Batura Glacier, northern Pakistan

Abstract   Calcretes can be observed on the surface of old moraines around Batura Glacier in the upper Hunza Valley, Karakoram Mountains, Pakistan. They develop as a calcareous crust cementing small gravels under boulders. In order to understand the genesis of the calcrete crust, a variety of methods were employed: (i) study of mineralogy and geochemistry of a calcrete crust precipitated on the lateral moraine using X-ray diffractometer and electron probe microanalysis; (ii) analysis of solute chemistry of surface water and ice bodies around the Batura Glacier; and (iii) accelerator mass spectrometry ¹⁴C dating of the crust itself. The results indicate that the calcrete crust has definite laminated layers composed of a fine-grain and compact calcite layer, and a mineral fragment layer. The chemical composition of the calcite layer is approximately 60% CaO and 1% MgO. The mineral fragment layer consists of rounded grain materials up to 0.2 mm in diameter. It shows a graded bedding structure with fine grains of quartz, albite and muscovite. Meanwhile, as the Paleozoic Pasu limestone is distributed around the terminal of Batura Glacier, Ca cations dissolve in the melt water of the glacier. Accordingly, the calcrete crust is precipitated by decreases in CO₂ partial pressure from glacier ice and evaporation of the melt water, including high concentration of Ca²⁺ at ephemeral streams and small ponds stagnating between the moraine and glacial ice. On the basis of the AMS ¹⁴C age, the calcrete is considered to have formed approximately 8200 calibrated years bp under the Batura glacial stage.     

石墨炉原子吸收光谱法测定土壤样品中镉

采用磷酸氢二铵作基体改进剂塞曼扣背景石墨炉原子吸收光谱法测定土壤样品中镉，方法检出限DL=0．012μg／g，精密度RSD在3．55％～7．33％，满足了土壤样品中镉测定的镉质量要求。     

Preliminary Characterisation of New Glass Reference Materials (GSA-1G, GSC-1G, GSD-1G and GSE-1G) by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Using 193 nm, 213 nm and 266 nm Wavelengths

New glass reference materials GSA-1G, GSC-1G, GSD-1G and GSE-1G have been characterised using a prototype solid state laser ablation system capable of producing wavelengths of 193 nm, 213 nm and 266 nm. This system allowed comparison of the effects of different laser wavelengths under nearly identical ablation and ICP operating conditions. The wavelengths 213 nm and 266 nm were also used at higher energy densities to evaluate the influence of energy density on quantitative analysis. In addition, the glass reference materials were analysed using commercially available 266 nm Nd:YAG and 193 nm ArF excimer lasers. Laser ablation analysis was carried out using both single spot and scanning mode ablation. Using laser ablation ICP-MS, concentrations of fifty-eight elements were determined with external calibration to the NIST SRM 610 glass reference material. Instead of applying the more common internal standardisation procedure, the total concentration of all element oxide concentrations was normalised to 100%. Major element concentrations were compared with those determined by electron microprobe. In addition to NIST SRM 610 for external calibration, USGS BCR-2G was used as a more closely matrix-matched reference material in order to compare the effect of matrix-matched and non matrix-matched calibration on quantitative analysis. The results show that the various laser wavelengths and energy densities applied produced similar results, with the exception of scanning mode ablation at 266 nm without matrix-matched calibration where deviations up to 60% from the average were found. However, results acquired using a scanning mode with a matrix-matched calibration agreed with results obtained by spot analysis. The increased abundance of large particles produced when using a scanning ablation mode with NIST SRM 610, is responsible for elemental fractionation effects caused by incomplete vaporisation of large particles in the ICP.     

泡沫塑料吸附分离富集-电感耦合等离子体质谱法测定稀土矿石中的镓

采用电感耦合等离子体质谱法(ICP-MS)测定稀土矿石中的镓,高含量的稀土元素会造成严重的质谱干扰。本文采用聚氨酯泡沫塑料在6 mol/L盐酸介质中吸附样品溶液中的镓后,以0.5 mol/L氯化铵水浴加热解脱30 min,镓的吸附-解脱效率超过99%,稀土元素等干扰物质基本不进入解脱液中,即在富集镓的同时实现了镓与基体元素的高效分离,降低了质谱干扰。本方法检出限低(0.022μg/g),经土壤及水系沉积物标准物质验证,镓的测定值与标准值吻合(绝对偏差为0.38%~4.70%),实际稀土矿石样品的加标回收率为94.1%~100.6%,精密度(RSD)低于4%(n=12),可应用于分析一般地质样品以及稀土矿石中的镓。     

土壤样品镉同位素分析中Cd与Sn有效分离方法的改进

保证Cd的高回收率以及彻底的Sn干扰去除是获得精确镉同位素组成的前提,目前报道的多种Cd分离与纯化方法获得的Cd回收率有较大差异(42.6%~99.8%),且去除Sn干扰的效果也不同(去除率在87.8%~97.4%之间),Cd回收率和Sn去除率均不理想。本文对前人报道的分离方法进行对比实验,发现0.1 mol/L氢溴酸-0.5 mol/L硝酸是分离Cd和Sn的有效试剂,增加该组混合酸的用量可淋洗出样品中更多的Sn且不会损失Cd,当混合酸的淋洗用量增加至30 mL时,Sn的淋洗率达到99.8%以上,Cd的回收率亦达到99.0%±0.5%,可满足土壤样品镉同位素的测定要求。本工作为获得高精度的镉同位素组成奠定了基础,为研究土壤环境中镉的污染来源提供了技术手段。     

无内标-多外标校正激光剥蚀等离子体质谱法测定磁铁矿微量元素组成

激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)常用于磁铁矿原位微量元素分析,按照校正策略不同,主要分为内标法和无内标法。内标法需要用电子探针(EMPA)预先测定磁铁矿中内标元素Fe的含量,过程较繁琐,且待测元素含量会受到内标元素含量测定的影响。本文采用铁含量较高的玄武质玻璃BCR-2G、BIR-1G、BHVO-2G和GSE-1G作为外标,避免了内标元素含量的测定,建立了无内标-多外标校正LA-ICP-MS测定磁铁矿微量元素组成的分析方法。利用该方法测定了科马提岩玻璃GOR-128g和自然岩浆磁铁矿BC 28的微量元素组成以评估方法的可靠性。结果表明,科马提岩玻璃的测定结果与推荐值及前人内标法的测定值一致,多数元素的相对标准偏差RSD5%;自然岩浆磁铁矿的测定结果与推荐值相比,多数元素的RSD7%,低于前人内标法的RSD(15%)。由此说明无内标-多外标法可以实现富铁硅酸岩或磁铁矿微量元素含量的准确校正,克服了基体效应的影响。因此,无内标-多外标法是一种原位测定磁铁矿微量元素含量的快速、准确方法,具有一定的应用潜力。