Hair analysis and the early detection of imbalances in trace elements for members of expeditions in Antarctica

In the framework of the Human Biology and Medicine Project of the National Program for Research in Antarctica (Programma Nazionale di Ricerche in Antartide, PNRA) a study was undertaken to explore the suitability of trace element determination in human hair as a tool for the early detection of the impact of extreme environmental conditions on the health of members of the Italian and French expeditions. This study included three campaigns, namely, the 1995–1996 expedition to the Italian base of Terra Nova Bay, as well as the 1997–1998 and 1998–1999 expeditions to both the Italian base of Terra Nova Bay and the Italian–French base of Dome C. Sampling of hair of participants in the expeditions was carried out both prior to departure and at the end of the period spent at the bases. As regards storage, pre-treatment and analysis of hair samples they were performed in accordance with previously established procedures. Acid-assisted microwave digestion was adopted as the best approach for preparing solutions for subsequent analysis by inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry. In the first part of this study, only the elements Ca, Cu, Fe, Mg and Zn were selected, while at a later stage it was decided to also include Co, Cr, Mn, Mo and Ni. Experimental results were subjected to basic statistical analysis to detect possible significant differences in element concentrations that occurred during the sojourn at the bases, with a view to identify possible remedial action to minimize adverse consequences.     

死后人体组织中15种金属元素的电感耦合等离子体质谱(ICP-MS)法检测及其结果分析

为了准确检测死后人体组织中金属元素含量,以铋（Bi）和铟（In）双内标在线校正仪器,采用微波消解-电感耦合等离子体质谱（ICP﹣MS）法同时测定死后人体肝、肾、肺、胃组织中镁（Mg）、铝（Al）、钙（Ca）、铬（Cr）、锰（Mn）、铁（Fe）、铜（Cu）、锌（Zn）、砷（As）、锶（Sr）、镉（Cd）、钡（Ba）、汞（Hg）、铊（Tl）、铅（Pb）等15种金属元素含量。结果线性良好,准确度高,加标回收率为82.1% ~ 116.3%,精密度相对标准偏差RSD≤3.42%。不同组织中元素含量的变异系数为27.0% ~ 224.2%,含量差异较大,为了探究不同组织中各金属元素之间的差异与关联性,对金属元素含量开展相关性分析和主成分分析并进行综合评价。结果表明,Cu和Zn等47对金属元素之间具备显著的相关性,相关系数最高达0.91（p＜0.01）,提取4个主成分,累计方差贡献率达72.942%,通过元素载荷值得出,Al、Mn、Fe、Cu、Zn、Cd等6种元素是死后人体组织15种元素中的主要特征金属元素。计算可知,肝脏中总体金属元素含量最高,其次是肾和肺,胃组织中总体金属元素含量最低。本研究采用的元素测定方法及基础数据的综合评价可以为法医金属元素中毒案件的检验鉴定提供方法参考和数据支撑。     

粗锌中镉的测定方法研究

采用火焰原子荧光法（FAFS）和电感耦合等离子体质谱法（ICP-MS）测定铅锌矿中的镉. 通过对比研究,两种方法的校准曲线相关系数良好（r>0.999 5）,方法检出限、准确度和精密度均符合质量规范要求. 经过铅锌矿实际样品的比对,两种方法不存在显著性差异. FAFS法比ICP-MS法测定时间短,精密度高,适用于大批量铅锌矿样品的测定.

     

Evaluation of liquid chromatography inductively coupled plasma mass spectrometry for arsenic speciation in water from industrial treatment of shale

This work describes an arsenic speciation analysis in aqueous effluent from a shale industrial plant using liquid chromatography coupled to inductively coupled plasma mass spectrometry (LC–ICP–MS). Arsenic species have been separated through an anion-exchange column and several parameters investigated, such as retention time, pH, flow rate and concentration of the mobile phase (ammonium carbonate), chloride interference and column conditioning time. The best conditions have been found by fixing the pH of the mobile phase at 8.7. Keeping the mobile phase flow rate at 1.5 ml min^− 1, arsenic species were separated by varying the concentration of the mobile phase and the time of elution, as follow: 1.5 mmol l^− 1 for 10 min, 12 mmol l^− 1 for 10 min and 20 mmol l^− 1 for 10 min, respectively. Up to 13 As species present in the samples were separated under these conditions and the following species could be identified and quantified: arsenite [As(III)], dimethylarsinic acid (DMA), monomethylarsonic acid (MMA) and arsenate [As(V)]. The limits of detection of the LC–ICP–MS method were 0.02, 0.06, 0.04 and 0.10 μg l^− 1 of As(III), DMA, MMA, and As(V), respectively. The concentration of these species in the samples were from 3.7 to 6.4 μg l^− 1, 6.9 to 13.2 μg l^− 1, 100 to 142 μg l^− 1 and 808 to 1363 μg l^− 1 for As(III), DMA, MMA and As(V), respectively. The accuracy, evaluated by recovery tests, varied from 94 to 105% and the precision, evaluated by the relative standard deviation was typically lower than 10%.     

电感耦合等离子体-质谱联用及其在环境和生物样品中铂族金属分析的应用进展

本文简述了电感耦合等离子体-质谱联用(LCP-MS)技术和仪器的发展,分析了环境和生物样品中铂族金属分析的主要困难,综述了90年代以来国内外ICP-MS技术在环境和生物样品中铂族金属分析的最新进展,引用文献47篇.     

两地土壤中的钚含量及同位素组成分析

采用三正辛胺 (TNOA)萃取色层和同位素稀释法 ,ICP MS测量了我国西北地区土壤中痕量Pu。实验结果表明 ,本流程Pu的本底为 (0 .0 36± 0 .0 2 5 )× 10 -12 g ,相应的定量限为 0 .2 5× 10 -12 g。实验测得甘肃某地及陕西西安地区土壤样品中的2 3 9Pu含量分别低于 1.0× 10 -12 和 0 .2× 10 -12 ;2 40 Pu/ 2 3 9Pu的同位素丰度比分别为 0 .15和 0 .18。该丰度比结果说明西安地区的Pu来自全球沉降 ,而甘肃地区的Pu则还另有来源。     

Application of laser ablation ICP-MS to elemental analysis of glasses

A technique involving the coupling of laser ablation and inductively coupled plasma mass spectrometer has been used for semi-quantitative analysis of glasses without sample dissolution. The characteristic features of this technique is low detection limit and accuracy between a few % up to 20%. An NIST glass standard (SRM 612) was dissolved and then analysed by ICP-MS in semi-quantitative mode. The results were in close agreement with the certified values for elements such as Mn, Sr, Y, Ti...Abbreviations AA atomic absorption - ICP-OES inductively coupled plasma optical emission spectroscopy - ICP-MS inductively coupled plasma mass spectrometry - LA laser ablation     

微波消解ICP-MS法测定小麦制品中的铝含量

采用密闭微波消解小麦制品,在优化微波消解条件的基础上,建立微波消解－电感耦合等离子体质谱(ICP-MS)法测定小麦制品中铝元素的方法。用电感耦合等离子体质谱法(ICP-MS)测定市场上多种小麦制品中Al元素的含量,该方法简单快速,准确度好、精密度高,标准曲线相关系数在0.9950~ 0.9999之间,是测定小麦制品中铝含量的一种有效分析方法。通过对小麦制品中铝含量的检测分析,为小麦制品的食用安全性提供了检测数据,同时也可为小麦制品加工业的质量控制提供借鉴。     

电感耦合等离子体质谱法测定镍基高温合金中磷含量的不确定度评定

采用电感耦合等离子体质谱(ICP-MS)法测定镍基高温合金中磷杂质含量,对该测定方法的不确定度进行评定。建立了不确定度评定的数学模型,对不确定度的来源进行了全面分析,通过计算得到扩展不确定度。采用ICP-MS法测定YSBC 41503-2012标准物质中的磷含量,测定值为0.0035%,测定结果与证书参考值一致。按照建立的不确定度评定方法得扩展不确定度为0.0002%(k=2)。该方法适用于ICP-MS法测定高温合金中磷含量的不确定度评定。     

电感耦合等离子体光谱和质谱法分析贻贝标准物质

采用电感耦合等离子体光谱和质谱法分析了贻贝标准物质,光谱法测定Ｋ、Ｎａ、Ｃａ、Ｍｇ、Ｐ、Ａｌ、Ｆｅ、Ｚｎ、Ｍｎ和Ｓｒ,质谱法测定Ａｓ、Ｂ、Ｃｄ、Ｃｏ、Ｃｒ、ＣｕＧａ、Ｇｅ、Ｍｎ、Ｍｏ、Ｎｉ、Ｐｂ、Ｓｅ、Ｓｒ、Ｕ和Ｖ。在优化的工作条件下,测定了来自基体元素Ｋ、Ｎａ、Ｃａ、Ｐ、Ｃｌ的Ｃ的多原子离子＾３９Ｋ＾１６Ｏ、＾３９Ｋ２、＾４０Ａｒ＾２３Ｎａ、＾４３Ｃａ＾１６Ｏ、＾４２Ｃａ＾１６Ｏ、＾３１Ｐ＾１６     

Simple,fast, and low-contamination microwave-assisted digestion procedures for the determination of chemical elements in biological and environmental matrices by sector field ICP-MS

A simple and convenient method for the digestion of animal tissues, lichens, and plants for 33 metals measured by sector field inductively coupled plasma mass spectrometry (SF-ICP-MS) was described. Microwave-assisted acid digestions were performed at atmospheric pressure by means of a multi-samples rotor designed for processing a large number of samples at once in screw-capped disposable polystyrene liners. The digested samples were filled up to final volume directly in the polystyrene liners ready for elemental quantification. Seven certified reference materials, namely BCR 184 (bovine muscle), BCR 186 (pig kidney), DORM-2 (dogfish muscle), BCR 422 (cod muscle), BCR 62 (olive leaves), BCR 100 (beech leaves), and BCR 482 (lichen) were analysed to verify the accuracy of the method. The linearity range, limit of quantification, precision, and recovery by addition of non-certified elements were also assessed. All elements, with the exception of Hg in BCR 184 and As in BCR 186, were above the quantification limit and blank concentrations, and good agreement existed between found and target values in bovine muscle, pig kidney, and cod muscle. Significant deviations were observed for Al, Co, Cr, Mn, and Ni in dogfish muscle and for Ca, Cr, Fe, and Hg in lichens and plants. The proposed digestion procedure offers a low contamination risk, simplicity, speed, low cost, and applicability in routine analysis, and the SF-ICP-MS method allowed metals from a fraction of ng?g^?1 to hundreds of µg?g^?1 to be quantified in one analytical run.     

黔产市售鱼腥草中重金属含量分析及膳食风险评估

为研究黔产市售鱼腥草中铅、镉、铬、砷4种重金属的含量水平及其膳食健康风险水平。以贵州贵阳(GY)、遵义(ZY)、铜仁(TR)、安顺(AS)、毕节(BJ)、六盘水(LPS)、黔东南(QDN)、黔西南(QXN)、黔南(QN)等9个市(州)市售鱼腥草为研究对象,利用微波消解处理样品,采用电感耦合等离子体质谱(ICP-MS)法同时测定样品中的4种重金属含量,利用单因子污染指数法、内梅罗综合污染指数法对重金属的污染程度进行评价,利用目标危害系数法进行膳食风险评估。结果显示,鱼腥草中Pb含量为0.084～0.12 mg/kg, Cd含量为0.041～0.068 mg/kg, Cr含量为0.076～0.43 mg/kg, As含量为0.074～0.14 mg/kg。TR、QDN、ZY市售鱼腥草Pb的单项污染指数均大于1,9个市(州)市售鱼腥草Cd、Cr、As的单项污染指数均小于1。不同市(州)市售鱼腥草的内梅罗综合污染指数大小次序为1>TR>QDN>ZY>AS>GY>BJ>QXN>0.7≥QN>LPS。单一重金属的膳食健康风险指数(THQ)总体上...     

Mass Spectrometric Observation of Doubly Charged Alkaline‐Earth Argon Ions

Doubly charged diatomic ions MAr²⁺ where M=Mg, Ca, Sr or Ba have been observed by mass spectrometry with an inductively coupled plasma ion source. Abundance ratios are quite high, 0.1 % for MgAr²⁺, 0.4 % for CaAr²⁺, 0.2 % for SrAr²⁺ and 0.1 % for BaAr²⁺ relative to the corresponding doubly charged atomic ions M²⁺. It is assumed that these molecular ions are formed through reactions of the doubly charged metal ions with neutral argon atoms within the ion source. Bond dissociation energies (D₀) were calculated and agree well with previously published values. The abundance ratios MAr⁺/M⁺ and MAr²⁺/M²⁺ generally follow the predicted bond dissociation energies with the exception of MgAr²⁺. Mg²⁺ should form the strongest bond with Ar [D₀ (MgAr²⁺)=124 to 130 kJ mol^?1] but its relative abundance is similar to that of the weakest bound BaAr²⁺ (D₀=34 to 42 kJ mol^?1). The relative abundances of the various MAr²⁺ ions are higher than those expected from an argon plasma at T=6000 K, indicating that collisions during ion extraction reduce the abundance of the MAr²⁺ ions relative to the composition in the source. The corresponding singly charged MAr⁺ ions are also observed but occur at about three orders of magnitude lower intensity than MAr²⁺.     

电感耦合等离子体质谱法测定土壤中痕量铀

建立电感耦合等离子体质谱法测定土壤样品中痕量铀含量的方法。采用硝酸、氢氟酸、高氯酸混合酸消解样品后,以铼为内标溶液校正基体干扰,用电感耦合等离子体质谱仪测定土壤中的痕量铀含量。实验结果表明,铀的质量浓度在0~20 ng/m L范围内与信号强度呈线性关系,相关系数r=0.999 9,方法检出限为0.006μg/g,测定结果的相对标准偏差小于5%(n=6),加标回收率在96%~103%之间。用该方法与标准方法对同一样品进行测定,两种方法测定结果一致。该方法准确可靠,满足土壤样品中痕量铀含量的测定要求。     

Elemental analyses of soil and sediment fused with lithium borate using isotope dilution laser ablation-inductively coupled plasma-mass spectrometry

Quantitative analysis using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remains challenging primarily due to the lack of appropriate reference materials available for the wide variety of samples of interest and to elemental fractionation effects. Isotopic dilution mass spectrometry (IDMS) is becoming the methodology of choice to address these issues because the different isotopes of an element represent near-perfect internal standards. In this work, we investigated the lithium borate fusion of powdered solid samples, including soils, sediments, rock mine waste and a meteorite, as a strategy to homogenously distribute, i.e. equilibrate the elements and the added isotopically enriched standards. A comparison of this methodology using two pulsed laser ablation systems (ArF* excimer and Nd:YAG) with different wavelengths as well as two ICP-MS instruments (quadrupole and double-focusing sector field) was performed. Emphasis was put on using standard equipment to show the potential of the proposed strategy for its application in routine laboratories. Cr, Zn, Ba, Sr and Pb were successfully determined by LA-ICP-IDMS in six Standard Reference Materials (SRMs) representing different matrices of environmental interest. Experimental results showed the SRM fused glasses exhibited a low level of heterogeneity (intra- and inter-sample) for both natural abundance and isotopically enriched samples (RSD <3%, n = 3, 1σ). A good agreement between experimental results and the certified values was also observed.     

Determination of Metals in Fruits of Cucurbitaceae Species from South Korea,to Characterize Potential Effects on Human Health

Recent research studies have confirmed that the dietary intake of vegetables and fruits has a positive and profound impact on human health, performance, and disease. This research was designed to determine the concentrations of essential trace elements; cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), selenium (Se), vanadium (V), and zinc (Zn), toxic metals; cadmium (Cd), mercury (Hg), and lead (Pb); and a metalloid; arsenic (As) in fruits of seven species of Cucurbitaceae family including gourd, zucchini, pumpkin, sweet pumpkin, melon, watermelon, and oriental melon commonly consumed in South Korea. The concentrations of As, Cd, Co, Cr, Cu, Pb, Se, and Zn were determined using inductively coupled plasma mass spectrometry, and Hg by a mercury analyzer. To analyze the samples after microwave digestion for the validation of analytical techniques, satisfactory values of all quality parameters of linearity, detection limits, precision, accuracy, and recovery experiments were obtained in all cases. On the whole, all analyzed elements were found in accordance to the published literature around the world and well within the critical recommended standards by CODEX and Ministry of Food and Drug Safety, Korea. The estimated daily intake values, and hazard quotients and indices of the analyzed samples were all below the World Health Organization, Joint Food and Agriculture Organization/World Health Organization Expert Committee on Food Additives, and European Food Safety Authority limits.     

电感耦合等离子体质谱法测定人血浆中20种微量元素

建立了人血浆样品中微量元素的ICP-MS测定方法。分析了100名健康成人和50名健康儿童血浆样品的20种微量元素,给出了参考值范围。该方法检出限为0.0001~1.60μg/L;精密度(RSD)介于0.78%~4.27%;多数元素回收率在100%±10%之内。方法简便(正常人血浆经超纯水,硝酸,TritonX-100,正丁醇稀释后直接测定其中的微量元素),快速,样品用量少(血浆0.2mL),可作为人体内多种微量元素的监测方法,同时为人血浆中微量元素正常值范围的确定提供了参考依据。     

A clean up step of fat content previous to trace metal characterization in mussel tissues by inductively coupled plasma mass spectrometry

Inductively coupled plasma mass spectrometry analysis of trace and major elements of mussel tissues can be quickly and accurately analyzed after cleaning up the interfering fat content before the sample is digested in a microwave oven. Making use of experimental designs, the clean up procedure was achieved by the extraction of 1 g of freeze-dried tissue sample stirred with 5 ml of dichloromethane during five minutes. The microwave assisted digestion of the fat free samples was carried out with 0.2 g of tissue sample, 15 ml of 7.0% nitric acid with a power of 980 W during 18 min. The analytical method efficiency (accuracy and precision) was evaluated with a CRM: (NIST 2977, mussel tissue) and real mussel samples analyzed previously. The results confirmed the accuracy of the analysis by agreement with the previous results but the precision was significantly improved. The developed method allows operating routinely permitting to large numbers of samples to be quickly screened for trace metals.     

微波消解/ICP-MS同时测定粮食、蔬菜中的11种重金属元素

建立了微波消解/电感耦合等离子体质谱法同时测定粮食和蔬菜中11种重金属元素(Cu、Mn、Cr、Pb、Cd、Ni、Sb、Hg、Co、Ag、As)的方法,优化了微波消解条件和仪器测定条件,采用HNO_3-HF-H_2O_2和HNO_3-H_2O_2两种混酸体系,将样品进行完全消解。结果显示,11种金属元素的线性系数不小于0.999 5,方法的检出限为0.001~10.00μg/L,测定的相对标准偏差(RSD,n=5)不大于5.0%。该方法具有快速、简便、灵敏度高、稳定性好、准确度高等优点。     

对藏族、回族、蒙古族、维吾尔族、哈萨克族和满族人发中7种微量元素的聚类分析

用等离子体发射光谱法对中国藏族、回族、蒙古族、维吾尔族和哈萨克族人发中的钙、镁、铁、锰、铜、锌、镉7种微量元素的含量进行了测定，对满族、蒙古族和维吾尔族3个民族，对藏族、回族、蒙古族、维吾尔族和哈萨克族5个民族进行了聚类分析，两组中每个民族基本上聚为一类，误判率分别小于10％和5％，说明上述民族的头发中7种元素含量的综合水平存在着较显著的差别。