干法灰化-原子荧光光谱法测定植物样中痕量锗

锗是对人体有益的重要稀有元素,但锗在植物样中含量很低。目前锗的前处理方法主要采用湿法消解和微波消解两种,以上的前处理方法试剂用量大,称样量小,检出限难以满足植物样中锗的分析要求。氢化物发生-原子荧光光谱法测定锗等易形成共价氢化物的元素相对其他的方法具有明显的优势。为降低测定植物样中锗的检出限,准确测定植物中的锗。实验采用干法灰化法对植物样中锗进行富集,建立了植物样中痕量锗的氢化物发生-原子荧光光谱测定方法。实验了温度对植物样灰化的影响,结果表明,即使温度高达900 ℃也不会造成锗的挥发损失,进一步试验表明在600 ℃灼烧4 h,即可将植物样灰化完全。实验了灰化后样品的消解方法,确定了灰化后样品采用硝酸、氢氟酸和硫酸进行分解。采用大称样量高温灰化减少了试剂用量,有效降低了方法检出限,改善了方法精密度。方法检出限达到0.27 ng·g-1,方法精密度(RSD)在3.99%～6.81%,经生物国家一级标准物质验证方法准确可靠。     

Comparison of Dry,Wet, and Microwave Ashing Methods for the Determination of Al,Zn, and Fe in Yogurt Samples by Atomic Absorption Spectrometry

Abstract

Digestion methods such as dry and wet ashing and microwave oven were examined at various conditions to determine a rapid, reliable, and simple digestion procedure for yogurt. Digestion by microwave oven was found to be an excellent method in comparison with dry and wet ashing methods when only Al and Zn in yogurt samples were determined. Iron in this matrix is not completely digested by the microwave oven method at the examined conditions. From the obtained results, yogurt can also be a good source of essential nutrients such as minerals in human diet, especially zinc. Aluminum concentrations in yogurt samples fermented in Al containers were found to be significantly higher than in plastic containers. Al concentrations of yogurt taken from the bottom of the container were found to be higher than from the center and top of Al containers. The determinations of metals were carried out via an atomic absorption spectrophotometer using calibration curve and standard additions methods. Aluminum concentrations in yogurt samples produced in big production centers were found to be significantly higher than the other yogurt samples produced in‐house when plastic containers were used.     

湿法消解-火焰原子吸收法测定动物样品中六种金属元素

使用硝酸-高氯酸湿法消解火焰原子吸收法测定大、小鼠的血清、粪便、尿液和不同组织器官(心、肾、胃、肝、脾、肠和肺)中Ca,Mg,K,Na,Cu,Fe等六种金属元素。以硝酸与高氯酸的混合液(4∶1,φ)为消解液,加热条件为120 ℃,标准曲线相关系数为0.999 4～0.999 8,相对标准偏差(RSD)在0.33%～4.52%(n=6)之间,加样回收率均在97.7%～104.2%之间,满足生物样品中各元素含量测定的要求。本研究建立的动物样品中六种金属元素含量的测定方法具有操作简便快捷、灵敏度高、所需样品量少、结果准确可靠等优点,可广泛用于生物样品中多种金属元素的测定。     

Chemical Vapor Generation with Slurry Sampling: A Review of Applications to Atomic and Mass Spectrometry

Abstract

A critical review of published analytical methods and techniques for chemical vapor generation (CVG) with slurry sample introduction for detection by atomic and mass spectrometry is presented. The nstrumentation used for the reaction as well as separation and transport of the species, influence of chemical and physical factors, and efficiency of the process are considered. A brief comparison of detection limits obtained with atomic absorption, emission, and fluorescence as well as mass spectrometry along with practical applications to analytical samples are summarized. The current state-of-the-art, including advantages and limitations of this approach, is discussed.     

Sample Preparation for the Determination of Metals in Food Samples Using Spectroanalytical Methods—A Review

Abstract

The present article gives an overview of recent publications and modern techniques of sample preparation for food analysis employing atomic and inorganic mass spectrometric techniques, such as flame atomic absorption spectrometry, chemical vapor generation atomic absorption and atomic fluorescence spectrometry, graphite furnace atomic absorption spectrometry, inductively coupled plasma optical emission spectrometry, and inductively coupled plasma mass spectrometry. Among the most frequently applied sample preparation techniques for food analysis are dry ashing, usually with the addition of an ashing aid, and acid digestion, preferably with the assistance of microwave energy. Slurry preparation, particularly with the assistance of ultrasound, is increasingly used to reduce acid consumption and sample preparation time. Direct analysis of solid samples is gaining importance in the field of food analysis as it offers the highest sensitivity, avoids the use of acids and other aggressive reagents, makes possible the analysis of micro‐samples, and can be applied for fast screening analysis, e.g., of fresh meat.     

涂锆石墨管石墨炉原子吸收法测定水样中的有机锡和无机锡

本文用涂锆石墨管石墨原子吸收光谱法直接进样测定了样品中总锡含量,用氢化物发生－有机溶剂萃取石墨炉原子吸收光谱法测定了样品中有机锡,并通过差减法求得无机锡含量,无机锡和有机锡的测定检测限分别为２７ｐｇ和５８ｐｇ,精工为２．０４％和２．１３％,该方法可用于不同水样中有机和无机锡的测定,回收率在９０．５％－９８．５％之间。     

原子吸收光谱法测定花粉中的微量元素

采用中温灰化样品,6 mol·L-1 HNO3浸取灰化物,用LaCl3和CsCl消除相关干扰,应用标准曲线法在同一溶液中利用空气-乙炔火焰原子吸收光谱法测定花粉中Zn,Cd,Fe,Mn,Pb,Mg,Cu,K,Ca和Na共10种元素含量。结果表明,花粉含有丰富的Zn,Mg,K,Ca,Na以及Fe,Mn,Cu,有害元素Pb的含量很低,Cd未检出。以野霍香花粉为例,详细研究确定了合适的样品处理及消除干扰条件,考察了方法的准确度和精密度。在选定的条件下,花粉中各元素间相互不干扰,可在同一份制备液中进行10种元素的分别测定。方法的加标回收率在93.4%～112.0%之间,相对标准偏差在0.3%～2.6%之间(n=5),测定结果准确可靠。     

苦菜的不同部位中13种金属元素含量的分析测定

用火焰原子吸收法测定了苦菜的不同部位(根,茎,叶,花)中矿物元素(Ca, Mg, K, Na, Cu, Zn, Mn, Cr, Co, Ni, Fe, Pb和Cd)的含量,并对结果进行了分析比较。苦菜中13种金属元素在各部位中的加合量(μg·g-1)由高到低的顺序依次为：叶(77 213.72)>花(47 927.15)> 杆 (42 280.99 )>根(28 131.18)。人体必需的生理上较重要的微量元素Zn, Fe, Mn, Cu等含量均较高。另外, 样品中亦检出微量有毒元素铅和镉。     

咖啡中14种无机元素的快速质谱分析

采用微波消解处理咖啡样品,建立了电感耦合等离子体质谱(ICP-MS)法测定其中Na,Mg,P,Ca,Cr,Mn,Fe,Co,Cu,Zn,As,Se,Mo,Pb等14种无机元素的分析方法。样品采用HNO₃+H₂O₂混合酸微波辅助消解,优化了仪器的工作参数。加标回收率测定结果表明,所有待测元素的相对标准偏差(RSD)均小于3.84%,回收率在92.00%～106.52%之间。该法准确度高,精密好,并能同时进行多种元素测定,完全能满足样品测定要求,可为咖啡中无机元素的快速检测提供科学依据。     

火焰原子吸收法测定食用仙人掌中微量元素含量

用灰化法溶解试样,配制混合标准系列溶液,加入LaCl₃和CsCl消除相关干扰,采用空气-乙炔火焰原子吸收法在同一试液中测定10种微量元素含量。建立了优化的仪器测定条件,方法简便、准确。结果表明,食用仙人掌中含Mg,K,Ca 为13～47 mg.g-1;Zn,Mn,Fe,Na为108～243 μg.g-1, Cu为34.8 μg.g-1;Ni和Sr为9.8～11.7 μg.g-1,其中Mg,K,Ca,Zn,Mn,Fe,Na,Cu的含量均显著高于胡萝卜中含量。     

火焰原子吸收光谱法测定兰州百合中的8种微量元素

采用HNO₃-HClO₄(3.5∶1)混酸作消化液,在常压微沸条件下消解百合样品,应用火焰原子吸收光谱法测定了兰州百合中的Zn,Fe,Cu,Mn,Co,Pb,Cd和Cr共8种元素的含量。研究了测定不同元素的仪器最佳工作条件,确定了合适的样品消化体系,考察了干扰情况、方法的准确度和精密度。在选定的实验条件下,百合中各元素间相互不干扰,可在同一份制备液中进行8种元素的分别测定。实验表明,兰州百合中含有丰富的Zn,Fe,以及Cu,Mn,有害元素Pb和Cd未检出。方法的加标回收率为94.20%～111.20%,RSD≤2.54%(n=6),测定结果准确可靠。     

萃取/反相萃取分离富集-氢化物无色散原子荧光法测定复杂地质样品中的痕量碲

采用MIBK萃取/反相萃取分离富集的方法,建立了氢化物无色散原子荧光法测定复杂地质样品中的痕量碲的新方法。实验了HCl-NaBr-MIBK体系萃取Te(Ⅳ)的能力,研究了Te(Ⅳ)在KMnO₄-HCl-MIBK体系中的反相萃取行为。当萃取条件为3.6 mol·L-1HCl-100 g·L-1NaBr时,Te(Ⅳ)可被MIBK完全萃取;用HCl-KMnO₄氧化MIBK相中的Te(Ⅳ),水相反相萃取Te(Ⅵ),成功分离了氢化物原子荧光法测定Te的Au,Ag,Pt,Pd,Cu,Pb,Co,Ni,Cd,As,Sb,Bi,Hg,Tl和Se等干扰元素,方法检出限为1.14×10-4 μg·g-1,相对标准偏差为6.84%,对国家标准物质样品分析的结果与所给参考值吻合,可用于复杂地质样品中痕量Te的测定。     

铝的空气-乙炔火焰原子吸收法测定的研究

本文建立了一种用空气－乙炔火焰原子吸收法直接测定土壤中铝的分析方法。研究了添加四甲基氯化铵（ＴＭＡＣ）对测定铝时的增感效果,方法简便,快速实用,应用于土壤标准样品的测定,获得满意的结果。     

火焰原子吸收光谱法测定中草药川东獐牙菜中的八种微量元素

用火焰原子吸收光谱法对川东獐牙菜中K, Ca, Na, Mg, Fe, Zn, Mn和Cu八种微量元素进行了分析测定。结果显示,用HNO₃-HClO₄(5∶1)混酸作消化液处理样品,精密度和回收率较好。在选定的实验条件下,川东獐牙菜各元素间相互不干扰,可在一份样品液中进行八种元素的分别测定。川东獐牙菜中含有较丰富的K,Ca和Na, 以及Mg和Zn,其含量K＞Ca＞Mg＞Na＞Zn＞Fe＞Cu＞Mn。方法的检出限均小于0.097 μg·mL-1,RSD≤2.34%(n=8),加标回收率89.32%～106.65%。     

火焰原子吸收光谱法测定东江河沙中8种微量元素

采用火焰原子吸收光谱法对东江河沙中Na,K,Cu,Fe,Mg,Mn,Co,Zn 8种微量元素进行检测与分析。方法简单、快速、灵敏度高以及精密度好。算出回归方程和相关系数, 相关系数(r)均在0.994～1.000之间。选用HNO₃-HF-H₂O₂混酸体系消化。结果表明,东江河沙中含有丰富的微量元素, 其含量由高到低顺序为Na>K>Fe>Mg>Mn>Zn>Co>Cu, 钠的含量最为丰富, 铜含量较少。实验结果为探讨东江河沙的保健作用提供了有用的依据。     

电感耦合等离子体发射光谱法同时测定野生葡萄籽中多元素的方法研究

文章研究的是电感耦合等离子体发射光谱法(ICP-AES)同时测定野生葡萄籽中多种元素。针对野生葡萄籽样品基质中有机成分对矿物质的影响,对干灰化法与酸消解湿法处理样品进行了比较,通过对植物标准物质GBW 07603样品分解, 表明选择HNO₃-HClO₄体系消解样品优于干灰化法。此方法测得结果相对误差在1.06%～8.82%和标准偏差在1.35%～8.88%之间。进行了葡萄籽和几种中草药中微量元素测定的对照实验,检测数据证明葡萄籽中微量元素丰富具有较高的药用和营养价值。     

KED-ICP-MS法测定尿样中21种无机元素

人体血液和尿液等生物样品中元素含量,能够有效反映不同途径元素暴露的体内负荷信息。因此,建立生物样本中精准、快速和高通量的元素检测方法具有重要的卫生学意义。目前应用较多的尿液前处理方法主要有消解法和直接稀释法,这两种方法均有各自的不足。以精准获得人体尿样中多元素含量为目的,建立应用碰撞池技术（KED）的电感耦合等离子体质谱（ICP-MS）法准确定量人体尿样中低浓度的锰（Mn）、钴（Co）、钒（V）、铜（Cu）和锌（Zn）等21种无机元素含量的分析方法。在直接稀释法基础上,经水浴超声前处理后,使用ICP-MS对尿样中21种无机元素进行分析,研究了各待测元素在KED模式下背景等价浓度（BEC）的变化情况,通过使用氦气为碰撞气,应用动能歧视和氦气原子与干扰分子间的碰撞裂解降低多原子干扰等质谱干扰对测定的影响,同时应用标准加入法和在线内标校正基质效应和信号漂移对测定的影响。通过考察不同He流速对各元素BEC影响,优化了碰撞气流速和Rpq,选择He流速3.8 mL·min-1,Rpq=0.45为优化后的检测条件,在此条件下获得21种无机元素的检出限介于0.004~12.08 μg·L-1之间,各元素在0~200 μg·L-1范围内的线性相关系数（r）≥0.999,方法具有良好的线性关系。采用高低两水平加标回收实验来验证方法的准确度和精密度,各元素加标回收率在81.8%~112.6%之间,相对标准偏差（RSD）小于5%。将该方法与《尿中多种金属同时测定电感耦合等离子体质谱法》（GBZ/T 308-2018）标准相比较,待测无机元素的检出限和相对标准偏差等方法学指标均有较大改善。本方法简便、快速,能够满足实验室日常尿样中多种无机元素的准确检测要求,能够为突发公共卫生事件和临床人体尿样中多种微量元素的准确分析提供参考和依据。     

Trace Metals Analysis of Legal and Counterfeit Cigarette Tobacco Samples Using Inductively Coupled Plasma Mass Spectrometry and Cold Vapor Atomic Absorption Spectrometry

ABSTRACT

A closed-vessel microwave-digestion method was developed for the determination of trace amounts of Be, V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Sb, Ba, Tl, and Pb by inductively coupled plasma mass spectrometry and Hg by cold-vapor atomic absorption spectrometry in cigarette tobacco samples. In order to gauge the effectiveness of the digestion procedure, recovery studies were conducted using solutions prepared from National Institute of Standards and Technology Standard Reference Material 1573a Trace Elements in Tomato Leaves and Polish Certified Reference Material Virginia Tobacco Leaves. Limits of detection were below 1 µg g^?1 for all elements studied. Samples from two genuine-brand and three counterfeit packs were analyzed. The mean amounts of Be, As, Mo, Cd, Sb, Tl, Pb, and Hg were higher in counterfeit cigarettes, while the amounts of V, Cr, Mn, Co, Cu, Zn, Se, and Ba were comparable among legal and counterfeit cigarettes; the amount of Ni was higher in the legal cigarettes. Evaluation of Be, As, Mo, Cd, Sb, Tl, Pb, and Hg with their potential hazards for smokers is briefly discussed.     

电感耦合等离子体发射光谱法测定食用菌中微量元素的方法研究

采用高压硝化罐在较低温度下进行缓慢样品消化,减少了消化过程中微量元素的损失。采用电感耦合等离子体发射光谱法测定了食用菌中Ca,Na,K,Mg,Mn,Ba,Fe,Co,Ge和Cu等多种微量元素的含量。高压硝化罐法测定各元素的相对标准偏差在0·16%～2·86%之间,湿法测定各元素的相对标准偏差在0·33%～3·49%之间。可见高压硝化罐法处理样品的测量精密度和湿法处理样品的测量精密度均比较好,前者的测量精密度更高一些。对高压硝化罐法和湿法处理样品的测量结果进行了t检验,t值在0·0024～2·473,均小于t0·99,9(3·25),说明两种方法的测量结果无显著性差异,即两种方法不存在系统误差。同时,高压硝化罐法处理样品的回收率在96·6%～103%之间,该方法具有简便、快速、灵敏、稳定、准确等优点,适于食用菌中微量元素的分析测定。     

ICP-MS测定电吸附找矿泡塑样品中微量元素

建立了电感耦合等离子质谱法(ICP-MS)测定电吸附找矿泡塑样品中钒、铬、锰、钴、镍、铜、锌、镓、铌、钼、银、镉、金、铊、铅和铋等16种微量元素的方法。进行了灰化法-王水提取、硝酸-过氧化氢消解-王水提取和沸水浴王水提取试样的比较实验,以硝酸-过氧化氢-王水提取法为最佳样品分解方法。对仪器工作参数进行了优化, 选取103Rh和185Re作为测定元素的内标元素, 进行了测定同位素的选择及干扰的消除等实验, 测定元素校准曲线的相关系数都在0.999 8以上, 各元素的检出限分别为0.001～2.2 μg·g-1, 精密度介于1.39%～4.84%之间, 样品加标回收率为94.86%～105.2%。方法简便快速,已应用于大量泡塑样品分析。