次氯酸钠氧化碘-电感耦合等离子体质谱法同时测定地表水样品中的碘及铜、铅、锌、锰、铁的含量

取地表水样90.0mL置于100mL容量瓶中,用硝酸及氢氧化钠溶液调节其酸度至pH7~9之间,加水至96mL,加入0.6%(质量分数)次氯酸钠溶液1mL,放置2h使碘完全氧化至非挥发性碘酸盐,再加入硝酸3mL酸化使溶液总体积至100.0mL。这一处理实现了采用电感耦合等离子体质谱法同时测定碘与水样中铜、铅、锌、锰、铁的含量。在质谱分析中,测定207Pb和127I使用标准(STD)模式,其余元素均采用动能歧视(KED)模式。经试验,选用钬作为测定碘的内标。所测定6种元素的质量浓度在一定范围内与其相应的信号强度之间呈线性关系。另按规定方法对空白样品进行测定,计算得到6种元素的检出限(3s)依次为0.096,0.071,0.062,0.065,0.044,0.19μg·L^-1。以地表水实际样品为基体,各加入上述6种元素的标准溶液,按方法分析并进行回收试验,测得回收率在83.2%~116%之间。测定值的相对标准偏差(n=5)在2.4%~7.3%之间。同一样品经本方法和国家标准方法对所涉及的6种元素进行测定,两方法的结果基本一致。     

Microwave-assisted solid phase extraction prior to ICP-MS determination of Pd and Pt in environmental and biological samples

A sensitive and selective microwave-assisted solid phase extraction procedure coupled to inductively coupled plasma-mass spectrometry (ICP-MS) is proposed for palladium (Pd) and platinum (Pt) quantification in environmental and biological samples. Pd and Pt were quantitatively retained on commercial thioureido propyl functionalised silica gel packed inside a home-made glass microcolumn, and later eluted with 0.5% thiourea solution under microwave irradiation, followed by ICP-MS determination. The main variables affecting the procedural stages (i.e., sorption and desorption) and ICP-MS determination were optimised. The best conditions found were: (a) sorption: sample acidity, 1?M HCl; sample flow rate, 3?mL?min^?1; (b) desorption: microwave radiation, power 800?W; eluent concentration, 0.5% thiourea; eluent flow rate, 0.5?mL?min^?1; (c) ICP-MS determination: nebuliser feeding, free aspiration (0.3?mL?min^?1); internal standard, Rh (5?µg?L^?1). Analyte recoveries were higher than 90% and concentration factors up to 90 and 92 were achieved for Pd and Pt, respectively. Depending on the conditions, the methodological limits of detection were down to 0.2?ng?L^?1 for both analytes and repeatability, expressed as RSD%, varied between 1.3 and 11.0%. A method selectivity evaluation showed that most of the ICP-MS interferents were either quantitatively separated or more than 86% eliminated, except for Cu (elimination efficiency around 30%). Finally, the method was successfully used to determine Pd in certified reference materials (i.e. human urine and serum) and Pd and Pt in PM₁₀ airborne particulate matter fractions.     

尿样中铀同位素的ICP-MS快速测量技术研究

核事故状态下的应急处理,要求对环境介质中的放射性核素进行快速分析。尿样中铀同位素测量作为内照射剂量评价的主要手段,其分析效率越高,则对核事故中涉铀人员的安全救治越及时、有效。而尿样中其它无机离子是铀含量的106倍,导致ICP-MS测量过程中尿盐堵塞进样毛细管。为降低样品的含盐量并获得较好的检测结果,本文对样品预处理过程进行优化。采用先加热氧化去除有机物,再进行1～10倍稀释后测试样品的铀同位素丰度及浓度。结果表明：将25 mL样品稀释至100 mL后效果最佳,分析方法不确定度为5.4 %,回收率95 %~105 %。     

Iodine determination in biological materials Options for sample preparation and final determination

This paper describes the development of various new acid sample decomposition methods, as well as an extraction (leaching) method and compares them with the “Sch?niger Combustion” technique. The methods have been developed as sample preparation techniques for iodine determination in biological materials, especially in solid samples. ICP-MS (inductively coupled plasma mass spectrometry) and a catalytic technique are employed and discussed for the final determination of iodine concentrations. Accuracy and reliability of the different analytical methods are shown in the examples of different CRMs (certified reference materials) available for iodine. The results of an interlaboratory comparison are specifically presented for the extraction (leaching) method. Received: 11 May 1998 / Revised: 14 June 1998 / Accepted: 16 June 1998     

微波消解-电感耦合等离子体质谱法测定乳制品中总碘

建立了乳制品中碘含量的微波消解-电感耦合等离子体质谱测试方法.方法以硝酸为消解介质,镨做内标.方法的检出限为0.02μg/kg,线性范围为0~100μg/L,相关系数r优于0.999 5.相对标准偏差RSD(%)均在5.0%以下,加标回收率在94.1%~97.7%之间,GBW10017奶粉标准物质的测定结果与标示值一致.试验结果表明所建立的方法灵敏度高、简便、快速、准确,适用于乳制品中碘含量的测定.     

ICP-MS multielemental determination of metals potentially released from dental implants and articular prostheses in human biological fluids

A sector field high-resolution (HR)-ICP-MS and an octapole reaction system (ORS)-ICP-MS have been compared for the simultaneous determination of traces of metals (Ti, V, Cr, Co, Ni, and Mo) released from dental implants and articular prostheses in human biological fluids. Optimum sample treatments were evaluated to minimize matrix effects in urine and whole blood. Urine samples were diluted tenfold with ultrapure water, whereas whole blood samples were digested with high-purity nitric acid and hydrogen peroxide and finally diluted tenfold with ultrapure water. In both matrices, internal standardization (Ga and Y) was employed to avoid potential matrix interferences and ICP-MS signal drift. Spectral interferences arising from the plasma gases or the major components of urine and whole blood were identified by (HR)-ICP-MS at 3,000 resolving power. The capabilities of (HR)-ICP-MS and (ORS)-ICP-MS for the removal of such spectral interferences were evaluated and compared. Results indicate that polyatomic interferences, which hamper the determination of such metallic elements in these biological samples, could be overcome by using a resolving power of 3,000. Using (ORS)-ICP-MS, all those elements could be quantified except Ti and V (due to the polyatomic ions ³¹P¹⁶O and ³⁵Cl¹⁶O, respectively). The accuracy of the proposed methodologies by (HR)- and (ORS)-ICP-MS was checked against two reference materials. Good agreement between the given values and the concentrations obtained for all the analytes under scrutiny was found except for Ti and V when analyzed by (ORS)-ICP-MS.     

ICP-MS同时测定植物性食品中稀土元素的方法研究

建立了植物性食品中16种稀土杂质(Sc、Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb和Lu)元素的电感耦合等离子体质谱(ICP-MS)的分析方法.考察了基体效应及质谱干扰,应用In内标,有效地补偿基体效应所引起的测量偏差,建立修正公式校正质谱干扰.对照分析了参考标准物质.对所测定元素,校正曲线的相关系数为＞0.9990,方法的检出限低于2.2 pg/g(Sc为95pg/g),回收率为92%～106%,RSD优于3.2%(n=7).     

电感耦合等离子体质谱法同时测定成品烟烟丝中7种微量元素

采用微波消解前处理样品,电感耦合等离子体质谱检测,同时测定了成品烟烟丝中Cr、Ni、Cu、As、Se、Cd、Pb等7种微量元素。方法的回收率92.8%~120%,检出限25.2~245 ng/L,相对标准偏差均小于10%。分析和比较了5种国外卷烟和10种国内卷烟烟丝中7种元素的含量。     

Multielement determination of trace metals in seawater by ICP-MS with aid of down-sized chelating resin-packed minicolumn for preconcentration

The multielement determination of trace metals in seawater was carried out by inductively coupled plasma mass spectrometry (ICP-MS) with aid of a down-sized chelating resin-packed minicolumn for preconcentration. The down-sized chelating resin-packed minicolumn was constructed with two syringe filters (DISMIC 13HP and Millex-LH) and an iminodiacetate chelating resin (Chelex 100, 200-400 mesh), with which trace metals in 50 mL of original seawater sample were concentrated into 0.50 mL of 2 M nitric acid, and then 100-fold preconcentration of trace metals was achieved. Then, 0.50 mL analysis solution was subjected to the multielement determination by ICP-MS equipped with a MicroMist nebulizer for micro-sampling introduction. The preconcentration and elution parameters such as the sample-loading flow rate, the amount of 1 M ammonium acetate for elimination of matrix elements, and the amount of 2 M nitric acid for eluting trace metals were optimized to obtain good recoveries and analytical detection limits for trace metals. The analytical results for V, Mn, Co, Ni, Cu, Zn, Mo, Cd, Pb, and U in three kinds of seawater certified reference materials (CRMs; CASS-3, NASS-4, and NASS-5) agreed well with their certified values. The observed values of rare earth elements (REEs) in the above seawater CRMs were also consistent with the reference values. Therefore, the compiled reference values for the concentrations of REEs in CASS-3, NASS-4, and NASS-5 were proposed based on the observed values and reference data for REEs in these CRMs.     

Determination of toxic elements in coal by ICP-MS after digestion using microwave-induced combustion

A microwave-induced combustion (MIC) procedure was applied for coal digestion for subsequent determination of As, Cd and Pb by inductively coupled plasma mass spectrometry (ICP-MS) and Hg using cold vapor (CV) generation coupled to ICP-MS. Pellets of coal (500 mg) were combusted using 20 bar of oxygen and ammonium nitrate as aid for ignition. The use of nitric acid as absorbing solution (1.7, 3.5, 5.0, 7.0 and 14 mol L⁻¹) was evaluated. For coal samples with higher ash content, better results were found using 7.0 mol L⁻¹ HNO₃ and an additional reflux step of 5 min after combustion step. For coal samples with ash content lower than 8%, 5.0 mol L⁻¹ nitric acid was suitable to the absorption of all analytes. Accuracy was evaluated using certified reference material (CRM) of coal and spikes. Agreement with certified values and recoveries was better than 95 and 97%, respectively, for all the analytes. For comparison of results, a procedure recommended by the American Society of Testing and Materials (ASTM) was used. Additionally, a conventional microwave-assisted digestion (MAD) in pressurized vessels was also performed. Using ASTM procedure, analyte losses were observed and a relatively long time was necessary for digestion (>6 h). By comparison with MAD procedure, higher sample mass can be digested using MIC allowing better limits of detection. Additionally, the use of concentrated acids was not necessary that is an important aspect in order to obtain low blank levels and lower limits of detection, respectively. The residual carbon content in digests obtained by MAD and MIC was about 15% and <1%, respectively, showing the better digestion efficiency of MIC procedure. Using MIC it was possible to digest completely and simultaneously up to eight samples in only 25 min with relatively lower generation of laboratory effluents.     

ICP-MS determination of Pt in biological fluids of patients treated with antitumor agents: evaluation of analytical uncertainty

The estimation of the uncertainty associated to the analytical methods is necessary in order to establish the comparability of results. Methods of Pt determination in biological fluids lack very often of information about uncertainty of results, with likely implications when results are used to interpret the mechanism of action of platinum compound or when they are considered to optimise the clinical therapies.An inductively coupled plasma-mass spectrometer (ICP-MS) method for the determination of Pt in biological fluids (plasma, ultrafiltrate and urine) of patients treated with antitumor agents has been developed and validated. The limits of quantification (LOQ) in the three matrices were 1.0, 0.1, and 2.0 μg/l, respectively.Intraday and interday precisions and accuracies were in good agreement with the FDA criteria for the validation of analytical methods. The validation study was implemented by assessing the uncertainty evaluation for Pt determination in the different matrices according to EURACHEM/CITAC Guide.     

ICP-MS法测定高纯铝中杂质不确定度的评定

利用ICP-MS测定高纯铝中杂质。用建立数学模型的方法对结果的不确定度进行评估和计算。对试料的称重、标准溶液的配制、工作曲线的拟合、测量重复性的各分量不确定度进行分析。得到了各分量不确定度和合成不确定度,最终得出更加客观的结果。     

ICP-MS法测定土壤中有效态砷的研究

分别以等离子体质谱法和原子荧光法,测定了国标土壤样品中有效态砷的含量,研究了两种方法的准确度;对等离子体质谱测定方法做消除基体干扰的对比研究。两种方法的测定值均在土壤样中有效砷的允许误差范围内,ICP-MS法的检出限为2.8 ng/g,精密度(RSD)在10％以下,符合分析测定要求。     

Determination of selenium in biological materials by means of RNAA and comparison of spectrophotometric and81mSe radiotracer recovery

Two methods for chemical yield measurement of Se in biological samples after radiochemical neutron activation analysis when using the⁷⁵Se nuclide are described, namely a Spectrophotometric technique and a radiotracer technique employing^81mSe. These two approaches were compared and evaluated by applying them to the analysis of Se in various certified reference materials.     

Development of a mild mercaptoethanol extraction method for determination of mercury species in biological samples by HPLC–ICP-MS

A mild, efficient and convenient extraction method of using 2-mercaptoethanol contained extractant solution combined with an incubator shaker for determination of mercury species in biological samples by HPLC–ICP-MS has been developed. The effects of the concentration of 2-mercaptoethanol, the composition of the extractant solution and the shaking time on the efficiency of mercury extraction were evaluated. The optimization experiments indicated that the quantitative extraction of mercury species from biological samples could be achieved by using 0.1% (v/v) HCl, 0.1% (v/v) 2-mercapoethanol and 0.15% (m/v) KCl extractant solution in an incubator shaker for shaking overnight (about 12 h) at room temperature. The established method was validated by analysis of various biological certified reference materials, including NRCC DOLT-3 (dogfish liver), IAEA 436 (tuna fish), IAEA MA-B-3/TM (garfish filet), IAEA MA-M-2/TM (mussel tissue), GBW 08193 (bovine liver) and GBW 08572 (prawn). The analytical results of the reference materials were in good agreement with the certified or reference values of both methyl and total mercury, indicating that no distinguishable transformation between mercury species had occurred during the extraction and determination procedures. The limit of detection (LOD) for methyl (CH₃Hg⁺) and inorganic mercury (Hg²⁺) by the method are both as 0.2 μg L⁻¹. The relative standard deviation (R.S.D.s) for CH₃Hg⁺ and Hg²⁺ are 3.0% and 5.8%, respectively. The advantages of the developed extraction method are that (1) it is easy to operate in HPLC–ICP-MS for mercury species determination since the extracted solution can be directly injected into the HPLC column without pH adjustment and (2) the memory effect of mercury in the ICP-MS measurement system can be reduced.     

Method for the determination of thorium and uranium in urine by ICP-MS

ICP-MS (inductively coupled plasma mass spectrometry) is shown as a very sensitive method for quantitative determination of Th and U concentration and excretion analysis in urine without any sample pretreatment. The current standard method for incorporation monitoring applies alpha-spectrometry, a very tedious and time consuming technique. ICP-MS offers an attractive alternative for monitoring of thorium and uranium body burdens in occupationally exposed subjects and also larger groups of the general population. A limit of determination of 0.5 ng/L in aqueous solutions and 1 ng/L in urine samples for both elements was achieved, with a precision of about ± 10% in the concentration range of appr. 10 ng/L. Due to the lack of a suitable reference material, the accuracy of the method was tested by comparing some of the results with those obtained by -spectrometry, especially for U. There was a sufficient agreement on both results.     

ICP-MS法测定磁致冷材料-钆硅锗系合金中Mo、 Mn、 Al、 V、 Ni、 Cu、 Ga、 Fe

建立了ICP-MS法测定磁致冷材料-钆硅锗系合金中Mo、 Mn、 Al、 V、 Ni、 Cu、 Ga、 Fe八种痕量杂质元素的方法, 并对ICP-MS工作参数及条件进行了优化. 方法的检出限为0.1～0.6 ng/mL, 测定下限为0.5～3 ng/mL, 回收率在95.5%～109%, 相对标准偏差(n=11)为1.3%～7.6%. 采用该方法对磁致冷材料-钆硅锗系合金实际样品进行了分析, 结果表明精密度和准确度均满足痕量分析的要求.     

KOH快速消解/ICP-MS测定婴幼儿乳粉中总碘含量

建立了一种简便、快速地测定不同乳粉基质中总碘含量的KOH快速消解/ICP-MS方法。优化了KOH溶液的浓度和消解温度等因素,并探讨了消解后溶液的稳定情况。结果表明,在105℃下,5%KOH溶液可在1 h内完全消解乳粉样品中的总碘,消解后的碘离子在氨水-Na2S2O3溶液中可稳定存在48 h,用141Pr作内标,ICP-MS直接测定其滤液中的碘含量,该方法相对于国标GB 5413.23-2010法减少了复杂的前处理沉淀和衍生萃取操作。碘的标准曲线在0~100μg/L浓度范围内呈良好线性,相关系数为1.000 0,方法检出限为1.5μg/kg。对标准物质GBW 10017、NIST SRM 1849a、奶基乳粉、豆基乳粉进行测定,测得样品的加标回收率为88.2%~107.4%,重复性和再现性相对标准偏差均小于5%,标准物质GBW 10017和NIST SRM 1849a的测定值与标示值一致。该方法准确、灵敏高、回收率好,适用于不同乳粉基质中总碘含量的测定。     

icp-ms法测定化妆品中铬的方法

用电感耦合等离子体质谱法(ICP-MS),建立了不同化妆品基质中铬的测定分析方法。样品预处理采用以HNO3水溶液作消化试剂的微波消解方法,并对5种不同化妆品基质中消化试剂的用量进行了比较。优化选择电感耦合等离子体质谱仪的工作参数,考察了测量过程中的基体效应及质谱干扰,针对不同化妆品样品,选择52Cr、53Cr作为测量同位素,72Ge为内标元素,对试样进行定量分析,有效地补偿基体效应所引起的测量偏差。实验证明,52Cr、53Cr的检测结果差异不大,均能满足化妆品中铬的测定要求。对照分析了参考标准物质。铬质量浓度在0.1~100μg/L范围内,校正曲线的相关系数为0.9999;铬添加质量浓度为0.5mg/kg,添加平均回收率为85.3%~104%;相对标准偏差(RSD)为1.5%~7.3%,52Cr检出限为0.052μg/kg,53Cr检出限为0.036μg/kg。     

古汉养生精中微量元素的ICP-MS分析

本文报道用ICP—MS法同时测定样品中Pb、As、Cu、Zn、Cd、Cr、Ni、Mn等8种微量元素。样品用微波消解。对影响测定的各种因素进行了研究,实验确定了最佳测定条件。本法的检出限为0．01～0．08μg／L,回收率为92．11％～112.82％,RSD小于4.30％。方法准确、快速、简便,应用于古汉养生精中微量元素的测定,结果满意。