Quantification of trace amounts of impurities in high purity cobalt by high resolution inductively coupled plasma mass spectrometry

A An analytical method using high resolution inductively coupled plasma mass spectrometry （HR-ICP-MS） for rapid simultaneous determination of 24 elements （Be, Mg, A1, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, As, Se, Mo, Ag, Cd, Sn Sb, Ba, Pt, Au, and Pb） in high purity cobalt was described. Sample digestions were performed in closed microwave vessels using HNO3 and HCI. The matrix effects because of the presence of excess HCI and Co were evaluated. The usefulness of high mass resolution for overcoming some spectral interference was demonstrated. The optimum conditions for the determination were tested and discussed. The standard addition method was employed for quantitative analysis. The detection limits were 0.016-1.50 ].tg·g^-1, the recovery ratios were 92.2%-111.2%, and the RSD was less than 3.6%. The method was accurate, quick, and convenient. It was applied to the determination of trace impurities in high purity cobalt with satisfactory results.

Determination of trace elements in high purity nickel by high resolution inductively coupled plasma mass spectrometry

The contents ofMg, Al, Si, Ti, Cr, Mn, Fe, Co, Cu, Ga, As, Se, Cd, Sb, Pb and Bi in high purity nickel were determined by high resolution inductively coupled plasma mass spectrometry （HR-ICP-MS）. The sample was dissolved in HNO3 and HCI by microwave digestion. Most of the spectral interferences could be avoided by measuring in the high resolution mode. The matrix effects because of the presence of excess HC1 and nickel were evaluated. Correction for matrix effects was made using Sc, Rh and T1 as internal standards. The optimum conditions for the determination were tested and discussed. The detection limits range from 0.012 to 1.76 ~tg/g depending on the type of elements. The applicability of the proposed method is also validated by the analysis of high purity nickel reference material （NIST SRM 671）. The relative standard deviation （RSD） is less than 3.3%. Results for determination of trace elements in high purity nickel were presented.

Quantification of Trace Amounts of Impurities in High Purity Cobalt by High Resolution Inductively Coupled Plasma Mass Spectrometry

An analytical method using high resolution inductively coupled plasma mass spectrometry （HR-ICP-MS） for rapid simultaneous determination of Be, Mg, Al, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, As, Se, Mo, Ag, Cd, Sn, Sb, Ba, Pt, Au and Pb in high purity cobalt was described. Sample digestions were performed in closed microwave vessels using HNO3 and HCl. The matrix effects due to the presence of excess HCl and Co were evaluated. The usefulness of high mass resolution for overcoming some spectral interference was demonstrated. The optimum conditions for the determination was tested and discussed. Correction for matrix effects, Sc, Rh and Bi were used as internal standards. The detection limits is 0.003-0.57 μg/g, the recovery ratio is 92.2%-111.2%, and the RSD is less than 3.6%. The method is accurate, quick and convenient. It has been applied to the determination of trace impurities in high purity cobalt with satisfactory results.

Direct Determination of Trace Impurities in High Purity Zinc Oxide by High Resolution Inductively Coupled Plasma Mass Spectrometry

The determination of trace impurities in high purity zinc oxide by high resolution inductively coupled plasma mass spectrometry （ HR-ICP-MS ） was investigated. To overcome some poteutially problematic spectral iuterference, measurements were acquired in both middle and high resolution modes. The matrix effects due to the presence of excess HCl and zinc were evaluated. The optimum conditions for the determination were tested and discussed. The standard addition method was employed for quantitative analysis. The detection limits ranged from 0.02μg/ g to 6 μg/ g depending on the elements. The experimental resalts for the determination of Na, Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Mo, Cd, Sb and Pb in several high purity zinc oxide powders were presented.

Determination of Trace Elements in High Purity Gold by High Resolution Inductively Coupled Plasma Mass Spectrometry

Trace elements were determined in high purity gold by high resolution inductively coupled plasma mass spectrometry （HR-ICP-MS）. Sample were decomposed by aqua regia. To overcome some potentially problematic spectra/ interference, measurements were acquired in both medium and high resolution modes. The matrix effects due to the presence of excessive HCl and Au were evaluated. The optimum conditions for the determination was tested and discussed. The standard addition method was employed for quantitative analysis. The detection limits range from 0.01ug/g to 0.28ug/g depending on the elements. The method is accurate, quick and convenient. It has been applied to the determination of trace elements in high purity gold with satisfactory results.

The determination of 52 elements in marine geological samples by an inductively coupled plasma optical emission spectrometry and an inductively coupled plasma mass spectrometry with a high-pressure closed digestion method

An improved analytical method to determine the content of 52 major, minor and trace elements in marine geological samples, using a HF-HCl-HNO_3 acid system with a high-pressure closed digestion method（HPCD）, is studied by an inductively coupled plasma optical emission spectrometry（ICP-OES） and an inductively coupled plasma mass spectrometry（ICP-MS）. The operating parameters of the instruments are optimized, and the optimal analytical parameters are determined. The influences of optical spectrum and mass spectrum interferences, digestion methods and acid systems on the analytical results are investigated. The optimal spectral lines and isotopes are chosen, and internal standard element of rhodium is selected to compensate for matrix effects and analytical signals drifting. Compared with the methods of an electric heating plate digestion and a microwave digestion, a high-pressure closed digestion method is optimized with less acid, complete digestion,less damage for digestion process. The marine geological samples are dissolved completely by a HF-HCl-HNO_3 system, the relative error（RE） for the analytical results are all less than 6.0%. The method detection limits are 2–40μg/g by the ICP-OES, and 6–80 ng/g by ICP-MS. The methods are used to determine the marine sediment reference materials（GBW07309, GBW07311, GBW07313）, rock reference materials（GBW07103, GBW07104,GBW07105）, and cobalt-rich crust reference materials（GBW07337, GBW07338, GBW07339）, the obtained analytical results are in agreement with the certified values, and both of the relative standard deviation（RSD） and the relative error（RE） are less than 6.0%. The analytical method meets the requirements for determining 52 elements contents of bulk marine geological samples.

高分辨率电感耦合等离子体质谱法测定钨钼矿石中金属元素含量的试验研究

试验采用高分辨率电感耦合等离子体质谱法(High-Resolution Inductively Coupled Plasma Mass Spectrometry,HR-ICP-MS)测定钨钼矿石中钨、钼、锂、铬、钴、镍、铜、锌、镓、锗、砷、硒、铷、铌、铟、锡、锑、铼、铊和铋等元素的含量。参考国家一级标准物质,对HR-ICP-MS进行数据比较和精确度验证,按照相关标准规定的方法确定HR-ICP-MS的检出限。结果表明,采用HR-ICP-MS测量钨钼矿石金属元素的相对标准偏差(Relative Standard Deviation,RSD)为0.86%~9.70%,各元素的检出限介于0.002~27.000 mg/kg,加标试验后的回收率损失小于2%,该方法可靠可信,准确度和精密度都能达到测试要求。

盐酸超声提取-高分辨电感耦合等离子体质谱法测定食用植物油中11种微量金属元素

提出了盐酸超声提取-高分辨电感耦合等离子体质谱法(HR-ICP-MS)快速测定食用植物油中铝、钡、镉、铜、铁、镁、锰、镍、铅、钒、锌等微量金属元素的方法。取2.0 g食用植物油样品,置于50 mL塑料离心管中,加入800μL ICP溶剂油,于旋涡混匀器上充分混匀,加入10 mL 2.0 mol·L^(-1)盐酸溶液,于70℃超声30 min,冷却。以转速10000 r·min^(-1)离心5 min,在水相与有机相分离后,收集水相,采用HR-ICP-MS测定其中11种元素含量,待测同位素^(51)V、^(56)Fe、^(27)Al、^(63)Cu、^(24)Mg、^(55)Mn、^(60)Ni、^(66)Zn选择中分辨率模式,而^(137)Ba、^(111)Cd和^(208)Pb选择低分辨率模式。结果表明:11种元素的质量浓度在100μg·L^(-1)以内与对应的信号强度呈线性关系,检出限(3s)为0.012~0.173μg·L^(-1);按照标准加入法对食用植物油进行回收试验,回收率为86.9%~107%,测定值的相对标准偏差(n=7)为1.1%~4.9%;方法用于分析3种植物油样品,本方法测定值与标准方法的测定值基本一致。

高盐食品基质中砷含量的测定

建立了一种基体匹配-动态反应池-电感耦合等离子体质谱法测定高盐食品基质中砷含量的方法,以解决高盐基体对砷测定的质谱干扰和基体干扰。研究电感耦合等离子体质谱法与氢化物发生原子荧光光谱法测定食品中总砷的技术要点,通过分析前处理消解方式、有机基质、氯含量和内标校正元素等对砷含量测定的影响,建立了高盐食品基质中砷含量的测定方法。实验结果表明,微波消解法并不太适用于氢化物发生原子荧光光谱法测定食品中总砷,有机基质和氯分别会对砷的质谱测定信号产生增敏效应和质谱干扰,74Ge比72Ge更适合作为电感耦合等离子体质谱法测定食品中总砷的内标元素。建立的检测方法定量限0.010 mg/kg,高盐基体中砷在0.010、0.025、0.20、0.50 mg/kg添加水平的回收率为91.50%~110.80%,相对标准偏差范围为0.76%~7.22%。本法和参照法对样品分析结果统计值均大于t0.90,10(1.81,双边),测定结果存在显著性差异,对实际样品测定结果表明动能歧视测定模式并不太适用于高盐食品基质样品中总砷的测定。该方法准确可靠,能用于高盐和高基体食品中砷含量的测定分析。

微波灰化-高效液相色谱-电感耦合等离子体质谱(ICP-MS)法测定茶叶中的铬酸铅

为了准确测定茶叶中铬酸铅的含量,为市场监管提供判断依据,茶叶样品经微波灰化仪在500℃的条件下灰化50 min后,用0.25 mol/L的NaOH和0.14 mol/L的Na_(2)CO_(3)混合碱性提取液在90~95℃下不间断搅拌提取10 min,提取液经色谱柱分离后,用电感耦合等离子体质谱(ICP-MS)法测定^(52)Cr,建立了微波灰化-高效液相色谱-电感耦合等离子体质谱仪测定茶叶中铬酸铅的方法。研究表明,方法在5.00~500μg/L线性良好,相关系数为0.9998,方法检出限低至2.5 mg/kg,三水平加标回收率为91.3%~95.3%,精密度在1.1%~2.0%。与电炉灼烧茶叶相比,微波灰化具有检出限低、精密度高、准确度良好等特性,能够满足茶叶中铬酸铅的测定。

高压密闭消解-电感耦合等离子体质谱法测定地球化学样品中6种元素的含量

提出了高压密闭消解-电感耦合等离子体质谱法(ICP-MS)测定地球化学样品中硼、钴、钼、镉、锗、铍等6种元素含量的方法。取样品0.1000 g于聚四氟乙烯坩埚中,加入3 mL 50%王水(体积比为3∶1∶4的盐酸-硝酸-水混合溶液)和0.5 mL氢氟酸,静置30 min后,于180℃烘箱中高压消解18 h。消解结束后,用水定容至50 mL,采用ICP-MS测定其中6种元素含量。结果表明:硼、钴元素的质量浓度在200μg·L^(-1)以内,钼、镉、锗、铍元素的质量浓度在10.0μg·L^(-1)以内与对应的谱峰强度与内标谱峰强度比呈线性关系,检出限(3s)为0.005~0.12 mg·kg^(-1);方法用于分析国家标准物质,测定值与认定值基本一致,并且测定值的相对标准偏差(n=12)均小于8.0%;方法用于两个实际地球化学样品的分析,其测定结果与DZ/T 0279-2016的基本一致,且相对标准偏差(n=12)均小于5.0%。

动能歧视碰撞-电感耦合等离子体质谱法测定高纯石英砂中16种元素

采用动能歧视碰撞模式消除多原子离子干扰,以干扰方程扣除Sr对Ca的双电荷干扰,建立一种用单四级杆电感耦合等离子体质谱仪同时测定Al、Ca、Cr、Cu、Fe、Ge、K、Li、Mg、Mn、Na、Ni、P、Sr、Ti、Zn 16种杂质元素含量的方法,检出限为0.001~0.1μg/g,样品回收率为92%~110%。将其应用于高纯石英标准物质测定,结果的相对误差(RE)为-29.03%~10.77%,相对标准偏差(RSD)不大于6.0%(n=10)(仅考察给出认定值的元素)。方法用于4N8纯度高纯石英砂中杂质含量的测定,结果满意。

高效液相色谱-电感耦合等离子体质谱法同时测定植物性富硒食品中7种硒元素形态含量

目的考察微波辅助下酶解法的提取效果,基于动态反应池(dynamic reaction cell,DRC),建立高效液相色谱-电感耦合等离子体质谱法(high performance liquid chromatography-inductively coupled plasma mass spectrometry,HPLC-ICP-MS)同时测定植物性富硒食品中7种硒元素(硒酸根、亚硒酸根、硒代胱氨酸、L-硒甲基硒代半胱氨酸、L-硒代蛋氨酸、甲基亚硒酸、硒代乙硫氨酸)形态的含量。方法样品经微波辅助胰蛋白酶酶解,高速离心后取上清液过水相滤膜。采用HPLC-ICP-MS仪,以甲烷为反应气体DRC模式消除质谱干扰,内标校正,以外标法进行定量分析。优化色谱和质谱条件,从酶的种类、酶的用量、萃取温度、萃取时间、加标回收率等方面考察前处理方法对待测物的提取效果。结果7种目标物在0.5~100.0μg/L范围内呈良好线性关系,相关系数(r)均大于等于0.9998,平均回收率为91.45%~102.75%,检出限为0.10~0.30μg/kg,定量限为0.30~0.90μg/kg,日间日内精密度(n=6)分别小于5%和9%。结论该方法准确、灵敏,适用于食品中7种硒元素形态的同时检测。

微波消解-三重四级杆电感耦合等离子体质谱法同时测定地球化学土壤中锗、砷、硒、镉、锡、碲

建立微波消解-三重四极杆电感耦合等离子体质谱法测定地球化学土壤中的锗、砷、硒、镉、锡、碲。在4mL硝酸-1 mL氢氟酸体系下,采用微波消解样品,利用三重四极杆电感耦合等离子体质谱仪的氧气反应模式和氦气碰撞模式去除干扰,氧气、氦气流量分别为0.25 mL/min和4 mL/min。通过向样品溶液中加入甲醇,使硒、碲检测灵敏度分别提高了约90%、40%;选用高灵敏截取锥嵌片,使硒、碲检测灵敏度均提高了约30%。锗、砷、硒、镉、锡、碲6种元素的质量浓度在一定范围内与荷质比强度线性关系良好,相关系数均大于0.999,方法检出限为0.005~0.16 mg/kg。采用所建方法对标准物质GBW 07403、GBW 07404和GBW 07405a进行测定,测定平均值均在标准值范围内,测定结果的相对标准偏差为2.45%~6.21%(n=12)。该方法操作简便、成本低、污染小,具有实际应用前景。

高效微波消解-电感耦合等离子体质谱法同时测定养殖鳗鱼中10种无机元素含量

目的:基于高效微波消解-电感耦合等离子体质谱(ICP-MS)法建立同时测定鳗鱼中铅、镉、汞、砷、铬、锰、镍、铜、锌、硒等10种无机元素含量的方法。方法:取均匀粉碎后鳗鱼肌肉,加优级纯硝酸经高效微波消解后,用电感耦合等离子体质谱仪进行分析,氦气碰撞检测模式,在线加内标,标准曲线法定量。结果:10种元素线性相关系数均大于0.9995,方法检出限0.0009mg/kg~0.0071mg/kg,加标回收率83.1%~102.8%,相对标准偏差RSD≤4.15%(n=6)。结论:本方法具有操作快捷、线性范围宽、检出限低、准确度和精密度高、回收率好、多元素同时测定的优点,适用于大批量养殖鳗鱼中多种无机元素含量的检测。

高压微波消解-电感耦合等离子体质谱法测定多产地红枣样品中铜铅锌镉铬镍砷

准确测定红枣中的重金属对控制和提高食品安全具有非常重要的意义。采用高压微波消解法用HF-H_(2)O_(2)体系处理样品,选择^(63)Cu、^(66)Zn、^(75)As、^(60)Ni、^(111)Cd、^(208)Pb、^(52)Cr为测量的同位素,采用仪器自带干扰公式校对Cd的测定结果进行校正,采用He气模式的碰撞反应池技术测定红枣样品中Cr和As,建立了电感耦合等离子体质谱(ICP-MS)法测定红枣样品中Cu、Pb、Zn、Cd、Cr、Ni、As的方法。通过前处理条件进行了优化,结果表明在本实验条件下,校准曲线的相关系数均不小于0.9995,检出限为0.0025~0.013μg/g,测定下限为0.012~0.42μg/g。按照本实验方法对红枣成分分析标准物质中Zn、Cr、Cu、Pb、Ni、Cd、As平行测定12次,各元素测定值与认定值基本保持一致,相对标准偏差(RSD)均在7.8%以内。采用实验方法对多产地红枣样品进行分析,结果表明本实验方法灵敏度高、结果稳定、测定量准确,可用于大批量红枣样品的测定。

岭南常用中药材外源性污染物分析研究

目的研究岭南不同产地200批次10种常用中药材(巴戟天、化橘红、何首乌、砂仁、广藿香、南板蓝根、黑老虎、鸦胆子、槟榔、益智)中农药残留、重金属外源性污染物含量,以期为南药质量控制提供依据。方法按照2020年版《中华人民共和国药典》(简称《中国药典》)对10种岭南常用中药材中重金属及有害元素、农药等外源性污染物进行测定并分析测定结果。结果何首乌、南板蓝根、黑老虎、槟榔、益智中农药残留量及铅、砷、镉、汞、铜限量均符合《中国药典》的限量标准,巴戟天、化橘红、砂仁、鸦胆子均存在重金属不符合,广藿香存在农药残留量不符合。结论对于研究的品种,农药残留控制较好,需要重点监控铅、汞元素。

酸溶-电感耦合等离子体质谱法测定煤系样品中稀土元素的方法研究

煤和含煤岩系在特定地质条件下可以富集稀土等金属元素。煤及矸石燃烧后产生的飞灰,其金属元素富集度更高,有望成为稀土等关键矿产的替代来源之一。针对煤系样品有机物含量高、基体组成复杂等问题,本文通过溶样方式、消解酸体系、浸提液、质谱干扰及扣除等条件实验研究,利用高压密闭酸溶法和半密闭酸溶法建立了分别适用于煤和煤系样品中稀土元素的电感耦合等离子体质谱(ICP-MS)分析方法。结果表明,硝酸-氢氟酸高压密闭酸溶法能够实现煤中稀土元素的准确测定,但对煤飞灰和煤矸石的稀土元素回收率不稳定,不同样品稀土回收率在37%~123%之间。在原有消解酸体系中,加入硫酸和高氯酸或改用盐酸复溶,均不能有效地提高稀土元素的回收率。五酸半密闭酸溶可以实现煤飞灰、煤矸石等煤系样品中稀土元素的完全分解。利用X射线衍射(XRD)和扫描电子显微镜(SEM)技术对煤系样品中元素的赋存状态进行了初步解析,揭示了高铝矿物是造成煤矸石等煤系样品中稀土元素溶出率低的主要原因,为实验方案的制定和优化提供了理论依据。利用标准物质和实际样品开展了方法验证,所建方法具有良好的精密度(相对标准偏差为0.05%~9.98%)和正确度(相对误差为-10.2%~7.62%),检出限低,可以实现煤系样品中稀土元素的多元素准确测定,适用于大批量样品中稀土元素的分析测试。

海水中三价与六价铬高效液相色谱-三重四级杆电感耦合等离子体质谱法(HPLC-TQ-ICP-MS)的联用测定

基于高效液相色谱(HPLC)与三重四级杆电感耦合等离子体质谱(TQ-ICP-MS)联用技术,构建海水中三价铬与六价铬在线分离与测定的检测方法。采用TQ-ICP-MS碰撞反应池(KED)技术消除^(35)Cl^(16)O1H^(+)、^(40)Ar^(12)C对^(52)Cr同位素测定可能存在的质谱干扰。选用Dionex IonPac AG 7 (4 mm×50 mm10μm)阴离子交换柱为分析柱,对流动相浓度及pH值进行优化,结果表明,当流动相浓度为0.08 mol/L NH_(4)NO_(3)、0.6 mmol/L EDTA,pH值7.5,流速1.0 mL/min时,仅需80 s就可以完成三价铬和六价铬的理想分离与测定。对络合剂EDTA的络合浓度、pH、温度及时间进行了深入研究,结果显示,当EDTA浓度为10 mmol/L、络合pH值7.5、络合温度50°C、络合时间2 h时,三价铬可以最大程度的被EDTA络合。在0.1~50.0μg/L标准浓度范围内,三价铬和六价铬浓度与信号强度的线性相关系数大于0.999 9,检出限分别为0.010和0.015μg/L,方法的回收率90.4%~107.9%,相对标准偏差RSD为1.66%~3.71%(n=6)。该方法灵敏度高,分离度高,分析时间短,准确性和精密度好,可作为海水及其他高盐样品中铬形态分析的理想方法,并可为海水环境质量评价提供科学依据。

高效液相色谱-电感耦合等离子体质谱法分析尿中6种砷形态

采用高效液相色谱-电感耦合等离子体质谱法(HPLC-ICP-MS)分析人尿中砷甜菜碱(AsB)、二甲基砷(DMA)、砷胆碱(AsC)、亚砷酸盐(As(Ⅲ))、一甲基砷(MMA)、砷酸盐(As(V))6种砷形态。样品经水稀释后,采用Dionex IonPac As7阴离子交换色谱柱为分析柱,20 mmol/L碳酸铵(2%甲醇)和100 mmol/L碳酸铵(含2%甲醇)为流动相,梯度洗脱,HPLC-ICP-MS分析砷形态。6种砷形态在0~100μg/L范围内线性关系良好,相关系数(r)均大于0.999,检出限为0.05~0.15μg/L,不同浓度水平砷形态的相对标准偏差(RSD)均小于5.0%。3种不同浓度水平的加标回收率为91.8%~108%,有证标准物质“冷冻人尿中砷形态”(NIST SRM 3669)中5种砷形态的测定结果在标准值范围内。实验结果表明,该方法准确可靠、灵敏度高、分析时间短,适用于人尿中砷形态的分析测定。同时研究了食用不同含砷食物后尿中砷形态的种类,结果显示不同的含砷食品,其砷在人体内的代谢转化不同。