微波消解-电感耦合等离子体质谱法测定地质样品中稀土元素

建立了微波消解-电感耦合等离子体质谱(ICP-MS)测定地质样品中稀土元素的方法,采用HNO3-HF体系-微波消解进行样品前处理,经赶酸后再用5 m L 1∶1 HNO3提取,整个过程安全、高效、无损失。利用ICP-MS进行测定,可以有效降低多原子离子质谱干扰,在优化仪器参数后,用内标铑(Rh)进行校正,弥补基体抑制效应和灵敏度漂移,测试结果更加准确。方法用于岩石标准物质(GBW07109,GBW07110和GBW07111)测试,其测定值与标准值相一致。结果表明,该方法的检出限低,准确度高,操作简单快捷,可同时测定多种元素,能满足批量测定地质样品中稀土元素含量的要求。     

ICP-MS法测定土壤中稀土元素的消解条件研究

本文采用"硝酸-氢氟酸-高氯酸-硫酸"的湿法消解体系,优化了各种酸的用量和消解条件,以103Rh、185Re为内标元素,采用He碰撞模式消除多原子离子对待测元素的干扰,建立了土壤中15种稀土元素ICP-MS检测的湿法消解及分析方法。在优化条件下,不同类型国家土壤标准样品中15种稀土元素的检测结果的回收率为82.3%～113%,相对标准偏差为1.5%～8.7%,方法检出限0.001～0.015mg·kg~(-1),方法测定下限0.004～0.060mg·kg~(-1),此方法可用于多种类型土壤中稀土元素的ICP-MS检测,具有普遍适用性。     

微波消解-电感耦合等离子体质谱(ICP-MS)法同时测定紫菜中16种稀土元素

以农贸市场和超市的紫菜为样品,经过微波消解,利用电感耦合等离子体质谱(ICP-MS)法对紫菜中16种稀土元素进行同时测定。通过在线引入内标溶液,在0~2.00μg/L范围内检测信号(CPS)与稀土元素含量之间呈现良好的线性关系,相关系数R2均大于0.999 9,相对标准偏差(RSD)小于3.3%。用来测定国家标准物质GBW10052(GSB-30)和GBW10045中的稀土元素,所得结果与标准值基本一致,从而建立了一种快速、准确测定紫菜中痕量稀土元素的方法。     

一体化碰撞反应(iCRC)-电感耦合等离子体质谱(ICP-MS)法测定地质样品中痕量稀土元素

钡以及轻稀土元素氧化物对中、重稀土元素的干扰一直是质谱测试中存在的问题。建立了石墨粉垫底碳酸钠-硼酸混合熔剂熔融前处理样品,以103 Rh为内标校正,一体化碰撞反应-电感耦合等离子体质谱(ICP-MS)法测定地质样品中稀土元素含量的方法。探讨了碳酸钠-硼酸混合熔剂熔融前处理样品注意事项、碰撞模式下碰撞气流量和离子透镜的参数优化、干扰校正实验等问题,采用国家标准物质GBW07403、GBW07405、GBW07427、GBW07429验证,实验结果表明,各元素线性关系良好,相关系数均大于0.999,方法检出限在0.01～0.03mg/kg,相对误差为0.13%～7.1%,相对标准偏差为0.79%～6.6%,测定结果与标准值相吻合。对实际样品分析,得到平滑的球粒陨石归一化的稀土元素配分曲线,证明测定结果是合理可信的。方法熔剂用量少,过程空白低,对器皿的侵蚀小,直接加热浸取,简化了操作过程,适用于大批量地质样品中稀土元素的测定。     

微波消解样品-电感耦合等离子体质谱法测定植物灰分中微量元素

应用电感耦合等离子体质谱法(ICP-MS)同时测定植物灰分中21种微量元素和15种稀土元素.用微波消解样品,对微波消解植物灰分样品的条件进行了试验.其优选微波消解条件为:微波压力为2 MPa,消解时间为10 min,以硝酸、盐酸、氢氟酸、高氯酸(体积比为6比2比1比1)的混合酸消解样品,对0.100 0 g植物标准物质(GBW 07603)进行10次平行测定,微量元素测定结果的相对标准偏差(n=10)在0.87%～5.96%之间,稀土元素测定结果的相对标准偏差(n=10)在2.14%～8.00%之间.     

电感耦合等离子体质谱测试硫化物中的微量元素

采用多种酸组合消解方法消解硫化物样品,最终选取A:HNO3密闭消解法;B:HCI+HF与HNO3两步消解法对硫化物标准物质GBW07267(黄铁矿)、GBW07268(黄铜矿),GBW07270(闪锌矿)及硫化物标准物质WMS-1a(块状硫化物)样品进行消解,采用ICP-MS测试了39种微量元素.结果表明,HNO3密闭...     

微波消解-ICP—MS法同时测定砖茶中的铅、铜、铬和16种稀土元素

采用微波消解处理样品,以电感耦合等离子质谱（ICP-MS）法同时测定砖茶中的铅、铜、铬和16种稀土元素。采用外标法绘制校准曲线,分析了茶叶国家标准物质GBW 10016,测定值与标准值吻合。检出限为0．055-0．765μg／蚝,样品测定结果的相对标准偏差为0．2％～4．7％（n=6）。用加标回收的方法评价了该方法的准确性,回收率为88．0％-102．7％。该方法测定结果与电热板湿法消解前处理测定结果相比差异不显著。     

电感耦合等离子体质谱(ICP-MS)法测定金绿宝石中16种痕量稀土元素

金绿宝石结构稳定,常规敞开酸溶、密闭酸溶、微波消解三种前处理方法并不能将其完全分解,测定结果偏低。本文采用碳酸钠-硼酸混合熔剂进行熔融,样品分解完全,建立了电感耦合等离子体质谱法(ICP-MS)测定金绿宝石中16种痕量稀土元素的分析方法。选择丰度高、干扰小的同位素、动能歧视碰撞池(KED)模式及干扰系数校正法消除质谱干扰,以185Re为内标元素及样品稀释降低基体干扰。实验表明：各稀土元素的校准曲线相关系数r值在0.9991~0.9998之间,方法检出限为0.0001~0.0134 μg/g,定量限为0.0005~0.0670 μg/g。采用国家标准物质GBW07151验证方法的精密度,计算出相对标准偏差(RSD, n=7)在1.3%~4.6%之间,并将此方法用于金绿宝石实际样品中稀土元素的测定,RSD为0.9%~3.2%,加标回收率为94%~104%,符合国家地质矿产行业标准,结果稳定、可靠。     

电感耦合等离子体质谱法(ICP-MS)测定稀土矿中钇、镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥和钪量

通过用四酸与微波消解法溶解样品对比,建立了用硝酸、盐酸、氢氟酸、高氯酸分解样品,采用电感耦合等离子体质谱法(ICP-MS)测定稀土矿中16种元素含量。方法采用_¹⁰³Rh作为内标消除干扰,确定了最优测定条件,16种稀土元素检出限为0.0029-0.0099ng/mL,测定范围为0.0005-0.020%。精密度试验、加标回收试验及标准物质检测,结果验证了方法的可行性及准确性。该方法简单易操作,结果可靠,能满足实验分析要求。     

ICP-AES和ICP-MS法测定光学玻璃中的15种稀土元素

采用Na₂O₂熔融分解样品,运用电感耦合等离子体发射光谱法（ICP-AES）和电感耦合等离子体质谱法（ICP-MS）测定光学玻璃中的稀土元素。采用该方法对国家一级标准物质GBW07158、GBW07159、GBW07160和GBW07161进行测定,其结果表明与标准值相符。方法选择性好、灵敏度好、定量准确,适用于光学玻璃中稀土元素的测定,结果令人满意。     

一体化碰撞反应 (iCRC)-电感耦合等离子体质谱法测定地质样品中痕量稀土元素

钡以及轻稀土元素氧化物对中、重稀土元素的干扰一直是质谱测试中存在的问题。建立了石墨粉垫底碳酸钠-硼酸混合熔剂熔融前处理样品,以_¹⁰³Rh为内标校正,一体化碰撞反应-电感耦合等离子体质谱仪法测定地质样品中稀土元素含量的方法。探讨了碳酸钠-硼酸混合熔剂熔融前处理样品注意事项、碰撞模式下碰撞气流量和离子透镜的参数的优化、干扰校正试验等问题,采用国家标准物质GBW07403、GBW07405、GBW07427、GBW07429验证,实验结果表明,各元素线性关系良好,相关系数均大于0.999,方法检出限在0.01～0.03mg/kg之间,相对误差为0.13%～7.1%,相对标准偏差为0.79%～6.59%,测试结果与标准值相吻合。对实际样品分析,得到平滑的球粒陨石归一化的稀土元素配分曲线,证明测定结果是合理可信的。该方法熔剂用量少,过程空白低,对器皿的侵蚀小,直接加热浸取,简化了操作过程,适用于大批量地质样品中稀土元素的测定。     

Flow injection on-line solid phase extraction coupled with inductively coupled plasma mass spectrometry for determination of (Ultra)trace rare earth elements in environmental materials using maleic acid grafted polytetrafluoroethylene fibers as sorbent

A new sorbent, maleic acid grafted polytetrafluoroethylene fiber (MA-PTFE), was prepared and evaluated for on-line solid-phase extraction coupled with inductively coupled plasma mass spectrometry (ICP-MS) for fast, selective, and sensitive determination of (ultra)trace rare earth elements (REEs) in environmental samples. The REEs in aqueous samples at pH = 3.0 were selectively extracted onto a microcolumn packed with the MA-PTFE fiber, and the adsorbed REEs were subsequently eluted on-line with 0.9 mol l(-1) HNO3 for ICP-MS determination. The new sorbent extraction system allows effective preconcentration and separation of the REEs from the major matrix constituents of alkali and alkali earth elements, particularly their separation from barium that produces considerable isobaric interferences of 134Ba16O1H+, 135Ba16O+, 136Ba16O1H+, and 137Ba16O+ on 151Eu+ and 153Eu+. With the use of a sample loading flow rate of 7.4 ml min(-1) for 120 s preconcentration, enhancement factors of 69-97 and detection limits (3s) of 1-20 pg l(-1) were achieved at a sample throughput of 22 samples h(-1). The precision (RSD) for 16 replicate determinations of 50 ng l(-1) of REEs was 0.5-1.1%. The developed method was successfully applied to the determination of (ultra)trace REEs in sediment, soil, and seawater samples.     

辉光放电质谱法测定稀土矿中的15种稀土元素

利用高纯铜粉与稀土矿石粉末均匀混合压片制样.混合15种高纯稀土氧化物制样建立标准工作曲线,校正15种稀土元素相对灵敏度因子,再进行定量分析.结果 表明,稀土元素工作曲线的线性方程相关系数R2均大于0.996,相对标准偏差(RSD)小于5％,满足定量分析要求.测定结果与电感耦合等离子体质谱法(ICP-MS)和电感耦合等离...     

Studies on the Calibration of Matrix Effects and Ployatomic Interference for Rare Earth Elements in Geochemical Samples by ICP-MS

The primary factors limiting accuracy and precision using inductively coupled plasma mass spectrometry (ICP-MS) in the determination of rare earth elements (REE) are matrix effects and polyatomic interference. Matrix effects is non-linear and the degree of machine drift differs from one mass to the next. In general, the method to overcome non-spectroscopic matrix effects is to use matrix-matched standards. Polyatomic ions is a potential interference owing to the oxide and hydroxide formation of the light REE s (LREE),which interfere the heavy REE s (HREE) and the barium oxides of seven naturally isotopes (130-138 m/z) are also a potential source of interference. The polyatomic interference can be minimized using a knowledge of the sample matrix.     

三重四极杆电感耦合等离子体质谱(ICP-MS)法测定氧化铕中13种稀土杂质元素

稀土杂质元素直接影响高纯单金属稀土材料的整体性能,是高科技领域许多材料的重要组成部分。通过考察最佳的消解酸量、温度、时间、氧气反应气流量、稀释气流量,建立了基于三重四极杆电感耦合等离子体质谱仪(ICP-MS/MS)直接测定氧化铕中13种稀土杂质元素分析方法。该方法采用0.1%基体直接进样,可以很大程度提高前处理分析效率。利用碰撞模式测定氧化铕稀土中的Y、La、Pr、Nd、Sm、Gd、Tb、Dy、Ho、Er、Yb、Lu元素,氧气质量转移模式测定氧化铕中的Tm,两种模式结合可以有效去除多原子干扰,实现氧化铕的稳定测试分析。通过对氧化铕标准物质（GBW02902）直接测定分析,结果表明,在碰撞和氧气质量转移模式下,各元素线性相关系数（r）均大于 0.9999,方法检出限为0.001~0.023 mg/kg,测试精密度优于1.99%,13种元素的测试值都在认定值的不确定度范围之内。该分析方法操作简单,测试稳定,效率高,为实验室进行氧化铕材料中REE杂质的准确测试分析提供思路和借鉴。     

Assessment of the ICP-MS method using the interlaboratory QA study of two Polish soil RMs

 Under an international collaborative certification programme, two new Polish soil reference materials, PL-1 (loess) and BPGM-1 (sandy loam soil), were analysed for 34 trace elements including all the rare earth elements using the acid decomposition method and inductively coupled plasma - mass spectrometry (ICP-MS). After the certification by the organisers, the analytical data obtained at our institute were compared with the certified data. 'Z-score' values calculated for individual trace elements helped in the assessment of the quality of the data. While the majority of the data obtained on ICP-MS was very precise and accurate, some of the data especially for elements such as Zr, Hf and Nb suffered from incomplete dissolution of the sample and spectroscopic interferences. For some trace elements, certified data are not available for comparison. These features together with the usefulness of interlaboratory collaborative programmes and ICP-MS for the certification of soil reference materials are discussed. Received: 6 August 1999 / Accepted: 28 February 2000     

Determination of nitrite with a nano-gold modified glassy carbon electrode by cyclic voltammetry

Abstract

Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) was employed to determine the concentration of rare earth elements (REEs) in plants and soils. Sample preparation and analytical conditions were investigated to set up a simple routine procedure for measuring rare earth elements. For prompt sample decomposition, a microwave digestion technique was successfully used with an acid mixture of HCl+HNO₃+HF. Detection limits, reproducibility, accuracy and possible interference were also studied. ICP-MS provided extremely low detection limits for REEs (0.6–6ng/l). Precision was typically better than 6% RSD (relative standard deviation) for soil and 10% for plant. The potential of the method was evaluated by analysis of standard reference materials of soils and plants. A good agreement between the experimental results and certified values was observed. The spectroscopic interference of Ba with Eu and light REEs(LREEs, La-Eu) with heavy REEs(HREEs, Gd-Lu) were eliminated by the algebra correction.

The results suggested that REEs in soil samples existed mainly as light REEs, and the same concentration distribution patterns of Oddo-Hakins law were observed, showing negative gradient from La to Lu concentrations. The REE contents in plants were very low, less than 20μg/g and varied with plant species. Apart from rape leaf(Brassica juncea), the REE distribution patterns in other plant leaves were consistent with soils, indicating that these plants generally absorbed REEs from soil without selectivity. Rape leaf showed selective absorption for LREEs, especially for La. The REE concentration distribution in parts of hot pepper(Capsicum annuum) was characteriaed by root>leaf>stem>fruit. The REEs absorbed by hot pepper concentrated mainly in roots and leaves, very little migrated into fruit. Transfer factors(TFs) of REEs in plants were very low. Although the contents of LREEs were relatively more than those of HREEs, no distinct difference of TFs between LREEs and HREEs was observed, meaning that LREEs and HREEs have the same abilities of transportation. However, for rape leaf, the TFs of LREEs were one or two orders of magnitude higher than those of HREEs.     

微波溶样ICP-MS直接测定茶叶中15种痕量稀土元素

本文报道用ＨＮＯ３－Ｈ２Ｏ２微波溶样，不经分离富集，用标准加入ＩＣＰ－ＭＳ法，直接测定茶叶中１５种痕量稀土元素．对微波溶样和等离子体质谱测定条件进行了优化选择．在最佳实验条件下，用本法测定了国家一级茶叶标准物质ＧＢＷ０７６０５中的单一稀土元素，测得值与标准值很好吻合