电感耦合等离子体质谱测定地质样品中多种元素

用电感耦合等离子体质谱(ICP-MS)测定了地质样品中多种元素。考察了测量过程中的基体效应及质谱干扰,利用In内标,补偿由于基体效应的影响所引起的测量偏差,建立校正公式校正质谱干扰。方法的检出限为0.06~250ng/L,精密度为1.7%~3.2%,加标回收率为91%~108%,方法适于批量地质样品分析。     

电感耦合等离子体质谱法测定高纯氧化钽中28种痕量杂质元素

建立了用电感耦合等离子体质谱仪(ICP-MS)测定高纯氧化钽中28种痕量杂质元素的方法。讨论了质谱干扰及接口效应,采用标准加入法消除基体效应。各元素的方法检出限为0.001~0.1μg/g,回收率为90%~115%,方法适用于纯度为99.999%的高纯氧化钽中痕量杂质元素的测定。     

电感耦合等离子体质谱(ICP-MS)法测定地质样品中镉、铬、钨、钽和铌

地质样品成分复杂,各元素物理化学性质差异大,在有盐酸介质存在的的情况下,敞口湿法一次消解容易出现易挥发元素Cd、Cr等测定结果不稳定;敞口湿法一次消解,难溶元素W、Ta、Nb等消解不完全。本文以HNO3—HF—HClO4—H2SO4为消解体系,用电热板湿法重复消解样品,建立起了ICP-MS同时测定地质样品种不同性质Cd、Cr、W、Ta、Nb的样品分析方法。通过优化仪器参数条件,选择带碰撞池He气模式（ked）,以50g/L酒石酸为测定介质,采用三通在线加入103Rh和185Re内标补偿基体效应和信号飘逸,解决了难溶元素W、Ta、Nb结果偏低、易挥发元素Cd、Cr结果精密度较差的问题。该方法用国家一级标准物岩石、土壤、水系沉积物质验证,相对标准偏差(RSD)小于8%,准确度(△lgC)均≤0.05,其测定值与标准值一致,用实际样品进行加标回收试验,回收率在89%～110%之间,方法检出限均小于多目标区域地球化学调查规范（DZ/T 0258—2014）。该方法分析流程较简单,结果准确可靠,可满足测定大批量地质样品中Cd、Cr、W、Ta、Nb元素含量的要求。     

电感耦合等离子体质谱(ICP-MS)法测定锆钛矿中的铪

锆钛矿组成成分复杂,存在耐高温的锆、钛化合物,不易分解,且铪以类质同象进入锆矿物,导致锆钛矿中的铪含量不均,因此完全分解锆钛矿并准确测定其中含量不同的铪成为一个难题。本文建立了碳酸钠-硼砂高温熔融,以178Hf为分析同位素及50 ng/mL185Re为内标,使用电感耦合等离子体质谱法（ICP-MS）测定锆钛矿中铪的新方法,可准确锆钛矿中含量不均的铪。实验研究了锆钛矿成分及其熔融方法,结果表明碳酸钠-硼砂高温熔融效果最好,可完全溶解耐高温难分解的锆钛矿,当碳酸钠-硼砂质量配比为2:1时熔融效果最佳。电感耦合等离子体质谱法具有检出限低、灵敏度高、线性范围宽等优势,可用于测定锆钛矿中含量不均的铪,ICP-MS蠕动泵转速为45 rpm、雾化流量为1.06 L/min时雾化效率最优。在选定的实验条件下,HfO2质谱强度与其质量浓度在0.01～250 ng/mL范围内呈良好的线性关系,相关系数为0.9997,背景等效浓度为0.029 ng/mL,方法检出限为0.0032 ng/mL。按实验方法对中国国家标准物质中的HfO2进行测定,测定值与认定值一致,相对标准偏差在1.6%~3.2%之间。按实验方法对锆钛矿样品中的HfO2进行测定并进行加标回收率实验,测定结果的相对标准偏差（RSDs,n=9）在0.9～3.4%之间,加标回收率在96%～106%之间,满足国家地质矿产行业标准DZ/T 0130—2006的要求。     

Determination of hafnium at the 10% level (relative to zirconium content) using neutron activation analysis,inductively coupled plasma mass spectrometry and inductively coupled plasma atomic emission spectrometry

Hafnium at the very low level of 1–8 ppm (in relation to zirconium) was determined in zirconium sulfate solutions (originating from investigations of the separation of ca. 44 ppm Hf from zirconium by means of the ion exchange method) by using three independent methods: inductively coupled plasma mass spectrometry (ICP MS), neutron activation analysis (NAA) and inductively coupled plasma atomic emission spectrometry (ICP-AES). The results of NAA and ICP MS determinations were consistent with each other across the entire investigated range (the RSD of both methods did not exceed 38%). The results of ICP-AES determination were more diverse, particularly at less than 5 ppm Hf (RSD was significantly higher: 29–253%). The ion exchange method exploiting Diphonix^® resin proved sufficient efficiency in Zr–Hf separation when the initial concentration ratio of the elements ([Zr]₀/[Hf]₀) ranged from 1200 to ca. 143,000.     

Determination of rare-earth elements in uranium-bearing materials by inductively coupled plasma mass spectrometry

A novel and simple analytical procedure has been developed for the trace-level determination of lanthanides (rare-earth elements) in uranium-bearing materials by inductively coupled plasma sector-field mass spectrometry (ICP-SFMS). The method involves a selective extraction chromatographic separation of lanthanides using TRU™ resin followed by ICP-SFMS analysis. The limits of detection of the method proposed is in the low pg g⁻¹ range, which are approximately two orders of magnitude better than that of without chemical separation. The method was validated by the measurement of reference material and applied for the analysis of uranium ore concentrates (yellow cakes) for nuclear forensic purposes, as a potential application of the methodology.     

锆中铪的原子发射光谱分析法

研究了在氩氧控制气氛条件下锆中铪的分析条件,对氩氧比、激发电流、曝光时间等实验参数进行了选择。在选定条件下对实际试样进行分析,回收率在90%～113%之间,相对标准偏差小于5%,方法可用于锆中铪的质量分数为0 005%～5 0%的实样分析。     

On-line ion-exchange separation and determination of niobium,tantalum, tungsten,zirconium and hafnium in high-purity iron by flow injection inductively coupled plasma mass spectrometry

A study was made to investigate the feasibility of using an anion-exchange resin for on-line separation of trace amounts of niobium, tantalum, tungsten, zirconium and hafnium from iron matrix samples. The incorporation of a micro-column packed with Dowex 1X8-100 ion-exchange resin into a flow injection system is presented. The detection was done with inductively coupled plasma mass spectrometry (ICP-MS). The sample treatment, optimization of analytical variables and measurable concentration levels are discussed. Recoveries from standard additions to a high-purity iron were for all the analytes close to 100%, with relative standard deviations ranging from 0.7 to 3.0%. The limits of quantification (10 s_n−1) calculated from a 5% (m/v) iron sample solution were 8, 5, 14, 12 and 10 ng g⁻¹ for Nb, Ta, W, Zr and Hf, respectively. The accuracy of the proposed method was tested by determining these elements in Euronorm-CRM 098-1 reference material. Recoveries from 0.250 g test portions of the above reference material spiked with 2.5 and with 12.5 ng each of the five analytes are reported.     

Speciation of arsenic compounds by coupling high-performance liquid chromatography with inductively coupled plasma mass spectrometry

There is considerable evidence that toxicity and physiological behavior of arsenic depends on its chemical forms. Arsenic speciation became therefore the subject of increasing interest in recent years. A sensitive method for the determination of arsenic species has been developed. The proposed procedure involves the use of high-performance liquid chromatography and inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Six arsenic compounds were separated by anion-exchange chromatography with isocratic elution using tartaric acid as mobile phase with an elution order: arsenocholine, arsenobetaine, dimethylarsinic acid, methylarsonic acid, arsenous acid and arsenic acid. The chromatographic parameters affecting the separation of the arsenic species were optimized. Analytical characterization of the method has been realized with standard solutions. The detection limits for six arsenic compounds were from 0.04 to 0.6 g/L as As element. The repeatability (expressed by R.S.D) was better than 7% for all investigated compounds. The HPLC-ICP-MS system was successfully applied to the determination of arsenic compounds in environmental and biological samples in g/L level.     

王水提取-电感耦合等离子体质谱法同时测定地质样品中微量银、镉、铋

样品用水浴加热、王水提取预处理,采用电感耦合等离子体质谱法同时测定了土壤、水系沉积物及岩石等地质样品中的痕量Ag、Cd和Bi。在样品预处理阶段,主要干扰元素Zr和Nb只有少量被溶出,而分析元素Ag、Cd和Bi的溶出趋于完全,这样在样品预处理阶段就完成了分析元素与干扰元素的有效分离,减小了多原子离子93Nb16O ,92Zr16OH ,92Mo16OH 对109Ag的干扰和95Mo16O ,94Zr16OH ,94Mo16OH 对111Cd的干扰。方法对实际样品的检出限(10σ,DF=300)Ag,Cd和Bi的质量分数分别为5.1,4.3和10.5ng/g。对不同含量样品7次测定的RSD为8.7%~1.8%。用该方法对土壤、水系沉积物及岩石等国家一级标准物质进行分析,分析数据均在标准推荐值的允许误差范围内。     

Determination of total and soluble chromium(VI) in compost by ion chromatography–inductively coupled plasma mass spectrometry

Abstract

As part of a project investigating the air-water exchange of nutrients and inorganic micropollutants to the North Sea, the atmospheric deposition of nutrients and trace metals in their different compositions and via various pathways was investigated. Intensive sampling campaigns were organised on the research vessel Belgica (ns 21/98 campaign from September 28 to October 1, 1998 and ns 10/99 campaign from April 19 to 23, 1999), at a sampling station near the Belgian coast (Knokke-Heist) and at the University campus of Antwerp. Simulation work and remobilisation experiments were carried out to obtain a general view of the kinetics of solubilisation of the constituents under investigation. Sample treatment requires a leaching system with a quantitative recovery of the species of interest in the leaching solution within a reasonably short period of time (30 min).

For this reason, a re-circulation leaching system was developed, tested, optimised and compared with a more accepted ultrasound leaching method.     

Determination of ultratrace impurity elements in high purity niobium materials by on-line matrix separation and direct injection/inductively coupled plasma mass spectrometry

The determination of 52 impurity elements in niobium materials (niobium metal, niobium oxide (V), and niobium pentaethoxide) was performed by inductively coupled plasma mass spectrometry (ICP-MS) with on-line anion exchange matrix separation as well as direct nebulization. Niobium material samples were decomposed with a mixture of hydrofluoric acid and nitric acid to prepare 10% niobium solutions. In the on-line anion exchange matrix separation/ICP-MS, the niobium and hydrofluoric acid concentrations in sample solution were adjusted to 5% and ca. 8 M, respectively. The solution was then injected into the carrier stream from the sample loop of injection valve to pass through an anion exchange resin column. In the anion exchange separation, niobium in the fluoro-complex form was adsorbed on the resin, while impurity elements were eluted. The eluted elements were introduced into ICP-MS for the determination of 25 impurity elements. On the other hand, 27 impurity elements could not be separated well from niobium matrix under the above anion exchange conditions, and then the sample solution with the niobium concentration of max. 0.2% containing internal standard elements was injected from the sample loop of injection valve directly to introduce into ICP-MS. As a result, 52 impurity elements in three kinds of niobium materials could be determined at the ng g⁻¹ level.     

萃取色层分离同位素稀释ICP-MS测定空气中费克 量钚

ICP-MS测定环境样品中超痕量^2^3^9Pu时,^2^3^8UH^+会对m/z239的测量带来干扰。测得UH^+的产生几率为4.6×10^-^5,通过三正辛胺色层分离后,对铀的去除率为10^4,可以有效地去除^2^3^8UH^+离子峰对^2^3^9Pu测定的干扰。钚的回收率为75%。同位素稀释法对^2^3^9Pu的检出限为4.5×10^-^1^5g/mL,方法的定量测定限为16×10^-^1^5g/mL。用所建立的方法测得我国某地区空气中^2^3^9Pu的浓度为4.8×10^-^1^7g/m^3。     

高效液相色谱-电感耦合等离子体质谱联用检测食品中的五种硒形态

建立了高效液相色谱-电感耦合等离子体质谱(HPLC-ICP-MS)联用检测硒酸盐(SeVI)、亚硒酸盐(SeIV)、硒代蛋氨酸(SeMet)、硒代胱氨酸(SeCys2)和硒代乙硫氨酸(SeEt)的方法。采用Hamilton PRP X-100色谱柱（250 mm×4.6 mm, 5 μm）,使用5 mmol/L的柠檬酸溶液(pH 4.5)作为流动相,电感耦合等离子体质谱(ICP-MS)检测,在21 min内可以完全分离5种硒形态。各形态硒的线性相关系数均大于0.9995, SeVI、SeIV、SeMet、SeCys2、SeEt的检出限分别为0.4、0.4、5.6、0.9、1.2 μg/L。探讨了不同提取方法的提取效果,鲜蘑菇和猪肉样品加标回收实验表明,对水溶性良好的无机硒和硒代蛋氨酸而言,采用柠檬酸溶液提取的效果非常好,SeIV和SeVI的回收率均在100%左右,SeMet的回收率为85.0%～95.3%;用蛋白酶水解提取,SeCys2和SeEt的回收率为79.9%～91.5%。该方法可完全满足食品中这5种硒形态的准确定量分析。     

Determination of hafnium in zirconium oxide using inductively coupled plasma emission spectrometry

Determination of Hf using Inductively Coupled Plasma Spectrometry down to 100 ppm and less in Zr matrix has been studied. Standard additions method has been applied for determination of Hf at different Hf wavelengths. Additionally, Hf was determined after its separation from Zr matrix using AG 1-X8 Biorad anion exchange resin. It has been observed that hf content determined following standard additions method at Hf line 356.166 nm compared well with the results obtained using prior separation method.     

Determination of cobalamins using capillary electrophoresis inductively coupled plasma mass spectrometry

The determination of cobalamins using capillary electrophoresis inductively coupled plasma mass spectrometry (CE-ICP-MS) was investigated. Both capillary zone electrophoresis (CZE) and micellar electrokinetic chromatography (MEKC) modes of operation were studied. The optimal separation of four cobalamin species (cyanocobalamin, hydroxocobalamin, methylcobalamin, and 5′-deoxyadenosylcobalamin) and a potentially harmful corrinoid analogue (cobinamide dicyanide) was obtained using CZE at a pH of 2.5. Both 20 mM phosphate and 20 mM formate buffers were used with success, although the formate buffer provided improved resolution. The CZE-ICP-MS method was used to quantify cyanocobalamin in a vitamin supplement and the analytical results were in good agreement (±5%) with values obtained by ICP-MS for total Co levels. The solution detection limits for cobalamins using CZE-ICP-MS were approximately 50 ng/ml. MEKC was found to be useful for the screening of vitamin preparations because it provided a rapid means of distinguishing cyanocobalamin (the form most commonly used in vitamin preparations) from free cobalt. The separation of free cobalt and cyanocobalamin using MEKC was achieved in less than 10 min.     

Liquid-liquid extraction of zirconium from hafnium and other elements with dicyclohexyl-18-crown-6

Zirconium was quantitatively extracted with 2.5 × 10^?2 M dicyclohexyl-18-crown-6 in dichloromethane from 8.5 M hydrochloric acid. It was stripped with 0.5 M hydrochloric acid and was determined spectrophotometrically as its complex with Arsenazo III. Hafnium was not extracted under these conditions, but from the residual aqueous phase it was extracted with 7.0 × 10^?2 M dicyclohexyl-18-crown-6 in dichloromethane from 9.0 M hydrochloric acid. It was stripped with 0.1 M perchloric acid and determined spectrophotometrically at 540 nm as its complex with xylenol orange. The separation of zirconium and hafnium from other metals is also described.     

电感耦合等离子体质谱法测定镁合金中的多种元素

用电感耦合等离子体质谱(ICP-MS)法测定了镁合金中的Be、Al、Ca、Fe、Mn、Ni、Cu、Zn、Ag、Cd、Sn、La、Ce、Pb14种元素,进行了稳定性实验以及Cu、Zn、Ni、Mg、Al基体实验,考察了共存元素的干扰.镁合金标准物质测定值与参考值符合较好,方法检出限为0.0002～0.3346 μg/g,相对标准偏差RSD＜10%.     

Determination of niobium(V) and tantalum(V) as 4-(2-pyridylazo)resorcinol–citrate ternary complexes in geological materials by ion-interaction reversed-phase high-performance liquid chromatography

A method for the simultaneous separation and determination of Nb(V) and Ta(V) as ternary complexes formed with 4-(2-pyridylazo)resorcinol (PAR) and citrate was developed using ion-interaction reversed-phase high-performance liquid chromatography on a C₁₈ column. Method parameters, such as pre-column complex formation conditions and composition of the complexes were investigated using spectrophotometry and HPLC. Under the optimum conditions, the Nb(V) and Ta(V) complexes were eluted within 12 min with a mobile phase of methanol–water (32:68, v/v) containing 5 mM acetate, 5 mM TBABr and 5 mM citrate buffer at pH 6.5, with detection at 540 nm. A typical separation efficiency was 33 000 and 20 000 theoretical plates per metre for Nb(V) and Ta(V), respectively. The relative standard deviation of retention times for the Nb(V) and Ta(V) complexes were 0.16% and 0.17% and for peak areas were 0.28% and 1.36%, respectively. The detection limits (signal-to-noise ratio=3) for Nb(V) and Ta(V) were 0.4 ppb and 1.4 ppb, respectively. Results obtained for standard reference rock samples agreed well with certified values and results obtained by inductively coupled plasma MS.     

混酸分解-电感耦合等离子体质谱（ICP-MS）法测定地质样品中铌钽锂铍铷钨

地质样品中的铌、钽、锂、铍、铷、钨元素含量相差大,且同一样品中各元素含量差异也较大。如在原矿中的含量只有几十至几百μg/g,而在精矿中的含量则达到了百分之几至百分之几十,高含量样品中的铌钽元素在强酸性溶液中不稳定,极易水解,准确测定这些元素需要多种方法,分析过程繁琐。传统的分析方法过程复杂、难以实现同时测定多种元素。通过考察分解体系酸的用量选择、提取剂的选择、提取剂用量的选择、测定内标元素的选择,建立了混酸分解-电感耦合等离子体质谱法同时测定地质样品中铌、钽、锂、铍、铷、钨元素的测定方法。本文采用氢氟酸-硝酸-盐酸-高氯酸-硫酸分解样品,用3～4滴氢氟酸+ 5 %硫酸+ 5 %过氧化氢萃取体系代替常规有机酸(酒石酸等。)萃取体系。采用ICP -MS同时测定各含量段地质中铌、钽、锂、铍、铷、钨的不同含量。采用该方法测定国家一级标准物质 GBW07155、GBW07153 、GBW07185,结果表明,各元素的检测结果与认定值无显著性误差,精密度RSD（n=6）0.45%～4.05%,准确度?lgC （n=6）在-0.008%～0.009%之间,适用于地质样品中的铌、钽、锂、铍、铷、钨元素的测定。