Arsenic speciation by ion chromatography with inductively coupled plasma mass spectrometric detection.

Four As compounds were successfully separated and detected by single-column ion chromatography with inductively coupled plasma (ICP) mass spectrometric detection. The mass spectral interferent ArCl+ was reduced by chromatographically resolving chloride from the negatively charged arsenic species. Determination of four As species was investigated in urine, club soda and wine. Detection limits of 0.16 ng of As(III), 0.26 ng of As(v), 0.073 ng of dimethylarsinic acid (DMA) and 0.18 ng of methylarsonic acid (MMA) in wine were obtained. Sensitivity was further improved by using an He-Ar mixed gas ICP as the ionization source. However, the intensity of the ArCl+ interference was also increased using this plasma. Detection limits of 0.063 ng of As(III), 0.037 ng of As(v), 0.032 ng of DMA and 0.080 ng of MMA in club soda were achieved using the He-Ar plasma source. Similar limits of detection were found in urine and wine.     

“Age” determination of irradiated materials utilizing inductively coupled plasma mass spectrometric (ICP-MS) detection

A gas pressurized extraction chromatography (GPEC) system has been developed to perform elemental separations on radioactive samples to determine total and isotopic compositions of Cs and Ba from an irradiated salt sample, fuel sample and two sealed radiation sources. The GPEC system employs compressed nitrogen to move liquid through the system, compared to gravity or pumped liquids that are typically used for separations. A commercially available Sr-Resin™ was used to perform the separation for the above mentioned analytes. A 1% acetic acid solution was determined to be the best extractant for Ba. A flow rate of 0.1 mL/min was determined to be optimal for the separation of Ba. Complete recovery of the Cs and Ba was achieved, within the systematic uncertainties of the experiments.     

Neptunium determination by inductively coupled plasma mass spectrometry (ICP-MS)

The determination of neptunium-237 (²³⁷Np) traditionally has been performed by alpha spectrometry or neutron activation analysis. These methods are labor intensive and require several days for completion. Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is a possible alternative for²³⁷Np determinations. This paper describes the analytical method developed for samples that have significant levels of uranium present. The lower reporting limits achievable by ICP-MS are competitive with the counting methods, but the real advantage for this laboratory lies in the lower cost and faster turnaround time provided by ICP-MS.     

Determination of plutonium by inductively coupled plasma mass spectrometry (ICP-MS)

Inductively coupled plasma mass spectrometry (ICP-MS) has been applied to the measurement of plutonium isotopes in soils. In the ICP-MS, a calibration curve method was conveniently utilized even in high viscosity solution using a Babington nebulizer. Plutonium concentrations in soil around the Kashiwazaki-Kariwa nuclear power station were found to be in the range of 0.054 to 1.0 Bq/kg with an average of 0.27 Bq/kg. The ratios of ²³⁹Pu/²⁴⁰Pu were also obtained with the ICP-MS to investigate the origin of Pu-isotopes. On the basis of this result, the origin of the Pu-isotopes was attributed to be fallout from the past atmospheric nuclear tests.     

Elemental speciation by chromatographic separation with inductively coupled plasma mass spectrometry detection

Separation techniques coupled to inductively coupled plasma mass spectrometry (ICP-MS) is reviewed. ICP-MS technique is described briefly. Coupling of the different separation techniques are described, together with the most common applications used for each technique that has been described in the literature. An overview for the future of separation techniques coupled to ICP-MS with regard to elemental speciation is discussed.     

Capillary electrochromatographic separation of metal ion species with on-line detection by inductively coupled plasma mass spectrometry

A bonded phase capillary column containing macrocyclic polyamine, [28]ane-N₆O₂ functional groups was used for the electrophoretic separation of arsenic, chromium and selenium species. A simple device interfacing this capillary electrochromatography (CEC) systems to an inductively coupled plasma mass spectrometer (ICPMS) is described. The dimension of the capillary column was 160 cm×100 μm i.d. To accommodate this electrophoretic separation, an auxiliary capillary was used with nitric acid (0.05 M) as makeup liquid. With the electrokinetic method at –20 kV, 20 s and a nebulizer gas flow rate of 1 l min⁻¹, the sample injected was analyzed with an applied potential of −20 kV. The background electrolyte buffer for the separation of CrO₄²⁻–Cr³⁺ was phosphate (20 mM, pH 6.5). That for HAsO₄²⁻–Ph₄As⁺ was pyromellitate (20 mM, pH 6.0) and for SeO₄²⁻–SeO₃²⁻ was acetate (20 mM, pH 6.0). The role of the buffer’s anion was also discussed. The separation efficiency of the bonded phase was compared with the bare fused silica. Concentration detection limits for these metal ions were in the low ppb range. In addition, the matrix effect of the established system with the bonded phase was found smaller than that with the bare fused silica.     

Separation of metalloporphyrins by capillary electrophoresis with UV detection and inductively coupled plasma mass spectrometric detection

Vitamin B12, cobalt protoporphyrin, manganese protoporphyrin, and zinc protoporphyrin were separated using capillary electrophoresis, and a comparison was made between detection with inductively coupled plasma mass spectrometry (ICP-MS) and UV detection. Absolute limits of detection were slightly better with ICP-MS detection than with UV detection, but for both methods absolute detection limits were in the picogram range. The migration times of the analytes decreased by several minutes when ICP MS detection was employed, and this phenomenon was believed to be a result of a "suction effect" that developed when the CE capillary was interfaced to the ICP-MS nebulizer. However, the resolution between species containing the same metal atom was not altered significantly, and the separation was completed in much less time relative to separations performed with UV detection.     

Gas chromatography with inductively coupled plasma mass spectrometric detection in speciation analysis

The state-of-the-art of gas chromatography coupled with inductively coupled plasma mass spectrometry (GC-ICP MS) is comprehensively reviewed. Particular attention is given to the recent advances in ICP MS detection including: GC-ICP interface designs; low power plasmas; and alternative mass analyzers (time-of-flight, double-focussing single collector, double-focussing and collision cell single-focussing multicollectors). On the level of sample preparation for speciation analysis by GC-ICP MS, new derivatization reagents and advances in extraction techniques, such as capillary purge-and-trap, solid phase microextraction and stirbar solid phase extraction are discussed. The increasing role of organometallic species labeled with stable isotopes for the detection of sources of errors during sample preparation and for isotope dilution quantification is highlighted. Applications of GC-ICP MS to the analysis of real-world samples are summarized with a focus on the areas which particularly benefit from the high ICP MS detection sensitivity and tolerance to sample matrix.     

Determination of arsenic species by inductively coupled plasma mass spectrometry with ion chromatography

Five arsenic species, trimethylarsine oxide, dimethylarsenic acid, monomethylarsonic acid, arsenobetaine and sodium arsenite, in urine were analysed by inductively coupled plasma mass spectrometry with ion chromatography (IC ICP MS). Since the toxicities of different arsenic compounds are different, speciation of arsenic compounds is very important in the investigation of metabolisms. In this paper, we applied ion chromatography (IC) as a separation device and inductively coupled plasma mass spectrometry (ICP MS) as a detection device. For separation of the five arsenic compounds, an anion-exchange column and, as mobile phase, tartaric acid were used. The eluent from the IC column was introduced directly into the nebulizer of the ICP MS and analysed at 75 amu. Detection limits were from 4 to 9 pg as arsenic.     

电感耦合等离子体质谱法测定血液和精液中的硼

采用HNO3-H2O2和氨水-甘露醇两种方法处理样品,电感耦合等离子体质谱法（ICP-MS）测定血液和精液中的硼。Be作内标补偿基体效应,并用标准加入法验证了方法的可靠性,标准加入法与外标法测定结果相吻合。在测定B的同时,还可进行Cr、Cu、Cd、Ba、Sr、Mn、Co、Tl、Li、Pb、Zn、Sc、Ti、V、As等多元素测定。两种样品处理方法的测定值呈显著正相关（r=0.99919）。方法检出限为0．11ng／mL（氨水-甘露醇法）,0.06ng／mL（HNO3-H2O2）。已用于测定某硼矿区血液和精液样品中的硼。     

Determination of rare earth elements in Indian kimberlite using inductively coupled plasma mass spectrometer (ICP-MS)

A method has been developed for the analysis of rare earth elements (REEs) in kimberlite samples using inductively coupled plasma mass spectrometer (ICP-MS). The samples were dissolved using sodium peroxide fusion and after appropriate dilutions the solutions were analyzed using ICP-MS. The paper presents the concentration of rare-earth elements as determined by ICP-MS in eight kimberlite samples from Central India. The method was validated using certified reference materials STSD-1 and STSD-2 from Canadian Certified Reference Material Project. The method detection limit of various REEs varies from 0.12 to 1.54?mg?kg^?1. The total REE concentrations range from 418 to 726?mg?kg^?1 and fall within the interval of those reported in the literature for kimberlites. Despite the marked difference in the REE contents, all the analyzed samples show similar REE patterns that resemble those for kimberlites. In order to compare ICP-MS results, the samples were analyzed using instrumental neutron activation analysis which is a reference method for determination of REEs in geological samples.     

Determination of trace elements in marine plankton by inductively coupled plasma mass spectrometry (ICP-MS)

A method has been developed for the determination of 23 elements in marine plankton in which inductively coupled plasma (ICP) source mass spectrometry (MS) was used to quantify the elements in the solution after digestion in a mixture of hydrofluoric and nitric acids in sealed PTFE vessels in a microwave field. The procedure was validated by the analysis of a standard reference soil (SRM 2709 San Joaquin Soil) and a standard reference fresh water plankton (CRM 414). The method was applied to the analysis of several marine plankton samples grown under controlled conditions including several whose growth media had been enriched with selenium. Matrix induced signal suppressions and instrumental drift were corrected by internal standardization. The suitabilities of germanium, indium, rhodium, scandium and yttrium as internal standard elements were evaluated. Neither scandium nor yttrium could be used due to the presence of these elements in the samples, germanium was used for the determination of As, Co, Cu, Fe, Ni, Se, Si and Zn, indium was used for Al, Ba, Ca, Eu, Sr, and Tl, and rhodium was used for Cd, Cr, Hg, Mg, Pb, Sb, Sn, and V. For Al, Ca, Cr, Cu, Fe, Mg, Mn, Ni, Si, Sr, V, and Zn internal standardization did not completely compensate for the suppressive effect of the heavier elements and the solutions were diluted. However, for As, Ba, Cd, Co, Eu, Hg, Pb, Sb, Se, Sn and Tl, it was possible to obtain accurate results despite the 35–¶40% suppression in the signals. Isobaric overlap was only a problem in the cases of ⁴²Ca and ⁷⁸Se; ⁴⁴Ca and ⁷⁷Se, respectively, were used. Memory effects were only observed with Hg for which a nitric acid-sodium chloride solution was the most effective wash-out solution. The marine plankton samples were able to tolerate a higher concentration of Hg as the selenium concentration increased.     

Chromium speciation using an automated liquid handling system with inductively coupled plasma - mass spectrometric detection

The speciation of inorganic chromium in environmental samples is required for accurate assessment of pollution levels. Of the two chromium oxidation states, Cr (VI) is a known carcinogen, while Cr (III) is an essential element. Total chromium measurement cannot be used to determine actual environmental impact due to the considerable difference in toxicity of the two elemental forms. An automated liquid handling system, the PrepLab™, can be used with an inductively coupled plasma-mass spectrometer (ICP-MS) to quantify Cr (III) and Cr (VI) in liquid samples. An autosampler is used to introduce discrete sample volumes into a solid-phase chelation resin column. The Cr (III) and Cr (VI) species are separated and are introduced on-line into the VG PlasmaQuad 3 ICP-MS for detection. The chromatographic data are collected in time resolved analysis mode with the capability of simultaneous multiple-isotopic detection.     

Minimization of mass interferences in quadrupole inductively coupled plasma mass spectrometric (ICP-MS) determination of palladium using a flow injection on-line displacement solid-phase extraction protocol

A flow injection on-line displacement solid-phase extraction protocol was employed to minimize mass interferences with determination of palladium by inductively coupled plasma mass spectrometry (ICP-MS). The developed method involved in on-line complexing of Ag⁺ with pyrrolidine dithiocarbamate (PDC), presorption of the resultant Ag–PDC onto a microcolumn packed with the cigarette filter, displacement sorption of Pd²⁺ through loading the sample solution onto the microcolumn due to on-line displacement reaction between Pd²⁺ and the presorbed Ag–PDC, elution of the retained Pd²⁺ with 50 μL of ethanol for on-line ICP-MS detection. Interferences from co-existing heavy metal ions with lower stability of their PDC complexes relative to Ag–PDC were minimized/eliminated. No interferences from 5 mg L^− 1 Zn and 3 mg L^− 1 Pb for ¹⁰⁴Pd, 0.4 mg L^− 1 Cu for ¹⁰⁵Pd, 6 mg L^− 1 Zn and 2 mg L^− 1 Cd for ¹⁰⁶Pd, 6 mg L^− 1 Zn and 3 mg L^− 1 Cd for ¹⁰⁸Pd, and 2 mg L^− 1 Cd for ¹¹⁰Pd were observed for the determination of 100 ng L^− 1 Pd. The enhancement factors of 71–75, sample throughput of 23 samples h^− 1 and detection limits of 2.8–3.5 ng L^− 1 were achieved with the consumption of 3.0 mL of sample solution. The precision (RSD) for eleven replicate determinations of Pd at the 100 ng L^− 1 level was 1.8–2.7%. The developed method was applied to the determination of palladium in rock samples.     

Determination of trace elements in marine plankton by inductively coupled plasma mass spectrometry (ICP-MS)

A method has been developed for the determination of 23 elements in marine plankton in which inductively coupled plasma (ICP) source mass spectrometry (MS) was used to quantify the elements in the solution after digestion in a mixture of hydrofluoric and nitric acids in sealed PTFE vessels in a microwave field. The procedure was validated by the analysis of a standard reference soil (SRM 2709 San Joaquin Soil) and a standard reference fresh water plankton (CRM 414). The method was applied to the analysis of several marine plankton samples grown under controlled conditions including several whose growth media had been enriched with selenium. Matrix induced signal suppressions and instrumental drift were corrected by internal standardization. The suitabilities of germanium, indium, rhodium, scandium and yttrium as internal standard elements were evaluated. Neither scandium nor yttrium could be used due to the presence of these elements in the samples, germanium was used for the determination of As, Co, Cu, Fe, Ni, Se, Si and Zn, indium was used for Al, Ba, Ca, Eu, Sr, and Tl, and rhodium was used for Cd, Cr, Hg, Mg, Pb, Sb, Sn, and V. For Al, Ca, Cr, Cu, Fe, Mg, Mn, Ni, Si, Sr, V, and Zn internal standardization did not completely compensate for the suppressive effect of the heavier elements and the solutions were diluted. However, for As, Ba, Cd, Co, Eu, Hg, Pb, Sb, Se, Sn and T1, it was possible to obtain accurate results despite the 35-40% suppression in the signals. Isobaric overlap was only a problem in the cases of 42Ca and 78Se; 44Ca and 77Se, respectively, were used. Memory effects were only observed with Hg for which a nitric acid-sodium chloride solution was the most effective wash-out solution. The marine plankton samples were able to tolerate a higher concentration of Hg as the selenium concentration increased.     

Coupling of inductively coupled plasma mass spectrometry (ICP-MS) with electrothermal vaporisation (ETV)

An inductively coupled plasma mass spectrometer (ICP-MS) was coupled on-line with an electrothermal vaporisation (ETV). The influence of aerosol gas flow as well as the variation of the coupling distance on the signal intensity was investigated and compared with the results of hydraulic high-pressure nebulizer (HHPN) measurements. Furthermore, temperature programs known from graphite furnace atomic absorption spectroscopy (GFAAS) were applied to ETV-ICP-MS. After optimisation of temperature programs, calibration series based on mono-element and multi-element solutions were carried out. The dynamic range and the detection limits of the method were determined. By use of internal standardisation it was tried to improve linearity and reproducibility. According to the results, internal standardisation does not have a great impact on linearity, but may be a useful tool to improve reproducibility. However, the latter is still low.     

Speciation of antimony(III) and antimony(V) in cell extracts by anion chromatography/inductively coupled plasma mass spectrometry

An analytical method for the separation and quantification of Sb(III) and Sb(V) using anion chromatography with ICP-MS is presented. The optimum conditions for the separation of the antimony species were established with 15 mmol/L nitric acid at pH 6 as eluent system on a PRP-X100 column. The retention times for antimony(V) and antimony(III) were 85 s and 300 s with detection limits of 0.06 microg/L and 0.29 microg/L, respectively. The proposed method was applied to cell extracts of Leishmania donovani, which were incubated with antimony(III) and antimony(V). Some metabolism seemed to occur within the cells.     

Speciation of antimony(III) and antimony(V) in cell extracts by anion chromatography/ inductively coupled plasma mass spectrometry

An analytical method for the separation and quantification of Sb(III) and Sb(V) using anion chromatography with ICP-MS is presented. The optimum conditions for the separation of the antimony species were established with 15 mmol/L nitric acid at pH 6 as eluent system on a PRP-X100 column. The retention times for antimony(V) and antimony(III) were 85 s and 300 s with detection limits of 0.06 μg/L and 0.29 μg/L, respectively. The proposed method was applied to cell extracts of Leishmania donovani, which were incubated with antimony(III) and antimony(V). Some metabolism seemed to occur within the cells.     

Study of laser ablation of brass materials using inductively coupled plasma atomic emission spectrometric detection

A XeCl laser and a Q-switched Nd:YAG laser operating at 1064, 532, 355 and 266 nm were used to ablate brass materials with varying concentrations of Zn and Cu. The ablated material was transported to an inductively coupled plasma for further atomization, excitation and ionization with an atomic emission spectrometric detection. A Zn enhancement was observed, which could be suppressed by using a Nd:YAG laser working at 266 nm with fluences higher than 400 J cm⁻² (equivalent to 80 GW cm⁻²). In contrast, a lack of linearity was observed for Cu as a function of the concentration, regardless of the wavelength and the fluence. The Cu problem seemed to occur during the ablation and was related to the structure of the brass material. Lack of linearity was also observed for Zn and other contained elements when samples from different origins were used.     

Determination of sources of lead in tap water by inductively coupled plasma mass spectrometry (ICP-MS)

We measured the concentrations of Pb and its isotope ratios in coconmittantly obtained tap water and plumbing materials by inductively coupled mass spectrometry (ICP-MS). The Pb concentrations were determined by external calibration with²⁰⁹Bi as an internal standard. Isotope ratios were measured and mass discrimination corrected by normalization to NIST SRM-981 (common lead isotopic standard). Student/s t-test was used to compare the isotopic ratios of²⁰⁶Pb/²⁰⁷Pb,²⁰⁶Pb/²⁰⁸Pb, and²⁰⁷Pb/²⁰⁸Pb in the tap water with those in various plumbing materials. The comparisons revealed that the source of Pb in most of the tap water samples was derived from copper pipe or solder.