Ion-exclusion chromatography combined with ICP-MS and hydride generation-ICP-MS for the determination of arsenic species in biological matrices

A sensitive and robust method for the determination of eight inorganic and organic arsenic species by ion-exclusion liquid chromatography combined with inductively coupled plasma mass spectrometry (LC-ICP-MS) and LC-hydride generation-ICP-MS (LC-HG-ICP-MS) is described. The species are arsenite (AsIII), arsenate (AsV), monomethylarsonic acid (MMAs), dimethylarsinic acid (DMAs), arsenobetaine (AsB), trimethylarsine oxide (TMAsO), tetramethylarsonium salt (TMAs) and arsenocholine salt (AsC). A good separation of seven arsenic species, AsIII, AsV, MMAs, DMAs, AsB, TMAsO, and AsC or TMAs, was achieved by using an ion-exclusion column packed with a carboxylated methacrylate resin and 0.35 mmol l−1 of a sodium sulfate solution adjusted to pH 3.8 as the mobile phase. The detection limits of the eight arsenic species obtained by LC-ICP-MS ranged from 0.067 to 0.34 ng As ml−1 using an injection volume of 50 µl. A hydride generation technique improved the detection limits of AsIII, AsV, MMAs, DMAs and TMAsO to 0.016–0.075 ng As ml−1, while AsB, TMAs and AsC were not detectable. The relative standard deviations of five replicates of a standard of each arsenic species by the former method ranged from 1.3 to 3.3% and those by the latter method, from 1.8 to 3.1%. The proposed methods were successfully applied to the determination of five arsenic species in human urine and six species in an extract from tuna fish tissue. The only necessary pretreatment for these analyses involved filtration with a 0.45 µm membrane and the ArCl polyatomic interference, due to a large amount of chloride in the biological samples on 75As measurement, was eliminated by the described LC separation. In addition, serious deterioration in column performance and a decrease in the sensitivity of ICP-MS were not observed during the experimental period of five months. The LC-ICP-MS and LC-HG-ICP-MS methods were validated by analyzing reference samples of human urine and tuna fish tissue.

[1]  R. Rubio,et al.  Speciation of arsenic in mussels by the coupled system liquid chromatography-UV irradiation-hydride generation-inductively coupled plasma mass spectrometry. , 1999, Talanta.

[2]  R. Wennrich,et al.  Separation of organic and inorganic arsenic species by HPLC-ICP-MS , 1999 .

[3]  Y. Inoue,et al.  Identification and quantification by LC-MS and LC-ICP MS of arsenic species in urine of rats chronically exposed to dimethylarsinic acid (DMAA) , 1999 .

[4]  A. R. Byrne,et al.  Separation of radiolabelled arsenic compounds produced by neutron irradiation of organoarsenic compounds , 1999 .

[5]  H. Tao,et al.  Sensitive determination of three arsenic species in water by ion exclusion chromatography-hydride generation-inductively coupled plasma mass spectrometry , 1999 .

[6]  J. Caruso,et al.  Speciation of arsenic in fish tissue using microwave-assisted extraction followed by HPLC-ICP-MS , 1999 .

[7]  B. Michalke,et al.  A new method for the analysis of arsenic species in urine by using HPLC-ICP-MS , 1998 .

[8]  E. Lebret,et al.  Speciation of arsenic compounds in urine by LC–ICP MS , 1998 .

[9]  C. Cámara,et al.  ARSENIC SPECIATION IN WATER AND HUMAN URINE BY HPLC-ICP-MS AND HPLC-MO-HG-AAS , 1998 .

[10]  Jian Zheng,et al.  Speciation of arsenic compounds by coupling high-performance liquid chromatography with inductively coupled plasma mass spectrometry , 1998 .

[11]  E. Larsen.  Method optimization and quality assurance in speciation analysis using high performance liquid chromatography with detection by inductively coupled plasma mass spectrometry , 1998 .

[12]  S. Pergantis,et al.  Speciation of arsenic animal feed additives by microbore high-performance liquid chromatography with inductively coupled plasma mass spectrometry. , 1997, The Analyst.

[13]  X. Le,et al.  Speciation of Arsenic Compounds Using High-Performance Liquid Chromatography at Elevated Temperature and Selective Hydride Generation Atomic Fluorescence Detection , 1996 .

[14]  S. Fukushima,et al.  Promoting effects of dimethylarsinic acid on N-butyl-N-(4-hydroxybutyl)nitrosamine-induced urinary bladder carcinogenesis in rats. , 1996, Carcinogenesis.

[15]  P. Apostoli,et al.  Determination of urinary arsenic by solvent extraction and electrothermal atomic absorption spectrometry. A comparison with directly coupled high-performance liquid chromatography–inductively coupled plasma mass spectrometry , 1996 .

[16]  J. Fritz,et al.  Simultaneous ion-exclusion chromatography-cation-exchange chromatography with conductimetric detection of anions and cations in acid rain waters , 1994 .

[17]  S. Okada,et al.  Mutagenicity of dimethylated metabolites of inorganic arsenics. , 1989, Chemical & pharmaceutical bulletin.

[18]  G. Batley,et al.  Interference of chloride in the speciation of arsenic by ion chromatography , 1986 .

[19]  P. Werner,et al.  Solvent Deuterium Isotope Effects on Acid-Base Reactions. Part III. Relative Acidity Constants of Inorganic Oxyacids in Light and Heavy Water. Kinetic Applications. , 1969 .