Electrospray ionization tandem mass spectrometric determination of monomethylarsonic acid and dimethylarsinic acid after adduct formation with citric acid

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Abstract

Inorganic arsenic species are metabolized to monomethylarsonic acid (MMA V) and dimethylarsinic acid (DMA V) and excreted into urine. A simple, rapid and sensitive method has been developed using electrospray ionization tandem mass spectrometry (ESI-MS-MS) for the simultaneous determination of MMA V and DMA V. MMA V and DMA V in a sample were allowed to react with citric acid (CiA). Adduct compounds were extracted together with isoamyl alcohol (IAA). An aliquot (1-μL) of the IAA layer was directly injected into the ESI-MS-MS instrument, and was detected within 1 min. Quantification was done using selected reaction monitoring for MMA V and DMA V as follows. [MMAH + 2CiA - 3H2O]+ → [MMAH + CiA - 2H2O]+ [DMAH + CiA + MeOH - 2H2O]+ → [DMAH + MeOH - H2O]+ Where, MMAH and DMAH denote the protonated forms of MMA V and DMA V, and MeOH denotes methanol (carrier liquid in ESI-MS-MS). This method was validated for the analysis of urine samples. The limit of detection of As was 0.3 μgL-1 for MMA V and 0.6 μgL-1 for DMA V using 10 μL of sample solution. Results were obtained in <10 min with a linear calibration range of 3-100 μgL-1. Inorganic arsenic compounds (and other organic arsenic compounds) found in urine did not interfere with the detection of MMA V and DMA V. Concentrations of MMA V and DMA V in the reference urine SRM 2670a were estimated after partial purification, and those in urine of a patient treated with As2O3 were measured after dilution.

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