Application of direct analysis in real time to study chemical vapor generation mechanisms: reduction of dimethylarsinic(V) acid with aqueous NaBH4 under non-analytical conditions

The aqueous-phase reaction of dimethylarsinc acid (DMAs(V)) with NaBH4 (THB) was studied under non-analytical conditions (1000 mu g/mL As, 0.1 M HCl, 1% NaBH4) with the aim of identifying intermediates and reaction products. The use of direct analysis in real time (DART) with high-resolution mass spectrometry (HRMS), in combination with two different chemical vapor generation systems, allowed the identification of some species not detected by GC-MS such as Me2As-AsMe-AsMe(2)and the arsonium species [Me3As-AsMe2](+) and [Me2As-AsMe2-AsMe2](+). Many other methylated species of arsenic containing up to four arsenic atoms have been observed. Unfortunately, the oxidation mechanism that took place in the DART source interfered with the identification of some of those species formed in solution following THB reduction. The species identified by DART-HRMS, together with those previously identified by GC-MS (Me2AsH, Me2AsOH, Me3As, Me3AsO, Me2AsAsMeH, Me2AsAsMe2, and Me2As-O-AsMe2), enabled the formulation of hypotheses on the possible reaction pathways and revealed an aqueous-phase reactivity of DMAs(V) which could not be explained on the basis of current knowledge.