Desorption electrospray ionization mass spectrometry (DESI-MS) applied to the speciation of arsenic compounds from fern leaves

Abstract

The different chemical forms of arsenic compounds, including inorganic and organic species, present distinct environmental impacts and toxicities. Desorption electrospray ionization mass spectrometry (DESI-MS) is an excellent technique for in situ analysis, as it operates under atmospheric pressure and room temperature and is conducted with no/minimal sample pretreatment. Aimed at expanding its scope, DESI-MS is applied herein for the quick and reliable detection of inorganic (arsenate--As(V): AsO4(3-) and arsenite--As(III): AsO2(-)) and organic (dimethylarsinic acid--DMA: (CH3)2AsO(OH) and disodium methyl arsonate hexahydrate: CH3AsO3·2Na·6H2O) arsenic compounds in fern leaves. Operational conditions of DESI-MS were optimized with DMA standard deposited on paper surfaces to improve ionization efficiency and detection limits. Mass spectra data for all arsenic species were acquired in both the positive and negative ion modes. The positive ion mode was shown to be useful in detecting both the organic and inorganic arsenic compounds. The negative ion mode was shown only to be useful in detecting As(V) species. Moreover, MS/MS spectra were recorded to confirm the identity of each arsenic compound by the characteristic fragmentation profiles. Optimized conditions of DESI-MS were applied to the analysis of fern leaves. LC-ICP-MS was employed to confirm the results obtained by DESI-MS and to quantify the arsenic species in fern leaves. The results confirmed the applicability of DESI-MS in detecting arsenic compounds in complex matrices.