Continuous flow hydride generation-atomic fluorescence spectrometric determination and speciation of arsenic in wine

Methods for the atomic fluorescence spectrometric (AFS) determination of total arsenic and arsenic species in wines based on continuous flow hydride generation (HG) with atomization in miniature diffusion flame (MDF) are described. For hydride-forming arsenic, L-cysteine is used as reagent for pre-reduction and complexation of arsenite, arsenate, monomethylarsonate and dimethylarsinate. Concentrations of hydrochloric acid and tetrahydroborate are optimized in order to minimize interference by ethanol. Procedure permits determination of the sum of these four species in 5-10-fold diluted samples with limit of detection (LOD) 0.3 and 0.6 mu g l(-1) As in white and red wines, respectively, with precision between 2% and 8% RSD at As levels within 0.5-10 mu g l(-1). Selective arsine generation from different reaction media is used for non-chromatographic determination of arsenic species in wines: citrate buffer at pH 5.1 for As(III); 0.2 mol l(-1) acetic acid for arsenite+dimethylarsinate (DMA); 8 mol l(-1) HCl for total inorganic arsenic [As(III)+As(V)]; and monomethylarsonate (MMA) calculated by difference. Calibration with aqueous and ethanol-matched standard solutions of As(Ill) is used for 10- and 5-fold diluted samples, respectively. The LODs are 0.4 mu g l(-1) for As(III) and 0.3 mu g l(-1) for the other three As species and precision is within 4-8% RSDs. Arsenic species in wine were also determined by coupling of ion chromatographic separation on an anion exchange column and HG-flame AFS detection. Methods were validated by means of recovery studies and comparative analyses by HG-AFS and electrothermal atomic absorption spectrometry after microwave digestion. The LODs were 0.12, 0.27, 0.15 and 0.13 mu g l(-1) (as As) and RSDs were 2-6%, 5-9%, 3-7% and 2-5% for As(III), As(V), MMA and DMA arsenic species, respectively. Bottled red and white wines from Bulgaria, Republic of Macedonia and Italy were analyzed by non-chromatographic and chromatographic procedures and the As(III), arsenite, has been confirmed as major arsenic species. (c) 2005 Elsevier B.V. All rights reserved.