Capillary electrophoresis coupled to electrospray mass spectrometry for the determination of organic and inorganic arsenic compounds in water samples.

Some compounds of arsenic are extremely toxic to the human body even at low levels. Long-term exposure from drinking contaminated water causes adverse health effects. This has led the European Union and other global organizations to reduce the maximum residue limit for the total arsenic up to 10 μg L-1 in water for human consumption. The toxicity of arsenic depends on the oxidation state, chemical structure and solubility in the biological environment. Main analytical procedures report on the determination of arsenic species in water samples which have been developed based on atomic spectroscopy -speciation performed in the sample treatment step- and inductively coupled plasma-mass spectrometry (ICP-MS). In such cases, speciation is performed by coupling to high-performance liquid chromatography (HPLC). As far as we know, the determination of arsenic species in water samples at low concentration levels by capillary electrophoresis (CE) coupled to electrospray mass spectrometry (ESI-MS) has not been described up to now. In this research CE-ESI(-)-MS is proposed for the identification and simultaneous quantification of organic and inorganic arsenic species in water samples for human consumption. The target compounds were dimethylarsinate (DMA), mono-methylarsonate (MMA), arsenite (i-As(III)) and arsenate (i-As(V)). Optimization of the composition and nature of both the electrophoretic separation medium -using hexafluoro-2-propanol (HFIP) as an additive- and the sheath liquid was performed and aimed at achieving the best sensitivity and separation efficiency for the CE-ESI(-)-MS coupling. Two simple sample treatments were proposed: one based on dispersive liquid-liquid micro-extraction (DLLME) intended for a rapid determination of the total content of inorganic arsenic in the water sample; and the second based on partial evaporation of the water sample to detect each of the four main arsenic species. For the second, limits of detection between 0.02 and 0.04 μg L-1 were found, which are similar results as the ones achieved with methods based on HPLC-ICP-MS. The DLLME + CE-ESI(-)-MS method was applied to the determination of total inorganic arsenic in eleven water samples in the province of Salamanca (Spain). Five of the analyzed samples had values close to, or superior to the maximum residue limit for the total of arsenic in water intended for human consumption (10 μg L-1). The validated method CE-ESI(-)-MS for arsenic speciation was applied with success to the analysis of the weakly mineralized water sample (dry residue < 50 mg L-1) of both groundwater and bottled water.