Sensitive arsenic speciation by capillary electrophoresis using UV absorbance detection with on-line sample preconcentration techniques

Abstract The World Health Organization (WHO) guideline states that the total arsenic concentration in drinking water must not exceed 10 ppb. However, arsenic toxicity varies significantly, with inorganic arsenic species being more toxic than organic species. Arsenic speciation is therefore important for evaluating the health risks from arsenic-contaminated drinking water. Capillary electrophoresis provides the necessary high performance separation to determine arsenic species in water, but its sensitivity with absorbance detection is far below than needed. Using a coated capillary, several on-line sample preconcentration techniques such as large volume sample stacking with an electroosmotic flow pump, field amplified sample injection (FASI), transient isotachophoresis (tITP), electrokinetic supercharging (EKS) combining FASI and tITP, and counter flow (CF)-EKS, were therefore investigated. With CF-EKS using phosphate and N -cyclohexyl-2-aminoethanesulfonate as leading and terminating electrolytes, respectively, standard samples of arsenite, arsenate, monomethylarsonic acid, and dimethylarsinic acid were preconcentrated from 6,300- to 45,000-fold. The limits of detection obtained with UV absorbance detection were 0.08–0.3 ppb As. For a spring water sample spiked with the four arsenic species, LODs of 2–9 ppb As were obtained, which are lower than the WHO guideline of 10 ppb total As.