On-line speciation analysis of inorganic arsenic in complex environmental aqueous samples by pervaporation sequential injection analysis

A proof of concept of a novel pervaporation sequential injection (PSI) analysis method for automatic non-chromatographic speciation analysis of inorganic arsenic in complex aqueous samples is presented. The method is based on hydride generation of arsine followed by its on-line pervaporation-based membrane separation and CCD spectrophotometric detection. The concentrations of arsenite (As(III)) and arsenate (As(V)) are determined sequentially in a single sample zone. The leading section of the sample zone merges with a citric acid/citrate buffer solution (pH 4.5) for the selective reduction of As(III) to arsine while the trailing section of the sample zone merges with hydrochloric acid solution to allow the reduction of both As(III) and As(V) to arsine at pH lower than 1. Virtually identical analytical sensitivity is obtained for both As(III) and As(V) at this high acidity. The flow analyzer also accommodates in-line pH detector for monitoring of the acidity throughout the sample zone prior to hydride generation. optimal conditions the proposed PSI method is characterized by a limit of detection, linear calibration range and repeatability for As(III) of 22 μg L−1 (3sblank level criterion), 50–1000 μg L−1 and 3.0% at the 500 μg L−1 level and for As(V) of 51 μg L−1, 100–2000 μg L−1 and 2.6% at the 500 μg L−1 level, respectively. The method was validated with mixed As(III)/As(V) standard aqueous solutions and successfully applied to the determination of As(III) and As(V) in river water samples with elevated content of dissolved organic carbon and suspended particulate matter with no prior sample pretreatment. Excellent relative recoveries ranging from 98% to 104% were obtained for both As(III) and As(V).