Speciation of Arsenic Using Chelation Solvent Extraction and High Performance Liquid Chromatography

Research interest in speciation of arsenic stems from its species dependent behavior in the environment and in living organisms. The complexity of the matrix to be analyzed and low concentrations of target arsenic species that may be labile or difficult to chromatogram, indicate that a suitable pre‐treatment methodology is required. This study investigated the usefulness of chelation solvent extraction – high performance liquid chromatography (CSE‐HPLC) for the speciation of arsenic in water. It involved reacting arsenic with the chelant known for its affinity towards arsenic, followed by extraction, separation, and identification of the arsenic‐chelant‐arsenic complex. Arsenic species having different physicochemical properties were investigated. Species, such as, As₂O₃, As₃O₅, KH₂AsO₄, Na₂HAsO₄, and NaAsO₂ were detected as a group of closely eluted peaks with different retention times and spectral properties, whereas, the organic arsenic species CH₃Na₂AsO₃, o‐arsanilic acid, roxarson and triphenyl arsine separated quite well on the EnviroseP‐CM HPLC column. Key method parameters, such as, type of HPLC column, composition of mobile phase and organic solvents affecting peak resolution and sensitivity were optimized. Real environmental matrices contaminated with arsenic were analyzed under varying wavelengths (λ_max = 190, 210, 220, 234, 244, and 282 nm), with good precision. Different arsenic species were detected in these samples with excellent background and signal‐to‐noise ratios demonstrating the robustness of the method. The detection limit, reproducibility, selectivity, accuracy, and dynamic range of the calibration curves were evaluated.