Oxidation state-differentiated measurement of aqueous inorganic arsenic by continuous flow electrochemical arsine generation coupled to gas-phase chemiluminescence detection.

The electrochemical reduction of inorganic As on a graphite cathode depends on the current density. We observed that while only inorganic As(III) is reduced to AsH(3) at low current densities, at high current densities both forms of inorganic As are reduced. We describe a unique electrochemical reactor in which the cylindrical anode compartment is isolated from the outer concentric cathode compartment by a Nafion tube in which a hole is deliberately made and the entire anode compartment is inside the cylindrical cavity of a small volume (∼115 μL) cathode chamber. The evolved arsine is then quantitated by gas-phase chemiluminescence (GPCL) reaction with ozone; the latter is generated from oxygen formed during electrolysis. For the dimensions used, inorganic As(III) can be selectively determined at a current of 0.1 A while total inorganic As (both As(III) and As(V)) respond equally at an applied electrolysis current at 0.85 A, without any sample treatment. For a 1-mL sample, the system provides a limit of detection (LOD, S/N = 3) of 0.09 μg/L for total As (i = 0.85 A) and an LOD of 0.76 μg/L for As(III) (i = 0.10 A); As(V) is obtained by difference. Comparison of ICP-MS results for total As in groundwater samples that span a large range of concentration and total inorganic As determined by the present method showed a high correlation (r(2) = 0.9975) and a near unity slope. The basic electrochemical arsine generation technique and current-differentiated oxidation state speciation should be applicable as the front end to many other arsenic measurements techniques, including atomic spectrometry.