Determination of arsenic and antimony in seawater by voltammetric and chronopotentiometric stripping using a vibrated gold microwire electrode.

The oxidation potentials of As(0)/As(III) and Sb(0)/Sb(III) on the gold electrode are very close to each other due to their similar chemistry. Arsenic concentration in seawater is low (10-20 nM), Sb occurring at ~0.1 time that of As. Methods are shown here for the electroanalytical speciation of inorganic arsenic and inorganic antimony in seawater using a solid gold microwire electrode. Anodic stripping voltammetry (ASV) and chronopotentiometry (ASC) are used at pH ≤2 and pH 8, using a vibrating gold microwire electrode. Under vibrations, the diffusion layer size at a 5 μm diameter wire is 0.7 μm. The detection limits for the As(III) and Sb(III) are below 0.1 nM using 2 min and 10 min deposition times respectively. As(III) and Sb(III) can be determined in acidic conditions (after addition of hydrazine) or at neutral pH. In the latter case, oxidation of As(0) to As(III) was found to proceed through a transient As(III) species. Adsorption of this species on the gold electrode at potentials where Sb(III) diffused away is used for selective deposition of As(III). Addition of EDTA removes the interfering effect of manganese when analysing As(III). Imposition of a desorption step for Sb(III) analysis is required. Total inorganic arsenic (iAs=As(V)+As(III)) can be determined without interference from Sb nor mono-methyl arsenious acid (MMA) at 1.6<pH<2 using E(dep)=-1 V. Total inorganic antimony (iSb=Sb(V)+Sb(III)) is determined at pH 1 using E(dep)=-1.8 V without interference by As. The methods were tested in samples from the Irish Sea (Liverpool Bay). As(III) was determined on-board ship immediately after sampling. As(III) concentrations were found to range from 0.44 to 1.56 nM and were higher near the coast. Sb(III) was below the detection limit (<0.1 nM Sb(III)), iAs was comprised between 8 and 25 nM while iSb varied from 0.5 to 1.7 nM.