Seasonal variation of total dissolved arsenic and arsenic speciation in a polluted surface waterway

Seasonal differences in the dissolved arsenic concentration and speciation in a contaminated urban waterway in northwest England have been determined using a coupled ion chromatography- inductively coupled plasma-mass spectrometry (IC-ICP-MS) technique. Waters sampled in the vicinity of an industrial works during relatively dry conditions in April 2000 were found to contain total arsenic concentrations (ΣAs) of up to 132 μg L-1, more than an order magnitude greater than the 4 μg L-1 maximum found in December 2000. The difference in ΣAs between the April and December sampling periods is speculated to be largely due to the irregular anthropogenic supply of arsenic to the watercourse. For both sampling periods, the dissolved arsenic was exclusively inorganic in nature and had an As(V)/ΣAs ratio of between 0.6 and 0.8. Analysis of samples taken downstream of the industrial site, after the confluence with a relatively As-poor stream, revealed that As(III), As(V) and ΣAs concentrations were lower than would be expected from conservative mixing. The As(V)/ΣAs ratio was also observed to decrease markedly. The loss of arsenic from solution is thought to be due to adsorption on the iron oxyhydroxide-rich sediment observed to coat the riverbed downstream of the confluence. The reduction in the As(V)/ΣAs ratio is believed to be due to the more rapid adsorption of As(V) compared to that of As(III). Deviations from conservative behaviour were more marked during the relatively dry April 2000 sampling period and suggest the increased importance of adsorption processes controlling arsenic availability during this time.