Distribution and reactivity of oxyanions (Sb, As, V, Mo) in the surface freshwater reaches of the Gironde Estuary (France)

The present work reports on the temporal variations of Sb, As, V and Mo concentrations in the surface freshwater reaches of the Gironde Estuary (SW France). Dissolved (<0.2 and <0.02 μm) and particulate Sb, As, V and Mo concentrations were measured in samples collected with high temporal resolution (every 30 min) during two consecutive tides at a fixed station located upstream of the city of Bordeaux and the maximum turbidity zone (MTZ). In addition, measurements of suspended particulate matter concentration, physico-chemical parameters, Cl− concentration, water depth, current velocity and particulate Th concentration were performed either at the same time resolution or continuously. The data obtained suggested that variations in particulate As, V and Mo concentrations were most probably related to tidal cycling near the sampling site of fine grained particles from the MTZ located downstream. Significant differences in the behavior of the dissolved target oxyanions, mostly present in the <0.02 μm fraction, occurred. The behavior of Sb was conservative. Variations of the dissolved As and V concentrations showed similar cycling trends, strongly related to tidal cycles. These As and V cycles were interpreted as a mixing between upstream freshwater and downstream water enriched in dissolved As and V by desorption from the MTZ particles. The observed trend in the variation of the dissolved Mo was more complex than that of As and Sb and attributed to the mixing of the water bodies mentioned above coupled to a point source input of dissolved Mo from an intra-estuarine source. The contribution of this suspected Mo source to the dissolved Mo concentrations measured at the sampling site was estimated from the ratio of dissolved Mo to dissolved As concentrations. The additional dissolved Mo signal, coupled to the monitored ebb and flood length and associated current velocities, suggested an anthropogenic input which may derive from industrial activity near the city of Bordeaux. Extrapolating these results to the annual scale suggested that this dissolved Mo may be equivalent to 45–90% of the annual dissolved Mo flux into the Garonne Branch, highlighting the importance to further investigate the origin and behavior of Mo in the fluvial estuary near Bordeaux.