New insights into trace metal speciation and interaction with phytoplankton in estuarine coastal waters

Abstract

In coastal productive zones, phytoplankton activity may influence trace metal speciation and partitioning at short temporal scale. We coupled hourly in situ voltammetry quantification of the lead (Pb), cadmium (Cd), and copper (Cu) potentially bioavailable fractions, using an innovative submersible sensing probe (the TracMetal), to surface water sampling for the quantification of the targeted trace metals in the dissolved <0.2 μm and <0.02 μm fractions, suspended particles, and phytoplankton nets in the Gironde Estuary mouth. The in situ TracMetal monitoring reflected real-time dynamic Cd and Cu regeneration related to algal cells under post-bloom conditions as well as Pb remobilization due to photoreduction of colloids. The potentially bioavailable fraction consisted in 30, 30-50 and <10 % of the total dissolved fraction for Pb, Cd, and Cu, respectively, representing crucial ecotoxicological information. Metal bioconcentration factors using the dynamic fraction concentrations showed levels up to 10⁷ for Cu in phytoplankton.

Keywords: Bioavailability; Cadmium; Copper; In situ autonomous monitoring; Lead; Primary production.