Mixing behaviour and sources of Ag, Pd, and other trace elements in the Estuary and Gulf of St. Lawrence under winter conditions.

The marine chemistry of platinum group elements is poorly documented despite robust evidence of their widespread emissions and deposition around the globe. Here, we report the concentrations and discuss the geochemical behaviours of Ag, Pd and other trace and ultra-trace elements in the Estuary and Gulf of St. Lawrence (EGSL). We highlight the contrasting mixing behaviours of these elements, i.e., conservative (Cd, Re) vs. non-conservative (Ag, Pd), in samples collected during the winter and under ice-covered conditions. We ascribe the contrasting geochemical behaviour of these elements to their differential affinity for reactive surfaces carried into the estuary from the frozen watersheds. We also report an increase of the concentrations of Ag (up to 40 pmol L), Pd (up to 10 pmol L) and Pt (up to 0.4 pmol L) in the bottom and oxygen-depleted waters of the Gulf of St. Lawrence (GSL). A strong correlation between dissolved Pt concentrations and the stable carbon isotopic composition of the dissolved inorganic carbon (δC-DIC) suggests that the increased mobility of Pt may result from the aerobic mineralization of organic carbon or the oxidation of Pt-bearing organic complexes. Molar Pt/Pd ratios in the three water masses that compose the water column in the EGSL highlight a potential influence of anthropogenic sources near urban centers. The signature of continental end-members will be required to confirm the impacts of road traffic on the estuarine geochemistry of these elements.