Corrosion-induced release of zinc and copper in marine environments

Abstract: This licentiate study was initiated by copper, zinc and galvanized steel producers in Europe, who felt a need to assess runoff rates of copper and zinc from the pure metals and commercial products at marine exposure conditions. Their motive was the increasing concern in various European countries and the on-going risk assessments of copper and zinc within the European commission. Also the circumstance that available runoff rates so far, had been reported for mainly urban exposure conditions, rather than marine. A collaboration was therefore established with the French Corrosion Institute, which runs a marine test site in Brest, and a set of vital questions were formulated. Their answers are the essence of this licentiate study.Based on the ISO corrosivity classification and one-year exposures, the marine atmosphere of Brest is fairly corrosive for zinc (class C3) and highly corrosive for copper (C4). Despite higher corrosivity classifications for both metals in Brest compared to the urban site of Stockholm, used as a reference site, nearly all runoff rates assessed for copper, zinc and their commercial products were lower in Brest compared to Stockholm. This was attributed to a higher surface wetting in Brest and concomitant higher removal rate of deposited chloride and sulphate species from the marine-exposed surfaces. The comparison shows that measured corrosion rates cannot be used to predict runoff rates, since different physicochemical processes govern corrosion and runoff respectively.For copper, the runoff rate in Brest was approximately 1.1 g m-2 yr-1 with cuprite (Cu2O) as main patina constituent. During periods of very high chloride and sulphate deposition, paratacamite (Cu2Cl(OH)3) formed which increased the runoff rate to 1.5 g m-2 yr-1. For zinc, with hydrozincite (Zn5(CO3)2(OH)6) as the main patina constituent, the runoff rate was relatively stable at 2.6 g m-2 yr-1 throughout the year, despite episodes of heavy chloride and sulphate deposition.The application of organic coatings of varying thickness on artificially patinated copper or on different zinc-based products resulted in improved barrier properties and reduced runoff rates that seem highly dependent on thickness. The thickest organic coating (150 µm thick), applied on hot dipped galvanized steel, reduced the runoff rate by a factor of 100. No deterioration of organic coatings was observed during the one-year exposures. Alloying zinc-based products with aluminium resulted in surface areas enriched in aluminium and concomitant reduced zinc runoff rates.The release rate and bioavailability of copper from different anti-fouling paints into artificial seawater was also investigated. It turned out that the release rate not only depends on the copper concentration in the paint, but also on paint matrix properties and other released metal constituents detected. Far from all copper was bioavailabe at the immediate release situation. In all, the results suggest the importance of assessing the ecotoxic response of anti-fouling paints not only by regarding the copper release, but rather through an integrated effect of all matrix constituents.