Seasonal cycle of copper speciation in Gullmar Fjord, Sweden

The chemical speciation of dissolved Cu was investigated by voltammetric methods in Gullmar Fjord, Sweden, over the course of a year from September 1996 until August 1997. Sampling was carried out on a roughly monthly basis, with an intensive survey carried out in May 1997. Surface water temperatures ranged from -1 to 22degreesC, whereas bottom waters in the fjord were approximately 6 C throughout. Macronutrient concentrations in the fjord during the period of the survey were investigated independently by the Goteborgs och Bohus Tans VattenvArdsforbund (Water Quality Association of Goteborg and Bohus). Surface phosphate concentrations were highest in early spring with low levels (<0.1 mu mol kg(-1)) over the late spring and summer. Nitrate and silicate showed a similar pattern to phosphate with the exception of high concentrations encountered in surface waters when low salinity plumes caused by runoff were encountered. A period of calm, sunny weather in January 1997 saw the initiation of the spring bloom some 2 months earlier than usual. Dissolved Cu speciation was dominated by organic complexation (over 99.8%) throughout this study. Strong Cu binding ligands (log K > 12.5) were not detected during the winter or early spring and could be related to the temperature-related seasonal appearance of the cyanobacterium Synechoccocus in these waters. The appearance of the strong Cu ligands led to a decrease in the concentration of free copper, resulting in a seasonal cycle for free copper in the fjord. This is the first study to examine Cu speciation over an annual cycle in a coastal environment.