Analysis of dissolved metal fractions in coastal waters: An inter-comparison of five voltammetric in situ profiling (VIP) systems

This paper presents the results of an inter-comparison exercise undertaken to test the reliability and performance of a voltammetric in situ profiling system (VIP system) and carried out by partners based in Italy, Sweden, Switzerland and the UK. The VIP system was designed to allow in situ simultaneous monitoring of the dynamic fractions (i.e. the maximum potentially bioavailable fractions) of Cu(II), Pb(II) and Cd(II) in natural waters at a frequency of 2–3 analyses h− 1.The four participating groups used the VIP systems under laboratory conditions to determine dissolved concentrations of Cu, Pb and Cd in river, estuarine and coastal water reference materials (SLRS-3/4, SLEW-2/3 and CASS3/4, respectively). The accuracy of the VIP method was comparable to that of established methodologies, including inductively coupled plasma mass spectrometry and voltammetric methods using mercury-electrodes. The VIP systems were also applied to determine the dynamic fractions of the target analytes in freshly collected samples ex situ, as well as in situ in contrasting European marine waters. There was good agreement between the concentrations of the dynamic metal fractions determined in laboratory analyses, and observed during the simultaneous deployment of up to five VIP instruments for periods of several hours in coastal waters. The simultaneous in situ deployment of two VIP instruments in an estuary showed a consistent analytical performance over several days of continuous operation. The results of this inter-comparison exercise show that the VIP system is a reliable submersible probe for accurate, sensitive and high resolution in situ monitoring of dissolved metal fractions in the picomolar (Cd, Pb) and nanomolar (Cu) concentration ranges.