Modelling the equilibrium speciation of nickel in the Tweed Estuary, UK: Voltammetric determinations and simulations using WHAM |
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| Authors: | Andrew Turner Manuela Martino |
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| Institution: | aSchool of Earth, Ocean and Environmental Sciences, University of Plymouth, Drake Circus, Plymouth, PL4 8AA, UK |
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| Abstract: | The complexation of dissolved Ni has been evaluated in a rapidly-flushed, rural estuary (Tweed, UK) by ligand exchange-adsorptive cathodic stripping voltammetry. Results suggest the presence of strongly binding ligands, L, throughout, with average stability constants of about 1019 and which are saturated by ambient Ni concentrations. Equilibrium speciation calculations incorporating these constants in WHAM, version 6, predict an increase in Ni complexation (as NiL) from about 50% of total dissolved Ni in fresh water to over 90% in sea water. Equivalent calculations using the default-mode fulvic and humic substances (FS and HS, respectively) encoded in the WHAM database predict a reduction in complexation (as NiFS + NiHS) from about 20% in fresh water to less than 1% in sea water. Discrepancies arising from the two approaches are largely attributed to the different analytical detection windows employed. Thus, a better representation of Ni complexation is derived from including both types of complexant in the speciation calculations, resulting in estimates of net complexation in excess of 60% of total dissolved Ni throughout the estuary. The uncertainties and assumptions inherent in all computations illustrate the difficulty in measuring or predicting metal complexation in estuaries. |
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| Keywords: | Nickel Complexation Speciation Voltammetry Estuaries WHAM |
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