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• W1587923623 abstract "This thesis describes the development of an analytical technique to measure the freecopper ion concentration (pCurree) in seawater. Ion-Selective Electrode (ISE)potentiometry is the only analytical technique that can directly measure pCufreewithout manipulating the sample matrix, or making assumptions about thethermodynamic behaviour of the metal species. Flow analysis techniques wereinvestigated with the aim of overcoming problems inherent in batch analysis,including sluggish response at low analyte concentrations, cross contamination fromone sample to another, contamination by membrane dissolution and/or silverchloride precipitation, and an offset in response due to adsorption of natural organicmatter present in seawater.Surface studies of a rotating disk ISE by Electrochemical Impedance Spectroscopy(EIS) confirmed that the effect of organic matter was small (- 0.1 pCu units) andwas unlikely to significantly effect the analysis of marine samples. Flow analysisstudies showed that the chloride interference was less significant in a flow systemthan in batch mode, and that the chloride signal could be separated from the coppersignal by kinetic discrimination. On the basis of preliminary flow injection studies and the EIS results, ContinuousFlow Analysis (CFA) was tested and a method for the routine analysis of openoceanand contaminated samples was developed. CFA reduced the effect ofmembrane dissolution and silver chloride precipitation, and eliminated sample crosscontamination, by virtue of the sample stream flowing past the electrode. Lowsample throughput, a result of sluggish response at low concentrations of copper,was increased by using an extrapolation technique. This technique is based on thefitting of an empirical mathematical expression to the electrode time-response curve,enabling the prediction of the final steady-state potential. Predicted potentials fellwithin 0.5 mV of the true steady state potential, and sample analysis time wasreduced by a factor of 3 - 6.The CFA method was used to study the effect of copper on the unicellular benthicmarine diatom Nitzschia closterium (Ehrenberg) W. Smith. N. closterium isextremely sensitive to low concentrations of copper, and a strong relationshipbetween pCurree and growth inhibition was established at two salinities. Growthinhibition bioassays of samples from a severely contaminated estuary showed notoxic effects, despite elevated levels of total and copper. Speciationmeasurements in salinity 20 waters showed that labile copper grossly overestimatedthe toxicity of the samples, while pCufree measurements indicated that there wasinsufficient free copper to cause a toxic effect. Mild toxicity was observed in somesamples at salinity 30, however this could not be explained by ISE measurements, as pCufree, levels were below the toxic threshold. In contrast to earlier studies of thecopper complexing capacity of the estuary, ISE results showed that more than 99.9%of the total copper was bound to ligands, probably originating from the surroundingbutton grass and hardwood forests in the catchment areas of the two majorfreshwater sources." @default.
• W1587923623 created "2016-06-24" @default.
• W1587923623 creator A5034903383 @default.
• W1587923623 date "2000-01-01" @default.
• W1587923623 modified "2023-09-26" @default.
• W1587923623 title "Analysis and toxicity of pCufree in seawater" @default.
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