Selective solvent bar micro-extraction as a single-step approach for the measurement of Cu fractions in seawater.

Hollow fibre-supported liquid membrane was used for Cu fractionation in marine waters, using di-2-pyridylketone benzoylhydrazone (dPKBH) as a carrier due to its capacity to transport dissolved inorganic Cu at natural seawater pH. Optimized conditions were dPKBH (0.5 mmol L-1), HNO3 (0.5 mol L-1) as acceptor agent, extraction time of 120 min and stirring speed of 800 rpm. Additionally, the selectivity of the method for the extraction of the inorganic Cu fraction was validated by comparing the experimental results with theoretical data, and a mathematical model was obtained for estimation of Cu linked to dissolved organic matter. The method was applied for the measurement of Cu fractions in real seawater samples. Results were successfully compared with the reference material BCR 403 and recovery analysis in waters from the Gulf of Cádiz, showing that it could be used as a simple approach for the study of different Cu fractions in marine waters. Graphical abstract.

A Critical Study of the Effect of Polymeric Fibers on the Performance of Supported Liquid Membranes in Sample Microextraction for Metals Analysis.

Popularity of hollow fiber-supported liquid membranes (HF-SLM) for liquid-phase microextraction (HF-LPME) has increased in the last decades. In particular, HF-SLM are applied for sample treatment in the determination and speciation of metals. Up to the date, optimization of preconcentration systems has been focused on chemical conditions. However, criteria about fiber selection are not reflected in published works. HFs differ in pore size, porosity, wall thickness, etc., which can affect efficiency and/or selectivity of chemical systems in extraction of metals. In this work, Ag+ transport using tri-isobutylphosphine sulfide (TIBPS) has been used as a model to evaluate differences in metal transport due to the properties of three different fibers. Accurel PP 50/280 fibers, with a higher effective surface and smaller wall thickness, showed the highest efficiency for metal transport. Accurel PP Q3/2 exhibited intermediate efficiency but easier handling and, finally, Accurel PP S6/2 fibers, with a higher wall thickness, offered poorer efficiency but the highest stability and capability for metal speciation. Summarizing, selection of the polymeric support of HF-SLM is a key factor in their applicability of LPME for metals in natural waters.