Comparison of copper speciation in estuarine water measured using analytical voltammetry and supported liquid membrane techniques

The supported liquid membrane (SLM) is a promising separation and preconcentration technique that is well-suited for trace metal speciation in natural waters. The technique is based on the selective complexation of metal ions by a hydrophobic ligand (carrier) dissolved in a water-immiscible organic solvent immobilized in a porous, inert membrane. This membrane separates two aqueous solutions: the test (or donor) solution and the strip (or acceptor) solution. The metal carrier complex is transported by diffusion across the membrane from the source to the strip solution where metal ions are back-extracted. The technique offers great potential to tune the selectivity by incorporating different complexing ligands in the membrane. A SLM was used to analyze the dissolved (< 0.45 mu m) copper speciation from two sites in the San Francisco Bay estuary; Dumbarton Bridge, [Cu](total) approximate to 27 nM, and San Bruno Shoals, [Cu](total) 23 nM. The sites were also characterized independently by differential pulse anodic stripping voltammetry (DPASV) using a Nafion-coated thin mercury film electrode (NCTMFE). The SLM employed 10 mM lasalocid, a naturally occurring carboxylic polyether ionophore, in nitrophenyl octyl ether (NPOE) as the membrane complexing ligand, supported by a microporous, polypropylene, hydrophobic membrane. This is the first study where SLM technique has been compared with an independent speciation technique in marine waters. Results of copper speciation measurements from Dumbarton Bridge, a site in South San Francisco Bay where copper speciation has been well-characterized in previous studies using various voltammetric techniques, indicated that only about 3% (0.9 nM) of the total dissolved copper was SLM labile. The corresponding DPASV labile copper fraction was < 0.4% (< 0.1 nM) of total dissolved copper. The concentration of total copper binding ligands measured by the membrane technique was 471 nM as compared to 354 nM measured by DPASV, more than 1 order of magnitude higher than the total dissolved copper concentration. The SLM measurements were consistent with earlier copper speciation measurements that were made in South San Francisco Bay using other voltammetric stripping techniques.