RESUMO
The different species of nickel present in natural waters exhibit different transport behaviour through bulk liquid membranes (BLMs). This fact has been used to design and optimise a separation/pre-concentration system applicable to separate labile and non-labile nickel fractions. A hydrazone derivative-1,2-cyclohexanedione bis-benzoyl-hydrazone (1,2-CHBBH) dissolved in toluene/dimethyl formamide (2% DMF)-was used as a chemical carrier of nickel species, from an aqueous source solution (sample) to a receiving acidic solution. Both chemical and hydrodynamic conditions controlling the transport system were studied and optimised. Under optimum conditions, variations in the transport of nickel ions as a function of organic (humic acids) and inorganic (chloride ions) ligands were studied. Relationships between the permeability coefficient (P) or recovery efficiency (%R) and the concentrations of ligands and nickel species were analysed using Winhumic V software. A negative correlation between P and the concentration of organic nickel complexes was found, suggesting that only labile nickel species are transported through the liquid membrane, with non-labile complexes remaining in the water sample; allowing for their separation and subsequent quantification in natural waters.
RESUMO
The current work presents a large systematic screening of 61 possible organic solvents used as supported liquid membranes (SLM) in electromembrane extraction (EME). For each organic solvent, recovery, current across the SLM, and stability considerations have been investigated and correlated to relevant solvent properties through partial least square regression analysis. The five unpolar basic drugs pethidine, haloperidol, methadone, nortriptyline, and loperamide were used as model analytes. Efficient EME solvents were found to have a low water solubility (<0.5 g L(-1)) and belonged to cluster 2 of a Kamlet-and-Taft-based solvent classification system (high dipole moments and proton acceptor properties). These parameters were especially found in nitroaromatic compounds and ketones. Small molecules with low log P value and high water solubility were unsuitable, as they tended to give unstable extractions, caused by a high current across the SLM. This was often combined with substantial solvent-related interferences and the generation of an electroosmotic flow across the SLM, with resulting acceptor solution expansion. Large molecules with a high log P value were classified as inefficient. For these solvents, no current was measured across the SLM and no analytes were extracted. This is the first time systematic knowledge on the SLM in EME has been gathered and investigated, and the presented results could be highly beneficial for future development and optimization of EME.
RESUMO
In the last years, some analytical methodologies have been identified as a source of pollution, receiving increasing attention to decrease their impact on the environment. In this sense, the so-called solvent-less methodologies appear as a green alternative to reduce the volume of solvents used in many sample treatment procedures and, consequently, the volume of toxic wastes produced. Among these techniques, analytical methodologies based on liquid-phase microextraction are being continuously developed, although most applications are focused on organic compounds. In this work, a three-phase hollow-fibre liquid-phase microextraction (HF-LPME) system has been developed for the preconcentration of nickel in natural waters, prior to the analysis by atomic absorption spectrometry. Under optimum conditions, the new system allowed an enrichment factor of 29.80 to be obtained after 60 min of experiment, and it was successfully applied to the determination of nickel in both saline and non-saline water samples, at ppb and ppt levels. The results were compared with those obtained using a well-established methodology based on liquid solvent extraction showing no significant differences (α = 0.05) between both values. In addition, the new HF-LPME presents the advantages of a green analytical technique, as its greenness profile shows, with the additional reduction of sample manipulation and time cost.