In this work, Cd(II) extraction in natural waters by organophosphorus extractants as organic phase, as well as its back-extraction in an acidic media, has been studied. Cadmium extraction behavior at natural waters’ pH conditions (values in the range 7–8) was studied with two different extractants and co-ions, obtaining the highest extraction efficiency when using 0.1M Cyanex 272 in kerosene as organic phase and 0.1 M NO3 − as co-ion. Once they were selected, the effect on the extraction efficiency of sample pH, buffer concentration, extraction time, Cyanex 272 concentration as well as back-extractant concentration, was studied. The presence of the main inorganic and organic ligands in the sample was also studied, observing that extraction efficiency was affected most significantly when chlorides were present, with a decrease of about 14%, proving negligible for the others. Under the selected conditions, spiked real samples were successfully analyzed.

Supported liquid membranes have been used to implement a hollow fibre liquid-phase microextraction (HF-LPME) method for the preconcentration of Cd(II) in natural waters as a sample preparation step for its determination by high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS-GFAAS). This system was designed to use four hollow fibres simultaneously with the same sample, thus improving the simplicity, speed and reproducibility of the results. The organic liquid membrane bis-(2,4,4-trimethylpentyl) phosphinic acid (Cyanex® 272) dissolved in dihexylether (DHE) was immobilised into the pores of the walls of polypropylene hollow fibres. After extraction, the cadmium-enriched acidic phases were recovered and analysed by triplicate. To optimise the extraction process, the effect of both physical and chemical variables was studied, and optimum results with an enrichment factor (EF) of 292 were obtained for a fibre length of 6 cm, 1.06 M Cyanex 272, 0.04 M HNO3, stirring rate of 600 rpm and an extraction time of 4.26 h. For practical applications, extraction time was reduced to 2 h, keeping the EF as high as 130. Under these conditions, a detection limit of 0.13 ng L−1 Cd(II) was obtained, with a reproducibility of 3.3 % and a linear range up to 3 µg L−1 being achieved. The proposed method was successfully applied to the determination of cadmium in mineral, tap and seawater samples.

Abstract. Heavy metals are normally found, in natural waters, in very low concentrations. Some of them are essential for life in low level; however, in higher level they are toxic. Therefore, analyzing their bio-available fraction is of main interest. Standard methodology is based in the collection of a number of samples from a water body. Collected samples must be stored, pre-treated and then analyzed. Pre-treatment usually involves pre-concentrating the metal, with the corresponding risk of contamination or loss of analyte. This way, punctual information is obtained from every sampling campaign. As an alternative, passive sampling techniques allow the continuous and coupled sampling-pre-treatment for heavy metals analysis, giving a better approach in the characterization of the studied water body. Liquid phase micro-extraction (LPME) is a green analytical alternative for liquid-liquid extraction that promotes a reduction of sample volume, solvent needed and waste generation. Using these systems, polypropylene hollow fibers (HF) with pores in their walls can be used. A few micro-liters of organic solvent are supported in the pores. The sample is placed in the outer part of the fiber and a receiving phase is placed in its inner part, allowing continuous liquid extraction of the metal from the sample. Several fibers with different physical features have been employed to analyzed total concentration and bio-availability of some heavy metals (Ag, Ni, Cu) in natural water samples. Thanks to fibers configuration, devices for passive sampling based in HF-LPME could be designed. Advantages of this methodology over existing ones are supported because the receiving phase is liquid. As a consequence, retained metals do not need to be eluted from the acceptor prior to instrumental analysis.