Noves metodologies d'anàlisi de compostos volàtils mitjançant trampes d'agulla. Aplicació a l'anàlisi d'alè, atmosfèrica i d'aigües

S'ha desenvolupat una nova tècnica de preconcentració per a compostos volàtils basada en trampes d'agulla. Les trampes d'agulla consisteixen en agulles d'acer inoxidable farcides amb un o més adsorbents, cosa que permet la preconcentració dels anàlits que flueixen pel seu interior. S'han estudiat els diferents paràmetres que afecten el procés de sorció/desorció (dimensions de les agulles i de la cambra de vaporització, temperatura de l'injector, temps sense divisió de flux, efecte memòria i estabilitat d'emmagatzematge). En el cas de les mostres líquides, on cal acoblar les trampes d'agulla amb la tècnica d'espai de cap, s'han avaluat quatre modalitats de presa de mostra, tant actives com passives. La metodologia més adequada quant a simplicitat i sensibilitat és la presa de mostra de l'espai de cap emprant diversos cicles de presa de mostra d'un volum petit i fix. Una vegada trobades les millors condicions d'anàlisi, el mètode ha estat validat per a mostres tant gasoses com líquides. Els resultats obtinguts indiquen que les trampes d'agulla són una nova metodologia vàlida per a l'anàlisi de mostres gasoses (per exemple, alè i ambientals) i líquides.A new preconcentration technique has been developed for the analysis of volatile compounds based on the use of needle traps. These traps are made of stainless steel needles filled with one or more adsorbents, allowing the preconcentration of the analytes inside the trap by passing a gas flow through the needle. The parameters affecting the sorption/desorption process have been assessed (e. g. needle and liner dimensions, injector temperature, splitless time, memory effects, and stability inside the needle). For liquid samples, four different passive and active sampling methodologies were studied. The best results in terms of simplicity and sensitivity are obtained by sampling the headspace with various cycles of small fixed volume. Once the best analysis conditions of analysis were determined, the method was validated for gas and liquid samples. The results show that needle traps are a good methodology for analysing breath, atmospheric and liquid samples

Screen-printed electrodes incorporated in a flow system for the decentralized monitoring of lead, cadmium and copper in natural and wastewater samples

Mercury-based screen-printed electrodes (SPE) combined with square-wave anodic stripping voltammetry (SWASV) techniques for the analysis of copper, cadmium, lead, and zinc in different water samples have been applied. The detection system has been implemented in a flow cell and different experimental conditions have been tested in view of its application for in-situ monitoring. In particular, an acetate buffer together with a low chloride concentration (0.025 M NaCl) provided best performance and reproducible results. Additionally, the flow system was validated for the first time in terms of limits of detection, linearity, repeatability and recovery. Limits of detection of 2.8 μg L-1, 4.1 μg L-1, and 7.5 μg L-1 for cadmium, lead and copper respectively and repeatabilities lower than 10% (as RSD) were found. Good recoveries have been obtained for the three cations and in particular for copper, even in the presence of zinc. Finally, the method has shown its efficiency for the rapid screening of lead, cadmium and copper contained in both natural waters and wastewater samples. © 2013 Copyright Taylor and Francis Group, LLC.Financial support from CTQ2008-06847-C02-02/TECNO, MAT2008-03079/NAN and WARMER project (FP6-034472) are acknowledged.Peer Reviewe

A Polymer Inclusion Membrane for Sensing Metal Complexation in Natural Waters

Metal speciation studies are of great importance in assessing metal bioavailability in aquatic environments. Functionalized membranes are a simple tool to perform metal chemical speciation. In this study, we have prepared and tested a polymer inclusion membrane (PIM) made of the polymer cellulose triacetate (CTA), the extractant di-(2-ethylhexyl) phosphoric acid (D2EHPA), and the plasticizer 2-nitrophenyloctyl ether (NPOE) as a sensor for Zn and Cu complexation studies. This PIM, incorporated in a device with an 0.01 M HNO3 receiving solution, is shown to effectively transport free metal ions, and it is demonstrated that the presence of ligands that form stable complexes with divalent metallic ions, such as ethylenediaminetetraacetic acid (EDTA) and humic acid (HA), greatly influences the accumulation of the metals in the receiving phase due to the increasing metal fraction complexed in the feed phase. Moreover, the effect of major ions found in natural waters has been investigated, and it is found that the presence of calcium did not decrease the accumulation of either Zn or Cu. Finally, the PIM sensor has been used successfully to evaluate metal complexation in a river water affected by Zn pollution

The Use of a Polymer Inclusion Membrane for Arsenate Determination in Groundwater

A polymer inclusion membrane (PIM) containing the ionic liquid methyltrioctylammonium chloride (Aliquat 336) as the carrier has been used satisfactorily for the preconcentration of arsenate present in groundwater samples, allowing its determination by a simple colorimetric method. The optimization of different chemical and physical parameters affecting the membrane performance allowed its applicability to be broadened. The transport of As(V) was not affected by the polymer used to make the PIM (cellulose triacetate (CTA) or poly(vinyl chloride) (PVC)) nor the thickness of the membrane. Moreover, the use of a 2 M NaCl solution as a stripping phase was found to allow the effective transport of arsenate despite the presence of other major anions in groundwater. Using the PIM for the analysis of different groundwaters spiked at 100 μg L−1 resulted in recoveries from 79% to 124% after only 5 h of contact time. Finally, the validated PIM-based method was successfully applied to the analysis of waters containing naturally occurring arsenate

Design of a Hollow Fiber Supported Liquid Membrane System for Zn Speciation in Natural Waters

A supported liquid membrane-hollow fiber system (HFSLM) has been developed to determine zinc speciation in aquatic environments. The liquid membrane consisted of an organic solution of bis-(2-ethylhexyl)phosphoric acid (D2EHPA) impregnated in the microporous of a polypropylene hollow fiber. The membrane contacted both the donor solution, that contained the metal and the stripping solution, placed in the lumen of the hollow fiber, where the metal was preconcentrated. Different parameters affecting the Zn2+ transport efficiency have been evaluated such as the composition of both the donor and stripping solutions as well as the membrane phase. Extraction and transport efficiencies of free Zn(II) higher than 90% were obtained with a liquid membrane consisting of a 0.1 M D2EHPA solution in dodecane and a 0.1 M HNO3 solution as the stripping phase. The developed HFSLM was used to study the effect of different ligands (EDTA and citric acid) in the donor phase of Zn(II) transport and to investigate the selectivity of the membrane towards Zn when other metals were also present. Finally, the HFSLM system was successfully applied to estimate the free Zn(II) concentrations in three water samples from a mining area. Moreover, the HFSLM system facilitates the analytical determination of trace Zn(II) levels allowing the achievement of enrichment factors of around 700 in the stripping phase

Preparation and Characterization of Nanoparticle-Doped Polymer Inclusion Membranes. Application to the Removal of Arsenate and Phosphate from Waters

Nanoparticle-doped polymer inclusion membranes (NP-PIMs) have been prepared and characterized as new materials for the removal of arsenate and phosphate from waters. PIMs are made of a polymer, cellulose triacetate (CTA), and an extractant, which interacts with the compound of interest. We have used the ionic liquid (IL) trioctylmethylammonium chloride (Aliquat 336) as the extractant and have investigated how the addition of nanoparticles can modify membrane properties. To this end, inorganic nanoparticles, such as ferrite (FeO), SiO and TiO, and multiwalled carbon nanotubes (MWCNTs), were blended with the polymer/extractant mixture. Scanning electron microscopy (SEM), infrared spectroscopy (FT-IR), and contact angle measurements have been used to characterize the material. Moreover, PIM stability was checked by measuring the mass loss during the experiments. Since Aliquat 336 acts as an anion exchanger, the NP-PIMs have been explored in two different applications: (i) as sorbent materials for the extraction of arsenate and phosphate anions; (ii) as an organic phase for the separation of arsenate and phosphate in a three-phase system. The presence of oleate-coated ferrite NP in the PIM formulation represents an improvement in the efficiency of NP-PIMs used as sorbents; nevertheless, a decrease in the transport efficiency for arsenate but not for phosphate was obtained. The ease with which the NP-PIMs are prepared suggests good potential for future applications in the treatment of polluted water. Future work will address three main aspects: firstly, the implementation of the FeO-PIMs for the removal of As(V) in real water containing complex matrices; secondly, the study of phosphate recovery with other cell designs that allow large volumes of contaminated water to be treated; and thirdly, the investigation of the role of MWCNTs in PIM stability

New methodologies for the analysis of volatile compounds using needle traps. Applications to breath, atmospheric and water analysis

S’ha desenvolupat una nova tècnica de preconcentració per a compostos volàtils basada en trampes d’agulla. Les trampes d’agulla consisteixen en agulles d’acer inoxidable farcides amb un o més adsorbents, cosa que permet la preconcentració dels anàlits que flueixen pel seu interior. S’han estudiat els diferents paràmetres que afecten el procés de sorció/desorció (dimensionsde les agulles i de la cambra de vaporització, temperatura de l’injector, temps sense divisió de flux, efecte memòria i estabilitat d’emmagatzematge). En el cas de les mostres líquides, on cal acoblar les trampes d’agulla amb la tècnica d’espai de cap, s’han avaluat quatre modalitats de presa de mostra, tant actives com passives. La metodologia més adequada quant a simplicitat i sensibilitat és la presa de mostra de l’espai de cap emprant diversos cicles de presa de mostra d’un volum petit i fix. Una vegada trobades les millors condicions d’anàlisi, el mètode ha estat validat per a mostres tant gasoses com líquides. Els resultats obtinguts indiquen que les trampes d’agulla són una nova metodologia vàlida per a l’anàlisi de mostres gasoses (per exemple, alè i ambientals) i líquides.Paraules clau: Trampes d’agulla, espai de cap, anàlisi d’alè, anàlisi atmosfèrica, anàlisi d’aigües.A new preconcentration technique has been developed for the analysis of volatile compounds based on the use of needle traps. These traps are made of stainless steel needles filled with one or more adsorbents, allowing the preconcentration of the analytes inside the trap by passing a gas flow through the needle. The parameters affecting the sorption/desorption process have been assessed (e. g. needle and liner dimensions, injector temperature, splitless time, memory effects, and stabilityinside the needle). For liquid samples, four different passive and active sampling methodologies were studied. The best results in terms of simplicity and sensitivity are obtained by sampling the headspace with various cycles of small fixed volume. Once the best analysis conditions of analysis were determined, the method was validated for gas and liquid samples. The results show that needle traps are a good methodology for analysing breath, atmospheric and liquid samples.Keywords: Needle traps, headspace, breath analysis, atmospheric analysis, water analysis