Facilitating inorganic arsenic speciation and quantification in waters: Polymer inclusion membrane preconcentration and X-ray fluorescence detection.

BACKGROUND: Arsenic, classified as a priority pollutant and human carcinogen by the IARC, is subject to stringent regulatory limits in food and water. Among various arsenic species found in water samples, arsenite (As(III)) is identified as the most toxic form. Given the limitations of conventional spectroscopic techniques in speciation analysis, there is a crucial need for innovative and sustainable methodologies that enable arsenic speciation. Simplifying these methodologies is essential for widespread applicability and effective environmental monitoring. RESULTS: This study proposes a simple and cost-effective analytical methodology for speciating inorganic arsenic in water samples. The method involves extracting As(III) into a polymer inclusion membrane (PIM) containing the extractant Cyanex 301 (bis(2,4,4-trimethylpentyl) dithiophosphinic acid), followed by analysis using energy dispersive X-ray fluorescence (EDXRF) spectrometry. The concentration of arsenate was measured after a reduction step using a thiosulfate/iodide mixture. This simple methodology allows a limit of quantification for trivalent arsenic (2 µg L-1), which is well below the World Health Organization's recommended maximum permissible level of As in drinking water (10 µg L-1). The method that is developed allows the determination of As at trace levels in waters with naturally occurring arsenic. SIGNIFICANCE AND NOVELTY: This study represents a significant advance in the field, providing a novel and efficient methodology for arsenic speciation analysis in water samples. By combining the advantages of polymer inclusion membrane (PIM) extraction with energy dispersive X-ray fluorescence (EDXRF) spectrometry, this study offers a cost-effective and environmentally friendly approach to address the critical issue of arsenic contamination in water sources, thereby contributing to enhanced environmental monitoring and public health protection.

Sexual hormones monitoring in surface waters and wastewaters from Northern Italy by thin film microextraction coupled with HPLC-MS/MS.

The occurrence of sex steroid hormones, viz. oestrogens and progestins, in aquatic ecosystems is of global concern due to their role as endocrine disrupting chemicals, even at low concentration (µg L-1 or less). Thus, it is essential to monitor these organic pollutants to get a realistic picture of their presence and to control their contamination levels in environmental water bodies. In this respect, we have explored the use of self-prepared polymeric films as novel sorptive phase for the microextraction of 17ß-estradiol, 17α-ethinylestradiol, estrone, progesterone, medroxyprogesterone acetate and hydroxyprogesterone. The thin film microextraction procedure has been developed, evaluating different film compositions, sample volumes and elution conditions to recover the sorbed analytes. The overall method provides good reproducibility (RSD < 12%) and recoveries higher than 60%. The final method has been applied to environmental monitoring in surface waters (river and lake samples) and urban wastewater treatment plant effluents and influents from Northern Italy, to get a contamination snapshot of this highly urbanized area.

Deep eutectic solvents incorporated in a polymeric film for organophosphorus pesticide microextraction from water samples.

BACKGROUND: Organophosphorus pesticides (OPPs) were extensively used in agriculture. Due to their adverse effect, there is a need for sensitive and reliable methods to determine these agrochemicals. Microextraction techniques (ME) afford the opportunity to substantially reduce the amount of organic solvent used in classical extraction methods for pesticide analysis. Moreover, deep eutectic solvents (DES) made of components of natural origin, have been applied in microextraction techniques as a green alternative to organic solvents. The combination of thin film microextraction and DES can be seen as an alternative for thin film microextraction of OPPs from water samples. RESULTS: We describe a thin film microextraction-GC-MS method for the determination of OPPs from water samples. The thin film was prepared by solvent casting using cellulose triacetate (CTA) as the polymer and a deep eutectic solvent as the extracting phase. Lidocaine, menthol, dodecanoic acid, and camphor were tested as the components for DES-based film. With a film containing 70 % (w) of CTA and 30 % of the DES dodecanoic acid:lidocaine, quantitative results for the extraction of an OPPs mix were achieved. Then, the elution was performed with 2 mL of ethyl acetate. The validation of the TFME method was performed with a piece of the film suspended in 20 mL of sample solution with a contact time of 1 h. Limits of detection in the low µg L-1 range were obtained using a single quadrupole mass analyser. The thin film with pipette tip configuration was tested and preliminary results for chlorpyrifos were satisfactory. SIGNIFICANCE: This represents the first approach to use polymeric films made of CTA and DES for TFME of OPPs, in two configuration the suspended film and pipette tip.

Biochar-based polymeric film as sustainable and efficient sorptive phase for preconcentration of steroid hormones in environmental waters and wastewaters.

BACKGROUND: The environmental impact of sample preparation should be minimized through simplification of the procedures and the use of natural, renewable and/or reusable materials. In such scenario, thin-film microextraction fulfils the former criteria, as it enables few steps and miniaturization, thus small amount of extraction phase. At the same time, the use of sorbents such as biochars obtained from biomass waste is even more promoted due to their availability at low cost and increased life-cycle in a circular economy vision. However, it is not always easy to combine these criteria in sample preparation. RESULTS: A thin film microextraction was developed for the determination of steroids in aqueous samples, entailing a membrane made of cellulose triacetate and a wood-derived biochar (Nuchar®) as carbon precursor. Different characterization techniques showed the successful preparation, whereas the sorption kinetics experiments demonstrated that biochar is responsible for the extraction with the polymer acting as a smart support. After a study about membranes' composition in terms of biochar amounts (4 %, 10 %, 16 % wt) and type of synthesis set up, the ceramic 3D-mold was selected, achieving reproducible and ready-to-use membranes with composition fixed as 10 %. Different elution conditions, viz. type and time of agitation, type, composition and volume of eluent, were evaluated. The final microextraction followed by HPLC-MS/MS quantification was successfully validated in river and wastewater treatment plant effluent samples in terms of accuracy (R% 64-123 %, RSD<19 % in river; R% 61-118 %, RSD <18 % in effluent, n = 4), sensitivity (MQLs 0.2-8.5 ng L-1) and robustness. SIGNIFICANCE: This novel biochar-based polymeric film proved to be a valid and sustainable sorbent, in terms of extraction capability, ease of preparation and greenness. By comparison with literature and the greenness evaluation with the most recent metric tools, this method expands the potential applicability of the thin-film microextraction and opens up innovative scenarios for sustainable procedures entailing the use of biochars entrapped in bio-polymers.

A Comprehensive Study on the Effect of Plasticizers on the Characteristics of Polymer Inclusion Membranes (PIMs): Exploring Butyl Stearate as a Promising Alternative.

This study investigated the influence of various plasticizers commonly used in the manufacture of polymer inclusion membranes (PIMs), such as 2-nitrophenyl octyl ether (NPOE), phthalates, adipates, and sebacates on the mechanical, thermal, and transport properties of membranes. Additionally, butyl stearate (BTS), chosen for its non-toxic nature compared to phthalates and its cost-effectiveness relative to adipates and sebacates, was evaluated as a plasticizer in PIMs for the first time. All plasticizers were incorporated in PIMs made of either cellulose triacetate (CTA) or poly(vinyl chloride) (PVC) as the base polymers and the task-specific ionic liquid trioctylmethylammonium thiosalicylate (TOMATS) as the carrier. The plasticizers were found to significantly affect the characteristics of membrane hydrophilicity, mechanical flexibility, and thermal stability. Transport experiments using Hg(II) as a model target ion revealed that, for CTA-based PIMs, the plasticizer did not significantly affect transport efficiency. However, for PVC-based PIMs, BTS exhibited better efficiency when compared to NPOE. These findings highlight the potential of BTS as an attractive alternative to currently used plasticizers in PVC-based PIM formulations.

Multiwalled Carbon Nanotubes Embedded in a Polymeric Matrix as a New Material for Thin Film Microextraction (TFME) in Organic Pollutant Monitoring.

It is essential to monitor organic pollutants to control contamination levels in environmental water bodies. In this respect, the development of new materials based on functionalised polymeric films for the measurement of toxic compounds is of interest. In this study, we prepare new films based on polymer cellulose triacetate modified with multi-walled carbon nanotubes for the monitoring of selected compounds: a fungicide (chlorpyrifos) and two emerging contaminants, the musk tonalide and the bactericide triclosan, which are used in the formulation of personal care products. The films, upon contact with water samples and following the principles of thin film microextraction, allow the determination of organic pollutants at low concentration levels. The contact time of the film with a predetermined volume of water is fixed at 60 min, and the compounds are eluted with a small volume (1 mL) of organic solvent for GC-MS analysis. Parameters such as repeatability for different films and detection limits are found to be satisfactory. Applying the method to river water demonstrates its suitability and, in the cases of chlorpyrifos and tonalide, the absence of a significant matrix effect.

New Insights on the Effects of Water on Polymer Inclusion Membranes Containing Aliquat 336 Derivatives as Carriers.

Surface characterization of polymer inclusion membranes (PIMs) using the polymers cellulose triacetate and polyvinyl chloride, containing different ionic liquids (ILs) as carriers, has been performed. Three different ILs have been tested: commercial trioctyl methylammonium chloride (Aliquat 336-AlqCl-) and two derivatives bearing the counter anion NO3- or SCN- (AlqNO3 and AlqSCN, respectively). Surface analysis was performed by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) for both dry membranes and PIMs immersed for 4 days in ultrapure water to investigate the effect of the interaction of water with the membrane's morphology and composition. XPS analysis of the PIMs revealed that immersion in ultrapure water causes a decrease in the atomic concentration percentage (A.C.%) of the specific IL atoms (Cl, S, and N) when compared with dry samples. Moreover, SEM images of the PIMs containing the IL AlqNO3 showed an alteration in the morphology of the membrane due to water contact at surface level, whereas no changes were observed at a bulk level. These changes in the surface composition of the water equilibrated PIMs may be associated with the solubilization of the IL in the water solution, which, therefore, may affect the reactivity of the membrane's surface. To better understand this effect, PIMs containing both AlqCl and AlqNO3 as carriers were used for arsenic (V) transport. It was found that AlqCl was the most effective IL and that the effectivity of the PIM on As(V) removal was not affected after five cycles of the membrane's reuse.

Determination of elemental bioavailability in soils and sediments by microwave induced plasma optical emission spectrometry (MIP-OES): Matrix effects and calibration strategies.

In the past few years, microwave induced plasma optical emission spectrometry (MIP-OES) has generated great interest as an alternative technique to inductively coupled plasma-based techniques due to its lower operational cost. Since MIP-OES suffers from severe matrix effects due to easily ionizable elements (EIEs) (Na, Ca, etc.), it is unclear whether this technique could be employed for elemental bioavailability studies in soils and sediments since the main extractant solutions employed in such works may contain high levels of these elements. Thus, the aim of this work was to evaluate the feasibility of MIP-OES as a detector for such applications. To this end, the influence of different extractant solutions (0.25 mol L-1 MgCl2, 0.25 mol L-1 CaCl2, 0.10 mol L-1 acetic acid, 0.05 mol L-1 Na2EDTA, 0.25 mol L-1 NaNO3, 0.25 mol L-1 NaOAc/HOAc and 0.10 mol L-1 NH2OH·HCl) on the analyte emission of several elements (As, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb, Rh, Se, Sr and Zn) was investigated. Results were compared to those obtained using a reference solution made of 5% w w-1 HNO3 solution. For saline extractant solutions, both the optimum nebulizer gas flow rate (Qg) and analyte emission were modified with regard to the reference solution. In general, the optimum Qg was reduced by between 0.1 and 0.2 L min-1 for both ionic and atomic lines. Under optimum Qg conditions, analyte emission was supressed by saline solutions except for atomic lines with an upper electronic state below 4 eV, which were enhanced. The magnitude of matrix effects was strongly dependent on EIE ionization energy. The lower the ionization energy, the greater the matrix effects were registered. No measurable matrix effects were registered on both Qg and analyte emission within experimental uncertainties for NH2OH·HCl and acetic acid extractant solutions. Experimental data suggest that matrix effects were related to changes in plasma characteristics and the analyte excitation/ionization mechanism. To mitigate matrix effects and improve long-term MIP-OES performance, internal standardization using either Rh (343.489 nm and 369.236 nm) or OH molecular emission band (308.958 nm) was required. This calibration methodology was successfully applied to the study of the elemental bioavailability in soil samples from a vineyard affected by copper-based fungicides and sediment samples from an area affected by mining waste.

Effective concentration signature of Zn in a natural water derived from various speciation techniques.

The uptake of nutrients or toxicants by different organisms in aquatic systems is known to correlate with different fractions of the nutrient's or toxicant's total concentration. These fractions can be provided by different analytical techniques, from which the better correlation is expected to be found for those with a characteristic length comparable to that in the considered organism uptake. An effective concentration signature can be built up with the concentration values associated to the availability (i.e. fluxes in dynamic techniques) of the nutrient or toxicant measured by various analytical techniques with different characteristic lengths. Here, this new representation was obtained for the pool of Zn complexes in the Mediterranean stream Riera d'Osor (Girona, Catalonia, Spain) with a suite of four analytical techniques. Absence of Gradients and Nernstian Equilibrium Stripping (AGNES) and Polymer Inclusion Membrane (PIM) devices provided the free Zn concentration. Linear Anodic Stripping Voltammetry provided a labile fraction (defined here as cLASV, higher than the free concentration), related to the diffusion layer scale. Diffusion Gradients in Thin-films provided higher labile fractions (known as DGT concentrations, cDGT) connected to the different characteristic lengths of different configurations (e.g. one or two resin discs) longer, in any case, than that corresponding to LASV. The combination of the information retrieved by the techniques allowed to quantify lability degrees of the pool of Zn complexes and to build up the effective concentration signature for this water.

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 (Fe3O4), SiO2 and TiO2, 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 Fe3O4-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.

Investigation of Volatiles in Cork Samples Using Chromatographic Data and the Superposing Significant Interaction Rules (SSIR) Chemometric Tool.

This study describes a new chemometric tool for the identification of relevant volatile compounds in cork by untargeted headspace solid phase microextraction and gas chromatography mass spectrometry (HS-SPME/GC-MS) analysis. The production process in cork industries commonly includes a washing procedure based on water and temperature cycles in order to reduce off-flavors and decrease the amount of trichloroanisole (TCA) in cork samples. The treatment has been demonstrated to be effective for the designed purpose, but chemical changes in the volatile fraction of the cork sample are produced, which need to be further investigated through the chemometric examination of data obtained from the headspace. Ordinary principal component analysis (PCA) based on the numerical description provided by the chromatographic area of several target compounds was inconclusive. This led us to consider a new tool, which is presented here for the first time for an application in the chromatographic field. The superposing significant interaction rules (SSIR) method is a variable selector which directly analyses the raw internal data coming from the spectrophotometer software and, combined with PCA and discriminant analysis, has been able to separate a group of 56 cork samples into two groups: treated and non-treated. This procedure revealed the presence of two compounds, furfural and 5-methylfurfural, which are increased in the case of treated samples. These compounds explain the sweet notes found in the sensory evaluation of the treated corks. The model that is obtained is robust; the overall sensitivity and specificity are 96% and 100%, respectively. Furthermore, a leave-one-out cross-validation calculation revealed that all of the samples can be correctly classified one at a time if three or more PCA descriptors are considered.

Silencing against the conserved NAC domain of the potato StNAC103 reveals new NAC candidates to repress the suberin associated waxes in phellem.

Both suberin and its associated waxes contribute to the formation of apoplastic barriers that protect plants from the environment. Some transcription factors have emerged as regulators of the suberization process. The potato StNAC103 gene was reported as a repressor of suberin polyester and suberin-associated waxes deposition because its RNAi-mediated downregulation (StNAC103-RNAi) over-accumulated suberin and associated waxes in the tuber phellem concomitantly with the induction of representative biosynthetic genes. Here, to explore if other genes of the large NAC gene family participate to this repressive function, we extended the silencing to other NAC members by targeting the conserved NAC domain of StNAC103 (StNAC103-RNAi-c). Transcript profile of the StNAC103-RNAi-c phellem indicated that StNAC101 gene was an additional potential target. In comparison with StNAC103-RNAi, the silencing with StNAC103-RNAi-c construct resulted in a similar effect in suberin but yielded an increased load of associated waxes in tuber phellem, mainly alkanes and feruloyl esters. Globally, the chemical effects in both silenced lines are supported by the transcript accumulation profile of genes involved in the biosynthesis, transport and regulation of apoplastic lipids. In contrast, the genes of polyamine biosynthesis were downregulated. Altogether these results point out to StNAC101 as a candidate to repress the suberin-associated waxes.

Chloroanisoles and Other Chlorinated Compounds in Cork from Different Geographical Areas.

Cork quality is crucial for the fabrication of corks intended to be used to seal wine bottles. This work has focused on the determination of chloroanisoles (CAs)-exogenous compounds with a low perception threshold-in cork. The identification and quantification of these compounds was carried out with Bond Elut-ENV solid phase extraction and gas chromatography with mass spectrometry detection. Cork samples were obtained from oaks from Catalonia, Extremadura and Italy, and the presence of CAs was evaluated. Moreover, cork affected by the presence of yellow stains (a defect present in cork, mainly originated from the growth of the fungus Armillaria mellea) was analysed separately. The results obtained from cork macerates revealed the presence of trichloroanisole (TCA) in Catalan and Italian cork. Furthermore, TCA concentration was not statistically different when comparing cork affected and non-affected by the growth of A. mellea. Other chlorinated compounds were identified by comparison of their mass spectra with the data from the NIST library.

First Report on a Solvent-Free Preparation of Polymer Inclusion Membranes with an Ionic Liquid.

A novel and environmentally-friendly procedure for the preparation of polymer inclusion membranes (PIMs) containing an ionic liquid is presented for the first time. Traditionally, PIMs are prepared by a solvent casting method with the use of harmful organic solvents. Here we report a new solvent-free procedure based on a thermal-compression technique which involve the melting of the components of the PIM and the application of a high pressure to the melted specimen to form a flat-sheet film. In our study, we have tested different polymers, such as two cellulose derivatives as well as two thermoplastic polymers, polyurethane (TPU) and poli ε-caprolactone (PCL). The ionic liquid (IL) trioctylmethylammonium chloride (Aliquat 336) has been used to produce PIMs with a fixed composition of 70% polymer-30% IL (w/w). Both TPU and PCL polymers provide successful membranes, which have been thoroughly characterized. PIMs based on the polymer PCL showed a high stability. To test whether the properties of the IL were affected by the preparation conditions, the extraction ability of Aliquat 336 was investigated for both PCL and TPU membranes in terms of Cr(VI) extraction. Satisfactory values (90% extraction) were obtained for both membranes tested, showing this novel procedure as a green alternative for the preparation of PIMs with ILs.

Automatic determination of arsenate in drinking water by flow analysis with dual membrane-based separation.

The sequential application of a polymer inclusion membrane (PIM), composed of poly(vinylidenefluoride-co-hexafluoropropylene) and the anionic extractant Aliquat 336, and a microporous polytetrafluoroethylene (PTFE) gas-permeable membrane was utilized for the first time to develop a flow analysis (FA) system, for the automatic determination of trace levels of arsenate (As(V)) in drinking water as arsine. The system incorporated a flow-through extraction cell for separation and preconcentration of arsenate and a gas-diffusion cell for the separation of arsine prior to its spectrophotometric determination based on the discoloration of a potassium permanganate solution. Under optimal conditions the FA system is characterized by a limit of detection of 3.0 µg L-1 As(V) and repeatability of 1.8% (n = 5, 25 µg L-1 As(V)) and 2.8% (n = 5, 50 µg L-1 As(V)). The newly developed FA method was successfully applied to the determination of arsenate in drinking water samples in the µg L-1 concentration range.

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.

Comparison of different speciation techniques to measure Zn availability in hydroponic media.

Four analytical techniques are compared: AGNES (Absence of Gradients and Nernstian Equilibrium Stripping), LASV (Anodic Stripping Voltammetry with Linear stripping), DGT (Diffusive Gradients in Thin films) and PIM (Polymer Inclusion Membranes). These techniques have been designed to provide the free ion concentration or a labile fraction, complementarily contributing to an integrated description of speciation and availability. Their simultaneous application to the determination of free Zn concentrations or labile fluxes in seven solutions of a hydroponic medium reveals characteristics of each technique and correlations between their results. All dynamic results can be interpreted in terms of a general theoretical framework on fluxes. Indeed, in techniques under diffusion-limited conditions in the sample, the flux can be split into the free contribution (linearly proportional to the free fraction), plus the contribution of the complexes (where mobility, lability and abundance of complexation are intertwined). A methodology to compute lability degrees is developed. Measurements with PIM devices confirm that diffusion in the sample solution is not rate limiting, so its flux is proportional to the free metal in the donor solution. A proportionality between the responses of any given two techniques is observed, which suggests that, for the low ligand-to-metal concentration ratios used in the present work, any of these techniques would correlate similarly with uptake, toxic or nutritional measurements.

A new extraction phase based on a polymer inclusion membrane for the detection of chlorpyrifos, diazinon and cyprodinil in natural water samples.

A simple and effective method for the detection of three pesticides (chlorpyrifos, diazinon and cyprodinil) is developed using a polymer inclusion membrane (PIM) prior to gas chromatography and mass spectrometry detection (GC-MS). Analytes are extracted from natural water samples using a 3 cm2 PIM made of the polymer, cellulose triacetate (CTA), and the plasticizer, nitrophenyl octyl ether (NPOE). Addition of the plasticizer to the CTA matrix is found to be necessary for the extraction of pesticides. After extraction, analytes are recovered from the membrane with 1 mL of acetonitrile and injected into the GC-MS system. The main factors affecting the extraction efficiency are evaluated, including membrane composition, stirring mode, extraction and elution time. Ultrasonic assisted elution of the extracted pesticides is accomplished after 15 min of contact. The PIM-assisted extraction method makes it possible for pesticides to be determined in the range of 50-1000 ng L-1 with good linearity (coefficient of determination ≥0.995) and suitable recoveries (85-119%) and precision (<21%, n = 3) using 100 mL of a water sample. This methodology is shown to be suitable for the detection of chlorpyrifos in local river waters.

Polymer inclusion membrane to access Zn speciation: Comparison with root uptake.

Metal speciation studies can be performed with a new technique based on a functionalized membrane. The estimation of not only the total amount of metal, but also the metal available to living organisms is very important. In this context, we have investigated the use of a polymer inclusion membrane (PIM) in a new tool for the determination of free metal ion concentration. In order to check the usefulness of PIM devices in metal speciation studies and metal availability to potato plants (Solanum tuberosum), Zn has been chosen as a case study. The PIM designed for Zn transport uses polyvinyl chloride (PVC) as polymer and di-(2-ethylhexyl) phosphoric acid (D2EHPA) as carrier, with 0.01M nitric acid in the receiving solution. The stability of the PIM has been demonstrated and good linearity of PIM-device fluxes (JPIM) with free metal concentration was observed for total metal concentrations ranging from 3µM up to 70µM. The presence of different ligands, such as ethylenediaminetetraacetic acid (EDTA), humic acid (HA) and citrate, greatly influences the measured JPIM because the formation of metal complexes in the donor phase decreases the free Zn concentration in the sample. Good correlation has been found when comparing PIM fluxes and metal accumulation in potato plants roots in the presence of EDTA. But, the root uptake did not change when adding citrate and HA to the hydroponic medium, so the uptake does not always follows the Free Ion Activity Model (FIAM). These ligands might induce physiological changes in the roots and enhance metal uptake.

The Identification and Quantification of Suberin Monomers of Root and Tuber Periderm from Potato (Solanum tuberosum) as Fatty Acyl tert-Butyldimethylsilyl Derivatives.

INTRODUCTION: Protective plant lipophilic barriers such as suberin and cutin, with their associated waxes, are complex fatty acyl derived polyesters. Their precise chemical composition is valuable to understand the specific role of each compound to the physiological function of the barrier. OBJECTIVES: To develop a method for the compositional analysis of suberin and associated waxes by gas chromatography (GC) coupled to ion trap-mass spectrometry (IT-MS) using N-(tert-butyldimethylsilyl)-N-methyl-trifluoroacetamide (MTBSTFA) as sylilating reagent, and apply it to compare the suberin of the root and tuber periderm of potato (Solanum tuberosum). METHODOLOGY: Waxes and suberin monomers from root and periderm were extracted subsequently using organic solvents and by methanolysis, and subjected to MTBSTFA derivatisation. GC analyses of periderm extracts were used to optimise the chromatographic method and the compound identification. Quantitative data was obtained using external calibration curves. The method was fully validated and applied for suberin composition analyses of roots and periderm. RESULTS: Wax and suberin compounds were successfully separated and compound identification was based on the specific (M-57) and non-specific ions in mass spectra. The use of calibration curves built with different external standards provided quantitative accurate data and showed that suberin from root contains shorter chained fatty acyl derivatives and a relative predominance of α,ω-alkanedioic acids compared to that of the periderm. CONCLUSION: We present a method for the analysis of suberin and their associated waxes based on MTBSTFA derivatisation. Moreover, the characteristic root suberin composition may be the adaptive response to its specific regulation of permeability to water and gases. Copyright © 2016 John Wiley & Sons, Ltd.