Manuela Hidalgo

The selective adsorption of gold (III) and palladium (II) on new phosphine sulphide-type chelating polymers bearing different spacer arms: Equilibrium and kinetic characterisation

Abstract New resins, with a functional group based on triisobutyl phosphine sulphide and containing different spacer arms between the polymeric matrix and the functional group, are evaluated in order to determine and characterise the mechanism of the metal adsorption process. These polymers are selective towards gold and palladium from other noble (Pt, Rh and Ir) and base (Fe, Cu, Ni and Zn) metals. Selectivity is higher in the case of gold (2.8 mmol Au/g resin for polymer 3 and 6.5 for polymer 4) than for palladium (0.5 mmol Pd/g resin for polymer 3 and 0.7 for polymer 4). The application of the Langmuir model to the data permits the determination of the adsorption mechanism, which we found to be a chelating process. The result shows that spacer heteroatoms become involved in the adsorption process. The kinetics of the adsorption is faster for palladium than for gold. The elution of these two metals is accomplished by the use of sodium nitrite and thiourea as eluting compounds.

Development of novel and sensitive methods for the determination of sulfide in aqueous samples by hydrogen sulfide generation-inductively coupled plasma-atomic emission spectroscopy

Two new, simple and accurate methods for the determination of sulfide (S(2-)) at low levels (microgL(-1)) in aqueous samples were developed. The generation of hydrogen sulfide (H(2)S) took place in a coil where sulfide reacted with hydrochloric acid. The resulting H(2)S was then introduced as a vapor into an inductively coupled plasma-atomic emission spectrometer (ICP-AES) and sulfur emission intensity was measured at 180.669nm. In comparison to when aqueous sulfide was introduced, the introduction of sulfur as H(2)S enhanced the sulfur signal emission. By setting a gas separator at the end of the reaction coil, reduced sulfur species in the form of H(2)S were removed from the water matrix, thus, interferences could be avoided. Alternatively, the gas separator was replaced by a nebulizer/spray chamber combination to introduce the sample matrix and reagents into the plasma. This methodology allowed the determination of both sulfide and sulfate in aqueous samples. For both methods the linear response was found to range from 5microgL(-1) to 25mgL(-1) of sulfide. Detection limits of 5microgL(-1) and 6microgL(-1) were obtained with and without the gas separator, respectively. These new methods were evaluated by comparison to the standard potentiometric method and were successfully applied to the analysis of reduced sulfur species in environmental waters.

Dispersive micro solid-phase extraction using multiwalled carbon nanotubes combined with portable total-reflection X-ray fluorescence spectrometry for the determination of trace amounts of Pb and Cd in water samples

In this paper the combination of dispersive micro solid-phase extraction (DMSPE), using multiwalled carbon nanotubes (MWCNTs) as solid sorbents, with total-reflection X-ray fluorescence spectrometry (TXRF) is proposed for preconcentration and determination of lead and cadmium ions in water samples. The proposed sample preparation is quite simple and economic. After the sorption processes of the metals on the MWCNTs, the aqueous sample is separated by centrifugation and the metal loaded MWCNTs are suspended using a small volume of an internal standard solution and analyzed directly by TXRF. Parameters affecting the extraction process (complexing agent, pH of the aqueous sample, amount of MWCNTs) and TXRF analysis (volume of the deposited suspension on the reflector, drying mode, and instrumental parameters) have been carefully evaluated to test the real capability of the developed methodology for the determination of Cd and Pb at trace levels. For both elements the linear range is observed up to 50 ng mL−1. Under optimized conditions detection limits are 1.0 ng mL−1 and 2.1 ng mL−1 for Cd(II) and Pb(II) ions, respectively. Both of the examined elements can be determined with quantitative recoveries (ca. 100%) and with an adequate precision (RSD = 6.0% and 10.5% for Cd(II) and Pb(II), respectively). Our results give insight into the possibilities of the combination of DMSPE and TXRF for trace metal determination in different types of environmental waters (sea, river and waste water).

Selective enrichment of palladium from spent automotive catalysts by using a liquid membrane system

Abstract A supported liquid membrane (SLM) system for the separation and concentration of palladium from aqueous feed chloride solutions containing SCN − has been developed and characterized by using triisobuthylphosphine sulfide (Cyanex 471) as a carrier. Special attention has been paid to the effect of the organic solvent on the stability of the membrane. Among the different solvents tested in this work, the aliphatic diluent decaline provided the best results in terms of the stability of the LM. Moreover, the influence of chemical parameters such as Cyanex 471 and SCN − concentration on palladium permeability has also been determined for the liquid membrane in flat-sheet configuration. Based on these results, the system was implemented in hollow fiber geometry and the influence of chemical parameters as well as the mode of operation of the HFSLM system has been studied. The selectivity of the proposed LM system was evaluated by using synthetic feed solutions containing Pd(II), Pt(IV) and Rh(III) in chloride media to which small amounts of thiocyanate were added. The results revealed palladium as the only metal transported. This HFSLM system has been successfully applied for the selective recovery and concentration of palladium from solutions obtained from the leaching of spent automotive catalysts.

Analytical possibilities of total reflection X-ray spectrometry (TXRF) for trace selenium determination in soils.

Selenium content of soils is an important issue due to the narrow range between the nutritious requirement and toxic effects upon Se exposure. However, its determination is challenging due to low concentrations within complex matrices that hamper the analysis in most spectroscopic techniques. In this study, we explored the possibilities of several analytical approaches combined with total reflection X-ray (TXRF) spectrometry for soil Se determinations. The direct analysis of a solid suspension using 20 mg of fine ground material (<50 μm) has a relatively high Se limit of detection (LOD) of 1 mg/kg (worldwide Se average in soils = 0.4 mg/kg) and is therefore only suitable for seleniferous soils. Several fast and simple analytical strategies were developed to decrease matrix effects and improve the LOD for Se determination in soil digests. On one hand, the application of a liquid-liquid extraction procedure using ethyl ether and the introduction of a Cr absorbent in the instrument configuration were carried out to avoid the associated problems on TXRF analysis of soil extracts due to the high Fe concentrations (∼700 mg/L). On the other hand, a dispersive liquid-liquid microextraction procedure (DLLME) before the TXRF analysis of the soil digest was also developed. The effects of various experimental parameters such as sample volume, effect of major elements present in the soil matrix (Fe), and Se concentration in the sample were investigated. The LOD using this analytical methodology (0.05 mg/kg of Se) was comparable to or lower than those obtained in previous works using other popular spectrometric techniques such as GFAAS, ICPMS, and AFS. The calculated Se concentration for JSAC-0411 ([Se] = 1.32 ± 0.27 mg/kg) using the combination of DLLME and TXRF ([Se] = 1.40 ± 0.23 mg/kg) was in agreement with the certified value.

Comparison of nutrient and contaminant fluxes in two areas with different hydrological regimes (Empordà Wetlands, NE Spain)

Nutrient (N and P), heavy metal (Ni, Cd, Cr, Cu and Pb) and pesticide (DDT, DDD, DDE, lindane, aldrin, endrin, dieldrin, permethrin, atrazine and simazine) concentrations in water and sediment were analysed in the Empordà Wetlands, a Mediterranean wetland area in NE Spain. Mean nutrient and contaminant concentrations and input and output loads via tributaries were compared in two marshes with different water turnover: a freshwater marsh (FWM), with a high water turnover rate due to continuous surface water inputs and outputs, and a brackish water marsh (BWM), with lower turnover and no continuous surface output, where water remains confined during dry periods. Mean concentrations of most heavy metals exceeded the maximum permissible concentration (MPC) in BWM, whilst only some pesticides reached MPC in FWM. The confined waters of BWM showed higher sensitivity to contaminant input loadings than FWM due to the lack of continuous water outputs. Non-point source pollution inputs during runoff (mainly in FWM) and concentration during confinement (mainly in BWM) showed as the main environmental problems related to nutrients and contaminants in these ecosystems. Thus, the importance of confinement and its effect on pollutant concentrations must be borne in mind to achieve correct management of Mediterranean wetlands.

Determination of non-steroidal anti-inflammatory drugs in sewage sludge by direct hollow fiber supported liquid membrane extraction and liquid chromatography-mass spectrometry

In this study, a three-phase hollow fiber liquid-phase microextraction (HF-LPME) method combined with liquid chromatography-mass spectrometry was developed for direct determination of four non-steroidal anti-inflammatory drugs (ketoprofen, naproxen, diclofenac and ibuprofen) in sewage sludge. The drugs were extracted from non-spiked and spiked slurry samples with different amounts of sludge into an organic phase and then back-extracted into an aqueous phase held in the lumen of the hollow fiber. High enrichment factors ranging from 2761 to 3254 in pure water were achieved. In sludge samples, repeatability and inter-day precision were tested with relative standard deviation values between 10-18% and 7-15%, respectively. Average concentrations of 29±9, 138±2, 39±5 and 122±7 ng/g were determined in dried sludge from Källby sewage treatment plant (Sweden) for ketoprofen, naproxen, diclofenac and ibuprofen, respectively.

Preconcentration Methods for the Analysis of Liquid Samples by X-Ray Fluorescence Techniques

Abstract This article gives an overview of the state-of-the-art of multi-element and single-element preconcentration procedures prior to X-ray fluorescence (XRF) analysis of liquid samples. Many of these preconcentration methods were developed long ago and the purpose of this review is to present some new efficient variations of these methods and new techniques extending the possibilities of XRF for liquid solutions analysis. In addition, trends and future perspectives in this domain are also commented on and discussed in the last section of the review.

Analysis of inlet and outlet industrial wastewater effluents by means of benchtop total reflection X-ray fluorescence spectrometry

The monitoring of heavy metals in industrial waste water effluents is an important activity in many laboratories. Of special interest is the screening of elemental composition of inlet effluents and quantitative analysis of outlet effluents to study the efficiency of chemical treatment process to eliminate metals and to comply with current established concentration limits, respectively. In this sense, fast analytical methodologies which entail simple sample preparation are desired. In the present work, the possibilities and drawbacks of a benchtop total reflection X-ray fluorescence spectrometer (TXRF) for the rapid and simple determination of some inorganic impurities (As, Ba, Cd, Cu, Cr, Sn, Fe, Mn, Ni, Pb, Se and Zn) in inlet and outlet industrial waste water effluents from metallurgical and tanning leather factories have been tested. An evaluation of different simple sample treatments is presented and it is followed by a discussion of spectral and chemical matrix effects when dealing with this type of samples. Analytical figures of merit such as accuracy, precision and limits of detection have also been carefully studied. Finally, the data obtained by direct TXRF analysis has been compared to that obtained by ICP-OES/ICP-MS after a microwave digestion.

Liquid phase microextraction strategies combined with total reflection X-ray spectrometry for the determination of low amounts of inorganic antimony species in waters

In the present study, and taking into account the microanalytical capability of total reflection X-ray spectrometry (TXRF), we explored the possibilities of hollow fibre liquid-phase microextraction (HF-LPME) and dispersive liquid-liquid microextraction (DLLME) combined with TXRF for the determination of low amounts of inorganic Sb species in waters. For each of the LPME configurations aforementioned, experimental parameters affecting Sb extraction but specially the proper sample preparation process (deposition volume on the reflective carrier and drying mode) and measurement conditions for subsequent TXRF analysis have been carefully evaluated. The best analytical strategy for the determination of Sb(III) and Sb(V) in the low μg L(-1) range was found to be the application of the DLLME mode before TXRF analysis. The developed methodology was successfully applied to the determination of inorganic Sb speciation in different types of spiked water samples.