Victòria Salvadó

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.

Evaluation of the seasonal performance of a water reclamation pond-constructed wetland system for removing emerging contaminants

The capacity of a full-scale reclamation pond-constructed wetland (CW) system to eliminate 27 emerging contaminants (i.e. pharmaceuticals, sunscreen compounds, fragrances, antiseptics, fire retardants, pesticides, and plasticizers) and the seasonal occurrence of these contaminants is studied. The compounds with the highest concentrations in the secondary effluent are diclofenac, caffeine, ketoprofen, and carbamazepine. The results show that the constructed wetland (61%) removes emerging contaminants significantly more efficiently than the pond (51%), presumably due to the presence of plants (Phragmites and Thypa) as well as the higher hydraulic residence time (HRT) in the CW. A greater seasonal trend to the efficient removal of these compounds is observed in the pond than in the CW. The overall mass removal efficiency of each individual compound ranged from 27% to 93% (71% on average), which is comparable to reported data in advanced treatments (photo-fenton and membrane filtration). The seasonal average content of emerging contaminants in the river water (2488 ng L(-1)) next to the water reclamation plant is found to be higher than the content in the final reclaimed water (1490 ng L(-1)), suggesting that the chemical quality of the reclaimed water is better than available surface waters.

Evaluation of aquatic plants for removing polar microcontaminants: A microcosm experiment

Microcosm wetland systems (5 L containers) planted with Salvinia molesta, Lemna minor, Ceratophyllum demersum, and Elodea canadensis were investigated for the removal of diclofenac, triclosan, naproxen, ibuprofen, caffeine, clofibric acid and MCPA. After 38 days of incubation, 40-99% of triclosan, diclofenac, and naproxen were removed from the planted and unplanted reactors. In covered control reactors no removal was observed. Caffeine and ibuprofen were removed from 40% to 80% in planted reactors whereas removals in control reactors were much lower (2-30%). Removal of clofibric acid and MCPA were negligible in both planted and unplanted reactors. The findings suggested that triclosan, diclofenac, and naproxen were removed predominantly by photodegradation, whereas caffeine and naproxen were removed by biodegradation and/or plant uptake. Pseudo-first-order removal rate constants estimated from nonlinear regressions of time series concentration data were used to describe the contaminant removals. Removal rate constants ranged from 0.003 to 0.299 d(-1), with half-lives from 2 to 248 days. The formation of two major degradation products from ibuprofen, carboxy-ibuprofen and hydroxy-ibuprofen, and a photodegradation product from diclofenac, 1-(8-Chlorocarbazolyl)acetic acid, were followed as a function of time. This study emphasizes that plants contribute to the elimination capacity of microcontaminants in wetlands systems through biodegradation and uptake processes.

Occurrence and behavior of emerging contaminants in surface water and a restored wetland

Pollution mitigation is an important target for restored wetlands, and although there is much information in relation to nutrient removal, little attention has been paid to emerging contaminants. This paper reports on the occurrence and attenuation capacity of 17 emerging contaminants in a restored wetland and two rivers in North-East Denmark. The compounds belong to the groups of pharmaceuticals, fragrances, antiseptics, fire retardants, pesticides, and plasticizers. Concentrations in surface waters ranged from 2 to 1476 ng L(-1). The compounds with the highest concentrations were diclofenac, 2-methyl-4-chlorophenoxyacetic acid (MCPA), caffeine, and tris(2-chloroethyl) phosphate (TCEP). The herbicide concentrations increased after a rain-fall event, demonstrating the agricultural run-off origin of these compounds, whereas the concentration of the other emerging contaminants was rather conservative. The mitigation capacity of the restored wetland for the compounds ranged from no attenuation to 84% attenuation (19% on average). Hence, restored wetlands may be considered as a feasible alternative for mitigating emerging contaminants from river waters.

Evaluation of an extraction method in the determination of the 2,4,6-trichloroanisole content of tainted cork

A method based on solvent extraction and GC-electron-capture detection analysis for the determination of 2,4,6-trichloroanisole (TCA) from cork has been evaluated and optimised. Our sample treatment consists of an extraction stage with pentane while the sample and solvent are kept in contact in a mechanical shaker (shake-flask extraction). Different extraction conditions have been tested in order to find the best compromise between efficiency and time of analysis. Different columns were evaluated for use in the concentration and purification step. A silica column was found to give the best performance in terms of recovery of TCA and repeatability. Pentane and mixtures of pentane-diethyl ether at different ratios were tested as eluting agents. It was found that 10 ml pentane allowed the recovery of retained TCA. Finally, the eluate was concentrated and injected into the chromatograph for TCA determination. The optimised chromatographic conditions enabled the quantification of TCA and 2,6-dichloroanisole, which was assayed as the internal standard. The shake-flask extraction method was compared with Soxhlet and ultrasound assisted extraction procedures using pentane as a solvent. Similar results were obtained for the shake-flask and Soxhlet extraction methods, while sonication gave significantly lower recoveries. The optimised shake-flask method was applied to determine the distribution of TCA in naturally contaminated cork bark.

The ability of biologically based wastewater treatment systems to remove emerging organic contaminants—a review

Biologically based wastewater treatment systems are considered a sustainable, cost-effective alternative to conventional wastewater treatment systems. These systems have been used and studied for the treatment of urban sewage from small communities, and recently, it has been reported that they can also effectively remove emerging organic contaminants (EOCs). EOCs are a new group of unregulated contaminants which include pharmaceutical and personal care products, some pesticides, veterinary products, and industrial compounds among others that are thought to have long-term adverse effects on human health and ecosystems. This review is focused on reporting the ability of biologically based wastewater treatment systems to remove EOCs and the main elimination mechanisms and degradation processes (i.e., biodegradation, photodegradation, phytoremediation, and sorption) taking place in constructed wetlands, ponds, and Daphnia and fungal reactors.

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.

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.

Comparison of micellar and microemulsion electrokinetic chromatography for the analysis of water- and fat-soluble vitamins

Separation and determination of water- and fat-soluble vitamins by micellar (MEKC) and microemulsion electrokinetic chromatography (MEEKC) are compared. MEKC is only useful in the quantitative analysis of water-soluble vitamins when sodium dodecylsulfate (SDS) is used as the surfactant. However, the separation of mixtures containing water- and fat-soluble vitamins is only achieved by MEEKC using a microemulsion prepared by mixing SDS as the surfactant, butanol as the co-surfactant, octane as the non-polar modifier and propanol as the second co-surfactant. The injection time and the solvent used for the dilution of samples have a significant effect on the analysis of lypophilic compounds. The most reproducible results in the analysis of fat-soluble vitamins are obtained by using the same microemulsion electrolyte as the solvent for samples and an injection time of 10 s.