Marinel la Farré

Institut Marqués, Spain, Barcelona, Barcino, Catalonia, Spain

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Publications (13)47.41 Total impact

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    ABSTRACT: The occurrence and sources of 21 perfluoroalkyl substances (PFASs: C4-C14, C16, C18 carboxylate, C4, C6-C8 and C10 sulfonates and C8 sulfonamide) were determined in water, sediment, and biota of the Llobregat River basin (NE Spain). Analytes were extracted by solid phase extraction (SPE) and determined by liquid chromatography triple quadrupole mass spectrometer (LC-QqQ-MS). All samples were contaminated with at least one PFAS, being the most frequently found perfluorobutanoate (PFBA), perfluorooctanoate (PFOA) and perfluorooctane sulfonate (L-PFOS). In general, mean PFAS concentrations measured in sediments (0.01-3.67ngg(-1)) and biota (0.79-431μgkg(-1)) samples were higher than those found in water (0.01-233ngL(-1)). L-PFOS presented very high levels in biota and water, particularly in the Anoia River where a maximum concentration of 2.71μgL(-1) was related to important industrial activities. However, this pollution does not extend down the Llobregat River according to cumulated values. None of the hazard quotients (HQ) calculated indicate potential risk for the different tropic levels considered (algae, Daphnia sp. and fish). According to Maximum Allowable Concentration (MAC) proposed by the European Commission (L-PFOS) and to Provisional Health Advisory (PHA) values (PFOA, L-PFOS) established by the United States Environmental Protection Agency (US EPA), only two water samples exceeded PHA concentration for L-PFOS.
    Full-text · Article · Jun 2014 · Science of The Total Environment
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    ABSTRACT: Triclosan is a commonly used bactericide that survives several degradation steps in WWTP (wastewater treatment plants) and potentially reaches fluvial ecosystems. In Mediterranean areas, where water scarcity results in low dilution capacity, the potential environmental risk of triclosan is high. A set of experimental channels was used to examine the short-term effects of triclosan (from 0.05 to 500μgL⁻¹) on biofilm algae and bacteria. Environmentally relevant concentrations of triclosan caused an increase of bacterial mortality with a no effect concentration (NEC) of 0.21μgL⁻¹. Dead bacteria accounted for up to 85% of the total bacterial population at the highest concentration tested. The toxicity of triclosan was higher for bacteria than algae. Photosynthetic efficiency was inhibited with increasing triclosan concentrations (NEC=0.42μgL⁻¹), and non-photochemical quenching mechanisms decreased. Diatom cell viability was also affected with increasing concentrations of triclosan. Algal toxicity may be a result of indirect effects on the biofilm toxicity, but the clear and progressive reduction observed in all the algal-related endpoints suggest the existence of direct effects of the bactericide. The toxicity detected on the co-occurring non-target components of the biofilm community, the capacity of triclosan to survive through WWTP processes and the low dilution capacity that characterizes Mediterranean systems extend the relevance of triclosan toxicity beyond bacteria in aquatic habitats.
    Full-text · Article · Nov 2010 · Aquatic toxicology (Amsterdam, Netherlands)
  • Yolanda Picó · Marinel la Farré · Ramon Segarra · Damià Barceló
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    ABSTRACT: This study deals with a simple strategy to pinpoint potential unknown compounds in full scan mass spectrometry (MS) experiments. Forty samples of apples and pears intended for human consumption were analyzed by ultra-high performance liquid chromatography quadrupole-time-of-flight (UPLC-QqTOF-MS), after extraction of the possible contaminants by rinsing the peel of the fruit with ethyl acetate. The peaks were visually recognized in the total ion chromatogram (TIC). Two major types of postharvest treatments were detected in this set of samples: imazalil (IMZ)/ethoxyquin (EQ) and thiabendazole (TBZ)/diphenylamine (DPA). The present work also describes the metabolites formed by degradation of EQ (to our knowledge not previously reported) and DPA (there was mass spectral evidence of some of them but full identification was not pursued). Hydroxy-DPA, n-phenyl-4-quinoneimine, methoxy-DPA, demethyl-EQ, demethyldehydro-EQ, EQ-dimer, methyl-EQ, EQ-N-oxyl and 2',2,4,-trimethyl-6-quinolone were unequivocally identified and confirmed. Some relationships between the applied postharvest treatment and the metabolites formed were established. Remarkably, they may constitute a useful fingerprint in further investigations of postharvest treatments. Among other significant results, the study also reveals for the first time the presence of some EQ metabolites in fruits, which are different from those previously reported in animal tissues. There is not information on the occurrence of EQ metabolites in fruits and the DPA ones have not been studied extensively in pears and apples. The levels of the metabolites found exceeded several times those of the parent compounds.
    No preview · Article · Apr 2010 · Talanta
  • Sandra Pérez · Farré · Damià Barceló
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    ABSTRACT: Due to their unique properties, carbon-based nanomaterials (CNMs) have attracted considerable interest in many fields of research, including materials sciences, microelectronics and biomedicine. The potential, the growing use and the mass production of fullerenes and carbon nanotubes have stimulated research on their potential impact on the environment and human health. To gather proper information about hazards of CNMs, it is important to have reliable analytical data on them, to find out how they behave in the environment and to evaluate ecotoxicological information about them.This review presents the latest research carried out to assess the risks of engineered CNMs in the aquatic environment, including analytical methods and ecotoxicity assessment. We pay special attention to the surface properties of CNMs, which are vitally important for their aggregation behavior, their mobility in aquatic systems, their interactions with aquatic organisms, and their possible entry into the food chain. We also consider interactions with natural organic matter and other interactions that can alter aggregation behavior in water.
    No preview · Article · Jun 2009 · TrAC Trends in Analytical Chemistry
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    ABSTRACT: Endocrine disrupters (EDs) continue to be the focus of extensive research. Their effects and mode of action as well as their occurrence and fate in the aquatic environment are still largely unknown and need investigation. Wastewater treatment plant effluents are for most of them the main source of contamination in water bodies. A large number of EDs are relatively polar compounds that pass easily wastewater treatments and reach the aquatic environment, where they can exert undesirable effects on both wildlife and humans. Their removal during waste-water treatment, very often inefficient, is usually estimated from the comparison of the concentrations detected at the influent and the effluent and the technique of choice for their analysis is in many cases liquid chromatography—(tandem)mass spectrometry (LC—(tandem)MS). Herein we review the analytical methods, including sample preparation and analysis, based on LC—(tandem)MS described in the literature for the determination of different classes of EDs (pesticides, phthalates, bisphenol A, alkylphenolic compounds, perfluorinated compounds, pharmaceuticals, and estrogens) in wastewater and their occurrence in this kind of matrix.
    No preview · Chapter · May 2009
  • Nilgun Tokman · Carla Soler · Marinel la Farré · Yolanda Picó · Damià Barceló
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    ABSTRACT: A method has been developed for identification and quantification of the acaricide amitraz and its transformation products, 2,4-dimethylaniline (DMA), 2,4-dimethylformamidine (DMF) and N-2,4-dimethylphenyl-N-methylformamidine (DMPF) in pears. The analytes were extracted using ethyl acetate and anhydrous sodium sulphate. Analysis was performed by liquid chromatography-electrospray tandem mass spectrometry (LC-ESI-MS/MS) in the positive ion mode using a triple quadrupole (QqQ) instrument. Two precursor-product ion transitions were monitored for each compound in the selected reaction monitoring (SRM) mode. The method was validated with pears taken from the orchard before the amitraz treatment and spiked at the limit of quantification (LOQ), 10 times the LOQ and the maximum residue limit (MRL). Recoveries were between 70 and 106% and relative standard deviations were below 19% (n=5 at each spiked level). Excellent sensitivity resulted in limits of detection (LODs) for all the compounds below 10 microg kg(-1). Quantification was carried out using matrix-matched standards calibration, response was a linear function of the concentration from the LOQs to, at least, three orders of magnitude. Recoveries and standard deviations were comparable to those obtained after hydrolysis of amitraz and its metabolites to DMA. Occurrence of amitraz and its metabolites in field-treated pears showed that, seven days after the treatment, DMPF and DMF are the main degradation products. This work reports for the first time the use of a conventional pesticide multiresidue method and LC-ESI-MS/MS for determining amitraz and its metabolites in pears.
    No preview · Article · Mar 2009 · Journal of Chromatography A
  • Marinel la Farré · Sandra Pérez · Lina Kantiani · Damià Barceló
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    ABSTRACT: There has been a great effort to study the fate, the occurrence and the ecotoxicology of emerging pollutants in the aquatic environment. Recently, several articles have focused on degradation products of emerging pollutants and the study of their toxicological effects.We review the fate and the ecotoxicology of emerging pollutants, especially focusing on their metabolites and transformation products (TPs) in the aquatic environment, including pharmaceuticals, hormones, perfluorinated compounds, by-products of drinking-water disinfection, sunscreens or UV filters, benzotriazoles and naphthalenic acids.We describe analytical methodologies for the quantitative analysis of emerging pollutants, their metabolites, and their TPs in sewage and surface waters, and we give the results of monitoring surveys obtained from the application of these analytical methodologies.
    No preview · Article · Dec 2008 · TrAC Trends in Analytical Chemistry
  • Yolanda Picó · Marinel la Farré · Nilgun Tokman · Damià Barceló
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    ABSTRACT: Liquid chromatography under high pressure in combination with quadrupole time-of-flight mass spectrometry (QqTOF-MS and MS/MS) has been used to detect amitraz degradation products in pears, to characterize their structures, and to evaluate their occurrences in samples of different origins. Using the proposed approach, the parent pesticide and four degradation products were identified. To this end, pear samples were extracted with ethyl acetate and anhydrous sodium sulphate. Amitraz was found to be rapidly decomposed into four related compounds, of which N-(2,4-dimethylphenyl)formamidine (DMPF) was the most abundant and persistent. N,N'-bisdimethylphenylformamidine (BDMPF), 2,4-dimethylformamidine (DMF) and 2,4-dimethyl aniline (DMA) were also main metabolites of amitraz. To our knowledge this is the first report that confirms the presence of BDMPF in pears. The method was validated using MS and MS/MS for those standard available (analytical or not). In MS, recoveries ranged from 83 to 101% with relative standard deviation (RSD) from 9 to 19% at the limit of quantification (LOQ) (between 5 and 20 microg kg(-1)). Using MS/MS, recoveries, linearity and precision were similar but LOQs were higher because the intense fragmentation of the protonated molecules in the product mass spectrum. BDMPF, as an approximation, was quantified based on the DMF metabolite. The results demonstrated that high-pressure LC-QqTOF-MS and MS/MS techniques enhance further the capabilities of LC-MS in the identification of polar species in complex food samples.
    No preview · Article · Aug 2008 · Journal of Chromatography A
  • Yolanda Picó · Marinel. la Farré · Carla Soler · Damià Barceló
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    ABSTRACT: Ultra-high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC-QqTOF-MS) is an emerging technique offering more rapid and efficient separation, as well as the possibility to obtain accurate mass measurement and tandem mass spectrometry (MS/MS). This paper deals with the use of UPLC-QqTOF-MS to identify the pesticide residues present in complex pear extracts. Carbendazim, imazalil, and ethoxyquin were successfully identified because of the accurate mass determination of their protonated molecule and their major fragments in the product ion mass spectra. A few plastic and latex additives were also found, most of them probably coming from the packaging transfer to the fruits. The potential of the UPLC-QqTOF-MS and UPLC-QqTOF-MS/MS techniques as a quantification tool is also discussed taking imazalil as example. For quantification, calibration curves were linear over a dynamic range of 2 orders of magnitude, whereas higher calibration ranges are better adjusted to polynomial curves of second and third order. Quantification using different mass windows was also assessed. Accurate quantification required mass windows as wide as 20 mDa, narrower mass windows of 5 mDa provided erroneous quantification, probably because the low ion abundance. The mean recoveries and percentage relative standard deviation (RSD) of 35 determinations for imazalil were 76% (13% RSD) by MS and 77% (14% RSD) by MS/MS. The theoretical limit of detection was 0.4 microg kg(-1), with a validated limit of quantification of 2 microg kg(-1). The quantitative data obtained using UPLC-QqTOF-MS were compared with those obtained using conventional liquid chromatography (LC)-MS/MS with a triple quadrupole (QqQ). It was concluded that UPLC-QqTOF-MS might become a powerful analytical tool for both, unknown's identification and quantification of target pesticides.
    No preview · Article · Jan 2008 · Journal of Chromatography A
  • Marinel•la Farré · Damià Barceló
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    ABSTRACT: This chapter discusses the use of sensor, biosensors, and molecularly imprinted polymers (MIP) based sensors for quality control analysis in the food industry. A chemosensor is composed of two main parts. The first part is where the selective chemistry occurs, and the second part is the transducer. The chemical reaction produces a signal such as color change, fluorescence, and change in the oscillation frequency of a crystal, and the transducer translates the physico-chemical event into a recognizable physical signal. Biosensors use biologically derived components integrated with a suitable transducer. Electrochemical devices transform the effect of the electrochemical interaction between an analyte and the electrode into a primary signal. Metal oxide could be used to develop a pH electrode with wide applications at high temperatures and pressures. Electrochemical biosensors are based on monitoring electro-active species that are produced or consumed by the action of the biological elements, and can be performed basically under potentiometric and amperometric measurements. Electrochemical immunosensors have been widely used for food analysis in amperometric, potentiometric, and conductometric configurations.
    No preview · Chapter · Dec 2007
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    ABSTRACT: In the present work a combined analytical method involving toxicity and liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) was developed for the determination of pharmaceutical compounds in water samples. The drugs investigated were the analgesics: ibuprofen, ketoprofen, naproxen, and diclofenac, the decomposition product of the acetyl salicylic acid: salicylic acid and one lipid lowering agent, gemfibrozil. The selected compounds are acidic substances, very polar and all of them are analgesic compounds that can be purchased without medical prescription. The developed protocol consisted, first of all, on the use Microtox and ToxAlert 100 toxicity tests with Vibriofischeri for the different pharmaceutical drugs. The 50% effective concentration (EC50) values and the toxicity units (TU) were determined for every compound using both systems. Sample enrichment of water samples was achieved by solid-phase extraction procedure (SPE), using the Merck LiChrolut EN cartridges followed by LC-ESI-MS. Average recoveries loading 11 of samples with pH=2 varied from 69 to 91% and the detection limits in the range of 15-56 ng/l. The developed method was applied to real samples from wastewater and surface-river waters of Catalonia (north-east of Spain). One batch of samples was analyzed in parallel also by High Resolution Gas Chromatography coupled with Mass Spectrometry (HRGC-MS) and the results have been compared with the LC-ESI-MS method developed in this work.
    No preview · Article · Jan 2002 · Journal of Chromatography A
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    ABSTRACT: A cost-effective strategy combining chemical analysis and bioassays for the identification of polar toxic compounds in sewage sludge is reported. ToxAlert 100 bioluminescence inhibition assay was used in combination with chemical analysis involving extraction, clean-up, chromatographic separation and mass spectrometry detection. This methodology was applied to real samples of sludge from three wastewater treatment plants (WWTP) located in Catalonia (Spain) during a 3 month period. In the first step, sewage sludge was lyophilized, treated by sonication with a mixture of methanol and chloroform and finally cleaned up using a sequential solid phase extraction (SSPE) with an octadecylsilica cartridge (C18) in series with a polymeric Lichrolut EN cartridge (Lic EN). In the second step, the toxicity of each fraction of the sludge sample was investigated using the ToxAlert 100. The unequivocal identification and quantification of polar organic cytotoxic substances present in the fractionated extracts were determined by liquid chromatography-mass spectrometry (LC-MS). Major toxic compounds identified were: non-ionic polyethoxylated surfactants (nonylphenol polyethoxylates, alcohol polyethoxylates), their intermediates (polyethylene glycol polyethoxylated, nonylphenol carboxylates and polyethoxylated alcohol carboxylates), linear alkylbenzenesulfonates and heavy metals. The toxic response (in terms of bioluminescence inhibition using ToxAlert 100), defined by the 50% effective concentration (EC50), and the toxicity units (TU) for every standard non-ionic surfactant were calculated. The results provided the identification of polar cytotoxic compounds as well as the evaluation of their contribution to the total toxicity observed in sewage sludge.
    No preview · Article · Mar 2001 · Journal of Environmental Monitoring
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    ABSTRACT: The toxic response of commonly used non-ionic surfactants with different bioluminescence inhibition assays (ToxAlert®100 and Microtox®) were established. The 50% effective concentration (EC50) values were determined for every standard substance using each assay, together with toxicity units (TU). A sigmoidal curve was fitted and the (EC50) was calculated.Chemical analysis and bioassays were used in conjunction to provide a determination of aquatic toxicity in wastewaters. This methodology was applied to real samples of influent and effluent wastewater treatment works in Spain and Portugal and also for untreated textile wastewater effluents.The protocol used in this paper involved different steps. First, the aquatic toxicity evaluation for every effluent was carried out using ToxAlert®100. For every one, a sigmoidal curve was fitted, the (EC50) and the toxicity impact index (TII50) were calculated. Second, the identification and quantification of polar organic cytotoxic substances and their contribution to the total toxicity was obtained, using sequential solid-phase extraction (SSPE) followed by liquid chromatography-mass spectrometry (LC-MS).The use of toxicity results (in terms of bioluminescence inhibition) like a screening parameter, is proposed. This procedure excludes the chromatographic analysis if the sample has less than the 20% inhibition. Overall, this procedure presented here helps to reduce the large number of samples and sub-samples that need to be processed in wastewater monitoring.
    Full-text · Article · Jan 2001 · Analytica Chimica Acta