Rapid and sensitive method for the simultaneous determination of PAHs and alkyl-PAHs in scrubber water using HS-SPME-GC-MS/MS.

Scrubber water, a waste stream generated by ships exhaust gas cleaning systems, may pose a threat when released into the marine environment due to potential contamination with polycyclic aromatic hydrocarbons (PAHs) and their alkyl derivatives (alkyl-PAHs). This study aims to develop a reliable analytical procedure combining headspace solid-phase microextraction (HS-SPME) with gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-MS/MS) to simultaneously separate and determine target compounds in aqueous samples. Method validation demonstrated good linearity up to 200 ng L-1 (r2> 0.996) and low limits of detection (0.33 to 1.67 ng L-1, except for naphthalene at 3.3 ng L-1). The method shows good precision (RSD<20%) and satisfactory analytical recoveries. The methodology was successfully applied to scrubber water samples collected from a container ship and the results highlight the prevalence of naphthalene, phenanthrene, and their alkyl derivatives.•Rapid and reproducible HS-SPME-GC-MS/MS method for the analysis of PAHs and alkyl-PAHs in scrubber water.•The capacity of SPME to analyze both filtered and unfiltered samples was assessed, showing that the more hydrophobic PAHs may be lost during filtration.

Analysis of microplastics in the environment: Identification and quantification of trace levels of common types of plastic polymers using pyrolysis-GC/MS.

This work describes the development of analytical workflows based on pyrolysis coupled with gas chromatography-mass spectrometry (Pyr-GC/MS) for the qualitative and quantitative analysis of 12 of the most common plastic polymers in environmental samples. The most suitable characteristic pyrolyzate compounds and respective indicator ions were selected for each polymer in order to obtain the most appropriate response for analytical purposes. Additionally, commercial pyrolyzates and polymers libraries were used to confirm the identity of the detected microplastics. The method was validated, showing a good linearity for all the plastic polymers (R2 > 0.97) and limits of detection between 0.1 (polyurethane) to 9.1 µg (polyethylene). The developed methodology was successfully applied for the analysis of plastic polymers in environmental microplastic samples collected in three Mediterranean beaches (NE Spain).•Fast and reproducible Pyr-GC/MS method for the analysis of the 12 most common plastic polymers in a single GC/MS run•Straightforward analytical workflows using pyrolyzates and polymers libraries enable a fast identification and quantification of microplastics in environmental samples.

Could we estimate industrial wastewater flows composition using the UN-ISIC classification system?

Although we have extensive datasets on the location and typology of industries, we do not know much on their generated and discharged wastewater. This lack of information compromises the achievement of the sustainable development goals focused on water (Sustainable Development Goal 6) in Europe and globally. Thus, our goal was to assess to which degree the chemical composition of industrial wastewater could be estimated based on the industry's typology according to its International Standard Industrial Classification of All Economic Activities (ISIC) class. We collected wastewater effluent water samples from 60 industrial wastewater effluents (before any wastewater treatment process), accounting for 5 samples each of 12 ISIC classes, analyzed the composition of key contaminants (i.e. European Commission rated priority compounds and watchlist), and statistically assessed the similarities and differences amongst ISIC classes using ordination and random forest analyses. The results showed statistically significant linkages between most ISIC classes and the composition of produced wastewater. Among the analytical parameters measured, the random forest methodology allowed identifying a sub-set particularly relevant for classification or eventual contamination prediction based on ISIC class. This is an important applied research topic with strong management implications to (i) determine pollution emission caps for each individual ISIC class, (ii) define monitoring schemes to sample and analyze industrial wastewater, and (iii) enable predicting pollutant loads discharged in river basins with scarce information. These encouraging results urge us to expand our work into other ISIC classes and water quality parameters to draw a full picture of the relationship between ISIC classes and produced wastewater.

N-Nitrosamines and their precursors in wastewater effluents from selected industries in Spain.

N-nitrosamines (NAs), and N-nitrosodimethylamine (NDMA) in particular, are hazardous disinfection byproducts (DBPs) relevant when wastewater impacts drinking water sources and, in water reuse practices. Our study investigates the concentrations of NDMA and five additional NAs and their precursors in industrial wastewater effluents. Aiming to identify potential differences between industrial typologies, wastewaters from 38 industries belonging to 11 types of the UN International Standard Industrial Classification of All Economic Activities system (ISIC) were analysed. Results show that the presence of most NAs and their precursors cannot be linked to a specific industry type as these were in general very different within the classes. Nevertheless, N-nitrosomethylethylamine (NMEA) and N-nitrosopiperidine (NPIP) as well as precursors for N-nitrosodiethylamine (NDEA), NPIP and N-nitrosodibuthylamine (NDBA) could be rank with different concentrations between ISIC classes (p-value < 0.05). Specific industrial wastewater with notable high concentrations of NAs and their precursors were identified too. The effluents with the highest concentration of NDMA belong to the ISIC C2011 class (Manufacture of basic chemical), while the effluents with the highest concentration of NDMA precursors were from the ISIC C1511 class (Tanning and dressing of leather; dressing and dyeing of fur). Other relevant NAs found were NDEA in ISIC class B0810 (Quarrying of stone, sand, and clay) and ISIC class C2029 (Manufacture of other chemical products).

Occurrence of regulated pollutants in populated Mediterranean basins: Ecotoxicological risk and effects on biological quality.

Chemical stressors co-occur in mixtures into watercourses and this complicates predicting their effects on their ecological status. Our knowledge of river basin specific pollutants (RBSPs) is still limited, but it remains necessary to ensure the good chemical and ecological status. We performed an exercise on Mediterranean river sites exposed to urban and industrial pressures in order to, i) prioritize the occurring chemicals, ii) assessing the site's specific chemical risk (RQsite), and iii) relating the chemical risk to the biological quality, using as evidences invertebrates and diatom indices. Mediterranean rivers suffer from strong pressures which lead to a poor dilution ability, which makes the inhabiting biota highly vulnerable. The most frequent pollutants in the 89 sites surveyed included pharmaceutical products such as the antibiotics azithromycin, clarithromycin, and erythromycin, and the anti-inflammatory diclofenac, and products of industrial origin such as perfluorinated PFOS, nickel, and nonylphenol. Both the diatom index IPS and the macroinvertebrate index IBMWP hold strong negative correlations to RQsite, indicating a significant contribution of chemicals to biological impairment. Chemical contaminants (but not nutrients or dissolved organic carbon) were associated with significant changes to the taxonomic composition of invertebrate communities, but not to that of diatom communities. Our analyses indeed reveal that the impact of co-occurring chemicals translates onto negative effects in the biological quality. Our approach may be of use to evidence impacts on water resources and water quality in rivers under strong human pressure.

Occurrence and assessment of environmental risks of endocrine disrupting compounds in drinking, surface and wastewaters in Serbia.

The present study is the first comprehensive monitoring of 13 selected endocrine disrupting compounds (EDCs) in untreated urban and industrial wastewater in Serbia to assess their impact on the Danube River basin and associated freshwaters used as sources for drinking water production in the area. Results showed that natural and synthetic estrogens were present in surface and wastewater at concentrations ranging from 0.1 to 64.8 ng L-1. Nevertheless, they were not detected in drinking water. For alkylphenols concentrations ranged from 1.1 to 78.3 ng L-1 in wastewater and from 0.1 to 37.2 ng L-1 in surface water, while in drinking water concentrations varied from 0.4 to 7.9 ng L-1. Bisphenol A (BPA) was the most abundant compound in all water types, with frequencies of detection ranging from 57% in drinking water, to 70% in surface and 84% in wastewater. Potential environmental risks were characterized by calculating the risk quotients (RQs) and the estrogenic activity of EDCs in waste, surface and drinking water samples, as an indicator of their potential detrimental effects. RQ values of estrone (E1) and estradiol (E2) were the highest, exceeding the threshold value of 1 in 60% of wastewater samples, while in surface water E1 displayed potential risks in only two samples. Total estrogenic activity (EEQt) surpassed the threshold of 1 ng E2 L-1 in about 67% of wastewater samples, and in 3 surface water samples. In drinking water, EEQt was below 1 ng L-1 in all samples.

Fate of priority pharmaceuticals and their main metabolites and transformation products in microalgae-based wastewater treatment systems.

The present study evaluates the removal capacity of two high rate algae ponds (HRAPs) to eliminate 12 pharmaceuticals (PhACs) and 26 of their corresponding main metabolites and transformation products. The efficiency of these ponds, operating with and without primary treatment, was compared in order to study their capacity under the best performance conditions (highest solar irradiance). Concentrations of all the target compounds were determined in both water and biomass samples. Removal rates ranged from moderate (40-60 %) to high (>60 %) for most of them, with the exception of the psychiatric drugs carbamazepine, the ß-blocking agent metoprolol and its metabolite, metoprolol acid. O-desmethylvenlafaxine, despite its very low biodegradability in conventional wastewater treatment plants, was removed to certain extent (13-39 %). Biomass concentrations suggested that bioadsorption/bioaccumulation to microalgae biomass was decisive regarding the elimination of non-biodegradable compounds such as venlafaxine and its main metabolites. HRAP treatment with and without primary treatment did not yield significant differences in terms of PhACs removal efficiency. The implementation of HRAPs as secondary treatment is a feasible alternative to CAS in terms of overall wastewater treatment, including organic micropollutants, with generally higher removal performances and implying a green, low-cost and more sustainable technology.

Impact of fullerenes in the bioaccumulation and biotransformation of venlafaxine, diuron and triclosan in river biofilms.

A huge variety of organic microcontaminants are presently detected in freshwater ecosystems, but there is still a lack of knowledge about their interactions, either with living organisms or with other contaminants. Actually, carbon nanomaterials like fullerenes (C60) can act as carriers of organic microcontaminants, but their relevance in processes like bioaccumulation and biotransformation of organic microcontaminants by organisms is unknown. In this study, mesocosm experiments were used to assess the bioaccumulation and biotransformation of three organic microcontaminants (venlafaxine, diuron and triclosan) in river biofilms, and to understand how much the concomitant presence of C60 at environmental relevant concentrations could impact these processes. Results indicated that venlafaxine exhibited the highest bioaccumulation (13% of the initial concentration of venlafaxine in water), while biotransformation was more evident for triclosan (5% of the initial concentration of triclosan in water). Furthermore, biotransformation products such as methyl-triclosan were also present in the biofilm, with levels up to 42% of the concentration of accumulated triclosan. The presence of C60 did not involve relevant changes in the bioaccumulation and biotransformation of microcontaminants in biofilms, which showed similar patterns. Nevertheless, the study shows that a detailed evaluation of the partition of the organic microcontaminants and their transformation products in freshwater systems are important to better understand the impact of the co-existence of others microcontaminants, like carbon nanomaterials, in their possible routes of bioaccumulation and biotransformation.

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.

Equilibrium and kinetic studies of the adsorption of antibiotics from aqueous solutions onto powdered zeolites.

The performances of two FAU-type zeolites with different SiO2/Al2O3 ratios were evaluated for the removal of antibiotics of three different classes, namely azithromycin, ofloxacin, and sulfamethoxazole, from aqueous solutions. Commercial zeolites were used, without any previous treatment. Use of a small adsorbent dosage resulted in fast antibiotic adsorption that followed pseudo-second order kinetics. The removals of azithromycin and sulfamethoxazole were highly pH-dependent, with low removal percentages observed under acid (pH 2.5-4.5) and basic (pH 8.5-10.5) conditions, respectively. The Freundlich isotherm model provided the best fits to the adsorption data. The adsorption mechanisms appeared to involve both electrostatic and H-bonding interactions. Using an antibiotics mixture, percentage removals of azithromycin and ofloxacin onto the zeolites of up to 79% were obtained. Both materials presented good adsorption (>50%) of azithromycin and ofloxacin from a real sample of effluent wastewater. The results showed that zeolites with FAU structure can be used as effective adsorbents for the removal of antibiotics with different physicochemical properties, including molecules with large volumes, such as azithromycin.

Development of an online SPE-UHPLC-MS/MS method for the multiresidue analysis of the 17 compounds from the EU "Watch list".

During the last decades, the quality of aquatic ecosystems has been threatened by increasing levels of pollutions, caused by the discharge of man-made chemicals, both via accidental release of pollutants as well as a consequence of the constant outflow of inadequately treated wastewater effluents. For this reason, the European Union is updating its legislations with the aim of limiting the release of emerging contaminants. The Commission Implementing Decision (EU) 2015/495 published in March 2015 drafts a "Watch list" of compounds to be monitored Europe-wide. In this study, a methodology based on online solid-phase extraction (SPE) ultra-high-performance liquid chromatography coupled to a triple-quadrupole mass spectrometer (UHPLC-MS/MS) was developed for the simultaneous determination of the 17 compounds listed therein. The proposed method offers advantages over already available methods, such as versatility (all 17 compounds can be analyzed simultaneously), shorter time required for analysis, robustness, and sensitivity. The employment of online sample preparation minimized sample manipulation and reduced dramatically the sample volume needed and time required, dramatically the sample volume needed and time required, thus making the analysis fast and reliable. The method was successfully validated in surface water and influent and effluent wastewater. Limits of detection ranged from sub- to low-nanogram per liter levels, in compliance with the EU limits, with the only exception of EE2. Graphical abstract Schematic of the workflow for the analysis of the Watch list compounds.

Development of a sensitive and robust online dual column liquid chromatography-tandem mass spectrometry method for the analysis of natural and synthetic estrogens and their conjugates in river water and wastewater.

An online ultra-high-performance-liquid chromatography-triple quadrupole tandem mass spectrometry (UHPLC-MS/MS) method for detection and quantification of natural and synthetic estrogens and their conjugates in aqueous matrices was developed. Target compounds include the natural estrogen estradiol (E2) and its main metabolites estrone (E1) and estriol (E3), the synthetic estrogens ethinylestradiol (EE2) and diethylstilbestrol (DES) and their conjugates estrone 3-sulfate (E1-3S), estriol 3-sulfate (E3-3S), estradiol 17-glucuronide (E2-17G), estrone 3-glucuronide (E1-3G), and estriol 16-glucuronide (E3-16G). After pH adjustment, sample filtration and addition of internal standards (IS), water samples (5 mL) were preconcentrated on a Hypersil GOLD aQ column after which chromatographic separation was achieved on a Kinetex C18 column using methanol and water as a mobile phase. The experimental parameters, such as sample loading flow rate, elution time, the percentage of organic solvent in the aqueous-organic eluent mixture, pH, and volume of analyzed samples, were optimized in detail. The benefits of the method compared to previously published methods include minimum sample manipulation, lower detection limits, reduced total analysis time, and overall increased method accuracy and precision. Method detection limits (MDLs) are in subnanogram per liter, complying with the requirements of the EC Decision 2015/495 (Watch list) for hormones listed therein. Applicability of the developed method was confirmed by analysis of river and raw wastewater samples taken directly from urban sewerage systems before being discharged into the river. Graphical abstract Sheme of online SPE-UHPLC-MS/MS system.

Fate of NDMA precursors through an MBR-NF pilot plant for urban wastewater reclamation and the effect of changing aeration conditions.

The removal of N-nitrosodimethylamine (NDMA) formation potential through a membrane bioreactor (MBR) coupled to a nanofiltration (NF) pilot plant that treats urban wastewater is investigated. The results are compared to the fate of the individual NDMA precursors detected: azithromycin, citalopram, erythromycin, clarithromycin, ranitidine, venlafaxine and its metabolite o-desmethylvenlafaxine. Specifically, the effect of dissolved oxygen in the aerobic chamber of the MBR pilot plant on the removal of NDMA formation potential (FP) and individual precursors is studied. During normal aerobic operation, implying a fully nitrifying system, the MBR was able to reduce NDMA precursors above 94%, however this removal percentage was reduced to values as low as 72% when changing the conditions to minimize nitrification. Removal decreased also for azithromycin (68-59%), citalopram (31-17%), venlafaxine (35-15%) and erythromycin (61-16%) on average during nitrifying versus non-nitrifying conditions. The removal of clarithromycin, o-desmethylvenlafaxine and ranitidine could not be correlated with the nitrification inhibition, as it varied greatly during the experiment time. The MBR pilot plant is coupled to a nanofiltration (NF) system and the results on the rejection of both, NDMA FP and individual precursors, through this system was above 90%. Finally, results obtained for the MBR pilot plant are compared to the percentage of removal by a conventional full scale biological wastewater treatment plant (WWTP) fed with the same influent. During aerobic operation, the removal of NDMA FP by the MBR pilot plant was similar to the full scale WWTP.

Determination of 15 N-nitrosodimethylamine precursors in different water matrices by automated on-line solid-phase extraction ultra-high-performance-liquid chromatography tandem mass spectrometry.

A new methodology based on on-line solid-phase extraction (SPE) ultra-high-performance-liquid chromatography coupled to a triple quadrupole mass spectrometer (UHPLC-MS-MS) for the determination of 15 individual anthropogenic N-nitrosodimethylamine (NDMA) precursors was developed. On-line SPE was performed by passing 2mL of the water sample through a Hypersil GOLD aQ column and chromatographic separation was done using a Kinetex Biphenyl column using methanol and 0.1% formic acid aqueous solution as a mobile phase. For unequivocal identification and confirmation, two selected reaction monitoring (SRM) transitions were monitored per compound. Quantification was performed by internal standard approach and matrix match calibration. The main advantages of the developed method are high sensitivity (limits of detection in the sub ng/L range), selectivity due to the use of tandem mass spectrometry, precision and minimum sample manipulation as well as fast analytical response. Process efficiency and recovery were also evaluated for all the target compounds. As part of the validation procedure, the method was applied in a sampling campaign for the analysis of influent and secondary effluent of a wastewater treatment plant (WWTP) in Girona, Spain. Additionally, the effluent from a nanofiltration (NF) membrane system used for water recycling was monitored. The percentage of NDMA formation explained by the measured precursors was also quantified.

Occurrence and spatial distribution of EDCs and related compounds in waters and sediments of Iberian rivers.

The environmental presence of chemicals capable of affecting the endocrine system has become a matter of scientific and public concern after certain endocrine disruptor compounds (EDCs) have been detected in the aquatic environment. In this work, 31 different EDCs and related compounds (suspect EDCs) belonging to different contaminant classes were studied: 10 estrogens, natural and synthetic, 8 alkylphenolic compounds, bisphenol A, triclosan and triclorocaraban, 4 parabens, 2 benzotriazoles, 3 organophosphorous flame retardants and the chemical marker caffeine, in river water and sediment of four Iberian rivers (Ebro, Llobregat, Júcar and Guadalquivir). An extensive sampling has been undertaken in two monitoring campaigns (2010 and 2011). A total of 77 samples of water and 75 sediments were collected. For this propose two different multiresidue analytical methods were applied, using the automated online EQuan/TurboFlow™ liquid chromatography coupled to mass spectrometry detection in tandem. In terms of concentrations the compounds found at the highest average concentrations were: nonylphenol monocarboxylate (NP1EC), tolyltriazole (TT), tris(chloroisopropyl)phosphate (TCPP) found at average concentrations above 100 ng/L, followed by 1H-benzotriazole and tris(butoxyethyl)phosphate (TBEP) found at average concentration higher than 50 ng/L. Natural and synthetic hormones were found at low levels not exceeding 16 ng/L and 7 ng/g for water and sediment, respectively, however they contributed to more than 80% of the total estrogenicity of the samples (expressed as the equivalents of estradiol EEQ, ng/L). Regarding the spatial distribution of these contaminants, the Llobregat river was found to be the most contaminated river basin, having sites near the mouth of the river the ones with the highest contaminant load. In the Ebro river basin several hot spots were identified and Júcar showed to be the least contaminated. Overall, the study confirmed the presence of complex mixtures of unregulated contaminants, thus raising concern about their potential interactive effects.

Analysis of endocrine disrupters and related compounds in sediments and sewage sludge using on-line turbulent flow chromatography-liquid chromatography-tandem mass spectrometry.

A novel fully automated method based on dual column switching using turbulent flow chromatography followed by liquid chromatography coupled to tandem mass spectrometry (TFC-LC-MS/MS) was applied for the determination of endocrine disruptors (EDCs) and related compounds in sediment and sewage sludge samples. This method allows the unequivocal identification and quantification of the most relevant environmental EDCs such as natural and synthetic estrogens and their conjugates, antimicrobials, parabens, bisphenol A (BPA), alkylphenolic compounds, benzotriazoles, and organophosphorus flame retardants, minimizing time of analysis and alleviating matrix effects. Applying this technique, after the extraction of the target compounds by pressurized liquid extraction (PLE), sediment and sewage sludge extracts were directly injected to the chromatographic system and the analytes were concentrated into the clean-up loading column. Using six-port switching system, the analytes were transferred to the analytical column for subsequent detection by MS-MS (QqQ). In order to optimize this multiplexing system, a comparative study employing six types of TurboFlow™ columns, with different chemical modifications, was performed to achieve the maximum retention of analytes and best elimination of matrix components. Using the optimized protocol low limits of quantification (LOQs) were obtained ranging from 0.0083 to 1.6 ng/g for sediment samples and from 0.10 to 125 ng/g for sewage sludge samples (except for alkylphenol monoethoxylate). The method was used to evaluate the presence and fate of target EDCs in the Ebro River which is the most important river in Spain with intensive agricultural and industrial activities in the basin that contribute to deteriorating soil and water quality.

Assessment of the matrix effect on the headspace solid-phase microextraction (HS-SPME) analysis of chlorophenols in wines.

In this paper, we propose a comparative study to check the matrix effect on the extraction of three chlorophenols, 2,4,6-trichlorophenol (TCP), 2,3,4,6-tetrachlorophenol and pentachlorophenol, direct precursors of 2,4,6-trichloroanisole, in synthetic and commercial wines (white and red wines). A rapid, simple and sensitive methodology based on solid-phase microextraction (SPME) and GC with electron capture detection (GC-ECD) and mass spectrometric detection (GC-MS) was developed and the variables affecting the extraction process (temperature, time and salt content) were examined employing a factorial design at two levels. Since GC-ECD does not allow the clear identification of target analytes in white wine, owing to overlapped interferences, GC-MS/MS was used for subsequent examinations. Calibration curves were constructed in synthetic, white and red wine. Significant differences between the slopes of synthetic and red wine, with the exception of TCP, were observed. Analytical parameters were evaluated and satisfactory results were obtained, showing the usefulness of the headspace SPME (HS-SPME) method for determining chlorophenolic compounds in wines.

Assays on the simultaneous determination and elimination of chloroanisoles and chlorophenols from contaminated cork samples.

A method for the simultaneous determination of the chloroanisoles and chlorophenols in cork samples with gas chromatography has been evaluated in view to its application. All the stages of the suggested procedure have been submitted to an in-depth examination using spiked ground corks. The recoveries of the method, which involves a simultaneous extraction with n-pentane followed by a second extraction using an aqueous basic solution where the phenolic derivates are transferred and, subsequently, derivatised, have been satisfactory for the all analytes at the studied spiking concentration levels. Good precision data and limits of detection between 1 ng/g and 2 ng/g were obtained for almost all compounds. As real samples, naturally contaminated cork slabs taken from different sources have been analysed, showing the presence of 2,4,6-trichloroanisole (TCA) and, in lesser extent, its direct precursor, 2,4,6-trichlorophenol (TCP). Removal studies have been performed by washing these tainted cork slabs with different solutions: Milli-Q water, sodium hydroxide and commercial products. Sodium hydroxide solutions have led to better analyte elimination, and the complete removal of TCP from the cork has been accomplished together with 72% of TCA reduction has been achieved.

Ethanol/Water extraction combined with solid-phase extraction and solid-phase microextraction concentration for the determination of chlorophenols in cork stoppers.

The appearance of 2,4,6-trichloroanisole (TCA) in cork stoppers is of great concern because it can cause off-flavors in bottled wine. To prevent this sensorial defect, there should not be any traces of 2,4,6-trichlorophenol (TCP), 2,3,4,6-tetrachlorophenol (TeCP), or pentachlorophenol (PCP) in the finished corks, because they are the direct precursors of TCA. In the course of this study two methodologies based upon an extraction with ethanol/water mixtures to determine the chlorophenolic content in cork matrices were developed. The cork extract is preconcentrated using both solid-phase extraction and solid-phase microextraction methodologies. The latter was optimized by applying a full two-level factorial design. Finally, spiked ground corks at nanogram per gram levels of each chlorophenol were analyzed under optimal conditions and by applying both procedures. The obtained results demonstrate that chlorophenols can be detected in corks contaminated at the nanogram per gram level and, thus, these approaches can be successfully applied as quality control measures in the cork industry.