Sample preparation for suspect and non-target screening of xenobiotics in human biofluids by liquid chromatography-High resolution tandem mass spectrometry.

The concept of exposome covers all the exposures an individual suffers from conception to death, which can be partially assessed through the monitoring of human biofluids. In there, target analytical approaches tend to focus on a limited set of xenobiotics, whereas exposomic studies need broad scopes in search of a full understanding. Given the issue, suspect and non-target screening are feasible alternatives. However, adequate sample preparation procedures should minimize interferences without significantly reducing the number of xenobiotics. Within this context, the present article aims to describe comprehensive sample preparation procedures for suspect or non-target screening of organic xenobiotics in several human biofluids, all coupled to unified separation and detection conditions based on ultra-high performance liquid chromatography-high resolution tandem mass spectrometry (UHPLC-HRMS/MS). The referred biofluids consist of human urine, breast milk, saliva and ovarian follicular fluid.•Analytical methods for untargeted analysis of a wide range of xenobiotics in human biofluids are fully described in order to ensure reproducibility.•The sample preparation procedures balance selectivity and sensitivity.•Unified analysis conditions allow simultaneous analysis of diverse biofluids.

Evaluating membrane bioreactor treatment for the elimination of emerging contaminants using different analytical methods.

Since wastewater treatment plants (WWTPs) were not originally designed to eliminate contaminants of emerging concern (CECs), alternative strategies like membrane bioreactor (MBR) technology are gaining importance in achieving effective CEC removal and minimising their environmental impact. In this study, composite wastewater samples were collected from the biggest WWTP in the Basque Country (Galindo, Biscay) and the performance of two secondary treatments (i.e. conventional activated sludge treatment, CAS, and MBR) was assessed. The combination of a suspect screening approach using liquid chromatography tandem high-resolution mass spectrometry (LC-HRMS) and multitarget analysis by gas chromatography-mass spectrometry (GC-MS) allowed the detection of approximately 200 compounds in the WWTP effluents. The estimated removal efficiencies (REs) revealed that only 16 micropollutants exhibited enhanced removal by MBR treatment (RE > 70% or 40 - 60%). The environmental risk posed by the non-eliminated compounds after both treatments remained similar, being anthracene, clarithromycin, bis(2-ethylhexyl) phthalate (DEHP) and dilantin the most concerning pollutants (RQ > 1). The Microtox® bioassay confirmed the MBR's efficiency in removing baseline toxicity, while suggesting a similar performance of CAS treatment. These minimal differences between treatments call into question the worthiness of MBR treatment and emphasise the need to seek more efficient alternative treatment methods.

Exploratory optimisation of a LC-HRMS based analytical method for untargeted metabolomic screening of Cannabis Sativa L. through Data Mining.

BACKGROUND: Recent increase in public acceptance of cannabis as a natural medical alternative for certain neurological pathologies has led to its approval in different regions of the world. However, due to its previous illegal background, little research has been conducted around its biochemical insights. Therefore, in the current framework, metabolomics may be a suitable approach for deepening the knowledge around this plant species. Nevertheless, experimental methods in metabolomics must be carefully handled, as slight modifications can lead to metabolomic coverage loss. Hence, the main objective of this work was to optimise an analytical method for appropriate untargeted metabolomic screening of cannabis. RESULTS: We present an empirically optimised experimental procedure through which the broadest metabolomic coverage was obtained, in which extraction solvents for metabolite isolation, chromatographic columns for LC-qOrbitrap analysis and plant-representative biological tissues were compared. By exploratory means, it was determined that the solvent combination composed of CHCl3:H2O:CH3OH (2:1:1, v/v) provided the highest number of features from diverse chemical classes, as it was a two-phase extractant. In addition, a reverse phase 2.6 µm C18 100 Å (150 × 3 mm) chromatographic column was determined as the appropriate choice for adequate separation and further detection of the diverse metabolite classes. Apart from that, overall chromatographic peak quality provided by each column was observed and the need for batch correction methods through quality control (QC) samples was confirmed. At last, leaf and flower tissues resulted to provide complementary metabolic information of the plant, to the detriment of stem tissue, which resulted to be negligible. SIGNIFICANCE: It was concluded that the optimised experimental procedure could significantly ease the path for future research works related to cannabis metabolomics by LC-HRMS means, as the work was based on previous plant metabolomics literature. Furthermore, it is crucial to highlight that an optimal analytical method can vary depending on the main objective of the research, as changes in the experimental factors can lead to different outcomes, regardless of whether the results are better or worse.

Multitarget and suspect screening of antimicrobials in soil and manure by means of QuEChERS - liquid chromatography tandem mass spectrometry.

The present work aimed to develop an accurate analytical method for the simultaneous analysis of twenty-four antimicrobials in soil:compost and animal manure samples by means of ultra-high performance liquid chromatography coupled to a triple-quadrupole mass spectrometer (UHPLC-QqQ). For this purpose, the effectiveness of two extraction techniques (i.e. focused ultrasound solid-liquid extraction (FUSLE) and QuEChERS (quick, easy, cheap, effective, rugged and safe)) was evaluated, and the clean-up step using solid-phase extraction (SPE) was also thoroughly studied. The method was successfully validated at 10 µg·kg-1, 25 µg·kg-1, and 50 µg·kg-1 showing adequate trueness (70-130%) and repeatability (RSD < 30%), with few exceptions. Procedural limits of quantification (LOQPRO) were determined for soil:compost (0.45 to 7.50 µg·kg-1) and manure (0.31 to 5.53 µg·kg-1) samples. Pefloxacin could not be validated at the lowest level since LOQPRO ≥ 10 µg·kg-1. Sulfamethazine (7.9 ± 0.8 µg·kg-1), danofloxacin (27.1 ± 1.4 µg·kg-1) and trimethoprim (4.9 ± 0.5 µg·kg-1) were detected in soil samples; and tetracycline (56.8 ± 2.8 µg·kg-1), among other antimicrobials, in the plants grown on the surface of the studied soil samples. Similarly, sulfonamides (SAs), tetracyclines (TCs) and fluoroquinolones (FQs) were detected in sheep manure in a range of 1.7 ± 0.3 to 93.3 ± 6.8 µg·kg-1. Soil and manure samples were also analysed through UHPLC coupled to a high-resolution mass-spectrometer (UHPLC-qOrbitrap) in order to extend the multitarget method to suspect screening of more than 22,281 suspects. A specific transformation product (TP) of sulfamethazine (formyl-sulfamethazine) was annotated at 2a level in manure samples, among others. This work contributes to the efforts that have been made in the last decade to develop analytical methods that allow multitarget analysis of a wide variety of antimicrobials, including TPs, which is a complex task due to the diverse physicochemical properties of the antimicrobials.

Comprehensive micropollutant characterization of wastewater during Covid-19 crisis in 2020: Suspect screening and environmental risk prioritization strategy.

Micropollutants monitoring in wastewater can serve as a picture of what is consuming society and how it can impact the aquatic environment. In this work, a suspect screening approach was used to detect the known and unknown contaminants in wastewater samples collected from two wastewater treatment plants (WWTPs) located in the Basque Country (Crispijana in Alava, and Galindo in Vizcaya) during two weekly sampling campaigns, which included the months from April to July 2020, part of the confinement period caused by COVID-19. To that aim, high-resolution mass spectrometry was used to collect full-scan data-dependent tandem mass spectra from the water samples using a suspect database containing >40,000 chemical substances. The presence of > 80 contaminants was confirmed (level 1) and quantified in both WWTP samples, while at least 47 compounds were tentatively identified (2a). Among the contaminants of concern, an increase in the occurrence of some compounds used for COVID-19 disease treatment, such as lopinavir and hydroxychloroquine, was observed during the lockdown. A prioritization strategy for environmental risk assessment was carried out considering only the compounds quantified in the effluents of Crispijana and Galindo WWTPs. The compounds were scored based on the removal efficiency, estimated persistency, bioconcentration factor, mobility, toxicity potential and frequency of detection in the samples. With this approach, 33 compounds (e.g. amantadine, clozapine or lopinavir) were found to be considered key contaminants in the analyzed samples based on their concentration, occurrence and potential toxicity. Additionally, antimicrobial (RQ-AR) and antiviral (EDRP) risk of certain compounds was evaluated, where ciprofloxacin and fluconazole represented medium risk for antibiotic resistance (1 > RQ-AR > 0.1) in the aquatic ecosystems. Regarding mixture toxicity, the computed sum of toxic unit values of the different effluents (> 1) suggest that interactions between the compounds need to be considered for future environmental risk assessments.

Comparison of conventional and dispersive solid phase extraction clean-up approaches for the simultaneous analysis of tetracyclines and sulfonamides in a variety of fresh vegetables.

The extensive use of antibiotics in agriculture has led to the occurrence of residual drugs in different vegetables frequently consumed by humans. This could pose a potential threat to human health, not only because of the possible effects after ingestion but also because the transmission of antibiotic-resistant genes could occur. In this work, two accurate sample preparation procedures were developed and validated for the simultaneous analysis of sulfonamides (SAs) and tetracyclines (TCs) in four of the most widely consumed vegetables (lettuce, onion, tomato, and carrot) in Europe. The evaluated protocols were based on QuECHERS for extraction and subsequent clean-up by SPE (solid phase extraction) or dispersive SPE. Parameters affecting both extraction and clean-up were carefully evaluated and selected for accuracy of results and minimal matrix effect. Overall, apparent recoveries were above 70% for most of the target analytes with both analytical procedures, and adequate precision (RSD<30%) was obtained for all the matrices. The procedural limits of quantification (LOQPRO) values for SPE clean-up remained below 4.4 µg kg-1 for TCs in all vegetables except for chlortetracycline (CTC) in lettuce (11.3 µg kg-1) and 3.0 µg kg-1 for SAs, with the exception of sulfadiazine (SDZ) in onion (3.9 µg kg-1) and sulfathiazole (STZ) in carrot (5.0 µg kg-1). Lower LOQPRO values (0.1-3.7 µg kg-1) were obtained, in general, when dSPE clean-up was employed. Both methods were applied to twenty-five market vegetable samples from ecological and conventional agriculture and only sulfamethazine (SMZ) and sulfapyridine (SPD) were detected in lettuce at 1.2 µg kg-1 and 0.5 µg kg-1, respectively.

Characterization of the contamination fingerprint of wastewater treatment plant effluents in the Henares River Basin (central Spain) based on target and suspect screening analysis.

The interest in contaminants of emerging concern (CECs) has increased lately due to their continued emission and potential ecotoxicological hazards. Wastewater treatment plants (WWTPs) are generally not capable of eliminating them and are considered the main pathway for CECs to the aquatic environment. The number of CECs in WWTPs effluents is often so large that complementary approaches to the conventional target analysis need to be implemented. Within this context, multitarget quantitative analysis (162 compounds) and a suspect screening (>40,000 suspects) approaches were applied to characterize the CEC fingerprint in effluents of five WWTPs in the Henares River basin (central Spain) during two sampling campaigns (summer and autumn). The results indicated that 76% of the compounds quantified corresponded to pharmaceuticals, 21% to pesticides and 3% to industrial chemicals. Apart from the 82 compounds quantified, suspect screening increased the list to 297 annotated compounds. Significant differences in the CEC fingerprint were observed between summer and autumn campaigns and between the WWTPs, being those serving the city of Alcalá de Henares the ones with the largest number of compounds and concentrations. Finally, a risk prioritization approach was applied based on risk quotients (RQs) for algae, invertebrates, and fish. Azithromycin, diuron, chlortoluron, clarithromycin, sertraline and sulfamethoxazole were identified as having the largest risks to algae. As for invertebrates, the compounds having the largest RQs were carbendazim, fenoxycarb and eprosartan, and for fish acetaminophen, DEET, carbendazim, caffeine, fluconazole, and azithromycin. The two WWTPs showing higher calculated Risk Indexes had tertiary treatments, which points towards the need of increasing the removal efficiency in urban WWTPs. Furthermore, considering the complex mixtures emitted into the environment and the low dilution capacity of Mediterranean rivers, we recommend the development of detailed monitoring plans and stricter regulations to control the chemical burden created to freshwater ecosystems.

Suspect screening workflow comparison for the analysis of organic xenobiotics in environmental water samples.

Suspect screening techniques are able to determine a broader range of compounds than traditional target analysis. However, the performance of the suspect techniques relies on the procedures implemented for peak annotation and for this, the list of potential candidates is clearly a limiting factor. In order to study this effect on the number of compounds annotated in environmental water samples, a method was validated in terms of absolute recoveries, limits of quantification and identification, as well as the peak picking capability of the software (Compound Discoverer 2.1) using a target list of 178 xenobiotics. Four suspect screening workflows using different suspect lists were compared: (i) the Stoffident list, (ii) all the NORMAN lists, (iii) suspects containing C, H, O, N, S, P, F or Cl in their molecular formula with more than 10 references in Chemspider and (iv) the mzCloud library. The results were compared in terms of the number of annotated compounds at each confidence level. The same 8 compounds (atenolol, caffeine, caprolactam, carbendazim, cotinine, diclofenac, propyphenazone and trimetoprim) were annotated at the highest confidence level using the four workflows. Remarkable differences were observed for lower confidence levels but only 4 features were annotated at different levels by the four workflows. While the third approach provided the highest number of annotated features, the workflow based on the mzCloud library rendered satisfactory results with a simpler approach. Finally, this latter approach was extended to the analysis of organic xenobiotics in different environmental water samples.

Suspect and non-target screening: the last frontier in environmental analysis.

Suspect and non-target screening (SNTS) techniques are arising as new analytical strategies useful to disentangle the environmental occurrence of the thousands of exogenous chemicals present in our ecosystems. The unbiased discovery of the wide number of substances present over environmental analysis needs to find a consensus with powerful technical and computational requirements, as well as with the time-consuming unequivocal identification of discovered analytes. Within these boundaries, the potential applications of SNTS include the studies of environmental pollution in aquatic, atmospheric, solid and biological samples, the assessment of new compounds, transformation products and metabolites, contaminant prioritization, bioremediation or soil/water treatment evaluation, and retrospective data analysis, among many others. In this review, we evaluate the state of the art of SNTS techniques going over the normalized workflow from sampling and sample treatment to instrumental analysis, data processing and a brief review of the more recent applications of SNTS in environmental occurrence and exposure to xenobiotics. The main issues related to harmonization and knowledge gaps are critically evaluated and the challenges of their implementation are assessed in order to ensure a proper use of these promising techniques in the near future.

Migration of photoinitiators, phthalates and plasticizers from paper and cardboard materials into different simulants and foodstuffs.

The migration of photoinitiators, phthalates and plasticizers from two paper and cardboard materials into food simulants (50% and 95% EtOH and Tenax) and foodstuffs (rice, cereals and milk powder) was studied. In the case of liquid simulants migration was observed to reach the equilibrium after 60 min and depended on the material type and the physicochemical parameters of the migrants, whereas the temperature (room temperature and 60 °C) did not show significant effects. The study of migration of the compounds from a baking paper to Tenax at high temperatures (150 and 250 °C) evidenced an increment of migration when increasing temperature, except for the most volatile analytes. Finally, the migration to foodstuffs was studied using fully validated analytical protocols. Overall, the comparison of the migration rates demonstrated that Tenax was adequate for the simulation of the migration to rice and cereals, but underestimated the migration to infant milk powder, for which 95% EtOH resulted a more suitable simulant.

Focused ultrasound-based extraction for target analysis and suspect screening of organic xenobiotics in fish muscle.

The development of multitarget and/or suspect screening methods for the analysis of xenobiotics in fish samples is compulsory due to the lack of works in the literature where a deep evaluation of the variables affecting extraction and clean-up steps is performed. The aim of the present work was to optimize and validate a multitarget (180 compounds) method for the analysis of priority and emerging xenobiotics in fish muscle using focused ultrasound-assisted solid-liquid extraction. From the different extraction solvents studied, a single extraction in cold acetonitrile rendered the best consensus results in terms of absolute recoveries and the number of target compounds extracted. Matrix effect was minimized using commercially available Captiva ND-Lipid filters, which provided clean extracts and satisfactory repeatability compared to other approaches. Absolute recoveries were corrected using matrix-matched calibration and apparent recoveries in the 43%-105%, 73%-131% and 78%-128% ranges were obtained at low (20 ng g-1), medium (100 ng g-1), and high (200 ng g-1) spiking levels, respectively. A 60% of the xenobiotics showed limits of identification lower than 20 ng g-1. The developed method was successfully applied to the quantification and suspect screening of samples bought in a local market (hake, gilt-head bream, sea bass and prawn) and fished (thicklip grey mullet) at the Urdaibai estuary (north of Spain). Food additives, antiparasitic drugs and PFOS were quantified at ng g-1 level. Moreover, the targeted method was extended to the suspect screening, revealing the presence of plastic related products (caprolactam, phthalates, polyethylenglycols), pharmaceutical products (albendazole, mebendazole, valpromide) and pesticides or insect repellents (icaridin, myristyl sulfate, nootkatone). Therefore, FUSLE in cold acetonitrile combined with Captiva ND-Lipid filters and liquid chromatography tandem high-resolution mass spectrometry (LC-q-Orbitrap) were successfully applied to both multitarget quantitative analysis and suspect screening of approx. 17,800 compounds.

Target and suspect screening of substances liable to migrate from food contact paper and cardboard materials using liquid chromatography-high resolution tandem mass spectrometry.

This work describes the analysis of both target and non-target compounds in paper and cardboard materials together with the characterization of their migration to Tenax® by means of liquid chromatography coupled to both low (LC-QqQ) and high resolution tandem mass spectrometry (LC-q-Orbitrap), respectively. To this aim, an entire analytical procedure was fully developed and validated for both matrices: paper/cardboard and Tenax®. A total of 97 chemicals, including photoinitiators, phthalates, biocides, antioxidants, etc., listed by the European Regulation, were found in the materials under study together with other substances not included in this list. Moreover, the majority of annotated substances were present in the simulant, giving evidence of their migration capacity. Migration percentages of 10 photoinitiators, 4 phthalates, bisphenol A, bis-(2-ethylhexyl) adipate, acetyltributyl citrate and caprolactam to Tenax® were quantified. Despite not exceeding the established specific migration limit (SML) in any case, benzophenone, 4-phenylbenzophenone and bisphenol A concentrations in some paper and cardboard materials were very close to the SML values established by the EU legislation.

Occurrence and Fate of Organic and Organometallic Pollutants in Municipal Wastewater Treatment Plants and Their Impact on Receiving Waters (Adour Estuary, France).

To achieve a "Good Environmental Status by 2015," as demanded by the water framework directive, monitoring programs are needed to furnish data on target compounds. In this study, a first evaluation of influents and main emissions of 3 local wastewater treatment plants (WWTP) in the Adour estuary (southwest of France) was performed for 23 pollutants (10 musk fragrances, 5 alkylphenols, and 8 organometallics), as well as receiving estuarine water from the same area. High frequency of occurrence of these compounds was found in influents samples (musks: 22-100%; alkylphenols 11-100%; organometallics 0-100%) and effluents (musks: 0-100%; alkylphenols 0-100%; organometallics 0-100%). The removal efficiencies were calculated and varied from negative values up to 98% with the lowest values for synthetic musk compounds. Temporal variability of the target compounds also was studied, and a few tendencies were observed. Estimation of the daily output of each WWTP into the estuary also showed that galaxolide, nonylphenol, monobuthyltin, and inorganic mercury were the compounds discharged into the environment at the highest concentrations. Finally, the occurrence of these compounds in estuarine waters was evaluated; most of them were present at concentrations below the limits of quantification (musks: 0.53-41.5 ng/L; alkylphenols 3.4-410 ng/L; organometallics 0.02-0.70 ng/L) suggesting a low impact in the resulting receiving waters.

Tetraphasic polar organic chemical integrative sampler for the determination of a wide polarity range organic pollutants in water. The use of performance reference compounds and in-situ calibration.

In the present work, a homemade polar organic chemical integrative sampler (POCIS) was studied for the determination of 16 target analytes. The suitability of the combination of triphasic mixture (used in so called pesticides-POCIS) and octadecyl-functionalized silica gel (C18) as sorbent for POCIS was evaluated for the determination of alkylphenols (APs), several hormones, bisphenol-A (BPA), synthetic musk fragrances and herbicides such as trifluralin (Tri) and alachlor (Ala). With this purpose, POCIS laboratory calibration study, using a continuous-flow calibration system, was carried out in order to determine the uptake behavior and sampling rate (Rs) values for each target analyte. While the most hydrophobic compounds, (synthetic musk fragrances, some APs and Tri), showed poor linearity and low accumulation, a linear accumulation was observed for compounds whose logarithmic octanol-water partition coefficient (log Kow) ranged from 5.3 (4-tert-octylphenol, 4t-OP) to 3.1 (cis-androsterone, ADT). The Rs values obtained ranged from 0.190Lday-1 (4t-OP) to 0.042Lday-1 (BPA and equilin, EQ). The addition of C18 to the commonly used triphasic mixture increased the applicability of the POCIS sampler to compounds slightly more non-polar, such as 4t-OP. As far as we know, this is the first time that a combination of tetraphasic sorbent composed by the commercially available triphasic sorbent (Isolute ENV+polystyrene divinylbenzene and Ambersorb 1500 carbon dispersed on S-X3 Biobeads) and C18 was evaluated for passive sampling of the target analytes. The developed POCIS samplers were applied in field experiments from Halle (Germany) wastewater treatment plant (WWTP) effluent. Concerning the calculation of Rs values, the time weighted average (TWA) water concentration CWTWA values were determined considering three different approaches: (i) Rs from laboratory calibration (ii) Rs from laboratory calibration corrected with the use of performance reference compounds (PRCs) and (iii) Rs derived from field experiments or in-situ calibration. Several deuterated compounds such as, [2H3]-17ß-estradiol ([2H3]-E2), [2H4]-nonylphenol ([2H4]-NP), [2H4]-equilin ([2H4]-EQ), [2H3]-tonalide ([2H3]-AHTN) and [2H15]-musk xylene ([2H15]-MX) were also studied for their applicability as PRCs. Finally, a reasonable agreement between grab sampling and CWTWA was found when results from in-situ calibration were considered, but not when PRCs were used for correction.

Uptake of perfluorooctanoic acid, perfluorooctane sulfonate and perfluorooctane sulfonamide by carrot and lettuce from compost amended soil.

Sewage sludge, which acts like a sink for many pollutants, including metals, pathogens and organic pollutants, that are not completely removed in waste water treatment plants (WWTPs), is applied as a nutrient rich organic fertilizer in many agricultural applications. In the present work, carrot and lettuce crops were grown in two different compost amended soils fortified with perfluorooctanoic acid (PFOA), perfluorosulfonate acid (PFOS) and perfluorosulfonamide (FOSA) and cultivated in a greenhouse. The plants were harvested and divided into root core, root peel and leaves in the case of carrots and into heart and leaves for lettuces. Concentrations for all the different compartments were determined to assess the bioconcentration factors (BCFs) and the plant distribution of the target analytes. The highest carrot BCFs for PFOA and PFOS were determined in the leaves (0.6-3.4), while lower values were calculated in the core (0.05-0.6) and the peel (0.05-1.9) compartments. However, PFOA was taken up in the translocation stream and accumulated more than PFOS in the edible part of lettuce. FOSA was totally degraded in the presence of carrot; however, a lower FOSA degradation was observed in presence of the lettuce, which was dependent on the total organic carbon (TOC) content of the soil. The higher the TOC value, the higher the FOSA degradation observed. No degradation was observed in the crop absence. In the case of the carrot experiments, different polymeric materials (polyethersulfone, PES, polyoxymethylene, and silicone rod) were tested to predict the concentration in the cultivation media. A high correlation (r(2)>0.63) was observed for the BCFs in the PES and in the carrot core and peel for PFOA and PFOS. It could be, concluded that the PES can be used as a first approach for the determination of the uptake of compounds such as PFOS and PFOA in carrot.

Uptake of 8:2 perfluoroalkyl phosphate diester and its degradation products by carrot and lettuce from compost-amended soil.

The present work studied the uptake of 8:2 perfluoroalkyl phosphate diester (diPAP) by two different crops (lettuce and carrot) and two different amended soils. Firstly, the possible degradation of 8:2 diPAP in the absence of crop was studied and 8:2 monoPAP (monophosphate), 8:2 FTCA (saturated fluorotelomer carboxylate), 8:2 FTUCA (unsaturated fluorotelomer carboxylate), 7:3 FTCA (saturated fluorotelomer carboxylate), PFHpA (perfluoroheptanoic acid), PFHxA (perfluorohexanoic acid) and PFOA (perfluorooctanoic acid) were detected. In the presence of crops, different degradation products were detected in the soil and, while PFNA (perfluorononanoic acid), PFHpA, PFHxA, PFPeA (perfluoropentacoic acid), PFBA (perfluorobutanoic acid), 7:3 FTCA and PFOA were determined in the cultivation media when carrot was grown, PFOA was the only degradation product detected in the case of lettuce experiments. Regarding the uptake in carrot, all the degradation products except 7:3 FTCA were translocated from the soil to the carrot. Carrot core, peel and leaves bioconcentration factors, BCFs, were determined for 8:2 diPAP and its degradation products. Values lower than method detection limits for core and low BCFs in peel (0.025-0.042) and leaves (0.028-0.049) were achieved for 8:2 diPAP. Regarding to the degradation products, the higher their water solubility, the higher the plant translocation. In this sense, the lower the carbon chain length of PFCAs, the higher the BCFs determined (PFBA > PFHxA > PFHpA > PFOA > PFNA). In general, lower total BCFs were achieved when the total organic carbon of the soils increased. For lettuce experiments, 8:2 diPAP (0.04-0.18) and PFOA (0.28-1.57) were only determined in lettuce heart.

Fast and simple determination of perfluorinated compounds and their potential precursors in different packaging materials.

A simple and fast analytical method for the determination of fourteen perfluorinated compounds (PFCs), including three perfluoroalkylsulfonates (PFSAs), seven perfluorocarboxylic acids (PFCAs), three perfluorophosphonic acids (PFPAs) and perfluorooctanesulfonamide (PFOSA) and ten potential precursors, including four polyfluoroalkyl phosphates (PAPs), four fluorotelomer saturated acids (FTCAs) and two fluorotelomer unsaturated acids (FTUCAs) in different packaging materials was developed in the present work. In order to achieve this objective the optimization of an ultrasonic probe-assisted extraction (UPAE) method was carried out before the analysis of the target compounds by liquid-chromatography-triple quadrupole-tandem mass spectrometry (LC-QqQ-MS/MS). 7 mL of 1 % acetic acid in methanol and a 2.5-min single extraction cycle were sufficient for the extraction of all the target analytes. The optimized analytical method was validated in terms of recovery, precision and method detection limits (MDLs). Apparent recovery values after correction with the corresponding labeled standard were in the 69-103 % and 62-98 % range for samples fortified at 25 ng/g and 50 ng/g concentration levels, respectively and MDL values in the 0.6-2.2 ng/g range were obtained. The developed method was applied to the analysis of plastic (milk bottle, muffin cup, pre-cooked food wrapper and cup of coffee) and cardboard materials (microwave popcorn bag, greaseproof paper for French fries, cardboard box for pizza and cinema cardboard box for popcorn). To the best of our knowledge, this is the first method that describes the determination of fourteen PFCs and ten potential precursors in packaging materials. Moreover, 6:2 FTCA, 6:2 FTUCA and 5:3 FTCA analytes were detected for the first time in microwave popcorn bags.

Uptake of polybrominated diphenyl ethers by carrot and lettuce crops grown in compost-amended soils.

The uptake of polybrominated diphenyl ethers (PBDEs) by carrot and lettuce was investigated. Degradation of PBDEs in soil in the absence of the plants was discarded. Different carrot (Nantesa and Chantenay) and lettuce (Batavia Golden Spring and Summer Queen) varieties were grown in fortified or contaminated compost-amended soil mixtures under greenhouse conditions. After plant harvesting, roots (core and peel) and leaves were analyzed separately for carrot, while for lettuce, leaves and hearts were analyzed together. The corresponding bioconcentration factors (BCFs) were calculated. In carrots, a concentration gradient of 2,2',3,4,4',5'-hexabromodiphenyl ether (BDE-138) became evident that decreased from the root peel via root core to the leaves. For decabromodiphenyl ether (BDE-209) at the low concentration level (7 and 20 ng g(-1)), the leaves incorporated the highest concentration of the target substance. For lettuce, a decrease in the BCF value (from 0.24 to 0.02) was observed the higher the octanol-water partition coefficient, except in the case of BDE-183 (BCF = 0.51) and BDE-209 (BCF values from 0.41 to 0.74). Significant influence of the soils and crop varieties on the uptake could not be supported. Metabolic debromination, hydroxylation or methylation of the target PBDEs in the soil-plant system was not observed.

Multiscreening determination of organic pollutants in molluscs using matrix solid phase dispersion.

This work describes the optimisation, validation and application of matrix solid-phase dispersion (MSPD) coupled to gas chromatography mass spectrometry, both single quadrupole (GC-MS) and tandem (GC-MS/MS), for the quantification in molluscs of up to 40 different analytes belonging to several families of priority and emerging organic contaminants, including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), organochlorine pesticides (OCPs), organophosphorus pesticides (OPPs) and musk fragrances. The MSPD procedure was fully optimised with a special focus on the clean-up strategy. The best recoveries were obtained using glass syringes, 0.30 g of freeze-dried sample, 0.30 g of Florisil as solid support, 4.00 g of activated silica and 25 mL of dichloromethane as elution solvent. Using GC-MS/MS the method afforded good linearities (r(2), between 0.980 and 0.9996), adequate repeatability and reproducibility (RSD<17% and 33%, respectively) and low instrumental limits of detection (between 0.010 and 2.74 ng mL(-1)). The accuracy of the method was evaluated using different approaches, i.e. assessment of spiked fish hatchery samples, laboratory reference material and standard reference material (SRM 2977). Satisfactory apparent recoveries were obtained for all the target analytes after correction with the corresponding labelled surrogate, except for PAHs in the case of SRM 2977, which required the use of the standard addition method. Finally, MSPD was applied to mollusc species collected in Colombia and Nicaragua, where PAHs, PCBs, musks and pesticides were detected at low ng g(-1) levels.

Simultaneous determination of a variety of endocrine disrupting compounds in carrot, lettuce and amended soil by means of focused ultrasonic solid-liquid extraction and dispersive solid-phase extraction as simplified clean-up strategy.

The present study is focused on the development of an analytical method based on focused ultrasonic solid-liquid extraction (FUSLE) followed by dispersive solid-phase extraction (dSPE) clean-up and liquid chromatography-triple quadrupole tandem mass spectrometry (LC-MS/MS) optimised for the simultaneous analysis of certain endocrine disrupting compounds (EDCs), including alkylphenols (APs), bisphenol A (BPA), triclosan (TCS) and several hormones and sterols in vegetables (lettuce and carrot) and amended soil samples. Different variables affecting the chromatographic separation, the electrospray ionisation and mass spectrometric detection were optimised in order to improve the sensitivity of the separation and detection steps. Under the optimised extraction conditions (sonication of 5min at 33% of power with pulse times on of 0.8s and pulse times off of 0.2s in 10mL of n-hexane:acetone (30:70, v:v) mixture using an ice bath), different dSPE clean-up sorbents, such as Florisil, Envi-Carb, primary-secondary amine bonded silica (PSA) and C18, or combinations of them were evaluated for FUSLE extracts before LC-MS/MS. Apparent recoveries and precision in terms of relative standard deviation (RSDs %) of the method were determined at two different fortification levels (according to the matrix and the analyte) and values in the 70-130% and 2-27% ranges, respectively, were obtained for most of the target analytes and matrices. Matrix-matched calibration approach and the use of labelled standards as surrogates were needed for the properly quantification of most analytes and matrices. Method detection limits (MDLs), estimated with fortified samples, in the ranges of 0.1-100ng/g for carrot, 0.2-152ng/g for lettuce and 0.9-31ng/g for amended soil were obtained. The developed methodology was applied to the analysis of 11 EDCs in both real vegetable bought in a local market and in compost (from a local wastewater treatment plant, WWTP) amended soil samples.