Polymorphisms within the ARNT2 and CX3CR1 Genes Are Associated with the Risk of Developing Invasive Aspergillosis.

Invasive aspergillosis (IA) is a life-threatening infection that affects an increasing number of patients undergoing chemotherapy or allo-transplantation, and recent studies have shown that genetic factors contribute to disease susceptibility. In this two-stage, population-based, case-control study, we evaluated whether 7 potentially functional single nucleotide polymorphisms (SNPs) within the ARNT2 and CX3CR1 genes influence the risk of IA in high-risk hematological patients. We genotyped selected SNPs in a cohort of 500 hematological patients (103 of those had been diagnosed with proven or probable IA), and we evaluated their association with the risk of developing IA. The association of the most interesting markers of IA risk was then validated in a replication population, including 474 subjects (94 IA and 380 non-IA patients). Functional experiments were also performed to confirm the biological relevance of the most interesting markers. The meta-analysis of both populations showed that carriers of the ARNT2rs1374213G, CX3CR1rs7631529A, and CX3CR1rs9823718G alleles (where the RefSeq identifier appears as a subscript) had a significantly increased risk of developing IA according to a log-additive model (P value from the meta-analysis [PMeta] = 9.8 · 10-5, PMeta = 1.5 · 10-4, and PMeta =7.9 · 10-5, respectively). Haplotype analysis also confirmed the association of the CX3CR1 haplotype with AG CGG with an increased risk of IA (P = 4.0 · 10-4). Mechanistically, we observed that monocyte-derived macrophages (MDM) from subjects carrying the ARNTR2rs1374213G allele or the GG genotype showed a significantly impaired fungicidal activity but that MDM from carriers of the ARNT2rs1374213G and CX3CR1rs9823718G or CX3CR1rs7631529A alleles had deregulated immune responses to Aspergillus conidia. These results, together with those from expression quantitative trait locus (eQTL) data browsers showing a strong correlation of the CX3CR1rs9823718G allele with lower levels of CX3CR1 mRNA in whole peripheral blood (P = 2.46 · 10-7) and primary monocytes (P = 4.31 · 10-7), highlight the role of the ARNT2 and CX3CR1 loci in modulating and predicting IA risk and provide new insights into the host immune mechanisms involved in IA development.

Subcellular localization of the magnetosome protein MamC in the marine magnetotactic bacterium Magnetococcus marinus strain MC-1 using immunoelectron microscopy.

Magnetotactic bacteria are a diverse group of prokaryotes that biomineralize intracellular magnetosomes, composed of magnetic (Fe3O4) crystals each enveloped by a lipid bilayer membrane that contains proteins not found in other parts of the cell. Although partial roles of some of these magnetosome proteins have been determined, the roles of most have not been completely elucidated, particularly in how they regulate the biomineralization process. While studies on the localization of these proteins have been focused solely on Magnetospirillum species, the goal of the present study was to determine, for the first time, the localization of the most abundant putative magnetosome membrane protein, MamC, in Magnetococcus marinus strain MC-1. MamC was expressed in Escherichia coli and purified. Monoclonal antibodies were produced against MamC and immunogold labeling TEM was used to localize MamC in thin sections of cells of M. marinus. Results show that MamC is located only in the magnetosome membrane of Mc. marinus. Based on our findings and the abundance of this protein, it seems likely that it is important in magnetosome biomineralization and might be used in controlling the characteristics of synthetic nanomagnetite.

Occurrence of venlafaxine residues and its metabolites in marine mussels at trace levels: development of analytical method and a monitoring program.

Coastal areas are subject to growing pressures and impacts because of the increase in human activities. Lipophilic organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs) or polychlorinated biphenyls (PCBs), have been monitored for decades within monitoring programs. However, until now, little information on the detection of so-called "emerging contaminants" such as hydrophilic organic compounds in the marine environment and no data on its metabolites or transformation products in marine organisms is available. In this report, a sensitive analytical methodology for identification and confirmation of venlafaxine (VEN) residues and five of its main metabolites in the marine mussels Mytilus galloprovincialis was validated. The sample preparation procedure was based on the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) approach. An analytical method was developed to quantify these compounds at trace levels by liquid chromatography coupled to high-resolution mass spectrometry. The method was then applied to marine mussels collected from the Mediterranean Sea in southeastern France. Residues of the antidepressant VEN were occasionally detected at ng/g dw level. In addition, the approach allowed us to identify several transformation products in the analyzed samples. N-desmethylvenlafaxine (NDV) was the most frequently detected metabolite followed by N,O-di-desmethylvenlafaxine (NODDV).

The impact of enterocin AS-48 on the shelf-life and safety of sardines (Sardina pilchardus) under different storage conditions.

The purpose of this study was to determine the effect of enterocin AS-48, packaged under normal atmosphere (NA), vacuum (VP) or modified atmosphere (MAP) on the shelf life and safety of fresh sardines (Sardina pilchardus) stored at 5 °C. We studied the effect of these hurdles, alone or combined, on the relevant autochthonous bacterial populations. Total volatile basic nitrogen (TVB-N) content was used as indicative of freshness. Levels of biogenic amines cadaverine, putrescine, tyramine, and histamine were also determined. The application of AS-48 did not reduce the mesophilic, psychrotrophic, or Gram negative bacteria viable cell counts under any of the storage conditions tested. AS-48 did cause significant reductions in viable staphylococci counts, especially under VP. In sardines under NA treated with AS-48, the populations of histamine- and tyramine-forming total and lactic acid bacteria (LAB) showed no significant reductions. MAP or VP with AS-48 allowed reductions (significant at some storage times) in histamine- and tyramine-forming LAB. The TVB-N content was also reduced under normal atmosphere and, especially, in sardines stored under MAP. The most interesting results are those concerning the decrease (by several fold) in the levels of the biogenic amines cadaverine, putrescine, tyramine, and histamine determined after treatment with AS-48.

Validation of a multiclass multiresidue method and monitoring results for 210 pesticides in fruits and vegetables by gas chromatography-triple quadrupole mass spectrometry.

A rapid, sensitive, accurate and reliable multiresidue method for the identification and quantification of 210 relevant pesticides in four representative fruit and vegetable commodities (tomato, potato, spring onion and orange) has been developed and validated by gas chromatography in tandem with triple quadrupole mass spectrometry. The method has been fully validated and applied to 292 samples from different countries. Prior to instrumental analysis, an extraction procedure based on a sample extraction of multiclass analytes, using the ethyl acetate method was employed. Mass spectrometric conditions were individually optimized for each compound in the selected reaction monitoring (SRM) mode to achieve maximum sensitivity. The pesticides were separated in less than 25 min. This was followed by an exhaustive control of the retention times. The Retention Time Locking Method was applied, working at a constant pressure throughout the analysis. System maintenance was reduced by using a purged capillary flow device that provided backflush capabilities by reversing column flow immediately after elution of the last compound of interest. Istotopically labelled internal standards were employed to improve the quality of the analytical results.

Evaluation of chemical contamination of crops produced in greenhouse by irrigation with reclaimed water.

Using reclaimed water for agricultural irrigation is increasing worldwide to compensate for water scarcity. The aim of this work was to evaluate the uptake of some of the most commonly detected organic contaminants of emerging concern (CECs) and pesticides in regenerated water in a field study. Furthermore, it was studied their distribution and accumulation in the different parts of a crop (soil, plant and fruit). Three crops (cucumber, pepper and melon) were grown under controlled agronomic conditions in a greenhouse. In order to make an accurate evaluation of the process, "regenerated blank water" was spiked with 70 chemicals (including antibiotics, anti-inflammatories, analgesics, anaesthetics, anxiolytics, anticonvulsants, pesticides) at environmental concentrations (∼1 µg/L) and used for continuous crop irrigation. After crop season, the average total concentration of contaminants detected in the soil samples ranged from 132 to 232 µg/kg d.w depending of the crops type. Between 7 and 10 different contaminants were found in the harvested fruits, up to levels of 27.8 µg/kg f.w. cucumber, 12.4 µg/kg f.w. melon and 7.8 µg/kg f.w pepper. In general, cucumber fruit showed higher accumulation levels of contaminants than pepper and melon for most target analytes. The accumulation rates followed the order: root (0.2 %) < stem/leaf (1-4 %) < fruit (1-6 %) < soil (17-30 %). The experimental data obtained in this study were also used to assess the risk associated with the reuse of reclaimed water for crop irrigation as well to identify those contaminants that, due to their physicochemical properties, show higher accumulation rates and environmental impact.

Long-term effects on the agroecosystem of using reclaimed water on commercial crops.

The use of reclaimed water for crop irrigation has been proposed as a suitable alternative for farmers in the coastal areas of Mediterranean countries, which suffer from greater water scarcity. In this work we study the impact on the water-soil-plant continuum of using reclaimed water for commercial crops irrigated over a long period, as well as the human risks associated with consuming the vegetables produced. Forty-four CECs were identified in the reclaimed water used for crop irrigation. Of these, twenty-four CECs were identified in the irrigated soil samples analysed. Tramadol, ofloxacin, tonalide, gemfibrozil, atenolol, caffeine, and cetirizine were the pharmaceuticals detected at the highest levels in the water samples (between 11 and 44 µg/L). The CECs with the highest average soil concentrations were tramadol (14.6 µg/kg), followed by cetirizine (13.2 µg/kg) and clarithromycin (12.7 µg/kg). In the irrigated vegetable samples analysed over the study period, carbamazepine, lidocaine, and caffeine were only detected at levels from 0.1 to 1.7 µg/kg. The CEC accumulation rate detected in the edible parts of the vegetables permanently irrigated with reclaimed water was very low (~1 %), whereas it was 33 % in the soils. The results revealed that consuming fruits harvested from plants irrigated for a long period with reclaimed water does not represent a risk to human health, opening the door to a circular economy of water. Nevertheless, for crop irrigation, future studies need to be conducted over longer periods and in other matrices to provide more scientific data on the safety of using reclaimed water.

The evolution of size of the uropygial gland: mutualistic feather mites and uropygial secretion reduce bacterial loads of eggshells and hatching failures of European birds.

Potentially, pathogenic bacteria are one of the main infective agents against which a battery of chemical and physical barriers has evolved in animals. Among these are the secretions by the exocrine uropygial gland in birds. The antimicrobial properties of uropygial secretions may prevent colonization and growth of microorganisms on feathers, skin and eggshells. However, uropygial gland secretions also favour the proliferation of feather mites that feed on secretions and microorganisms living on feathers that would otherwise reach eggshells during incubation if not consumed by feather mites. Therefore, at the interspecific level, uropygial gland size (as an index of volume of uropygial secretion) should be positively related to eggshell bacterial load (i.e. the risk of egg infection), whereas eggshell bacterial loads may be negatively related to abundance of feather mites eating bacteria. Here, we explore these previously untested predictions in a comparative framework using information on eggshell bacterial loads, uropygial gland size, diversity and abundance of feather mites and hatching success of 22 species of birds. The size of the uropygial gland was positively related to eggshell bacterial loads (mesophilic bacteria and Enterobacteriaceae), and bird species with higher diversity and abundance of feather mites harboured lower bacterial density on their eggshells (Enterococcus and Staphylococcus), in accordance with the hypothesis. Importantly, eggshell bacterial loads of mesophilic bacteria, Enterococcus and Enterobacteriaceae were negatively associated with hatching success, allowing us to interpret these interspecific relationships in a functional scenario, where both uropygial glands and mutualistic feather mites independently reduce the negative effects of pathogenic bacteria on avian fitness.

Antimicrobial characterization and safety aspects of the bacteriocinogenic Enterococcus hirae F420 isolated from Moroccan raw goat milk.

The F420 strain, isolated from raw goat milk and identified as Enterococcus hirae, was selected because of its strong activity against gram-positive bacteria, including Listeria monocytogenes. Interestingly, the F420 strain lacks the virulence genes and decarboxylase activity of histidine, lysine, and ornithine, and it is susceptible to 11 of 14 tested antibiotics, including vancomycin. The antimicrobial compounds produced by E. hirae F420 strain showed high resistance to heat treatment and to acidic and basic pHs. The MALDI-TOF mass spectrometry analysis coupled with the sequence of peptide and structural gene analysis of one of the purified enterocins showed 100% identity with enterocin P (EntP), previously described in E. faecium strains. The structural gene for EntP is located on a plasmid of 65 kb. Other enterocins with molecular mass higher than 7 kDa were also detected. This is the first report of the production of EntP by E. hirae species naturally occurring in foods. The biotechnological characteristics of the F420 strain and its enterocins indicate their potential for application in the control of L. monocytogenes and other undesirable bacteria in food systems.

Characterization of functional, safety, and probiotic properties of Enterococcus faecalis UGRA10, a new AS-48-producer strain.

Enterococcus faecalis UGRA10, a new AS-48-producer strain, has been isolated from a Spanish sheep's cheese. The inhibitory substance produced by E. faecalis UGRA10 was purified and characterized using matrix-assisted laser desorption ionization-time of flight mass spectrometry, confirming its identity with AS-48 enterocin (7.150 Da). Subsequent genetic analysis showed the existence of the as-48 gene cluster on a plasmid of approximately 70-kb. The UGRA10 strain was examined for safety properties such as enterococci virulence genes, biogenic amine production, and antibiotic resistance. As for most E. faecalis strains, PCR amplification revealed the existence of gene encoding for GelE, Asa1, Esp, EfaA, and Ace antigens and for tyrosine decarboxylase. This strain was sensitive to most of the antibiotics tested, being resistant only to aminoglycosides, lincosamide, and pristinamicins. In addition, UGRA10 developed an ability to form biofilms and to adhere to Caco 2 and HeLa 229 cells. More interestingly, this strain shows a high ability to interfere with the adhesion of Listeria monocytogenes to Caco 2 cells. Altogether, the results suggest that this broad-spectrum bacteriocin-producing strain has biotechnological potential to be developed as a protective agent in food preservation and as a probiotic.

Determination study of contaminants of emerging concern at trace levels in agricultural soil. A pilot study.

In this study, we aimed to develop and validate a quick, easy, and robust extraction method for the simultaneous determination of 30 organic contaminants of emerging concern (CECs) including some transformation products in soil samples. Three different extraction methods based on an ultrasonic cylindrical probe (UAE), a pressurized liquid extraction (PLE), and a QuEChERS method were compared. Ultra-performance liquid chromatography coupled with electrospray tandem mass spectrometry (LC-MS/MS) was used for identification and quantification of the target analytes. A modified QuEChERS method showed the best results in terms of extractability and accuracy. The extraction procedure developed provided adequate extraction performances (70% of the target analytes were recovered within a 70-99% range), with good repeatability and reproducibility (variations below 20%) and great sensitivity (LOQ < 0.1 ng/g in most cases). No matrix effects were observed for 70% of the compounds. Finally, the analytical methodology was applied in a pilot study where agricultural soil was irrigated with reclaimed water spiked with the contaminants under study. Of the 25 CECs added in irrigation water, a total of 13 pesticides and 5 pharmaceutical products were detected at concentration ranges from 0.1 to 1.2 ng/g (d.w) and from 0.1 to 2.0 ng/g (d.w), respectively.

Monitoring of pesticide residues in crops irrigated with reclaimed water by a multiresidue method based on modified QuEChERS.

In this study, we aimed to validate and apply a quick and easy extraction method for the simultaneous determination of 27 pesticide residues at trace levels in agricultural samples (soil, fruit, and leaf) to monitor the presence of these contaminants released from reclaimed water. The procedure was based on a salting-out extraction method with acidified acetonitrile, followed by a dispersive solid-phase extraction (d-SPE) clean-up step applying the C18 sorbent. Ultra-performance liquid chromatography coupled with electrospray tandem mass spectrometry (LC-MS/MS) was used for identification and quantification of the target analytes. This methodology provided recovery values higher than 70%, for all pesticides and matrices evaluated in the study, except for propamocarb in soil samples (35%). Repeatability and reproducibility results, calculated as relative standard deviations (RSD, %), ranged between 1% and 18% in both cases. No remarkable matrix effects were observed for vegetable samples, except for thiamethoxam in red cabbage, and hexythiazox in carrot and leaves (between 30 and 40%). Soil samples showed a moderate matrix effect (between 21 and 35%) for more than 80% of the compounds. Monitoring pesticide residues found in agricultural samples irrigated with contaminated reclaimed water under controlled conditions revealed the efficacy of the proposed method. Three common vegetables were grown to evaluate the different migration and distribution rates in crops and soil. Pesticide accumulation in the different parts of the crop (soil, fruit, and leaves) and the potential human exposure to pesticides through daily intake were also discussed.

Evaluation of an enterocin AS-48 enriched bioactive powder obtained by spray drying.

Enterocin AS-48 is a cationic cyclic bacteriocin produced by Enterococcus faecalis with broad bactericidal activity. Currently we are assaying the efficacy of AS-48 as biopreservative in foods. In this work we have applied the spray drying process to different AS-48 liquid samples to obtain active dried preparations. We have also assayed different methods, heat, UV irradiation and filtration, to inactivate/remove the AS-48 producer cells from the samples. Best results were obtained for the sample from CM-25 cation exchange, for which it was also possible to completely eliminate/inactivate the producer cells by heat or UV irradiation without loss of activity. When added at 0.016% or 5% to Brain Heart Infusion broth or to skim milk, respectively, the AS-48 powder caused early and complete inactivation of Listeria monocytogenes. A partial inhibition of Staphylococcus aureus was achieved in broth and in skim milk supplemented with 2.5% and 10% AS-48 powder, respectively.

Symbiotic bacteria living in the hoopoe's uropygial gland prevent feather degradation.

Among potential agents that might damage bird feathers are certain microorganisms which secrete enzymes that digest keratin, as is the case of the ubiquitous bacterium Bacillus licheniformis, present in both the feathers and skin of wild birds. It is therefore a good candidate for testing the effects of bird defences against feather-degrading microorganisms. One of these defences is the oil secreted by the uropygial gland, which birds use to protect their feathers against parasites. In previous studies we have shown how Enterococcus faecalis strains isolated from nestling hoopoes exert antagonistic effects against B. licheniformis, mediated by the production of bacteriocins. Consequently we hypothesized that this enterococcus and the bacteriocins it engenders might act as a defence against feather-degrading microorganisms in hoopoes. We investigated this hypothesis in a series of laboratory experiments and evaluated the extent to which the keratinolytic effects caused by B. licheniformis were reduced by the E. faecalis MRR10-3 strain, isolated from hoopoes, and its bacteriocins. In different treatments, feathers or pure keratin was incubated with B. licheniformis, B. licheniformis together with E. faecalis MRR10-3, and B. licheniformis together with the bacteriocins produced by E. faecalis MRR10-3. Our results were in accordance with the predicted effects on hoopoe feathers. There was a significant decrease both in pure keratin loss and in feather degradation in the presence of the symbiotic bacterium or its bacteriocin. These results suggest that by preening their feathers hoopoes benefit from their symbiotic relationship with bacteriocin-producing enterococci, which constitute a chemical defence against feather degradation.

Evaluation of ozone-based treatment processes for wastewater containing microcontaminants using LC-QTRAP-MS and LC-TOF/MS.

This article describes the development of an enhanced liquid chromatography-mass spectrometry (LC-MS) method for the analysis of a selected group of 57 organic contaminants in wastewater. This group comprises 39 pharmaceuticals belonging to different therapeutical classes and 10 of their most frequent metabolites. Six pesticides and two disinfectants were also included. The LC-MS method was developed using a hybrid quadrupole/linear ion trap (Q TRAP) analyzer operating in selected reaction monitoring (SRM) mode (in both positive and negative electrospray ionization) in combination with a time-of flight (TOF) mass analyser. The application of both techniques provided very good results in terms of accurate quantification and unequivocal identification. Quantification was based on the use of a linearly accelerating (LINAC) high-pressure collision cell, which enable the analysis of a high number of compounds with enough acquisition data points for an optimal peak definition in SRM. Unequivocal identification was provided by the acquisition of at least two SRM transitions and by obtaining accurate mass measurements of the identified compounds with errors lower than 2 ppm. As an alternative for compounds where a second transition cannot be detected by Q-Trap-MS, the application of survey scans in enhanced product ion (EPI) was evaluated. The analytical performance of the method was evaluated in effluent wastewater samples. Linearity of response over three orders of magnitude was demonstrated (R2>0.99 for most compounds). Matrix effects resulting in suppression of the response were frequently observed, between 2-50% for most of compounds, except 4-DAA and 4-AA, which exhibit higher values (68%). Signal enhancement was also detected in 16 compounds. Method limits of detection (LOD) were between 0.1-50 ng L(-1). Finally, the methodology was successfully applied to the evaluation of the efficiency of two ozone-based treatments applied to the effluent from the secondary clarifier of a municipal wastewater treatment facility. Preliminary results are presented demonstrating that ozonation of wastewaters degrade pharmaceuticals with a high efficiency. Removals higher than 90% were reached for most of target analytes.

Pilot survey monitoring pharmaceuticals and related compounds in a sewage treatment plant located on the Mediterranean coast.

A one-year monitoring study was performed to evaluate the occurrence, persistence and fate of a group of 14 organic compounds in a sewage treatment plant (STP) located in the south of Spain. These results are part of a more extensive study, financed by the Spanish Ministry of Research with the aim to evaluate the traceability of new pollutants on the Mediterranean coast and to determine the removal efficiency of sewage treatment plants (STP) for these pollutants. The compounds which have been analyzed include pharmaceuticals of various therapeutic categories (ibuprofen, acetaminophen, dipyrone, diclofenac, carbamazepine and codeine), pesticides (chlorfenvinfos and permethrin), caffeine, triclosan, bisphenol A and three of their more relevant metabolites (1,7-dimethylxanthine, carbamazepine 10,11-epoxide and 2,7/2,8-dichlorodibenzo-p-dioxin). An SPE/GC-MS multi-residue analytical method was developed and validated to facilitate simultaneous determination of these compounds in both influent and effluent wastewater. The method provided mean recoveries higher than 75%, with the exception of 2,7/2,8-dichlorodibenzo-p-dioxin, dipyrone and permethrin which exhibited recoveries lower than 22%. The overall variability of the method was below 14%. The method detection limit (LOD) was between 1 and 100 ng l(-1) and precision, which was calculated as relative standard deviation (RSD), ranged from 1.8% to 11.2%. The application of the proposed method has allowed the identification of all the target compounds at mean concentrations which ranged from 0.12 to 134 microg l(-1) in the influent and from 0.09 to 18.0 microg l(-1) in the effluent. The removal efficiencies of the STP for these compounds varied from 20% (carbamazepine) to 99% (acetaminophen), but in all cases resulted insufficient in order to avoid their presence in treated water and subsequently in the environment.

Toxicity evaluation with Vibrio fischeri test of organic chemicals used in aquaculture.

The evaluation of acute toxicity by Vibrio fischeri test for different organic chemicals (antibiotics, pesticides, therapeutants, herbicides) commonly applied in aquaculture and a degradation product of surfactants, 4-nonylphenol, is presented in this work. Simazine, atrazine, emamectin benzoate and leucomalachite green have no toxic effects on V. fischeri at the concentration tested (up to 6mgl(-1)) which correspond to the maximum water solubility. Ciprofloxacin, terbutryn and deltamethrin, caused inhibition effects of 28%, 22% and 30% at concentrations up to 5mgl(-1). Toxic effects were not observed in the case of flumequine and oxolinic acid at the maximum concentration tested (0.189mgl(-1)). According to the toxicity categories established in the EU legislation, ciprofloxacin, terbutryn and deltamethrin could be considered non-harmful for V. fischeri. Malachite green and 4-nonylphenol are "very toxic to aquatic organisms" (EC(50,30min)=0.031mgl(-1) and 0.48mgl(-1), respectively). Carbaryl is "toxic to aquatic organisms" (2.4mgl(-1)). and glyphosate is harmful to V. fischeri (EC(50,30min)=44.2mgl(-1)). The matrix effect was evaluated comparing the toxicity measurements of the target compounds solubilized in seawater and distilled water. Malachite green, 4-nonylphenol and glyphosate, showed higher toxicity in distilled water than in seawater. Carbaryl was more toxic in seawater. All the compounds tested in seawater were not harmful at concentrations of ngl(-1) (10 and 50). However, 4-nonlylphenol and malachite green may act as toxic compounds in the environment at a low ppb level, since both may be detected in water at this concentration level.

Identification of non-intentionally added substances in food packaging nano films by gas and liquid chromatography coupled to orbitrap mass spectrometry.

The control of chemical migration from new functionalized food contact materials (FCMs) is a challenge for meeting food safety requirements. The non-intentionally added substances (NIAS) constitute a group of chemicals that are not applied, but may be introduced or formed during the production process of FCMs. This study describes a multi-analytical approach for the evaluation of unknown substances that migrate from FCMs. A case study is presented using a developed polymer consisting of a monolayer film with polylactic acid (PLA), polylimonene (PL) and zinc oxide nanoparticles (ZnO NPs). This approach incorporates the platforms of ICP-MS (inductively coupled plasma mass spectrometry), to determine whether there is transference of ZnO NPs used as antimicrobial agent and, the systems GC-MS and LC-MS (gas / liquid chromatography coupled to a quadrupole orbitrap mass spectrometer) for the characterization of the chemical structure of NIAS using the molecular mass and specific features of mass fragmentation. The screening of unknown compounds comprised retrospective analysis and data processing using both, a mass spectral library and databases, for GC and LC data, respectively. This approach has provided the tentative identification and quantification of seven NIAS, 3 by GC (Tripropylene glycol diacrylate, 10-Heneicosene and α-Tocopherol acetate) and 4 by LC (N,N-Diethyldodecanamide, N-[(9Z)-9-Octadecen-1-yl]acetamide, 1-Palmitoylglycerol and Glycerol stearate). This migration study was carried out according to the standard protocols established by EU regulation for FCMs.

Shifting the paradigm in gas chromatography mass spectrometry pesticide analysis using high resolution accurate mass spectrometry.

In the last 10 years, the majority of the pesticide food control laboratories moved from GC-MS to GC-MS/MS as the preferred analytical technique to address GC amenable compounds. The main reason for this change was the negative impact on the single stage GC-MS analysis caused by the interference from coeluting matrix compounds. The new development of gas chromatography coupled to high resolution accurate mass spectrometry (GC-HRAMS) provides opportunities to overcome such matrix interferences as a result of its much higher selectivity; allowing laboratories to carry out full-scan analysis covering the most exigent analytical performance criteria. The aim of this work is the evaluation of the main analytical performance parameters for the multiresidue screening of pesticide residues by a gas chromatography-Orbitrap™ mass spectrometer in fruits and vegetables. Electron ionization and full-scan high resolution mass spectrometry was selected for this evaluation. Mass resolving power, selectivity, sensitivity, analyte identification and database generation are discussed in light of the analysis of various commodities and a large scope of pesticides. The selected operational conditions provided optimal mass accuracy, within ±1mDa and achieved LOQs of 10µg/kg or lower for practically all the selected pesticides and commodities. Applicability for quantitative residue analysis was verified by the validation of the 210 pesticides in four matrices (tomato, apple, leek and orange). The performance of the GC-EI-full scan Orbitrap HRAMS developed method was confirmed with the analysis of 102 real samples providing good results.

POCIS passive samplers as a monitoring tool for pharmaceutical residues and their transformation products in marine environment.

In the last years, several scientific studies have shown that carbamazepine (CBZ) is one of the most frequently detected pharmaceutical in aquatic environment. However, little data is available on its detection and its transformation products (TPs) in marine water. The use of polar organic chemical integrative sampling (POCIS) passive samplers as a semi-quantitative and qualitative tool for screening of pharmaceuticals and TPs in seawater has been studied. Furthermore, the uptake rates of the target compounds were also determined under laboratory experiments to characterize the levels accumulated in devices. The results confirmed the presence of residues of anticonvulsant CBZ as well as some of its main metabolites, over a 1-year monitoring campaign carried out in French coast on the Mediterranean Sea. The work reports for the first time the presence of two TPs (10,11-dihydro-10,11-trans-dihydroxycarbamazepine (TRANS) and 10-hydroxy-10,11-dihydrocarbamazepine (10OH)) in marine water. The results contribute in assessing the environmental and human health risk of pharmaceuticals on coastal areas.