RESUMEN
This study aims to characterize a complete volatile organic compound profile of pork neck fat for boar taint prediction. The objectives are to identify specific compounds related to boar taint and to develop a classification model. In addition to the well-known androstenone, skatole and indole, 10 other features were found to be discriminant according to untargeted volatolomic analyses were conducted on 129 samples using HS-SPME-GC×GC-TOFMS. To select the odor-positive samples among the 129 analyzed, the selection was made by combining human nose evaluations with the skatole and androstenone concentrations determined using UHPLC-MS/MS. A comparison of the data of the two populations was performed and a statistical model analysis was built on 70 samples out of the total of 129 samples fully positive or fully negative through these two orthogonal methods for tainted prediction. Then, the model was applied to the 59 remaining samples. Finally, 7 samples were classified as tainted.
Asunto(s)
Carne de Cerdo , Carne Roja , Porcinos , Masculino , Animales , Humanos , Escatol/análisis , Espectrometría de Masas en Tándem , Carne de Cerdo/análisis , Carne Roja/análisis , Odorantes/análisis , Carne/análisisRESUMEN
An analytical method coupling pressurized liquid extraction (PLE), pre-concentration by thermal desorption (ATD) and analysis by GC/MSMS was developed for the quantification of pesticides in air and dust near vineyards crops to evaluate potential exposure of residents living near these crops. PLE was done using acetonitrile and extracts were concentrated under fume hood to 1 mL. 100 µL of the extract was spiked in a Tenax TA tube and internal standards and N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide were added before thermal desorption at 300°C for 30 min. GC/MSMS analysis was done in MRM mode and limits of quantification and limits of detection were determined for each matrix (passive air sample, active air sample and dust). The method was applied in the field and shows good sensitivity and accuracy.
RESUMEN
There is a worldwide concern about the presence of persistent organic pollutants (POPs) in the environment because of their toxicity, bioaccumulation, and resistance to degradation. Various conventional monitoring techniques have been used to assess their presence in diverse environmental compartments. Most currently available methods, however, have limitations with regards to long-term monitoring. In the present work, juvenile Cornu aspersum (O. F. Müller, 1774) snails were tested in field microcosms as biomonitors for two major classes of organic pollutants, namely, polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). The study assessed their deployment in one suburban, one rural, and two industrial sites over an 18-week period and monitored for temporal variations of 16 PAHs and 22 PCBs. Sampling was conducted once every 3 weeks. Targeted pollutants were extracted from the caged snails using the QuEChERS extraction procedure and subsequently analyzed using gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). The results showed that the bioaccumulation of specific pollutants was site dependent; significantly higher levels of PCBs were observed at the industrial sites as compared to the suburban and rural ones. PAHs were bioaccumulated by the snails via ingestion of air and soil whereas PCBs were mainly bioaccumulated via soil contact and ingestion. The findings of this study indicate that C. aspersum is a reliable model organism for the biomonitoring of organic pollutants in air and soil compartments and can be used as part of an integrated environmental assessment.
Asunto(s)
Contaminantes Ambientales , Bifenilos Policlorados , Hidrocarburos Policíclicos Aromáticos , Animales , Bifenilos Policlorados/análisis , Especies Centinela/metabolismo , Monitoreo Biológico , Espectrometría de Masas en Tándem , Hidrocarburos Policíclicos Aromáticos/análisis , Monitoreo del Ambiente/métodos , Cromatografía de Gases y Espectrometría de Masas , Contaminantes Ambientales/análisis , Suelo/química , Caracoles/metabolismoRESUMEN
Neonicotinoids (neonics) are the most widely used insecticides worldwide and are considered to be of low risk to non-target organisms such as vertebrates. Further, they are reported to be rapidly excreted and metabolized, reducing their potential toxicity. Nevertheless, growing evidence of adverse effects of neonics on farmland bird species raise questions about the purported harmless nature of these pesticides. We attempted to search for pesticide residues in species of different trophic levels and at different life stages, by using multiple bird monitoring programs on a Long-Term Socio-Ecological Research (LTSER) platform. Three passerine birds-the blackbird (Turdus merula), cirl bunting (Emberiza cirlus), and common nightingale (Luscinia megarhynchos)-that feed on seeds and invertebrates were monitored during their reproductive period, and the grey partridge (Perdix perdix) that feeds on seeds was monitored during its wintering period. We also monitored chicks of an apex predator-the Montagu's harrier (Circus pygargus)-that preys mostly upon common voles but also upon insects. We found that the birds' blood samples showed presence of residues of five neonics: three banned since 2018 in France-clothianidin, thiacloprid, and thiamethoxam-and two-dinotefuran and nitenpyram-used for veterinary purposes only. While none of these neonics was detected in blackbirds, all were present in grey partridges. Clothianidin was detected in all species, except blackbirds. Concentrations of the three banned neonics were similar or higher than concentrations found in birds monitored elsewhere before the ban. These findings raise questions about the persistence of neonics within the environment and the mode of exposure to wild fauna. Future investigations on the sublethal effects of these neonics on life-history traits of these farmland birds may help in providing a better understanding of the effects of exposure of bird populations to these insecticides, and also to the consequent effect on human health.
Asunto(s)
Insecticidas , Pájaros Cantores , Animales , Humanos , Granjas , Neonicotinoides/toxicidad , Tiazoles , Nitrocompuestos , CodornizRESUMEN
RATIONALE: Multiple Reaction Monitoring (MRM) is a sensitive and selective detection mode for target trace-level analysis. However, it requires the fragmentation of labile bonds which are not present in molecules such as Polycyclic Aromatic Hydrocarbons (PAHs) and their heterocyclic derivatives (PANHs, PASHs). METHODS: We present the application of an alternative tandem mass spectrometry (MS/MS) mode called "pseudo-MRM" for the GCMS/MS analysis of Polycyclic Aromatic Compounds (PACs). This mode is based on the monitoring of transitions with no mass loss between the precursor and the product ion. Pseudo-MRM peak areas were compared with those of classic MRM on three different mass spectrometers: two triple quadrupoles and an ion trap. RESULTS: For all non-polar PACs studied here (PAHs, PANHs and PASHs), the pseudo-MRM transition was always the most intense. The classic MRM transitions exhibited peak areas 2 to 5 times lower. On the contrary, for the functionalized PACs (oxygenated and nitrated PAHs), classic MRM was favored over pseudo-MRM. These observations were confirmed on two triple quadrupoles (QqQs), and the real-world applicability of pseudo-MRM on QqQs was validated by the successful analysis of Diesel PM. However, a comparison with an ion trap showed that pseudo-MRM was never favored on that instrument, which caused fragmentation of non-polar PACs in MS/MS. CONCLUSIONS: The results of this study show an important gain in sensitivity when using pseudo-MRM instead of MRM for non-polar PACs on QqQ instruments. The selectivity of MRM is preserved in pseudo-MRM by applying non-zero collision energies to which only these non-polar PACs are resistant, not the isobaric interferences. No interference issue was observed when analyzing Diesel PM, a complex matrix, with our pseudo-MRM method. Therefore, we advise for a broader use of this MS/MS mode for trace-level determination of non-polar PAHs.
Asunto(s)
Hidrocarburos Policíclicos Aromáticos , Compuestos Policíclicos , Hidrocarburos Policíclicos Aromáticos/análisis , Espectrometría de Masas en Tándem/métodosRESUMEN
A new sensitive and selective analytical methodology to quantify glyphosate (GLY), aminomethylphosphonic acid (AMPA), and glufosinate (GLU) in both soil and earthworms (Allolobophora chlorotica) was developed. The extraction and purification methods were optimized. The samples were extracted with various aqueous solutions (HNO3, H2O, KOH and borate buffer) and derivatized with 9-Fluorenylmethyl chloroformate (FMOCCl). To optimize the extraction step, a method to remove the excess FMOCCl was applied based on liquid-liquid extraction with diethyl ether. The purification of derivatized extracts was carried out using XLB solid phase extraction (SPE) cartridges before internal standard quantification by liquid chromatography coupled to tandem mass spectrometry (LC/MS/MS). The elution step was optimized to obtain the best recoveries possible, which was with acidic methanol (1% formic acid) (67% for GLY, 70% for GLU and 65% for AMPA). The extraction and purification method followed by analysis of the two herbicides and AMPA in soils using LC/MS/MS determined limit of quantification (LOQ) values of 0.030⯵g gâ¯-â¯1 for GLY, 0.025⯵g gâ¯-â¯1 for AMPA and 0.020⯵g gâ¯-â¯1 for GLU . For earthworms, LOQ were 0.23⯵g gâ¯-â¯1 for GLY, 0.20⯵g gâ¯-â¯1 for AMPA and 0.12⯵g gâ¯-â¯1 for GLU. . The developed method was applied to determine these compounds in natural soils and earthworms.
Asunto(s)
Aminobutiratos/análisis , Técnicas de Química Analítica/métodos , Glicina/análogos & derivados , Oligoquetos/química , Organofosfonatos/análisis , Suelo/química , Aminobutiratos/aislamiento & purificación , Animales , Técnicas de Química Analítica/instrumentación , Cromatografía Liquida , Glicina/análisis , Glicina/aislamiento & purificación , Herbicidas/análisis , Herbicidas/aislamiento & purificación , Organofosfonatos/aislamiento & purificación , Extracción en Fase Sólida , Espectrometría de Masas en Tándem , GlifosatoRESUMEN
Medical cannabis is becoming increasingly popular for many different ailments and improvement of general well-being. Particularly CBD-rich extracts are easily available via online pharmacies, health stores or directly from producers. However, almost all of the extracts contain small amounts of THC. Thus, in case of continuous or heavy use of CBD rich cannabis, THC concentrations in hair may rise above accepted legal limits. In our study, we investigated THC, CBN and CBD in hair samples from regular CBD rich cannabis users. The goals were to determine levels of the cannabinoids in hair and to evaluate a possible correlation between regular CBD intake and CBD levels in hair. All participants consumed cannabis extracts from the same producer. It contained CBD at different concentrations and small amounts of THC with a CBD/THC concentration ratio of 30. The self-declared CBD dosage ranged from 4 to 128mg CBD/day, corresponding to a daily THC intake of 0.1 to 4.3mg. After extraction and derivatization, hair samples were analysed using a validated GC/MS-MS method. CBD concentrations ranged from 10 to 325pg/mg of hair, but no significant correlation was observed between CBD concentrations and the daily dose. THC was detected in one sample only at a concentration below our cut-off, whereas CBN was not detected. In this study, we showed that even after repeated consumption of CBD-rich cannabis extracts in medium to high doses, consumers are generally tested negative for THC in hair.
Asunto(s)
Cannabinoides/análisis , Cabello/química , Marihuana Medicinal/administración & dosificación , Administración Sublingual , Adulto , Anciano , Cromatografía de Gases , Relación Dosis-Respuesta a Droga , Femenino , Humanos , Masculino , Persona de Mediana Edad , Espectrometría de Masas en TándemRESUMEN
Gamma-hydroxybutyric acid (GHB) is a short-chain fatty acid used recreationally as a drug of abuse due its strong suppressive effect on the central nervous system. The detection window of GHB in blood and urine is very narrow (t1/2=30min) but can be substantially prolonged using alternative matrices such as hair. We here present a newly developed and limited validated method with a solid phase extraction (SPE) using GC-MS/MS to determine concentrations of GHB in hair samples. The soft extraction technique (water and 90min ultrasonic bath) preserves GHB with a high yield and clean extracts. In addition, endogenous GHB can be detected in hair of non-GHB users. However, little is known about GHB concentrations in hair of abstinent, frequent and chronic GHB users. Therefore, we present data from hair samples of healthy volunteers to evaluate the proposed endogenous GHB ranges, and from GHB-dependent patients to address GHB concentrations in hair with GHB intake. In 20 non-GHB users, a mean endogenous concentration of 1.1±0.6ng/mg hair (range of 0.3-2ng/mg) was found. In GHB-dependent patients, concentrations between 6.3-239.6ng/mg hair were found, with no correlation between concentrations in hair and dose of GHB intake. In summary, we present a new and limited validated method, adequately sensitive for the detection of GHB in hair, as well as first-time measurements of GHB concentrations in dependent patients in order to better understand the relationship between the frequency of use/dose and concentrations observed in hair samples.