RESUMO
Lung cancer is the deadliest cancer in developed countries. To reduce its mortality rate, it is important to enhance our capability to detect it at earlier stages by developing early diagnostic methods. In that context, the analysis of exhaled breath is an interesting approach because of the simplicity of the medical act and its non-invasiveness. Thermal desorption comprehensive two-dimensional gas chromatography time of flight mass spectrometry (TD-GCâ¯×â¯GC-TOFMS) has been used to characterize and compare the volatile content of human breath of lung cancer patients and healthy volunteers. On the sampling side, the contaminations induced by the bags membrane and further environmental migration of VOCs during and after the sampling have also been investigated. Over a realistic period of 6â¯h, the concentration of contaminants inside the bag can increase from 2 to 3 folds based on simulated breath samples. On the data processing side, Fisher ratio (FR) and random forest (RF) approaches were applied and compared in regards to their ability to reduce the data dimensionality and to extract the significant information. Both approaches allow to efficiently smooth the background signal and extract significant features (27 for FR and 17 for RF). Principal component analysis (PCA) was used to evaluate the clustering capacity of the different models. For both approaches, a separation along PC-1 was obtained with a variance score around 35%. The combined model provides a partial separation with a PC-1 score of 52%. This proof-of-concept study further confirms the potential of breath analysis for cancer detection but also underlines the importance of quality control over the full analytical procedure, including the processing of the data.
Assuntos
Testes Respiratórios/métodos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Neoplasias Pulmonares/metabolismo , Compostos Orgânicos Voláteis/análise , Idoso , Estudos de Casos e Controles , Feminino , Humanos , Neoplasias Pulmonares/diagnóstico , Masculino , Pessoa de Meia-Idade , Análise de Componente Principal , Manejo de EspécimesRESUMO
We report on the development and validation under ISO 17025 criteria of a multi-residue confirmatory method to identify and quantify 17 widely chemically different pesticides (insecticides: Carbofuran, Methiocarb, Pirimicarb, Dimethoate, Fipronil, Imidacloprid; herbicides: Amidosulfuron, Rimsulfuron, Atrazine, Simazine, Chloroturon, Linuron, Isoxaflutole, Metosulam; fungicides: Diethofencarb) and 2 metabolites (Methiocarb sulfoxide and 2-Hydroxytertbutylazine) in honey. This method is based on an on-column liquid-liquid extraction (OCLLE) using diatomaceous earth as inert solid support and liquid chromatography (LC) coupled to mass spectrometry (MS) operating in tandem mode (MS/MS). Method specificity is ensured by checking retention time and theoretical ratio between two transitions from a single precursor ion. Linearity is demonstrated all along the range of concentration that was investigated, from 0.1 to 20 ng g(-1) raw honey, with correlation coefficients ranging from 0.921 to 0.999, depending on chemicals. Recovery rates obtained on home-made quality control samples are between 71 and 90%, well above the range defined by the EC/657/2002 document, but in the range we had fixed to ensure proper quantification, as levels found in real samples could not be corrected for recovery rates. Reproducibility is found to be between 8 and 27%. Calculated CCalpha and CCbeta (0.0002-0.943 ng g(-1) for CCalpha, and 0.0002-1.232 ng g(-1) for CCbeta) show the good sensitivity attained by this multi-residue analytical method. The robustness of the method has been tested in analyzing more than 100 raw honey samples collected from different areas in Belgium, as well as some wax and bee samples, with a slightly adapted procedure.
Assuntos
Cromatografia Líquida/métodos , Mel/análise , Resíduos de Praguicidas/análise , Espectrometria de Massas em Tandem/métodos , Reprodutibilidade dos Testes , Sensibilidade e EspecificidadeRESUMO
The European Regulations laying down methods of sampling and analysis for the EU official control of levels of polychlorodibenzo-p-dioxins (PCDDs), polychloro-dibenzofurans (PCDFs), dioxin-like (DL) and non dioxin-like (NDL) PCBs in food and feed have been recently amended by EU Regulation Nos. 589/2014 and 709/2014. A major update is the recognition of gas chromatography (GC) triple quadrupole mass spectrometry (GC-QQQMS/MS) as a confirmatory tool for checking compliance with maximum levels (ML). These revisions have been initiated since this technology now exhibits similar performances to GC (magnetic sector) high resolution mass spectrometry (GC-HRMS). In this paper, we show a fully validated method for PCDD/Fs and DL-PCBs analysis in feed material of plant origin (vegetable oil) using GC-QQQMS/MS following the dedicated EU Regulation 709/2014. We show that individual analytical criteria (selectivity, linearity, quant/qual MRM transitions, accuracy around ML of 1.50ng WHO2005TEQ/kg, within-lab reproducibility, robustness, and background subtraction) meet the strict requirements set by the EU Regulation. We also propose a clear interpretation of instrumental limit of quantitation (iLOQ) as a 'performance-LOQ', defined in a specific way for GC-QQQMS/MS, and method limit of quantitation (mLOQ) as 'real-LOQ' that is used to report bound results. Eventually, the evaluation of measurement uncertainty, following a top-down approach and data produced with our method, demonstrates similar results than with GC-HRMS, thus offering a reliable alternative to the standard method for vegetable oil.
Assuntos
Dioxinas/análise , Análise de Alimentos/métodos , Óleos de Plantas/química , Bifenilos Policlorados/análise , Dibenzodioxinas Policloradas/análogos & derivados , União Europeia , Cromatografia Gasosa-Espectrometria de Massas/métodos , Espectrometria de Massas , Dibenzodioxinas Policloradas/análise , Reprodutibilidade dos TestesRESUMO
A fast clean-up procedure for the low level analysis of polychlorinated dibenzo-p-dioxins. polychlorinated dibenzofurans and coplanar polychlorinated biphenyls in highly fatty biological matrices using high capacity disposable multi-layer silica columns is presented. Results were compared with gel permeation chromatography for removal of lipids. Analytical criteria such as recovery rates, repeatability, reproducibility and robustness are evaluated through a broad range of biological matrices and reference materials analysis. The final proposed procedure for the complete analysis, including pressurized liquid extraction, Power-Prep system clean-up and GC-high-resolution MS analysis requires only 48 h, and allows the simultaneous preparation of up to 10 samples.
Assuntos
Benzofuranos/análise , Gorduras/química , Bifenilos Policlorados/análise , Dibenzodioxinas Policloradas/análogos & derivados , Dibenzodioxinas Policloradas/análise , Cromatografia em Gel , Controle de Qualidade , Padrões de Referência , Reprodutibilidade dos TestesRESUMO
Rapid screening of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans using quadrupole ion storage tandem-in-time mass spectrometry (QISTMS) conjointly with polyclonal antibody immunoassay has been considered. The optimisation of the fragmentation of the parent ion in the trap has been completed. The analysis of fly ashes from a municipal waste incinerator contaminated at different levels has then been realised. Results obtained using QISTMS, HRMS and immunoassay are compared.
Assuntos
Poluentes Atmosféricos/análise , Benzofuranos/análise , Dibenzodioxinas Policloradas/análise , Poluentes do Solo/análise , Cromatografia Gasosa , Dibenzofuranos Policlorados , Monitoramento Ambiental/métodos , Imunoensaio , Incineração , Espectrometria de Massas , Dibenzodioxinas Policloradas/análogos & derivados , Eliminação de Resíduos , Sensibilidade e EspecificidadeRESUMO
Congener-specific analyses of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) were performed on twenty-eight non-pooled fast food samples collected in Belgium, Switzerland, Czech Republic, United States of America and Australia. PCDD/F and PCB concentrations for the four investigated types of meals were very low. PCDD/F values ranged from non-detected to 1.40 pg WHO-TEQ/g fat and from 0.79 to 2.08 pg WHO-TEQ/g fat for lower and upper bound, respectively. Major contributors to the PCDD/F TEQ were 1,2,3,4,7,8-HxCDD, 1,2,3,6,7,8-HxCDD, 2,3,7,8-TCDF and 2,3,4,7,8-PeCDF. The relative contribution of PCBs to the total TEQ was 68%. For adults, an average estimated intake was 6.7 pg WHO-TEQ/kg bw/month, including consumption of all types of analyzed meals, representing 9.5% of the PTMI. For child, a value of 14.5 pg WHO-TEQ/kg bw/month was obtained, representing 20.6% of the PTMI.
Assuntos
Benzofuranos/análise , Análise de Alimentos , Bifenilos Policlorados/análise , Dibenzodioxinas Policloradas/análogos & derivados , Dibenzodioxinas Policloradas/análise , Austrália , Dibenzofuranos Policlorados , Ingestão de Alimentos , Europa (Continente) , Humanos , Estados UnidosRESUMO
Congener-specific analyses of 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs) and 4 non-ortho (coplanar) polychlorinated biphenyls (cPCBs) were performed on 35 samples of commercial long-life pasteurised cows' milk issued from eight different brands available in Walloon supermarkets (Belgium). The observed congener profile was characteristic of milk samples issued from industrialised countries with good inter and intra-brand reproducibility's. The PCDDs to PCDFs ratio was equal to 1.8 in concentration. The toxic equivalent (TEQ based on WHO-TEF) value for PCDD/Fs in all analysed milks was 1.09+/-0.30 pg TEQ/g fat (range 0.86-1.59), which is below the recommended EU non-commercialisation threshold value of 3 pg TEQ PCDD/Fs/g of milk fat. The mean TEQ value including cPCBs was 2.23+/-0.55 pg TEQ/g fat. These PCBs actually contributed for 49+/-8.6% of the total TEQ. Among PCDD/Fs and cPCBs, tetrachloro dibenzo-p-dioxin (TCDD), pentachloro dibenzo-p-dioxin (PeCDD), pentachloro dibenzofurans (PeCDFs) and 3,3',4,4',5-pentachloro biphenyl (PCB-126) were the most important contributors to the TEQ. Estimated daily intake (EDI) due to consumption of such milks was 0.34 pg TEQ/kg of body weight/day for PCDD/Fs and 0.69 pg TEQ/kg of body weight/day when cPCBs were included.
Assuntos
Benzofuranos/análise , Leite/química , Bifenilos Policlorados/análise , Dibenzodioxinas Policloradas/análogos & derivados , Dibenzodioxinas Policloradas/análise , Animais , Bélgica , Bovinos , Coleta de Dados , Dibenzofuranos Policlorados , Europa (Continente) , Conservação de Alimentos/métodosRESUMO
Congener-specific analyses of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and non-ortho (coplanar) polychlorinated biphenyls (cPCBs) were performed on 20 non-pooled breast milk samples collected in or close to an industrial area of Wallonia (Belgium). PCDD/F concentrations ranged between 16.0 and 52.1 pg TEQ/g fat, with a mean value of 29.4 pg TEQ/g fat. If coplanar PCBs (77, 126, 169) are included in TEQ calculations, levels ranged between 22.2 and 100.2 pg TEQ/g fat, with a mean value of 40.8 pg TEQ/g fat. It appears that 2,3,7,8-TCDD, 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and PCB-126 account for more than 90% of the TEQ. Estimated PCDD/F dietary intake is 76 pg TEQ/kg body weight (bw)/day. This value is almost 20 times higher than the World Health Organization tolerable daily intake. A value of 103 pg TEQ/kg bw/day represents the intake of PCDDs, PCDFs and cPCBs (no mono-ortho PCBs included).
Assuntos
Benzofuranos/análise , Poluentes Ambientais/análise , Bem-Estar do Lactente , Leite Humano/química , Bifenilos Policlorados/análise , Dibenzodioxinas Policloradas/análogos & derivados , Dibenzodioxinas Policloradas/análise , Poluentes do Solo/análise , Adulto , Bélgica , Dibenzofuranos Policlorados , Feminino , Humanos , Recém-Nascido , Gravidez , Valores de Referência , Organização Mundial da SaúdeRESUMO
Congener-specific analyses of 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs) and 4 non-ortho (coplanar) polychlorinated biphenyls (cPCBs) were performed on 197 foodstuffs samples of animal origin from Belgium during years 2000 and 2001. All investigated matrices (except horse) present background levels lower than the Belgian non-commercialization value of 5 pg TEQ/g fat. Pork was the meat containing the lowest concentration of both PCDD/Fs and cPCBs. The mean background concentration of 2,3,7,8-TCDD toxicity equivalent in milk was 1.1 pg/g of fat, with a congener distribution typical of non-contaminated milk. The relative contribution of 2,3,7,8-TCDD, 2,3,7,8-TCDF, 1,2,3,7,8-PeCDD and 2,3,4,7,8-PeCDF to the PCDD/Fs TEQ was 85+/-7.9% for all investigated matrices. The cPCBs contribution to the total TEQ was 47+/-19.0% for products of terrestrial species and 69+/-20.0% for aquatic species. Once the contribution of cPCBs was added to the TEQ, few foodstuffs such as horse, sheep, beef, eggs and cheese presented levels above the future European guidelines that currently only include PCDD/Fs but will be re-evaluated later in order to include 'dioxin-like' PCBs. Based on levels measured in the samples, the estimation of the dietary intake was 65.3 pg WHO-TEQ/day for PCDD/Fs only (1.00 pg WHO-TEQ/kg bw/day, for a 65 kg person) and 132.9 pg WHO-TEQ/day if cPCBs were included (2.04 pg WHO-TEQ/kg bw/day, for a 65 kg person). Meat (mainly beef), dairy products, and fish each account for roughly one third of the intake.
Assuntos
Benzofuranos/análise , Poluentes Ambientais/análise , Contaminação de Alimentos , Bifenilos Policlorados/análise , Dibenzodioxinas Policloradas/análogos & derivados , Dibenzodioxinas Policloradas/análise , Poluentes do Solo/análise , Bélgica , Dibenzofuranos Policlorados , Dieta , Ovos , Guias como Assunto , Humanos , Carne , Saúde Pública , Medição de Risco , Alimentos MarinhosRESUMO
Dioxins are harmful persistent organic pollutants (POPs) to which humans are exposed mostly via the consumption of animal products. They can enter the food chain at any stage, including crop fertilization. Fertilizers belong to several categories: synthetic chemicals providing the essential elements (mostly N, P and K) that are required by the crops but also organic fertilizers or amendments, liming materials, etc. Ninety-seven samples of fertilizers were taken in Belgium during the year 2011 and analyzed after a soft extraction procedure for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (DL-PCBs) using GC-IDHRMS. Only small qualitative differences could be observed between the main fertilizer categories since the PCDD:PCDF:DL-PCB average ratio obtained with the results expressed in TEQ was often close to 30:30:40 (typically for sewage sludge) or 40:30:30 (typically for compost). The median dioxin levels determined were generally lower than recorded previously and were the highest for sewage sludge and compost (5.6 and 5.5 ng TEQ/kg dry weight (dw), respectively). The levels in other fertilizers were lower including manure for which the median value was only 0.2 ng TEQ/kg dw. Several fertilization scenarios relying on the use of those fertilizers were assessed taking into consideration the application conditions prevailing in Belgium. From this assessment it could be concluded that the contribution of fertilizers to the overall soil contamination will be low by comparison of other sources of contamination such as atmospheric depositions. At the field scale, intensive use of compost and sewage sludge will increase dramatically the dioxin inputs compared with other fertilization practices but this kind of emission to the soil will still be relatively low compared to the dioxin atmospheric depositions.
Assuntos
Dioxinas/análise , Fertilizantes/análise , Poluentes do Solo/análise , Poluentes Químicos da Água/análise , Bélgica , Benzofuranos/análise , Monitoramento Ambiental , Cromatografia Gasosa-Espectrometria de Massas , Medição de Risco , Esgotos/análise , Solo/químicaRESUMO
Dioxins can enter the food chain at any stage, including crop fertilization. Therefore, we developed a simple method for estimating the introduction of dioxins in the food chain according to various fertilization practices. Using dioxin's contamination data taken from the literature, we estimated that fertilization accounts for approximately 20% of the dioxin inputs on agricultural soils at country scale. For the estimations at the field scale, 6 fertilization scenarios were considered: sludge, compost, digestate, manure, mineral fertilizers, and a common fertilization scenario that corresponds to an average situation in Belgium and combines mineral and organic fertilizers. According to our first estimations, mineral fertilizers, common fertilization practices or manure bring less than 1 ng TEQ/m² while atmospheric deposition or digestate bring between 1 and 3 ng TEQ/m² and sludge or compost bring more than 3 ng TEQ/m². The use of solid fertilizers could potentially increase the dioxin levels in the 30 cm agricultural soil layer by 0 to ~1.5% per year (up to ~9% for the 5 cm thick surface layer). For animals, the increase in dioxin ingestion linked to the fertilization practices is lower than 1% for most scenarios with the exception of the compost scenario. Increases in human dietary intake of dioxin are estimated to be lower than 1% for conventional rearing methods (i.e. grazing animals are reared outdoor while pigs and poultry are reared indoor). Spraying liquid fertilizers on meadows and fodder crops, even if very limited in practice, deserves much more attention because this application method could theoretically lead to higher dioxin's intake by livestock (from 6 to ~300%). Considering an average half-life of dioxins in soils of 13 years, it appears that the risks of accumulation in soils and in the food chain are negligible for the various fertilization scenarios.
Assuntos
Produtos Agrícolas/química , Dioxinas/metabolismo , Exposição Ambiental/análise , Poluentes Ambientais/metabolismo , Fertilizantes , Contaminação de Alimentos/análise , Bélgica , Cadeia Alimentar , Humanos , Medição de RiscoRESUMO
Dioxins, furans and dioxin-like polychlorinated biphenyls (PCBs) were analysed in muscle tissue from yellow phased European eel (Anguilla anguilla) from 38 sites in Belgium. Dioxin concentrations in eel vary considerably between sampling locations, indicating that yellow eel is a good indicator of local pollution levels. Measured levels of dioxin-like PCBs are much higher than those of the dioxins and furans. In the majority of the sites, eel has levels considered to be detrimental for their reproduction. Field levels of dioxin and dioxin-like PCBs are therefore suggested as an additional causal factor contributing to the decline of the European eel. 42% of the sampling sites show especially dioxin-like PCB levels exceeding the European consumption level (with a factor 3 on average). Human consumption of eel, especially in these highly contaminated sites, seems unjustified.
Assuntos
Anguilla/fisiologia , Dioxinas/toxicidade , Bifenilos Policlorados/toxicidade , Reprodução/efeitos dos fármacos , Animais , Bélgica , Dioxinas/análise , Monitoramento Ambiental , Contaminação de Alimentos , Óvulo/química , Bifenilos Policlorados/análiseRESUMO
The World Health Organization recommends assessing human exposure to contaminants on a regular basis. In order to assess the current dietary exposure of the Belgian adult population to PCDD/Fs and dioxin-like PCBs and to update exposure estimates of 2000-2001, a total diet study was designed. The mean dietary intake of PCDD/Fs and dioxin-like PCBs in the Belgian adult population in 2008 was estimated to be 0.72pgTEQkgbw(-1)d(-1) (middle bound concentrations, TEF of 1998) based on occurrence data of 2008 and national food consumption data of 2004. This value is clearly below the Tolerable Weekly Intake (TWI) of 14pgTEQkgbw(-1)week(-1) set by the Scientific Committee on Food of the European Commission and below the provisional tolerable monthly intake of 70pgTEQkgbw(-1)month(-1) set by the Joint FAO/WHO Expert Committee on Food Additives. Considering the cumulative distribution, the intake was less than 1pgTEQkgbw(-1)d(-1) for more than 80% of the population, and less than 2pgTEQkgbw(-1)d(-1) for the entire population. When using the 2005 TEF instead of the 1998 TEF, the mean dietary intake in the Belgian adult population was estimated to be 0.61pgTEQkgbw(-1)d(-1).