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INTRODUCTION: Percutaneous endoscopic gastrostomy (PEG) is considered a safe and effective method for nutritional support in patients with malnutrition and swallowing impairment with an estimated survival of over two months. Some indications, such as advanced cognitive decline, contraindicate the technique. MATERIALS AND METHODS: All patients who underwent PEG placement between January 2001 and May 2019 were included. Clinical data, indication, complications, and mortality were retrospectively analyzed. RESULTS: A total of 648 patients (46.5% male, mean age 70±18.5 years) were included. The most common indications for PEG were advanced cognitive decline (31.5%) and cerebrovascular disease (18.8%). The mean follow-up was 12.07 months (IQR 3.27-34.73). 39.5% of patients experienced complications (systemic 17.9%, local 28.5%). The most frequent were bronchoaspiration (9.7%) and rupture/dysfunction (13.9%), respectively. The presence of early complications (HR 1.63 [1.20-2.21]) and age (HR 1.02 [1.01-1.02]) were associated with shorter survival time, while female sex was a protective factor (HR 0.78 [0.66-0.94]). CONCLUSIONS: PEG is not without complications, with 39.5% of patients experiencing them. Patients with advanced dementia, male sex, older age, and systemic complications have lower survival following PEG placement.
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INTRODUCTION: the risk of hepatocellular carcinoma (HCC) after eradication of the hepatitis C virus (HCV) is highly variable in patients with advanced fibrosis (F3). Long-term surveillance for HCC after sustained virological response (SVR) is controversial in these patients. The objective of this study was to describe the post-SVR follow-up in clinical practice in patients with F3 and determine the predictive factors for the development of HCC. PATIENTS AND METHODS: a multicenter, observational and retrospective study was performed, which included HCV-monoinfected patients with F3 fibrosis determined by transient elastography who achieved SVR between 2015 and 2022, with follow-up until May 2023. Clinical-demographic, laboratory, elastography, and ultrasound variables were recorded before and after treatment. A descriptive and inferential analysis, Cox regression analysis and survival analysis were carried out with the R statistical software. RESULTS: two hundred and nineteen patients were included in the study (65.3 % males, median age 57 years), and 175 (79.9 %) received ultrasound screening after SVR for 62 (6-90) months. The prescribing service was the only independent variable related to performing ultrasound surveillance (p = 0.004). Eight patients developed HCC. In multivariate analysis adjusted for sex, age, presence of diabetes and alcohol consumption, a post-SVR FIB-4 ≥ 3.25 was associated with a 12-fold increase in HCC risk. The cumulative probability of HCC was higher in the group of patients with FIB-4 ≥ 3.25 after SVR (p < 0.001). CONCLUSION: post-SVR follow-up of patients with F3 fibrosis is variable in clinical practice. Using the FIB-4 after SVR allows us to identify those patients with a higher risk of HCC who benefit from biannual ultrasound screening.
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Carcinoma Hepatocelular , Cirrose Hepática , Neoplasias Hepáticas , Humanos , Masculino , Feminino , Carcinoma Hepatocelular/diagnóstico por imagem , Carcinoma Hepatocelular/etiologia , Pessoa de Meia-Idade , Neoplasias Hepáticas/diagnóstico por imagem , Neoplasias Hepáticas/etiologia , Estudos Retrospectivos , Cirrose Hepática/diagnóstico por imagem , Idoso , Hepatite C Crônica/complicações , Resposta Viral Sustentada , Adulto , Fatores de Risco , Antivirais/uso terapêutico , Técnicas de Imagem por Elasticidade , Ultrassonografia , SeguimentosRESUMO
We present the case of a 37-year-old Caucasian woman, with no history of interest, who came to the emergency room for an occlusive condition of 24 hours' evolution. The patient reported a weight loss of 12 kg in the last month, as well as the appearance of a lump in the left breast in the last week. A chest-abdominal CT scan revealed multiple solid-appearing nodules in the left breast, a metastatic liver lesion, and a tumor-like mass in the right iliac fossa measuring 90x60 mm. A biopsy of the breast lesion revealed a diffuse architectural pattern with destruction of the parenchyma and irregular medium-large cellularity with intense and diffuse expression of CD20, CD10 and Bcl6 and a proliferative index of practically 100%, consistent with lymphoma. Burkitt stage IV. Intestinal obstruction constitutes about 15% of hospital admissions for abdominal pain, representing a significant cause of hospital mortality. Although the most common causes of small bowel obstruction are benign (adhesions, hernias), intraluminal lesions such as inflammatory bowel disease or neoplasms are well-established causes associated with this clinical picture. Lymphomas constitute 25% of cases of intestinal obstruction of neoplastic origin; among them, Burkitt lymphoma is a rare type of B-cell lymphoma characterized by rapid and aggressive cell growth, the most common initial involvement of which is located at the abdominal and extra-nodal level.
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Linfoma de Burkitt , Obstrução Intestinal , Linfoma de Células B , Feminino , Humanos , Adulto , Linfoma de Burkitt/complicações , Linfoma de Burkitt/diagnóstico por imagem , Linfoma de Células B/patologia , Obstrução Intestinal/diagnóstico por imagem , Obstrução Intestinal/etiologia , Dor Abdominal/etiologiaRESUMO
A fast method for the screening and quantification of hexabromocyclododecane (sum of all isomers) by gas chromatography using a triple quadrupole mass spectrometer with atmospheric pressure chemical ionization (GC-APCI-QqQ) is proposed. This novel procedure makes use of the soft atmospheric pressure chemical ionization source, which results in less fragmentation of the analyte than by conventional electron impact (EI) and chemical ionization (CI) sources, favoring the formation of the [M - Br](+) ion and, thus, enhancing sensitivity and selectivity. Detection was based on the consecutive loses of HBr from the [M - Br](+) ion to form the specific [M - H5Br6](+) and [M - H4Br5](+) ions, which were selected as quantitation (Q) and qualification (q) transitions, respectively. Parameters affecting ionization and MS/MS detection were studied. Method performance was also evaluated; calibration curves were found linear from 1 pg/µL to 100 pg/µL for the total HBCD concentration; instrumental detection limit was estimated to be 0.10 pg/µL; repeatability and reproducibility, expressed as relative standard deviation, were better than 7% in both cases. The application to different real samples [polyurethane foam disks (PUFs), food, and marine samples] pointed out a rapid way to identify and allow quantification of this compound together with a number of polybrominated diphenyl ethers (BDE congeners 28, 47, 66, 85, 99, 100, 153, 154, 183, 184, 191, 196, 197, and 209) and two other novel brominated flame retardants [i.e., decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE)] because of their presence in the same fraction when performing the usual sample treatment.
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Retardadores de Chama/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Hidrocarbonetos Bromados/química , Animais , Organismos Aquáticos/química , Decapodiformes , Golfinhos , Poluentes Ambientais/química , Peixes , Humanos , Leite Humano/química , Estrutura Molecular , Espectrometria de Massas em Tandem/métodosRESUMO
The analysis of brominated flame retardants (BFRs) commonly relies on the use of gas chromatography coupled to mass spectrometry (GC-MS) operating in electron ionization (EI) and electron capture negative ionization (ECNI) modes using quadrupole, triple quadrupole, ion trap, and magnetic sector analyzers. However, these brominated contaminants are examples of compounds for which a soft and robust ionization technique might be favorable since they show high fragmentation in EI and low specificity in ECNI. In addition, the low limits of quantification (0.01 ng/g) required by European Commission Recommendation 2014/118/EU on the monitoring of traces of BFRs in food put stress on the use of highly sensitive techniques/methods. In this work, a new approach for the extremely sensitive determination of BFRs taking profit of the potential of atmospheric pressure chemical ionization (APCI) combined with GC and triple quadrupole (QqQ) mass analyzer is proposed. The objective was to explore the potential of this approach for the BFRs determination in samples at pg/g levels, taking marine samples and a cream sample as a model. Ionization and fragmentation behavior of 14 PBDEs (congeners 28, 47, 66, 85, 99, 100, 153, 154, 183, 184, 191, 196, 197, and 209) and two novel BFRs, decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), in the GC-APCI-MS system has been investigated. The formation of highly abundant (quasi) molecular ion was the main advantage observed in relation to EI. Thus, a notable improvement in sensitivity and specificity was observed when using it as precursor ion in tandem MS. The improved detectability (LODs < 10 fg) achieved when using APCI compared to EI has been demonstrated, which is especially relevant for highly brominated congeners. Analysis of samples from an intercomparison exercise and samples from the marine field showed the potential of this approach for the reliable identification and quantification at very low concentration levels.
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Bromobenzenos/análise , Monitoramento Ambiental/métodos , Retardadores de Chama/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Éteres Difenil Halogenados/análise , Animais , Monitoramento Ambiental/instrumentação , Desenho de Equipamento , Peixes/metabolismo , Cromatografia Gasosa-Espectrometria de Massas/instrumentação , Limite de Detecção , Reprodutibilidade dos Testes , Espectrometria de Massas em Tandem/instrumentação , Espectrometria de Massas em Tandem/métodosRESUMO
The potential of three capillary columns based on ß-cyclodextrin (i.e., Chirasil-Dex, BGB-172, and BGB-176SE) has been studied for the simultaneous enantiomeric separation of polychlorinated biphenyls (PCBs) and methylsulfonyl metabolites of PCBs (MeSO(2)-PCBs) employing a heart-cut multidimensional gas chromatographic system (heart-cut MDGC). Among the columns studied, the BGB-176SE capillary column provided the best results, allowing the simultaneous enantioselective resolution of six MeSO(2)-PCBs and six chiral PCBs; the Chirasil-Dex column did not resolve any of the studied MeSO(2)-PCBs; and a poor resolution was obtained for three MeSO(2)-PCBs when the BGB-172 column was employed. The developed method was successfully applied to two fish oil and one cow liver samples commercially available, which showed different enantioselective pattern. PCBs 91 and 176 presented a clear enrichment of the second eluted atropisomer in codfish oil, whereas in fish oil sample, slight enrichment of the first eluted atropisomer of CB45 and the second eluted atropisomer of CB136 were observed.
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Cromatografia Gasosa/métodos , Dimetil Sulfóxido/metabolismo , Óleos de Peixe/química , Fígado/química , Bifenilos Policlorados/química , Bifenilos Policlorados/isolamento & purificação , Sulfonas/metabolismo , Animais , Bovinos , Óleos de Peixe/metabolismo , Fígado/metabolismo , Bifenilos Policlorados/metabolismo , Estereoisomerismo , Temperatura , beta-Ciclodextrinas/químicaRESUMO
A comprehensive study on packaging used in commercially available milk products from Spanish markets has been presented. Concentrations of four phthalates, seven parabens and BPA were determined in forty-two milk products. Eleven brands and five types of packaging (metallic aluminium bag, carton, high-density polyethylene, metal pail and polyethylene terephthalate) were included in the study. BPA showed the lowest concentrations (8.3 pg/g f.w.), far below those of phthalates (6431 pg/g f.w.) and parabens (6234 pg/g f.w.). Metallic aluminium bags were the least migrating packaging (considering plasticisers and monomers) followed by HDPE bottles, in the case of phthalates. Parabens showed their highest concentrations for fresh-milk samples. Levels found were far below the specific migration limits established by the EU and the cumulative hazard index was lower than 1, indicating that adverse health effects were not expected. In general, the results found in Spanish samples were lower than those reported in other countries.
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Leite/química , Plastificantes/análise , Conservantes Farmacêuticos/análise , Animais , Compostos Benzidrílicos/análise , Humanos , Limite de Detecção , Parabenos/análise , Fenóis/análise , Ácidos Ftálicos/análise , EspanhaRESUMO
This paper reports the development of an LC-ESI-MS2 method for the sensitive determination of hydroxylated polychlorinated biphenyls (OH-PCBs) in human serum samples. Congener-specific separation was achieved by using a polar-embedded stationary phase, previously optimized for the working group, which provided better separation of isobaric compounds than the common octadecylsilane phases. MS fragmentation patterns and energies showed differences among OH-PCB congeners, mainly depending on the position of OH-group and the number of chlorine atoms in the molecule, although the most intense transitions were always those corresponding to the neutral loss of an HCl group from the quasi-molecular ion cluster. The method allowed the determination of OH-PCBs with good linearity (dynamic linear range of four orders of magnitude with R2 higher than 0.995) and precision (relative standard deviations of absolute areas lower than 10%), and with better sensitivity than other similar methods previously described in the literature. Matrix effect has been evaluated and reduced to less than 10% by the addition of isotopically labeled standards and a 10-fold dilution of the final sample extract. The low iLODs provided by the developed method (from 1.2 to 5.4 fg µL-1 for all the OH-PCBs studied, except 4'-OHCB108, whose iLOD was 61 fg µL-1) allows dilution without losses of detected peaks. Finally, the applicability of the method has been demonstrated by analyzing human serum samples belonging to an interlaboratory exercise.
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Cromatografia Líquida/métodos , Cromatografia de Fase Reversa/métodos , Bifenilos Policlorados/análise , Espectrometria de Massas em Tandem/métodos , Humanos , Hidroxilação , Bifenilos Policlorados/sangue , Bifenilos Policlorados/química , Espectrometria de Massas por Ionização por ElectrosprayRESUMO
This study provides information on the current status of contamination by organochlorines (DDTs, PCBs, PCDDs and PCDFs) in the declining red kite (Milvus milvus L.) population breeding in the Doñana National Park (DNP), south-western Spain. Analyses were performed in addled eggs collected between 1999 and 2001. DDE concentrations ranged from 0.1 to 33.5 microg/g ww, representing more than 86% of the total DDTs. Of the samples studied, 50% showed DDE levels above those associated with reproductive impairment in other raptor species. Concentrations of ortho PCBs (average 36.8 microg/g ww+/-37.7) in 50% of the eggs were much higher than levels reported to cause reduced hatching success, embryo mortality, and deformities in birds (>20 microg/g ww). It is remarkable that average ortho PCB and DDE concentrations showed an increase of one order of magnitude compared to previous data for the species during the 80s. Total PCDD/Fs showed levels in the low pg/g range (7.2-42 pg/g ww), having PCDDs and PCDFs similar contributions in most samples. Total mean TEQs were 238 pg/g (ww), being the range 7.02-667 pg/g (ww). Spatial variation within DNP was observed for PCBs, DDTs, as well as for TEQs. Since some eggs exceeded the NOEL (67%) and LOEL (33%) reported for other raptor species, we would expect the red kite to experience detrimental effects to dioxin-like toxicity. Our results suggest that organochlorine contaminants should be regarded as an element of concern in the population under study, in addition to other conservation problems already reported. Further investigations should be undertaken to identify potential sources of these chemicals in DNP, and to find out if organochlorine contamination is present in other predator species in the area, as well as their potential health effects on individuals and/or populations.
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Poluentes Ambientais/análise , Falconiformes , Hidrocarbonetos Clorados/análise , Animais , DDT/análise , Ovos , Bifenilos Policlorados/análise , EspanhaRESUMO
Knowledge about chemical communication in some vertebrates is still relatively limited. Squamates are a glaring example of this, even when recent evidences indicate that scents are involved in social and sexual interactions. In lizards, where our understanding of chemical communication has considerably progressed in the last few years, many questions about chemical interactions remain unanswered. A potential reason for this is the inherent complexity and technical limitations that some methodologies embody when analyzing the compounds used to convey information. We provide here a straightforward procedure to analyze lizard chemical secretions based on gas chromatography coupled to mass spectrometry that uses an internal standard for the semiquantification of compounds. We compare the results of this method with those obtained by the traditional procedure of calculating relative proportions of compounds. For such purpose, we designed two experiments to investigate if these procedures allowed revealing changes in chemical secretions 1) when lizards received previously a vitamin dietary supplementation or 2) when the chemical secretions were exposed to high temperatures. Our results show that the procedure based on relative proportions is useful to describe the overall chemical profile, or changes in it, at population or species levels. On the other hand, the use of the procedure based on semiquantitative determination can be applied when the target of study is the variation in one or more particular compounds of the sample, as it has proved more accurate detecting quantitative variations in the secretions. This method would reveal new aspects produced by, for example, the effects of different physiological and climatic factors that the traditional method does not show.
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Plasticizers and plastic monomers are commonly used in packaging. Most of them act as endocrine disrupters and are susceptible to migrate from the packaging to the food. We evaluated the migration of endocrine disrupting compounds from three different household food containers to four food simulants under different domestic treatments and for different periods of time, with the aim of reproducing real domestic conditions. The results showed that the migration to the simulants increased with the storage time, up to more than 50 times in certain cases. The heating power seemed to increase the migration processes (up to more than 30 times), and reusing containers produced an increase or decrease of the concentrations depending on the container type and the simulant. The concentrations found were lower than other concentrations reported (always less than 4000 pg/mL, down to less than 20 pg/mL), which might be a consequence of the domestic conditions used.
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Disruptores Endócrinos/análise , Contaminação de Alimentos/análise , Embalagem de Alimentos/instrumentação , Plastificantes/análise , Plásticos/análise , Cromatografia Líquida de Alta Pressão , Características da Família , Espectrometria de Massas , Plastificantes/efeitos adversos , Plásticos/efeitos adversosRESUMO
Chemical signaling is a widespread mode of communication among living organisms that is used to establish social organization, territoriality and/or for mate choice. In lizards, femoral and precloacal glands are important sources of chemical signals. These glands protrude chemical secretions used to mark territories and also, to provide valuable information from the bearer to other individuals. Ecologists have studied these chemical secretions for decades in order to increase the knowledge of chemical communication in lizards. Although several studies have focused on the chemical analysis of these secretions, there is a lack of faster, more sensitive and more selective analytical methodologies for their study. In this work a new GC coupled to tandem triple quadrupole MS (GC-QqQ (MS/MS)) methodology is developed and proposed for the target study of 12 relevant compounds often found in lizard secretions (i.e. 1-hexadecanol, palmitic acid, 1-octadecanol, oleic acid, stearic acid, 1-tetracosanol, squalene, cholesta-3,5-diene, α-tocopherol, cholesterol, ergosterol and campesterol). The method baseline-separated the analytes in less than 7min, with instrumental limits of detection ranging from 0.04 to 6.0ng/mL. It was possible to identify differences in the composition of the samples from the lizards analyzed, which depended on the species, the habitat occupied and the diet of the individuals. Moreover, α-tocopherol has been determined for the first time in a lizard species, which was thought to lack its expression in chemical secretions. Globally, the methodology has been proven to be a valuable alternative to other published methods with important improvements in terms of analysis time, sensitivity, and selectivity.
Assuntos
Glândulas Exócrinas/química , Cromatografia Gasosa-Espectrometria de Massas , Lagartos/metabolismo , Feromônios/análise , Animais , Ecossistema , Glândulas Exócrinas/metabolismo , Limite de Detecção , Feromônios/química , Espectrometria de Massas em TandemRESUMO
Identifying the factors that underlie signal divergences remains challenging in studies of animal communication. Regarding the chemical signalling, different compounds can be found in some species but be absent in others. We hypothesized that if the costs that are associated with the expression of some compounds are too high, their presence in the signal may be restricted. However, these compounds may be expressed and be functional when those costs are relaxed. Vitamin E (α-tocopherol), a dietary compound with metabolic relevancy, acts as an honest chemical sexual signal in many lizards but no in others such as the Carpetan Rock lizard (Iberolacerta cyreni). We investigated whether dietary supplementation favours the expression of this vitamin in scents of I. cyreni. We show that dietary constraints can preclude the expression of vitamin E in chemical secretions of wild males because was expressed when it was experimentally provided in the diet. Vitamin E supplementation also heightened the immune response of males and increased the interest of their scent for females, highlighting the vitamin E as a chemical sexual signal in this species. We suggest that diet could decisively act as a driver of intra- and interspecific divergences in the chemical signalling of lizards.
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Comunicação Animal , Expressão Gênica , Atrativos Sexuais/genética , Comportamento Sexual Animal , Animais , Feminino , Lagartos/fisiologia , MasculinoRESUMO
Polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) were measured in a temperate, deep-sea ecosystem, the Avilés submarine Canyon (AC; Cantabrian Sea, Southern Bay of Biscay). There was an increase of contaminant concentration with the trophic level of the organisms, as calculated from stable nitrogen isotope data (δ15N). Such biomagnification was only significant for the pelagic food web and its magnitude was highly dependent on the type of top predators included in the analysis. The trophic magnification factor (TMF) for PCB-153 in the pelagic food web (spanning four trophic levels) was 6.2 or 2.2, depending on whether homeotherm top predators (cetaceans and seabirds) were included or not in the analysis, respectively. Since body size is significantly correlated with δ15N, it can be used as a proxy to estimate trophic magnification, what can potentially lead to a simple and convenient method to calculate the TMF. In spite of their lower biomagnification, deep-sea fishes showed higher concentrations than their shallower counterparts, although those differences were not significant. In summary, the AC fauna exhibits contaminant levels comparable or lower than those reported in other systems.
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The polychlorinated biphenyl (PCB), polychlorinated dibenzo-p-dioxin, and dibenzofuran (PCDD/F) contents of six functional foods enriched with omega-3 were characterized. All the samples analyzed showed concentration levels below the maximal levels established by Regulation EC 1259/201120. PCB concentrations were higher than those of PCDD/Fs; oil supplements were the most contaminated samples [1.8 pg of WHO-TEQ/g of lipid weight (lw)] followed by chicken eggs (1.3 pg of WHO-TEQ/g of lw), cow's milk (0.23 pg of WHO-TEQ/g of lw), biscuits (0.15 pg of WHO-TEQ/g of lw), soy milks (0.11 pg of WHO-TEQ/g of lw), and soy lecithin (0.049 pg of WHO-TEQ/g of lw). The most abundant non-dl-PCBs were PCBs 52 and 101 in cow's milk, soy products, and biscuits, while in chicken eggs and oil supplements, they were PCBs 153 and 138. PCBs 118 and 105 were the most frequent dl-PCBs in all samples. Only oil supplements presented quantifiable concentrations for almost all PCDD/Fs, OCDD and OCDF being the most abundant. The estimated daily intake was 2.7 pg of WHO-TEQ/day for chicken eggs, 0.91 pg of WHO-TEQ/day for cow's milk, 0.45 pg of WHO-TEQ/day for soy milks, and 0.44 pg of WHO-TEQ/day for biscuits. For oil supplements, it was more variable, but always higher.
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Ovos/análise , Ácidos Graxos Ômega-3/análise , Contaminação de Alimentos/análise , Alimento Funcional/análise , Leite/química , Bifenilos Policlorados/análise , Bifenilos Policlorados/metabolismo , Dibenzodioxinas Policloradas/análise , Dibenzodioxinas Policloradas/metabolismo , Animais , Bovinos , Galinhas , Leite/metabolismo , EspanhaRESUMO
The content of 30 polychlorinated biphenyls (PCBs) and the enantiomeric fractions of 10 chiral PCBs were determined in 17 infertile eggs from three different predatory bird species collected in Doñana National Park (DNP, Spain) in the period 1999-2000. The highest PCB concentration was found in eggs from red kites (0.52-110 microg/g on a fresh weight basis, f.w.) followed by buzzard (0.08-13 microg/g f.w.) and booted eagle (0.10-1.5 microg/g f.w.). Seventy-five percent of the red kite eggs had PCB levels above 4.7 microg/g f.w., which is associated in the literature with reproductive failure. This could be related to the fact that red kite populations have decreased by more than 50% in the last five years in DNP. PCBs # 138, 153, and 180 were the most abundant in all cases. This is the first time that atropisomers of 10 chiral PCBs (PCBs # 45, 84, 91, 95, 132, 135, 136, 149, 174, and 176) in predatory bird eggs have been performed. The enantiomeric fractions (EFs) for most PCBs investigated were non-racemic (EF not = 0.5), ranging from 0.05 to 0.95. The results suggested that predatory birds, mainly red kite species, are highly polluted by PCBs, and PCBs # 95, 132, 135, 136, and 174 strongly deviate from the racemic-mixture values.
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Aves/fisiologia , Óvulo/química , Bifenilos Policlorados/análise , Animais , Poluentes Ambientais , Bifenilos Policlorados/química , Comportamento Predatório , Espanha , EstereoisomerismoRESUMO
This paper reports on the optimization, characterization, and applicability of gas chromatography coupled to triple-quadrupole tandem mass spectrometry (GC-QqQ(MS/MS)) for the determination of 14 polybrominated diphenylethers (PBDEs) and 2 emerging brominated flame retardants, 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) and decabromodiphenylethane (DBDPE), in functional food samples. The method showed satisfactory precision and linearity with instrumental limits of detection (iLODs) ranging from 0.12 to 7.1 pg, for tri- to octa-BDEs and BTBPE, and equal to 51 and 20 pg for BDE-209 and DBDPE, respectively. The highest ΣBFR concentrations were found in fish oil supplements (924 pg/g fresh weight, fw), followed by biscuits (90 pg/g fw), vegetable oil supplements (46 pg/g fw), chicken eggs (45 pg/g fw), cow's milk (7.7 pg/g fw), and soy products (1.6 pg/g fw). BDE-47, BDE-99, and DBDPE were the most abundant compounds. Foodstuffs enriched with omega-3 presented concentrations similar to or even lower than those of conventional foods commercialized in Spain since 2000.
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Ácidos Graxos Ômega-3/análise , Retardadores de Chama/análise , Alimentos Fortificados , Alimento Funcional/análise , Éteres Difenil Halogenados/análise , Animais , Bromobenzenos/análise , Cromatografia Gasosa , Ovos/análise , Óleos de Peixe/análise , Análise de Alimentos , Contaminação de Alimentos/análise , Halogenação , Limite de Detecção , Leite/química , Óleos de Plantas/química , Controle de Qualidade , Espanha , Espectrometria de Massas em TandemRESUMO
Sea turtles are susceptible to environmental pollution, since many harmful effects have been reported for different chemicals over the last two decades. In this context, persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) are of particular concern due to their endocrine-disrupting nature. The aims of this study were to provide additional baseline data on PCB and PBDE concentrations in eggs of Dermochelys coriacea; and to investigate whether any of the congeners could compromise reproductive success in this species. A total of 18 nests from different females were studied during the nesting season of 2008 at Reserva Pacuare Beach, in the Caribbean side of Costa Rica. Reproductive parameters (viability, fertility and hatching rates) were calculated for all nests and hatchling morphometrics were successfully measured in 8 of them. Two to three fresh eggs per nest were taken for contaminant study. Different congeners of POPs were purified and identified using gas chromatography (GC) coupled to an ion trap detector (GC-ITD MS/MS), as described below. Mean ± SD concentrations were calculated for POP congeners within each nest and clustering was also evaluated. Correlations were performed searching for potential relationships with reproductive parameters. POP levels were similar to those reported in French-Guiana populations and slightly lower than those associated to Florida populations. Sum of PBDEs showed a negative correlation to the hatching success, suggesting potential harmful effects of these contaminants on the reproduction of leatherbacks.
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Poluentes Ambientais/análise , Éteres Difenil Halogenados/análise , Óvulo/química , Bifenilos Policlorados/análise , Tartarugas , Animais , Costa Rica , Monitoramento Ambiental , Feminino , Cromatografia Gasosa-Espectrometria de Massas , Reprodução , Espectrometria de Massas em TandemRESUMO
A multi-residue analytical method was developed for the determination of a range of flame retardants (FRs), including polybrominated diphenyl ethers (PBDEs), emerging halogenated FRs (EFRs) and organophosphate FRs (PFRs), in food matrices. An ultrasonication and vacuum assisted extraction (UVAE), followed by a multi-stage clean-up procedure, enabled the removal of up to 1g of lipid from 2.5 g of freeze-dried food samples and significantly reduce matrix effects. UVAE achieves a waste factor (WF) of about 10%, while the WFs of classical QuEChERS methods range usually between 50 and 90%. The low WF of UVAE leads to a dramatic improvement in the sensitivity along with saving up to 90% of spiking (internal) standards. Moreover, a two-stage clean-up on Florisil and aminopropyl silica was introduced after UVAE, for an efficient removal of pigments and residual lipids, which led to cleaner extracts than normally achieved by dispersive solid phase extraction (d-SPE). In this way, the extracts could be concentrated to low volumes, e.g. <100 µL and the equivalent matrix concentrations were up to 100g ww/mL. The final analysis of PFRs was performed on GC-EI-MS, while PBDEs and EFRs were measured by GC-ECNI-MS. Validation tests were performed with three food matrices (lean beef, whole chicken egg and salmon filet), obtaining acceptable recoveries (66-135%) with good repeatability (RSD 1-24%, mean 7%). Method LOQs ranged between 0.008 and 0.04 ng/g dw for PBDEs, between 0.08 and 0.20 ng/g dw for EFRs, and between 1.4 and 3.6 ng/g dw for PFRs. The method was further applied to eight types of food samples (including meat, eggs, fish, and seafood) with lipid contents ranging from 0.1 to 22%. Various FRs were detected above MLOQ levels, demonstrating the wide-range applicability of our method. To the best of our knowledge, this is the first method reported for simultaneous analysis of brominated and organophosphate FRs in food matrices.