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1.
Rev Esp Enferm Dig ; 2024 Jan 12.
Artigo em Inglês | MEDLINE | ID: mdl-38214165

RESUMO

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. Our objective is 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, which included HCV-monoinfected patients with F3 fibrosis determined by transient elastography who achieved SVR between 2015 and 2022 and 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: 219 patients were included (65.3% men, median age 57 years). 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.

3.
Rev Esp Enferm Dig ; 114(11): 692, 2022 11.
Artigo em Inglês | MEDLINE | ID: mdl-35607925

RESUMO

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.


Assuntos
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/etiologia
4.
Food Chem ; 338: 128031, 2021 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-32950007

RESUMO

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.


Assuntos
Leite/química , Plastificantes/análise , Conservantes Farmacêuticos/análise , Animais , Compostos Benzidrílicos/análise , Humanos , Limite de Detecção , Parabenos/análise , Fenóis/análise , Ácidos Ftálicos/análise , Espanha
5.
J Chromatogr A ; 1626: 461353, 2020 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-32797833

RESUMO

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.


Assuntos
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 Electrospray
6.
Ecol Evol ; 8(4): 2032-2040, 2018 02.
Artigo em Inglês | MEDLINE | ID: mdl-29468022

RESUMO

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.

7.
J Chromatogr A ; 1514: 110-119, 2017 Sep 08.
Artigo em Inglês | MEDLINE | ID: mdl-28756892

RESUMO

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 Tandem
8.
Sci Total Environ ; 605-606: 589-597, 2017 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-28672247

RESUMO

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.

9.
Sci Rep ; 7(1): 6073, 2017 07 20.
Artigo em Inglês | MEDLINE | ID: mdl-28729717

RESUMO

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.


Assuntos
Comunicação Animal , Expressão Gênica , Atrativos Sexuais/genética , Comportamento Sexual Animal , Animais , Feminino , Lagartos/fisiologia , Masculino
10.
J Agric Food Chem ; 65(31): 6692-6700, 2017 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-28735545

RESUMO

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.


Assuntos
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 adversos
11.
J Agric Food Chem ; 65(16): 3396-3405, 2017 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-28391684

RESUMO

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.


Assuntos
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 , Espanha
12.
J Agric Food Chem ; 64(38): 7265-74, 2016 Sep 28.
Artigo em Inglês | MEDLINE | ID: mdl-27600263

RESUMO

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.


Assuntos
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 Tandem
13.
Chemosphere ; 146: 354-61, 2016 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-26735737

RESUMO

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.


Assuntos
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 Tandem
14.
Anal Bioanal Chem ; 408(2): 449-59, 2016 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-26554601

RESUMO

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.


Assuntos
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/métodos
15.
Anal Chim Acta ; 889: 156-65, 2015 Aug 19.
Artigo em Inglês | MEDLINE | ID: mdl-26343438

RESUMO

This paper reports on the optimisation, characterisation, validation and applicability of gas chromatography coupled to triple quadrupole mass spectrometry in its tandem operation mode (GC-QqQ(MS/MS) for the quantification of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs, dioxins) and dioxin-like polychlorinated biphenyls (DL-PCBs) in environmental and food matrices. MS/MS parameters were selected to achieve the high sensitivity and selectivity required for the analysis of this type of compounds and samples. Good repeatability for areas (RSD = 1-10%, for PCDD/Fs and DL-PCBs) and for ion transition ratios (RSD = 0.3-10%, for PCDD/Fs, and 0.2-15%, for DL-PCBs) and low instrumental limits of detection, 0.07-0.75 pg µL(-1) (for dioxins) and 0.05-0.63 pg µL(-1) (for DL-PCBs), were obtained. A comparative study of the congener specific determination using both GC-QqQ(MS/MS) and gas chromatography-high resolution mass spectrometry (GC-HRMS) was also performed by analysing several fortified samples and certified reference materials (CRMs) with low (feed and foodstuffs), median (sewage sludge) and high (fly ash) toxic equivalency (TEQ) concentration levels, i.e. 0.60, 1.83, 72.9 and 3609 pg WHO-TEQ(PCDD/Fs) g(-1). The agreement between the results obtained for the total TEQs (dioxins) on GC-QqQ(MS/MS) and GC-HRMS in all the investigated samples were within the range of ±4%, and that of DL-PCBs at concentration levels of 0.84 pg WHO-TEQs (DL-PCBs) g(-1), in the case of feedstuffs, was 0.11%. Both instrumental methods have similar and comparable linearity, precision and accuracy. The GC-QqQ(MS/MS) sensitivity, lower than that of GC-HRMS, is good enough (iLODs in the down to low pg levels) to detect the normal concentrations of these compounds in food and environmental samples. These results make GC-QqQ(MS/MS) suitable for the quantitative analysis of dioxins and DL-PCBs and a real alternative tool to the reference sector HRMS instruments.


Assuntos
Dioxinas/análise , Furanos/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Bifenilos Policlorados/análise , Espectrometria de Massas em Tandem/métodos , Animais , Benzofuranos/análise , Leite/química , Dibenzodioxinas Policloradas/análogos & derivados , Dibenzodioxinas Policloradas/análise , Polímeros/análise , Esgotos/química
16.
Anal Chem ; 87(19): 9892-9, 2015 Oct 06.
Artigo em Inglês | MEDLINE | ID: mdl-26354040

RESUMO

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.


Assuntos
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/métodos
17.
J Chromatogr A ; 1401: 33-41, 2015 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-25997844

RESUMO

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.


Assuntos
Poluentes Ambientais/análise , Retardadores de Chama/análise , Tecnologia de Alimentos/métodos , Cromatografia Gasosa-Espectrometria de Massas , Extração em Fase Sólida , Animais , Ovos/análise , Peixes , Éteres Difenil Halogenados/análise , Halogenação , Organofosfatos/análise , Alimentos Marinhos/análise , Vácuo
18.
Anal Chim Acta ; 853: 625-636, 2015 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-25467512

RESUMO

Phthalates (PAEs) are ubiquitous toxic chemical compounds. During the last few years, some phthalate metabolites (MPAEs) have been proposed as appropriate biomarkers in human urine samples to determine PAE human intake and exposure. So, it is necessary to have fast, easy, robust and validated analytical methods to determine selected MPAEs in urine human samples. Two different instrumental methods based on gas (GC) and ultra-high performance liquid (UHPLC) chromatography coupled to mass spectrometry (MS) have been optimized, characterized and validated for the simultaneous determination of nine primary and secondary phthalate metabolites in urine samples. Both instrumental methods have similar sensitivity (detection limits ranged from 0.03 to 8.89 pg µL(-1) and from 0.06 to 0.49 pg µL(-1) in GC-MS and UHPLC-MS(2), respectively), precision (repeatability, expressed as relative standard deviation, which was lower than 8.4% in both systems, except for 5OH-MEHP in the case of GC-MS) and accuracy. But some advantages of the UHPLC-MS(2) method, such as more selectivity and lower time in the chromatographic runs (6.8 min vs. 28.5 min), have caused the UHPLC-MS(2) method to be chosen to analyze the twenty one human urine samples from the general Spanish population. Regarding these samples, MEP showed the highest median concentration (68.6 µg L(-1)), followed by MiBP (23.3 µg L(-1)), 5cx-MEPP (22.5 µg L(-1)) and MBP (19.3µgL(-1)). MMP (6.99 µg L(-1)), 5oxo-MEHP (6.15 µg L(-1)), 5OH-MEHP (5.30 µg L(-1)) and MEHP (4.40 µg L(-1)) showed intermediate levels. Finally, the lowest levels were found for MBzP (2.55 µg L(-1)). These data are within the same order of magnitude as those found in other similar populations.


Assuntos
Cromatografia Líquida de Alta Pressão , Cromatografia Gasosa-Espectrometria de Massas , Ácidos Ftálicos/urina , Espectrometria de Massas por Ionização por Electrospray , Adulto , Estudos de Viabilidade , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Ácidos Ftálicos/metabolismo
19.
Sci Total Environ ; 472: 741-5, 2014 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-24333996

RESUMO

Concentrations of 17 brominated flame retardants (BFRs), including two "novel" BFRs (1,2-bis(2,4,6-tribromophenoxy)ethane, BTBPE and decabromodiphenylethane, DBDPE), have been determined to be in 35 commercial honey samples from Brazil, Spain, Portugal, Slovenia and Morocco. The results revealed the presence of low amounts (between

Assuntos
Monitoramento Ambiental , Poluentes Ambientais/análise , Retardadores de Chama/análise , Mel/análise , Brasil , Bromobenzenos/análise , Contaminação de Alimentos/análise , Contaminação de Alimentos/estatística & dados numéricos , Éteres Difenil Halogenados/análise , Portugal , Espanha
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