RESUMO
This study aimed to develop an efficient, sensitive, and reliable analytical method for trace analysis of 17 different pyrethroids and chlorpyrifos in the fatty content of animal products, including beef, chicken, eggs, fish, and milk. The method developed is based on an ultrasound extraction using lyophilized samples, a solid phase extraction cleanup with basic alumina and C18 cartridges in tandem, and analysis by gas chromatography coupled to tandem mass spectrometry in negative chemical ionization mode. Recovery values were in the range of 27-128 % with relative standard deviation always below 25 %, and chiral analysis of recovery data showed predominance of isomers of cis form over trans. Limits of detection (LODs) ranged from 0.002 to 6.43 ng g-1 lipid weight (lw), and limits of quantification (LOQs) ranged between 0.006 and 21.4 ng g-1 lw. The developed methodology was used for the analysis of 25 samples of fatty foods. All samples were positive for at least one of the pesticides, chlorpyrifos, bifenthrin, cyhalothrin, permethrin, cypermethrin, or deltamethrin, with mass fraction levels ranging from 0.03 to 270 ng g-1 lw. Graphical Abstract á .
Assuntos
Clorpirifos/isolamento & purificação , Análise de Alimentos/métodos , Contaminação de Alimentos/análise , Inseticidas/isolamento & purificação , Resíduos de Praguicidas/isolamento & purificação , Piretrinas/isolamento & purificação , Animais , Bovinos , Galinhas/metabolismo , Ovos/análise , Produtos Pesqueiros/análise , Cromatografia Gasosa-Espectrometria de Massas , Leite/química , Carne Vermelha/análise , Extração em Fase Sólida/métodos , Espectrometria de Massas em TandemRESUMO
Four previously unreported metabolism products of sulfaquinoxaline (SQX), a widely used veterinary medicine, were isolated and analyzed using liquid chromatography coupled to high-resolution Orbitrap mass spectrometry. Metabolites were structurally elucidated, and a fragmentation pathway was proposed. The combination of high-resolution MS(2) spectra, linear ion trap MS(2), in-source collision-induced dissociation (CID) fragmentation, and photolysis were used to analyze SQX and its metabolites. All metabolism products identified showed a similar fragmentation pattern to that of the original drug. Differential product ions were produced at m/z 162 and 253 which contain the radical moiety with more 16 Da units than sulfaquinoxaline. This occurs by a hydroxyl attachment to the quinoxaline moiety. With the exception of two low-intensity compounds, all the mass errors were below 5.0 ppm. The distribution of these metabolites in some animal species are also presented and discussed.
Assuntos
Sulfaquinoxalina/química , Animais , Biotransformação , Bovinos , Cromatografia Líquida de Alta Pressão , Radical Hidroxila/química , Hidroxilação , Indicadores e Reagentes , Fígado/química , Espectrometria de Massas , Aves Domésticas , Ovinos , Sulfaquinoxalina/metabolismo , Distribuição TecidualRESUMO
The widespread use and misuse of antibiotics and pesticides has been linked with several risks to the environment and human health. In the present report, the results of the monitoring of 64 pharmaceuticals and 134 pesticides occurrence in an urban river in Southern Brazil are presented and discussed. Sampling campaigns have covered the period 2016-2018. The identification and determination of the analytes were achieved by high-resolution mass spectrometry. The data were analyzed using chemometric tools to obtain spatial-temporal models. Toxicological evaluation was achieved using acute toxicity (zebrafish standardized protocol), and determination of risk quotient. Within the 198 analytes included in the targeted analysis method for surface water, 33 were identified in an urban river during 2 years of monitoring, being 20 pharmaceuticals and 13 pesticides. Using high-resolution mass spectrometry, a suspect screening approach was established in an un-target analysis. The evaluation was carried out using a data bank built from consumption data of drugs and pesticides, in the metropolitan region of Porto Alegre - RS and their respective metabolites. The suspect screening analysis done with a data bank with more than 1450 compounds results in 27 suspect findings. The target analysis results showed a continuous prevalence of non-steroidal anti-inflammatories, analgesics, antipyretics, beta-blockers, corticoids, and antibiotics. Regarding the pesticides, the main classes were fungicides, especially those from triazol and strobilurin classes.
Assuntos
Praguicidas , Poluentes Químicos da Água , Animais , Humanos , Rios/química , Monitoramento Ambiental/métodos , Poluentes Químicos da Água/análise , Peixe-Zebra , Brasil , Praguicidas/análise , Antibacterianos/análise , Preparações FarmacêuticasRESUMO
Analytical methodology for quantification of 15 antiparasitic drugs and their respective metabolites in laying hen eggs was optimized and validated. The method uses acetonitrile as solvent extraction, sodium chloride for salting-out, low-temperature purification and analysis by LC-MS/MS. A total of 348 egg samples were collected in 11 states of Brazil and 50% of the total samples presented antiparasitic residues, which were albendazole, fipronil, fenbendazole, ivermectin, oxibendazole and mebendazole. A total of 12.4% of the samples were considered non-compliant, and residues quantified in these samples were albendazole, fipronil, and mebendazole. Albendazole was always identified as albendazole sulfone. Only one sample presented fipronil and fipronil sulfone; all others exclusively the sulfone metabolite. Fenbendazole was characterized by the presence of both metabolites: sulfone and sulfoxide. Maximum limits adopted are based on the Normative Instruction 51/2019 of the Brazilian Health Regulatory Agency (ANVISA), but albendazole, fipronil, oxibendazole, ivermectin, and mebendazole do not have their maximum residue level established. In addition, metabolites of albendazole, fipronil and fenbendazole in eggs are not considered in this Instruction.
Assuntos
Albendazol , Espectrometria de Massas em Tandem , Albendazol/análise , Animais , Antiparasitários , Brasil , Galinhas/metabolismo , Cromatografia Líquida/métodos , Ovos/análise , Feminino , Fenbendazol , Ivermectina , Mebendazol , Sulfonas , Espectrometria de Massas em Tandem/métodosRESUMO
This study investigates degradation processes of three antimicrobials in water (norfloxacin, ciprofloxacin, and sulfamethoxazole) by photolysis, focusing on the prediction of toxicity endpoints via in silico quantitative structure-activity relationship (QSAR) of their transformation products (TPs). Photolysis experiments were conducted in distilled water with individual solutions at 10 mg L-1 for each compound. Identification of TPs was performed by means of LC-TOF-MS, employing a method based on retention time, exact mass fragmentation pattern, and peak intensity. Ten main compounds were identified for sulfamethoxazole, fifteen for ciprofloxacin, and fifteen for norfloxacin. Out of 40 identified TPs, 6 have not been reported in the literature. Based on new data found in this work, and TPs already reported in the literature, we have proposed degradation pathways for all three antimicrobials, providing reasoning for the identified TPs. QSAR risk assessment was carried out for 74 structures of possible isomers. QSAR predictions showed that all 19 possible structures of sulfamethoxazole TPs are non-mutagenic, whereas 16 are toxicant, 18 carcinogenic, and 14 non-readily biodegradable. For ciprofloxacin, 28 out of the 30 possible structures for the TPs are mutagenic and non-readily biodegradable, and all structures are toxicant and carcinogenic. All 25 possible norfloxacin TPs were predicted mutagenic, toxicant, carcinogenic, and non-readily biodegradable. Results obtained from in silico QSAR models evince the need of performing risk assessment for TPs as well as for the parent antimicrobial. An expert analysis of QSAR predictions using different models and degradation pathways is imperative, for a large variety of structures was found for the TPs.
Assuntos
Anti-Infecciosos , Poluentes Químicos da Água , Anti-Infecciosos/toxicidade , Ciprofloxacina/toxicidade , Mutagênicos/química , Norfloxacino/toxicidade , Fotólise , Sulfametoxazol , Água , Poluentes Químicos da Água/análiseRESUMO
Compiling and reporting data related to the presence of pharmaceuticals and pesticides are crucial means of assessing the risk those chemicals pose to human health and environment. Data sets from different sources were combined using a data fusion approach to produce a spatial and temporal variation of contaminants presents in water from Lake Guaíba (29°55'-30°24' S; 51°01'-51°20' W). Lake Guaíba is a 496 km2 water body situated in the geological depression of Rio Grande do Sul State, Brazil; that is fed by several rivers from the metropolitan area, the 5th largest metro area in Brazil, with approximately 5 million inhabitants. Analytical methodology to quantify pharmaceuticals and pesticides by LC-QTOF-MS and GC-MS/MS was validated for 41 pharmaceutical and 62 pesticides. Furthermore, 27 chemical elements were analyzed by ICP-MS, and physical chemical parameters were determined using established methodologies. All validation parameters were in accordance with the National Institute of Metrology, Standardization, and Industrial Quality. Thirty-five water samples were analyzed from January to August 2019, and 15 pharmaceuticals and 25 pesticides were present in concentrations ranging from 6.00 ng L-1 to 580.00 ng L-1. Twenty-seven elements were analyzed during the same period, and 18 were present in concentrations ranging from 0.2 µg L-1 to 7060 µg L-1. Samples were tagged according to the points and months of collection to identify temporal and spatial patterns. The main findings show that the compounds are distributed throughout the studied area without an apparent regular pattern, suggesting that events in a specific point affect the entire ecosystem. Conversely, temporal variations were well defined, as samples were grouped according to the climatic conditions of the months of collection. Considering the calculated quotient risks, atrazine, cyproconazole, diuron, and simazine showed the highest risk levels for algae; acetaminophen, diclofenac, and ibuprofen showed the highest risk levels for aquatics invertebrates.
Assuntos
Metaloides , Praguicidas , Preparações Farmacêuticas , Poluentes Químicos da Água , Brasil , Ecossistema , Monitoramento Ambiental , Humanos , Lagos , Praguicidas/análise , Rios , Espectrometria de Massas em Tandem , Poluentes Químicos da Água/análiseRESUMO
Acrylamide (AA) is routinely used in laboratories and industries, and its disposal is always a problem; consequently, offering an alternative for their treatment contributes to conducting research in a responsible way. Therefore, in this work, acrylamide solutions were degraded by ultraviolet radiation and hydrogen peroxide (H2O2), and their toxicity was evaluated using a Desmodesmus quadricauda microalgae growth assay. The AA solutions were exposed to different dosages of H2O2 and different exposure times to UV radiation. The degradation was evaluated by liquid chromatography, which allowed the identification of the acrylamide peak and subsequent by-product peaks. A 100% degradation of the 1.5 mg L-1 AA solution with UV/H2O2 (0.034 g L-1) was achieved in just 10 min. The by-products formed did not inhibit the growth of D. quadricauda microalgae. The number of D. quadricauda individuals that grew in acrylamide solutions exposed to 20 and 30 min of UV radiation, with 0.034 g L-1 of H2O2, was very similar to the number of individuals that grew in the control solution. Thus, the treatment proposed in this work using H2O2 combined with ultraviolet radiation degraded acrylamide into by-products with reduced toxicity.
Assuntos
Microalgas , Poluentes Químicos da Água , Acrilamida/toxicidade , Humanos , Peróxido de Hidrogênio , Oxirredução , Fotólise , Raios UltravioletaRESUMO
It is known that antibiotics are widely used in human and veterinary medicine. In some countries the use is controlled, however few restrictions to their use are enforced in many countries. Antibiotics and their metabolites can reach the water bodies through sewage systems, especially in those countries with partial or absent wastewater treatment systems. The overuse and misuse of antibiotics has been linked with the increase of antibiotic resistant bacteria. The relation between the occurrence of antibiotics and resistance genes in surface waters has been widely studied worldwide evincing the great importance of this subject. In this work, a methodology for quantification of 40 antibiotics of 5 different classes, in river water, by SPE-LC-MS/MS was validated. Samples were taken during a two-year period from Dilúvio River, a stream that crosses the city of Porto Alegre (RS - Brazil) and receives in nature domestic effluent. The methodology met the requirements of validation, with Limit of Quantification varying from 20 ng L-1 to 100 ng L-1. A total of 48 samples was analyzed for the presence of antibiotics for two years. From the 40 antibiotics analyzed, 8 of them (Azithromycin, Cephalexin, ciprofloxacin, clindamycin, norfloxacin, sulfadiazine, sulfamethoxazole and trimethoprim) were present in all sampling points in the range of Assuntos
Rios
, Poluentes Químicos da Água/análise
, Antibacterianos/farmacologia
, Brasil
, Cromatografia Líquida
, Cidades
, Resistência Microbiana a Medicamentos/efeitos dos fármacos
, Humanos
, Espectrometria de Massas em Tandem
, Águas Residuárias
RESUMO
This paper describes the development of an analytical methodology to determine eight beta-blockers in waste waters using molecularly imprinted polymers (MIPs) as extraction and pre-concentration material, followed by liquid chromatography-quadrupole-linear ion trap mass spectrometry (LC-QqLIT MS). The advantages offered by MIPs, in terms of selectivity and specificity, were compared with the most commonly polymeric materials used (the lipophilic-hydrophilic balanced Oasis HLB cartridges). Even though recoveries achieved with both sorbents were similar, ranging from 50 to 110% for sewage treatment plant (STP) effluent and 40-110 for STP influent, respectively, MIPs provided lower method detection limits than Oasis HLB, due to their specificity for target analytes and closely related analogues. Method detection limits (MDL) achieved using MIPs ranged from 0.2 to 6.4 ng/L for STP effluent and from 0.4 to 6.5 ng/L for STP influent. To highlight the advantages of MIPs against conventional polymeric cartridges, a detailed matrix effects study as well as cross reactivity tests were performed. For the latter purpose, the extraction efficiency of some pharmaceuticals and pesticides belonging to different therapeutic classes was assessed. LC-QqLIT MS, used for quantification and confirmation, proved to be a powerful analytical tool, as instrumental detection limits (IDL) achieved ranged from 0.2 to 2.7 pg injected (in multiple reaction monitoring mode (MRM)). In addition the inclusion of high sensitive MS/MS scans for each compound when working in Information Dependent Acquisition mode (IDA) provided extra confirmation for unequivocal identification of target compounds in complex environmental matrices.
Assuntos
Antagonistas Adrenérgicos beta/análise , Cromatografia Líquida/métodos , Espectrometria de Massas/métodos , Extração em Fase Sólida/métodos , Poluentes Químicos da Água/análise , Antagonistas Adrenérgicos beta/química , Antagonistas Adrenérgicos beta/isolamento & purificação , Polímeros/química , Reprodutibilidade dos Testes , Poluentes Químicos da Água/química , Poluentes Químicos da Água/isolamento & purificaçãoRESUMO
An increasing concern about food safety has been observed over the years. The presence of drugs residues in food is one of the major subjects of research in food safety. Feedingstuffs can be responsible for carryover into the food chain of residues of several drugs. This paper describes the development, validation and application of a fast and simple method for analysis of 24 antibiotic residues in feedingstuffs for cattle, pigs and poultry. Analytes include compounds from different antimicrobials classes, such as sulfonamides (sulfadiazine, sulfamethazine, sulfamethoxazole, sulfaquinoxaline, sulfachlorpyridazine, sulfadoxine, sulfadimethoxine, sulfizoxazole, sulfamerazine and sulfathiazole), fluoroquinolones (ciprofloxacin, enrofloxacin, norfloxacin, danofloxacin, difloxacin, sarafloxacin, flumequine, nalidixic acid and oxolinic acid), tetracyclines (tetracycline, doxycycline, oxytetracycline and chlortetracycline) and trimethoprim. Samples were extracted with methanol:water (70:30) 0.1% formic acid, followed by clean-up steps using centrifugation, low-temperature purification (LTP) and ultracentrifugation. Instrumental analysis was performed using liquid chromatography coupled to tandem mass spectrometry. Chromatographic separation was achieved using a C18 column and a mobile phase composed of acetonitrile and water, both with 0.1% formic acid. Validation parameters such as limit of detection (LOD), limit of quantification (LOQ), selectivity, linearity, accuracy, precision, decision limit (CCα) and detection capability (CCß) were determined and meet the adopted criteria. LOD and LOQ were set to 30 and 75 µg kg-1, respectively. Inter-day precision were in the range from 4.0 to 11.1%, and linearity provides values of r2 above 0.95 for all analytes. The optimised method was applied to the analysis of more than 1500 real samples within the period 2012-2017. Non-compliant results were discussed and classified in terms of analytes, feed types and target species. Multivariate analysis of the data was performed using principal component analysis.
Assuntos
Ração Animal/análise , Fluoroquinolonas/análise , Resíduos de Praguicidas/análise , Sulfonamidas/análise , Tetraciclinas/análise , Trimetoprima/análise , Animais , Bovinos , Galinhas , Cromatografia Líquida , Monitoramento Ambiental , Contaminação de Alimentos/análise , Espectrometria de Massas por Ionização por Electrospray , Suínos , Espectrometria de Massas em TandemRESUMO
Antibiotics are widely used in human medicine and veterinary production. Residues of these compounds reach the water sources through waste or direct application (e.g. aquaculture). The constant input of the parent drugs and their transformation products into the environment leads these pharmaceuticals to be considered as emerging pollutants. For some molecules, the pathway of degradation and formation in products is less known. To assess the impact of these substances in the environment and in the human health, it is necessary to elucidate the transformation products and their kinetic of degradation to evaluate the possible risks. In the present report, the characterization and the degradation kinetic of two widely used ß-lactams antibiotics - amoxicillin and ampicillin - was evaluated. Surface water samples containing these antibiotics were submitted to photolysis and analyzed by liquid chromatography coupled to mass spectrometry with Orbitrap detection in order to establish the profile of degradation and the formation of transformation products. Results showed that the degradation of amoxicillin and ampicillin is almost complete and reach their maximum at 48â¯h in river water. Moreover, a database containing >65 transformation products of amoxicillin and ampicillin was build and real samples of industrial wastewater were analyzed to investigate the occurrence of amoxicillin, ampicillin and their transformation products.
Assuntos
Amoxicilina/análise , Ampicilina/análise , Fotólise , Poluentes Químicos da Água/análise , Amoxicilina/química , Ampicilina/química , Humanos , Cinética , Modelos Químicos , Poluentes Químicos da Água/químicaRESUMO
Due to their renewable and sustainable nature, biodiesel blends boost studies predicting their stability during storage. Besides chemical degradation, biodiesel is more susceptible to biodegradation due to its raw composition. The aim of this work was to evaluate the deteriogenic potential (growth and degradation) of Pseudallescheria boydii and Meyerozyma guilliermondii in degrading pure diesel (B0), pure biodiesel (B100), and a B10 blend in mineral medium during storage. The biodeterioration susceptibility at different fuel ratios and in BH minimal mineral medium were evaluated. The biomass measurements of P. boydii during 45 days indicated higher biomass production in the B10 blend. The growth curve of M. guilliermondii showed similar growth in B10 and B100. Although there was no significant production of biosurfactant, lipase production was detected in the tributyrin agar medium of both microorganisms. The main compounds identified in the aqueous phase by GC-MS were alcohols, esters, acids, sulfur, ketones, and phenols. The results showed that P. boydii grew at the expense of fuels, degrading biodiesel esters, and diesel hydrocarbons. M. guilliermondii grew in B100 and B10; however, degradation was not detected.
Assuntos
Ascomicetos/fisiologia , Biocombustíveis/microbiologia , Gasolina/microbiologia , Biomassa , Brasil , Fatores de TempoRESUMO
Antibiotics are widely used in veterinary medicine mainly for treatment and prevention of diseases. The aminoglycosides are one of the antibiotics classes that have been extensively employed in animal husbandry for the treatment of bacterial infections, but also as growth promotion. The European Union has issued strict Maximum Residue Levels (MRLs) for aminoglycosides in several animal origin products including bovine milk, bovine, swine and poultry muscle. This paper describes a fast and simple analytical method for the determination of ten aminoglycosides (spectinomycin, tobramycin, gentamicin, kanamycin, hygromycin, apramycin, streptomycin, dihydrostreptomycin, amikacin and neomycin) in bovine milk and bovine, swine and poultry muscle. For sample preparation, an extraction method was developed using trichloroacetic acid and clean up with low temperature precipitation and C18 bulk. Liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was used to carry out quantitative analysis and liquid chromatography-quadrupole-time of flight-mass spectrometry (LC-QTOF-MS) was used to screening purposes. Both methods were validated according to the European Union Commission Directive 2002/657/EC. Good performance characteristics were obtained for recovery, precision, calibration curve, specificity, decision limits (CCα) and detection capabilities (CCß) in all matrices evaluated. The detection limit (LOD) and quantification limit (LOQ) were ranging from 5 to 100ngg(-1) and 12.5 to 250ngg(-1), respectively. Good linearity (r)-above 0.99-was achieved in concentrations ranging from 0.0 to 2.0×MRL. Recoveries ranged from 36.8% to 98.0% and the coefficient of variation from 0.9 to 20.2%, noting that all curves have been made into their own matrices in order to minimize the matrix effects. The CCß values obtained in qualitative method were between 25 and 250ngg(-1). The proposed method showed to be simple, easy, and adequate for high-throughput analysis of a large number of samples per day at low cost.
Assuntos
Espectrometria de Massas em Tandem , Aminoglicosídeos , Animais , Antibacterianos , Cromatografia Líquida , Leite , SuínosRESUMO
Silica (350 m(2) g(-1)) was chemically modified with Cp2ZrCl2 and (nBuCp)2ZrCl2 by grafting. Hybrid silica bearing surface indene groups was synthesized by the sol-gel method, followed by metallation with ZrCl(4)2THF. The resulting phases were characterized by Rutherford backscattering spectrometry (RBS), 13C and 29Si magic angle spin nuclear magnetic resonance, X-ray photoelectron spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy. According to RBS measurements, metal content was 0.2- to 0.3-wt% Zr/SiO2 for the grafted systems and 4.5-wt% Zr/SiO2 for the phase prepared by the sol-gel method. The solid phases were evaluated for the adsorption/preconcentration of lindane and heptachlor epoxide from aqueous solution. For comparative reasons, the commercial LC-18 phase was also evaluated. Analyte concentration was monitored by gas chromatography electron capture detection. For the grafted phases, the coordination sphere around the metal center seems not to influence the adsorption/desorption properties of these phases vis-a-vis the studied analytes. In the case of the phases prepared by the sol-gel method, recovery results were comparable to those observed for LC-18. Experiments using ZrO2 and ZrO2/SiO2 phases led to lower recovery results.
RESUMO
Photocatalytic degradation of rosuvastatin, which is a drug that has been used to reduce blood cholesterol levels, was studied in this work employing ZnO as catalyst. The experiments were carried out in a temperature-controlled batch reactor that was irradiated with UV light. Preliminary the effects of the photocatalyst loading, the initial pH and the initial rosuvastatin concentration were evaluated. The experimental results showed that rosuvastatin degradation is primarily a photocatalytic process, with pseudo-first order kinetics. The byproducts that were generated during the oxidative process were identified using nano-ultra performance liquid chromatography tandem mass spectrometry (nano-UPLC-MS/MS) and acute toxicity tests using Daphnia magna were done to evaluate the toxicity of the untreated rosuvastatin solution and the reactor effluent.
Assuntos
Fluorbenzenos/química , Inibidores de Hidroximetilglutaril-CoA Redutases/química , Fotólise , Pirimidinas/química , Sulfonamidas/química , Poluentes Químicos da Água/química , Animais , Daphnia , Fluorbenzenos/toxicidade , Inibidores de Hidroximetilglutaril-CoA Redutases/toxicidade , Cinética , Pirimidinas/toxicidade , Rosuvastatina Cálcica , Sulfonamidas/toxicidade , Testes de Toxicidade Aguda , Raios Ultravioleta , Poluentes Químicos da Água/toxicidadeRESUMO
This study describes the development and validation procedures for scope extension of a method for the determination of ß-lactam antibiotic residues (ampicillin, amoxicillin, penicillin G, penicillin V, oxacillin, cloxacillin, dicloxacillin, nafcillin, ceftiofur, cefquinome, cefoperazone, cephapirine, cefalexin and cephalonium) in bovine milk. Sample preparation was performed by liquid-liquid extraction (LLE) followed by two clean-up steps, including low temperature purification (LTP) and a solid phase dispersion clean-up. Extracts were analysed using a liquid chromatography-electrospray-tandem mass spectrometry system (LC-ESI-MS/MS). Chromatographic separation was performed in a C18 column, using methanol and water (both with 0.1% of formic acid) as mobile phase. Method validation was performed according to the criteria of Commission Decision 2002/657/EC. Main validation parameters such as linearity, limit of detection, decision limit (CCα), detection capability (CCß), accuracy, and repeatability were determined and were shown to be adequate. The method was applied to real samples (more than 250) and two milk samples had levels above maximum residues limits (MRLs) for cloxacillin - CLX and cefapirin - CFAP.
Assuntos
Antibacterianos/isolamento & purificação , Cefalosporinas/isolamento & purificação , Resíduos de Drogas/isolamento & purificação , Leite/química , Penicilinas/isolamento & purificação , Animais , Antibacterianos/química , Cefalosporinas/química , Cromatografia Líquida , Resíduos de Drogas/química , Contaminação de Alimentos/análise , Formiatos , Humanos , Limite de Detecção , Extração Líquido-Líquido , Metanol , Penicilinas/química , Reprodutibilidade dos Testes , Solventes , Espectrometria de Massas por Ionização por Electrospray , ÁguaRESUMO
Sulfonamides are widely used in human and veterinary medicine. The presence of sulfonamides residues in food is an issue of great concern. Throughout the present work, a method for the targeted analysis of 16 sulfonamides and metabolites residue in liver of several species has been developed and validated. Extraction and clean-up has been statistically optimized using central composite design experiments. Two extraction methods have been developed, validated and compared: i) pressurized liquid extraction, in which samples were defatted with hexane and subsequently extracted with acetonitrile and ii) ultrasound-assisted extraction with acetonitrile and further liquid-liquid extraction with hexane. Extracts have been analyzed by liquid chromatography-quadrupole linear ion trap-tandem mass spectrometry. Validation procedure has been based on the Commission Decision 2002/657/EC and included the assessment of parameters such as decision limit (CCα), detection capability (CCß), sensitivity, selectivity, accuracy and precision. Method׳s performance has been satisfactory, with CCα values within the range of 111.2-161.4 µg kg(-1), limits of detection of 10 µg kg(-1) and accuracy values around 100% for all compounds.
Assuntos
Antibacterianos/análise , Contaminação de Alimentos/análise , Rim/química , Fígado/química , Músculos/química , Sulfonamidas/análise , Animais , Galinhas , Cromatografia Líquida de Alta Pressão , Peixes , Inocuidade dos Alimentos , Cavalos , Extração Líquido-Líquido , Pressão , Reprodutibilidade dos Testes , Ovinos , Espectrometria de Massas em Tandem , UltrassomRESUMO
A fast and simple method for residue analysis of the antibiotics classes of macrolides (erythromycin, azithromycin, tylosin, tilmicosin and spiramycin) and lincosamides (lincomycin and clindamycin) was developed and validated for cattle, swine and chicken muscle and for bovine milk. Sample preparation consists in a liquid-liquid extraction (LLE) with acetonitrile, followed by liquid chromatography-electrospray-tandem mass spectrometry analysis (LC-ESI-MS/MS), without the need of any additional clean-up steps. Chromatographic separation was achieved using a C18 column and a mobile phase composed by acidified acetonitrile and water. The method was fully validated according the criteria of the Commission Decision 2002/657/EC. Validation parameters such as limit of detection, limit of quantification, linearity, accuracy, repeatability, specificity, reproducibility, decision limit (CCα) and detection capability (CCß) were evaluated. All calculated values met the established criteria. Reproducibility values, expressed as coefficient of variation, were all lower than 19.1%. Recoveries range from 60% to 107%. Limits of detection were from 5 to 25 µg kg(-1).The present method is able to be applied in routine analysis, with adequate time of analysis, low cost and a simple sample preparation protocol.
Assuntos
Antibacterianos/análise , Lincomicina/análise , Macrolídeos/análise , Leite/química , Músculos/química , Animais , Bovinos , Galinhas , Cromatografia Líquida de Alta Pressão , Contaminação de Alimentos/análise , Extração Líquido-Líquido , Carne/análise , Espectrometria de Massas por Ionização por Electrospray , Suínos , Espectrometria de Massas em Tandem , Drogas Veterinárias/análiseRESUMO
In residue analysis of veterinary drugs in foodstuff, matrix effects are one of the most critical points. This work present a discuss considering approaches used to estimate, minimize and monitoring matrix effects in bioanalytical methods. Qualitative and quantitative methods for estimation of matrix effects such as post-column infusion, slopes ratios analysis, calibration curves (mathematical and statistical analysis) and control chart monitoring are discussed using real data. Matrix effects varying in a wide range depending of the analyte and the sample preparation method: pressurized liquid extraction for liver samples show matrix effects from 15.5 to 59.2% while a ultrasound-assisted extraction provide values from 21.7 to 64.3%. The matrix influence was also evaluated: for sulfamethazine analysis, losses of signal were varying from -37 to -96% for fish and eggs, respectively. Advantages and drawbacks are also discussed considering a workflow for matrix effects assessment proposed and applied to real data from sulfonamides residues analysis.
Assuntos
Antibacterianos/isolamento & purificação , Resíduos de Drogas/isolamento & purificação , Ovos/análise , Fígado/química , Sulfonamidas/isolamento & purificação , Drogas Veterinárias/isolamento & purificação , Animais , Bovinos , Galinhas , Cromatografia Líquida/normas , Peixes , Especificidade de Órgãos , Controle de Qualidade , Suínos , Espectrometria de Massas em Tandem/normasRESUMO
Validation is a required process for analytical methods. However, scope extension, i.e. inclusion of more analytes, other matrices and/or minor changes in extraction procedures, can be achieved without a full validation protocol, which requires time and is laborious to the laboratory. This paper presents a simple and rugged protocol for validation in the case of extension of scope. Based on a previously reported method for analysis of sulfonamide residues using LC-MS/MS, inclusion of more analytes, metabolites, matrices and optimisation for the extraction procedure are presented in detail. Initially, the method was applied only to liver samples. In this work, milk, eggs and feed were also added to the scope. Several case-specific validation protocols are proposed for extension of scope.