RESUMEN
The analysis of pesticide residues and mycotoxins in baby food demands exceptionally low limits of quantitation, necessitating the use of highly sensitive instruments capable of conducting trace analyses. High-resolution instruments typically fail to detect such low levels. However, the latest advancements in liquid time-of-flight technology, when coupled with ion trapping, enable ion enrichment, thereby improving detection levels. This allows for the analysis of these substances at low concentration levels, benefiting from enhanced mass accuracy. Additionally, the use of mass accuracy data helped eliminate matrix interferences, thereby enabling high-confidence identification. We developed a multi-residue method to analyse 219 pesticide residues and 9 mycotoxin residues in baby food matrices. Utilizing a QuEChERS-based extraction method, the samples were then analysed using an LC-ZenoTOF 7600 system with mass window screening acquisition. For pesticides, the limit of quantitation was 0.001-0.003 mg/kg for 81 % of the evaluated compounds, 0.005 mg/kg for 13 %, 0.010 mg/kg for 4 % and 0.020-0.030 for 2 %; good linearities were obtained at these levels. Apparent recoveries were evaluated at 0.003, 0.005, and 0.010 mg/kg. At the lowest recovery level, 93 % of compounds showed recoveries between 70 and 120 %. The rest of the compounds were in the range of 63-129 %, with relative standard deviation values below 20 %. For mycotoxins, the limits of quantitation ranged from 0.0001 to 0.100 mg/kg, with matrix-matched concentrations assessed within this range. Recoveries were evaluated at low concentration range (0.001-0.003 mg/kg) and high range (0.020-0.050) with apparent recoveries values between 92 and 140 %. Finally, a total of 31 commercial baby food samples were analysed using this method. The results indicated that 16 samples contained pesticide residues, while two samples were found to have mycotoxins.
Asunto(s)
Contaminación de Alimentos , Alimentos Infantiles , Micotoxinas , Residuos de Plaguicidas , Micotoxinas/análisis , Residuos de Plaguicidas/análisis , Alimentos Infantiles/análisis , Contaminación de Alimentos/análisis , Espectrometría de Masas/métodos , Humanos , Límite de Detección , LactanteRESUMEN
This manuscript presents a comprehensive review of high-resolution mass spectrometry in the field of food analysis and metabolomics. We have followed the historical evolution of metabolomics, its associated techniques and technologies, and its increasing role in food science and research. The review provides a critical comparison and synthesis of tentative identification guidelines proposed for over 15 years, offering a condensed resource for researchers in the field. We have also examined a wide range of recent metabolomics studies, showcasing various methodologies and highlighting key findings as a testimony of the versatility of the field and the possibilities it offers. In doing so, we have also carefully provided a compilation of the software tools that may be employed in this type of studies. The manuscript also explores the prospects of high-resolution mass spectrometry and metabolomics in food science. By covering the history, guidelines, applications, and tools of metabolomics, this review attempts to become a comprehensive guide for researchers in a rapidly evolving field.
Asunto(s)
Análisis de los Alimentos , Metabolómica , Espectrometría de Masas/métodos , Metabolómica/métodosRESUMEN
Spices such as paprika, curry, turmeric, dry chilli, and black pepper are grown in various geographic locations and widely used by consumers across the world. Pesticides applied during crop production practices could contaminate the produce, affecting the quality and posing a health risk for consumers. The complexity of the spice matrix and the wide range of target pesticides potentially present require special sample extraction and clean-up treatments to overcome matrix interference and ion suppression. In this study, sample extracts from spice matrices (paprika/curry/turmeric/dry chilli/black pepper) were cleaned up by an automated µSPE clean-up method for multi-residue analysis of pesticides using LC-MS/MS. The automated µSPE clean-up method involves pre-filled cartridges containing various sorbent materials suitable for numerous co-extractives and the automated clean-up process was carried out using an autosampler. The regulatory limit for pesticides in spices varies with type, with a low MRL of 0.05 mg kg-1 or higher for 99% of the analytes. At spiking concentrations of 0.05 and 0.1 mg kg-1, good recoveries between 70 and 120% with RSD values below 20% were achieved for more than 98% of the compounds. With automatic clean-up of samples that takes 5 min/sample, 20% increased output per day shows an important advantage achieved compared to manual clean-up.
RESUMEN
A fast and sensitive method was validated for the analysis of pesticide residues in baby food. After an QuEChERS-based extraction, the samples were analysed with a dual-channel liquid chromatography instrument coupled to a triple quadrupole mass spectrometer. The method consisted of two independent injections per sample. In the first injection the sample was analysed with a mobile phase optimal for the positive polarity ionisation (water, methanol, formic acid, and ammonium formate), whereas in the second injection the mobile phase was optimised for the negative polarity ionisation (water, acetonitrile, acetic acid). The total number of pesticides was 264, out of which 238 were analysed with the methanol gradient and 26 with the acetonitrile gradient. The dual-channel instrument allowed for sample multiplexing. Thus, sample throughput was equivalent to that of a single-channel system. The limit of quantitation, determined according to the DG SANTE guidance document, was 0.003 mg/kg for 97% of the evaluated compounds. The validation study was followed by a real sample survey. In 42 samples, 16 positives were found.
Asunto(s)
Residuos de Plaguicidas , Cromatografía Liquida , Alimentos Infantiles/análisis , Residuos de Plaguicidas/análisis , Espectrometría de Masas en TándemRESUMEN
The use of high-resolution mass spectrometry (HRMS) for the simultaneous target and non-target analysis of pesticide residues in food control is a subject that has been studied over the last decade. However, proving its efficacy compared to the more established triple quadrupole mass spectrometers (QQQ-MS2) is challenging. Various HRMS platforms have been evaluated, seemingly showing this approach not to be as effective as QQQ-MS2 for quantitative analysis, especially in routine food testing laboratories. The two main reasons are (i) the lower sensitivity especially in the case of the fragment ions produced and (ii) the lack of familiarity and an understanding of the most appropriate combination of HRMS acquisition modes to use. In fact, the number of different acquisition modes can appear as a puzzle to inexperienced users. This work was therefore focused on obtaining experimental data to gain a better understanding of the extended acquisition capabilities of a new Q-Orbitrap platform. Experimental data were obtained for 244 pesticides and their degradation products in commodities of varying matrix complexity (tomato, onion, avocado, and orange) using various combinations of acquisition modes. The best results for targeted analysis were obtained with a combination of full scan (FS), all-ions fragmentation (AIF) and target MS2 (tMS2) modes, and for non-target analysis using full scan (FS) and data-dependent MS2 (ddMS2) modes. All these acquisition modes (FS, AIF, tMS2, and ddMS2) could be applied simultaneously with cycle times ≤ 1 s. The tMS2 especially, proved to be a very powerful approach to increase sensitivity for MS2 fragments and identification rates. Overall, the results for the various pesticide-commodity combinations were fully satisfactory in terms of limit of quantitation (LOQ) repeatability and identification when considered against the SANTE EU Guideline criteria. In addition, the screening capabilities were evaluated for a non-target survey with the use of spectral libraries, the presence of non-target compounds was detected, thus proving the efficacy of the proposed approach. Another issue often overlooked is the optimization of use of spectral libraries, but in our experiments the compounds present in these libraries were not blindly sought in the screening analyses. To minimize the potential for false positives detects in our study, the extractability of the compounds present in the libraries, was also taken into account. The extractability of compounds using a QuEChERS acetonitrile procedure was estimated based on the physicochemical properties of target compounds. By removing compounds that will not be extracted, reduces the occurrences of false detects, reducing the time required for data processing and thus improving the efficiency of the overall screening workflow.
Asunto(s)
Citrus sinensis , Residuos de Plaguicidas , Plaguicidas , Cromatografía Líquida de Alta Presión , Cromatografía Liquida , Residuos de Plaguicidas/análisis , Plaguicidas/análisis , Espectrometría de Masas en TándemRESUMEN
Dual-channel chromatography was evaluated for pesticide residue analysis in fruits and vegetables and for unknown compounds detection. A dual-channel system was tested coupled to triple quadrupole and high-resolution mass spectrometry. The first part of the investigation was related to the improvement of the sample throughput with a 100 mm column. The dual-channel system provided the same analytical results as the single-channel system, however, with the throughput higher of about 70% (80 injections vs 137 injections in 24 h). Two types of calibration (in-channel and cross-channel) were checked. In the article, also solvent consumption is discussed. Six proficiency test samples were analysed to assess the quality of the results. Nor false positives neither false negatives were found. Calculated z-scores were typically <1. In the second part, a different approach was investigated. The 100 mm column was replaced by a 150 mm column keeping shorter run times than single channel system and 100 mm. The longer column improved the sensitivity and selectivity what was demonstrated in the target pesticide residue analysis. Additionally, the 150 mm column was compared with the 100 mm column in the analysis of unknown natural matrix compounds by high resolution mass spectrometry. The longer column allowed to detect up to 26% unknown compounds more than the shorter column.
Asunto(s)
Cromatografía Liquida/instrumentación , Análisis de los Alimentos/métodos , Espectrometría de Masas , Residuos de Plaguicidas/análisis , Frutas/química , Reproducibilidad de los Resultados , Verduras/químicaRESUMEN
Plastic multilayers are widely used for baby food packaging. However, it is important to consider that migration of food contact materials (FCM) into the baby food can occur. The comprehensive identification of potential migrants, including intentionally added substances (IAS) and non-intentionally added substances (NIAS), is required to assess the safety of these packaging materials. In this study, high resolution accurate mass spectrometry (HRAMS) with a data-independent acquisition method of sequential mass windows enables the detection of substances with corresponding deconvoluted fragment mass spectra. The identification of unexpected migrants present in the food simulants and in real baby food was facilitated by filtering strategies and by an in-house library. This approach has allowed the identification of 42 migrants, including eight NIAS detected for the first time. Two oligomers were quantified by means of reference standard materials at concentration levels above 0.010â¯mg/kg, exceeding the maximum residue levels for baby food.
Asunto(s)
Contaminación de Alimentos/análisis , Embalaje de Alimentos/métodos , Alimentos Infantiles/análisis , Espectrometría de Masas/métodos , Plásticos , Análisis de los Alimentos/métodos , Plásticos/análisisRESUMEN
This manuscript reports a new pesticide residue analysis method employing a microflow-liquid chromatography system coupled to a triple quadrupole mass spectrometer (microflow-LC-ESI-QqQ-MS). This uses an electrospray ionization source with a narrow tip emitter to generate smaller droplets. A validation study was undertaken to establish performance characteristics for this new approach on 90 pesticide residues, including their degradation products, in three commodities (tomato, pepper, and orange). The significant benefits of the microflow-LC-MS/MS-based method were a high sensitivity gain and a notable reduction in matrix effects delivered by a dilution of the sample (up to 30-fold); this is as a result of competition reduction between the matrix compounds and analytes for charge during ionization. Overall robustness and a capability to withstand long analytical runs using the microflow-LC-MS system have been demonstrated (for 100 consecutive injections without any maintenance being required). Quality controls based on the results of internal standards added at the samples' extraction, dilution, and injection steps were also satisfactory. The LOQ values were mostly 5 µg kg(-1) for almost all pesticide residues. Other benefits were a substantial reduction in solvent usage and waste disposal as well as a decrease in the run-time. The method was successfully applied in the routine analysis of 50 fruit and vegetable samples labeled as organically produced.
Asunto(s)
Cromatografía Liquida/métodos , Residuos de Plaguicidas/análisis , Extracción en Fase Sólida/métodos , Solventes/química , Espectrometría de Masa por Ionización de Electrospray/métodos , Capsicum/química , Citrus sinensis/química , Solanum lycopersicum/química , Sensibilidad y EspecificidadRESUMEN
Drip irrigation systems using reclaimed water often present clogging events of biological origin. Microbial communities in biofilms from microirrigation systems of an experimental greenhouse in Almería, SE Spain, which used two different qualities of water (treated wastewater and reclaimed water), were analyzed by denaturing gradient gel electrophoresis and subsequent sequencing of amplified 16S rRNA gene bands. The most remarkable feature of all biofilms was that regardless of water origin, sequences belonging to Firmicutes were prevalent (53.5 % of total mean band intensity) and that almost all sequences recovered had some similarity (between 80.2 and 97 %) to thermophilic microorganisms. Mainly, sequences were closely related to potentially spore-forming organisms, suggesting that microbial communities able to grow at high temperatures were selected from the microbiota present in the incoming water. These pioneer results may contribute to improve management strategies to minimize the problems associated to biofouling in irrigation systems.
Asunto(s)
Riego Agrícola , Bacterias/clasificación , Fenómenos Fisiológicos Bacterianos , Biodiversidad , Biopelículas , Microbiología del Agua , Bacterias/genética , Datos de Secuencia Molecular , Prevalencia , ARN Ribosómico 16S/genética , España , Aguas Residuales/microbiologíaRESUMEN
The aim of the present work is to find out whether or not, and to what extent, the environmental impacts of reverse osmosis desalination are reduced when brackish groundwater is used instead of sea water. In order to answer this question, the Life-Cycle Assessment (LCA) methodology is used, and two water production plants are compared. The brackish groundwater scenario is based on a plant located in Almería (southern Spain), while the sea water scenario is based on literature data. Four impact categories and two environmental indicators, one of them related to brine discharge, are included. The results show that the key life-cycle issue of brackish groundwater desalination is electricity consumption, and since this is substantially reduced with regard to using sea water, the life-cycle impacts are found to be almost 50% lower. An uncertainty analysis based on Monte-Carlo simulation shows that these environmental savings are significant for all impact categories. Potential local impacts provoked by brine discharge are also found to be lower, due to a reduced content of salts. It is concluded that, when and wherever possible, exploitation of brackish groundwater resources should be assigned priority to sea water resources as an input for reverse osmosis desalination, although it must be taken into account that groundwater, as opposed to sea water, is a limited resource.
Asunto(s)
Ambiente , Salinidad , Agua de Mar , Purificación del Agua/métodos , Abastecimiento de Agua , Ósmosis , España , Incertidumbre , Purificación del Agua/instrumentaciónRESUMEN
Traditionally, the screening of unknown pesticides in food has been accomplished by GC/MS methods using conventional library-searching routines. However, many of the new polar and thermally labile pesticides are more readily and easily analysed by LC/MS methods and no searchable libraries currently exist (with the exception of some user libraries, which are limited). Therefore, there is a need for LC/MS libraries that can detect pesticides and their degradation products. This paper reports an identification scheme using a combination of LC/MS time-of-flight (accurate mass) and an Access database of 350 pesticides that are amenable to positive ion electrospray. The approach differs from conventional library searching of fragment ions. The concept consists of three parts: (1) initial screening of possible pesticides in actual market-place fruit extracts (apple and orange) using accurate mass and generating an accurate mass via an automatic ion-extraction routine, (2) searching the Access database manually for screening identification of a pesticide, and (3) identification of the suspected compound by accurate mass of at least one fragment ion and comparison of retention time with an actual standard. Imazalil and iprodione were identified in apples and thiabendazole in oranges using this database approach.
Asunto(s)
Cromatografía Liquida/métodos , Bases de Datos Factuales , Contaminación de Alimentos/análisis , Frutas/química , Espectrometría de Masas/métodos , Residuos de Plaguicidas/análisis , Aminoimidazol Carboxamida/análogos & derivados , Aminoimidazol Carboxamida/análisis , Estudios de Factibilidad , Análisis de los Alimentos/métodos , Hidantoínas/análisis , Imidazoles/análisis , Tiabendazol/análisisRESUMEN
Fifteen sediment samples were analysed in order to determine their content of polybrominated diphenylethers (PBDEs), polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs). Samples were collected from several hot spots on the Spanish coast, such as the harbours of Almeria and Tarragona, and the mouths of the Besos and Llobregat rivers in Barcelona. A generic analytical procedure based on Soxhlet extraction followed by an automated cleanup system and gas chromatography-ion trap-mass spectrometry was employed for determining the toxic congeners of PCDDs and PCDFs, as well as dioxin-like PCBs. As regards PBDE determinations, a rapid method based on the use of selective pressurized liquid extraction followed by gas chromatography-negative ion chemical ionization-mass spectrometry was applied. Total toxicity equivalent (WHO-TEQ) values were calculated using the toxicity equivalent factors proposed by WHO for dioxin-like PCBs, PCDDs and PCDFs. WHO-TEQ values ranged from 0.3 to 75 pg/g dry weight (dw), with PCB contribution on the toxicity of the samples between 1 and 84%. Total PBDE levels ranged from 2.7 to 134 ng/g dw, with BDE-209 contribution on the total PBDE contamination between 50 and 99%.
Asunto(s)
Benzofuranos/análisis , Contaminantes Ambientales/análisis , Sedimentos Geológicos/química , Bifenilos Polibrominados/análisis , Bifenilos Policlorados/análisis , Dibenzodioxinas Policloradas/análogos & derivados , Cromatografía de Gases/métodos , Monitoreo del Ambiente/métodos , Agua Dulce , Dibenzodioxinas Policloradas/análisis , EspañaRESUMEN
Traditionally, the screening of unknown pesticides in food has been accomplished by GC/MS methods using conventional library searching routines. However, many of the new polar and thermally labile pesticides and their degradates are more readily and easily analyzed by LC/MS methods and no searchable libraries currently exist (with the exception of some user libraries, which are limited). Therefore, there is a need for LC/MS approaches to detect unknown non-target pesticides in food. This report develops an identification scheme using a combination of LC/MS time-of-flight (accurate mass) and LC/MS ion trap MS (MS/MS) with searching of empirical formulas generated through accurate mass and a ChemIndex database or Merck Index database. The approach is different than conventional library searching of fragment ions. The concept here consists of four parts. First is the initial detection of a possible unknown pesticide in actual market-place vegetable extracts (tomato skins) using accurate mass and generating empirical formulas. Second is searching either the Merck Index database on CD (10,000 compounds) or the ChemIndex (77,000 compounds) for possible structures. Third is MS/MS of the unknown pesticide in the tomato-skin extract followed by fragment ion identification using chemical drawing software and comparison with accurate-mass ion fragments. Fourth is the verification with authentic standards, if available. Three examples of unknown, non-target pesticides are shown using a tomato-skin extract from an actual market place sample. Limitations of the approach are discussed including the use of A + 2 isotope signatures, extended databases, lack of authentic standards, and natural product unknowns in food extracts.