Screening of carbamates and ureas in fresh and processed tomato samples using micowave-assisted extraction and liquid chromatography

An analytical method, based on microwave-assisted extraction and liquid chromatography with diode array detection, for the determination of six carbamate and three urea pesticides in fresh and processed tomato samples is described. Significant parameters affecting extraction efficiency were optimized. Under optimum microwave-assisted extraction conditions (20mL acetonitrile, for 10 minutes, at 60º C), pesticides were extracted with recoveries ranging from 57.6 to 102% (RSDs<7%). Quantification limits between 6.5 and 39.6 µg=kg were obtained. A total number of 28 different fresh tomato samples and 6 processed tomato products were analysed. Confirmation of suspicious samples was performed by LC-MS.

Anodic adsorptive stripping voltammetric determination of atrazine in spiked soil samples with a gold microelectrode

Microwave-assisted solvent extraction was combined with anodic adsorptive stripping voltammetry at a gold microelectrode to extract and quantify the herbicide atrazine in spiked soil samples. A systematic study of the experimental parameters affecting the stripping response was carried out by square-wave voltammetry. The voltammetric procedure is based on controlled adsorptive accumulation of atrazine at the potential of 0.35V (versus Ag/AgCl) in the presence of Britton–Robinson buffer pH (2.0). The limit of detection obtained for a 30 sec collection time was 4.3x10-7 mol L-1. Recovery experiments, at the 1µgg-1 level of spiking, gave good results for the global procedure, and the values found were comparable to those obtained by HPLC.

Development of a SPME-GC-ECD methodology for selected pesticides in must and wine samples

A method for the determination of some pesticide residues in must and wine samples was developed using solid-phase microextraction (SPME) and gas chromatography – electron capture detection (GC/ECD). The procedure only needs dilution as sample pre-treatment and is therefore simple, fast and solvent-free. Eight fungicides (vinclozolin, procymidone, iprodione, penconazole, fenarimol, folpet, nuarimol and hexaconazole), one insecticide (chlorpyriphos) and two acaricides (bromopropylate and tetradifon) can be quantified. Good linearity was observed for all the compounds in the range 5–100 µg/L. The reproducibility of the measurements was found acceptable (with RSD’s below 20%). Detection limits of 11 µg/L, on average, are sufficiently below the proposed maximum residue limits (MRL’s) for these compounds in wine. The analytical method was applied to the determination of these compounds in Portuguese must and wine samples from the Demarcated Region of Alentejo, where any residues could be detected.

Flavored waters: influence of ingredients on antioxidant capacity and terpenoid profile by HS-SPME/GC-MS

The antioxidant profiles of 39 water samples (29 flavored waters based on 10 natural waters) and 6 flavors used in their formulation (furnished by producers) were determined. Total phenol and flavonoid contents, reducing power, and DPPH radical scavenging activity were the optical techniques implemented and included in the referred profile. Flavor extracts were analyzed by HS-SPME/GC-MS to obtain the qualitative and quantitative profiles of the volatile fraction of essential oils. Results pointed out a higher reducing power (0.14 11.8 mg of gallic acid/L) and radical scavenging activity (0.29 211.5 mg Trolox/L) of flavored waters compared with the corresponding natural ones, an interesting fact concerning human health. Bioactive compounds, such as polyphenols, were present in all samples (0.5 359 mg of gallic acid/L), whereas flavonoids were not present either in flavored waters or in flavors. The major components of flavor extracts were monoterpenes, such as citral, R-limonene, carveol, and R-terpineol.

Organochlorine pesticide residues in strawberries from integrated pest management and organic farming

A rapid, specific, and sensitive method based on theQuick Easy Cheap Effective Rugged and Safe (QuEChERS) method and a cleanup using dispersive solid-phase extraction with MgSO4, PSA, and C18 sorbents has been developed for the routine analysis of 14 pesticides in strawberries. The analyses were performed by three different analytical methodologies: gas chromatography (GC) with electron capture detection (ECD), mass spectrometry (MS), and tandem mass spectrometry (MS/MS). The recoveries for all the pesticides studied were from 46 to 128%, with relative standard deviation of <15% in the concentration range of 0.005-0.250 mg/kg. The limit of detection (LOD) for all compoundsmetmaximumresidue limits (MRL) accepted in Portugal for organochlorine pesticides (OCP). A survey study of strawberries produced in Portugal in the years 2009-2010 obtained from organic farming (OF) and integrated pest management (IPM) was developed. Lindane and β-endosulfan were detected above the MRL in OF and IPM. Other OCP (aldrin, o,p0-DDT and their metabolites, and methoxychlor) were found below the MRL. The OCP residues detected decreased from 2009 to 2010. The QuEChERS method was successfully applied to the analysis of strawberry samples.

Molecularly-imprinted materials for potentiometric transduction: application to the antibiotic enrofloxacin

Enrofloxacin (ENR) is an antimicrobial used both in humans and in food producing species. Its control is required in farmed species and their surroundings in order to reduce the prevalence of antibiotic resistant bacteria. Thus, a new biomimetic sensor enrofloxacin is presented. An artificial host was imprinted in specific polymers. These were dispersed in 2-nitrophenyloctyl ether and entrapped in a poly(vinyl chloride) matrix. The potentiometric sensors exhibited a near-Nernstian response. Slopes expressing mVΔlog([ENR]/M) varied within 48–63. The detection limits ranged from 0.28 to 1.01 µg mL 1. Sensors were independent from the pH of test solutions within 4–7. Good selectivity was observed toward potassium, calcium, barium, magnesium, glycine, ascorbic acid, creatinine, norfloxacin, ciprofloxacin, and tetracycline. In flowing media, the biomimetic sensors presented good reproducibility (RSD of ±0.7%), fast response, good sensitivity (47 mV/Dlog([ENR]/ M), wide linear range (1.0×10-5–1.0×10-3 M), low detection limit (0.9 µg mL-1), and a stable baseline for a 5×10-2 M acetate buffer (pH 4.7) carrier. The sensors were used to analyze fish samples. The method offered the advantages of simplicity, accuracy, and automation feasibility. The sensing membrane may contribute to the development of small devices allowing in vivo measurements of enrofloxacin or parent-drugs.

Evaluation of ochratoxin A exposure degree in two Portuguese cities through wheat and maize bread consumption during the winter 2007

The occurrence of OTA in fresh and packed wheat and in maize bread and the evaluation of the exposure degree through their consumption in two Portuguese populations from Porto and Coimbra, during the winter of 2007, were studied. One hundred and sixty eight bread samples, 61 maize and 107 wheat, were analysed by liquid chromatography–fluorescence detection (LC–FD). The results showed that 84% of samples were contaminated, with a maximum level of 3.85 ng/g (above the EU maximum limit, 3 ng/g). Fresh wheat bread presented higher levels than packed wheat bread. Moreover, the traditional maize bread, in either city, was consistently more contaminated than wheat bread, 0.25 vs 0.19 ng/g, and 0.48 vs 0.34 ng/ g for Porto and Coimbra, respectively. Avintes maize bread showed the highest mean contamination and maximum levels. The higher estimated daily intake of OTA from both types of bread in the population of Coimbra compared to Porto reflects the higher average contamination of bread in the first city.

Contribution of different vegetable types to exogenous nitrate and nitrite exposure

This study reports the levels of nitrate and nitrite of 34 vegetable samples, including different varieties of cabbage, lettuce, spinaches, parsley and turnips, collected in several locations of an intensive agricultural area (Modivas, Vila do Conde, northern Portugal). Nitrate levels ranged between 54 and 2440 mg NO-3 kg-1, while nitrite levels ranged between 1.1 and 57 mg NO-2 kg-1. The maximum residue levels established for nitrate in spinach and lettuce samples were not exceeded. Nitrate and nitrite levels reported in the literature for the same type of samples are reviewed, as well as the contribution of vegetables to nitrate and nitrite dietary exposure of populations.

Maltol determination in food by microwave assisted extraction and electrochemical detection

An electrochemical method is proposed for the determination of maltol in food. Microwave-assisted extraction procedures were developed to assist sample pre-treating steps. Experiments carried out in cyclic voltammetry showed an irreversible and adsorption controlled reduction of maltol. A cathodic peak was observed at -1.0 V for a Hanging Mercury Drop Electrode versus an AgCl/Ag (in saturated KCl), and the peak potential was pH independent. Square wave voltammetric procedures were selected to plot calibration curves. These procedures were carried out with the optimum conditions: pH 6.5; frequency 50 Hz; deposition potential 0.6 V; and deposition time 10 s. A linear behaviour was observed within 5.0 × 10-8 and 3.5 × 10-7 M. The proposed method was applied to the analysis of cakes, and results were compared with those obtained by an independent method. The voltammetric procedure was proven suitable for the analysis of cakes and provided environmental and economical advantages, including reduced toxicity and volume of effluents and decreased consumption of reagents.

Celiac disease diagnosis and gluten-free food analytical control

Celiac disease (CD) is an autoimmune enteropathy, characterized by an inappropriate T-cell-mediated immune response to the ingestion of certain dietary cereal proteins in genetically susceptible individuals. This disorder presents environmental, genetic, and immunological components. CD presents a prevalence of up to 1% in populations of European ancestry, yet a high percentage of cases remain underdiagnosed. The diagnosis and treatment should be made early since untreated disease causes growth retardation and atypical symptoms, like infertility or neurological disorders. The diagnostic criteria for CD, which requires endoscopy with small bowel biopsy, have been changing over the last few decades, especially due to the advent of serological tests with higher sensitivity and specificity. The use of serological markers can be very useful to rule out clinical suspicious cases and also to help monitor the patients, after adherence to a gluten-free diet. Since the current treatment consists of a life-long glutenfree diet, which leads to significant clinical and histological improvement, the standardization of an assay to assess in an unequivocal way gluten in gluten-free foodstuff is of major importance.

Influencing factors on bread-derived exposure to ochratoxin A: type, origin and composition

The nearly ubiquitous consumption of cereals all over the world renders them an important position in international nutrition, but concurrently allocates exposure to possible contained contaminants. Mycotoxins are natural food contaminants, difficult to predict, evade, and reduce, so it is important to establish the real contribution of each contaminated food product, with the aim to evaluate mycotoxin exposure. This was the key objective of this survey and analysis for ochratoxin A content on 274 samples of commercialized bread in the Portuguese market, during the winter 2007. Different bread products were analyzed through an HPLC-FD method, including traditional types, novel segments, and different grain based bread products. A wide-ranging low level contamination was observed in all regions and types of bread products analyzed, especially in the Porto and Coimbra regions, and in the maize and whole-grain or fiber-enriched bread. Nevertheless, the exposure through contaminated wheat bread continues to be the most significant, given its high consumption and dominance in relation to the other types of bread.

Flow-injection potentiometric method for the routine determination of chloride: application to bread analysis

Bread is consumed worldwide by man, thus contributing to the regular ingestion of certain inorganic species such as chloride. It controls the blood pressure if associated to a sodium intake and may increase the incidence of stomach ulcer. Its routine control should thus be established by means of quick and low cost procedures. This work reports a double- channel flow injection analysis (FIA) system with a new chloride sensor for the analysis of bread. All solutions are prepared in water and necessary ionic strength adjustments are made on-line. The body of the indicating electrode is made from a silver needle of 0.8 mm i.d. with an external layer of silver chloride. These devices were constructed with different lengths. Electrodes of 1.0 to 3.0 cm presented better analytical performance. The calibration curves under optimum conditions displayed Nernstian behaviour, with average slopes of 56 mV decade-1, with sampling rates of 60 samples h-1. The method was applied to analyze several kinds of bread, namely pão de trigo, pão integral, pão de centeio, pão de mistura, broa de milho, pão sem sal, pão meio sal, pão-de-leite, and pão de água. The accuracy and precision of the potentiometric method were ascertained by comparison to a spectrophotometric method of continuous segmented flow. These methods were validated against ion-chromatography procedures.

Electrochemical methods in pesticides control

The state of the art of voltammetric and amperometric methods used in the study and determination of pesticides in crops, food, phytopharmaceutical products, and environmental samples is reviewed. The main structural groups of pesticides, i.e., triazines, organophosphates, organochlorides, nitrocompounds, carbamates, thiocarbamates, sulfonylureas, and bipyridinium compounds are considered with some degradation products. The advantages, drawbacks, and trends in the development of voltammetric and amperometric methods for study and determination of pesticides in these samples are discussed.

Food consumption, physical activity and socio-economic status related to BMI, waist circumference and waist-to-height ratio in adolescents

Objective: To examine the association between obesity and food group intakes, physical activity and socio-economic status in adolescents. Design: A cross-sectional study was carried out in 2008. Cole’s cut-off points were used to categorize BMI. Abdominal obesity was defined by a waist circumference at or above the 90th percentile, as well as a waist-to-height ratio at or above 0?500. Diet was evaluated using an FFQ, and the food group consumption was categorized using sex-specific tertiles of each food group amount. Physical activity was assessed via a self-report questionnaire. Socio-economic status was assessed referring to parental education and employment status. Data were analysed separately for girls and boys and the associations among food consumption, physical activity, socio-economic status and BMI, waist circumference and waist-to-height ratio were evaluated using logistic regression analysis, adjusting the results for potential confounders. Setting: Public schools in the Azorean Archipelago, Portugal. Subjects: Adolescents (n 1209) aged 15–18 years. Results: After adjustment, in boys, higher intake of ready-to-eat cereals was a negative predictor while vegetables were a positive predictor of overweight/ obesity and abdominal obesity. Active boys had lower odds of abdominal obesity compared with inactive boys. Boys whose mother showed a low education level had higher odds of abdominal obesity compared with boys whose mother presented a high education level. Concerning girls, higher intake of sweets and pastries was a negative predictor of overweight/obesity and abdominal obesity. Girls in tertile 2 of milk intake had lower odds of abdominal obesity than those in tertile 1. Girls whose father had no relationship with employment displayed higher odds of abdominal obesity compared with girls whose father had high employment status. Conclusions: We have found that different measures of obesity have distinct associations with food group intakes, physical activity and socio-economic status.

Devolução de doses unitárias: análise de uma prática diária

A Distribuição Individual Diária em Dose Unitária deve assegurar o maior rigor no Processo de Distribuição de Medicamentos, o que nem sempre se verificou no Hospital Pedro Hispano, dado que as Doses Unitárias devolvidas pelos Serviços de Internamento, nem sempre seguiam os Parâmetros de Qualidade. Assim, desenvolveu-se um estudo quasi-experimental, longitudinal, prospetivo e analítico, entre 1 de Março a 30 de Junho de 2012, no qual se analisaram as Doses Unitárias, devolvidas pelos Serviços de Internamento da Unidade Local de Saúde de Matosinhos a funcionam com Distribuição Individual Diária em Dose Unitária, tendo-se recolhido as não conformes relativamente aos Parâmetros de Qualidade instituídos. Na 1.ª fase do estudo (Recolha de amostras), foram contabilizadas 337 amostras, correspondentes a uma perda de 471 €. Na 2.ª fase do estudo (Implementação de acções correctivas às amostras previamente recolhidas), foram rejeitadas definitivamente 129 amostras, correspondentes a uma perda de 198 €. Na 4.ª fase do estudo (Segunda recolha de amostras), foram contabilizadas 228 amostras, correspondentes a uma perda de 199 €. A 3.ª fase do estudo incluiu a divulgação dos resultados às enfermeiras chefes dos serviços envolvidos no estudo e a 5.ª fase a comparação dos resultados obtidos na 1.ª, 2.ª e 4.ª fase do estudo. As amostras foram recolhidas em 16 serviços de internamento, sendo os valores monetários mais relevantes associados ao Espessante para alimentos líquidos e ao Imipeno + Cilastatina. A prática observada e sujeita a estudo aumenta os riscos associados ao consumo do medicamento e os custos relativos ao Processo, sendo de eliminar. A sua monitorização deve constituir uma rotina, uma vez que houve mudança de comportamentos. A redução/eliminação desta prática não conforme conduz à integração de novas tarefas com valor acrescentado, com aumento da fiabilidade do Processo.