Evaluation by HPLC-UV of Polar Pesticides in Rice Fields

Direct Solid Phase Microextraction for the Determination of BTEX in Water and Wastewater

Surveillance of pesticide residues in fruits from Valencia during twenty months (2004/05)

Abstract The aim of this study was to investigate the pesticide residues in market fruits (oranges, tangerines, nectarines, peaches and khakis) from one Valencian Cooperative (Spain) and to conduct a monitoring of 32 organophosphorous, organonitrogen and organohalogenated pesticides and nine dithiocarbamate fungicides (DTCFs) usually applied on cultures of this area. Extracts were obtained by an official procedure for routine analysis based on ethyl acetate extraction. Residues of pesticides were determined by gas chromatography with nitrogen phosphorous detector (NPD), electron-capture detector (ECD) and mass spectrometry (MS) detectors. Mean recoveries obtained at fortification levels bet…

Analysis of carbamate pesticides and their metabolites in water by solid phase extraction and liquid chromatography: A review

Carbamates are an important, broad class of pesticides that are used extensively as insecticides, fungicides, and herbicides. Sensitive, economical, fast, and environmental friendly procedures are constantly developed to investigate their residues in water samples. The state of the art in methods based on solid phase extraction (SPE) and liquid chromatographic determination are examined here. SPE is presently the most extended method for preconcentration of carbamate pesticide residues and their transformation products from water samples. Advantages and limitations of alkyl bonded-silica, and polymeric sorbents, carbon, and mixed-phases in off-line and on-line procedures are discussed. Beca…

Incidence of enterotoxigenic staphylococci and their toxins in foods

Of 504 food samples collected from cafeterias, 19 (3.8%) yielded strains of enterotoxigenic staphylococci, and 10 (52.6%), 4 (21.1%), 3 (15.8%), and 2 (10.5%) of these strains produced enterotoxins C (SEC), D (SED), B (SEB), and A (SEA), respectively. Moreover, SEA, SEB, and SEC were isolated from three hamburger samples. Of 181 food samples collected from four restaurants before the implementation of the hazard analysis and critical control point (HACCP) system, 7 (3.9%) were found to contain enterotoxigenic strains, and SED, SEC, and SEA were produced by 4 (57.1%), 2 (28.6%), and 1 (14.3%) of these strains, respectively. One meatball sample with SEC was detected in a restaurant. After the…

Pressurized liquid extraction followed by liquid chromatography–mass spectrometry for determination of zearalenone in cereal flours

Abstract A method for determination of zearalenone in cereal flour has been developed applying pressurized liquid extraction (PLE) using methanol/acetonitrile (50:50 v/v) as the extraction solvent. The extracted samples were analyzed with liquid chromatography coupled to mass spectrometry (LC–MS) with an electro spray ionisation interface (ESI). The method was validated as a quantitative confirmatory method according to the Eu Commission Decision 2002/657/EC. Recoveries of the extraction step data were satisfactory with values higher then 70%. Quantification limits (LOQ) were 5 μg/kg for ESI (+) and 1 μg/kg for ESI (−). Twenty one flour samples produced in different countries were extracted…

Phenolic profile of oils obtained from “horchata” by-products assisted by supercritical-CO2 and its relationship with antioxidant and lipid oxidation parameters: Triple TOF-LC-MS-MS characterization

Abstract In this study, the effect of different supercritical CO 2 (SC-CO 2 ) pressures (10–40 MPa) on phenolic compounds extraction in oils obtained from “ horchata ” by-products was evaluated, and the results were compared to those obtained after conventional oil extraction (CE). Moreover, the relationship between the individual phenolic compounds and the total antioxidant capacity as well as oil oxidative quality parameters was compared. The phenolic profile and contents were largely influenced by extracting conditions. The main phenolic compound obtained by SC-CO 2 was the isohydroxymatairesinol, particularly at 30 and 40 MPa, while 3-vinylphenol was the predominant compound in oils ext…

Incidence of microbial flora in lettuce, meat and Spanish potato omelette from restaurants

A total of 370 samples including lettuce, meats (beef, pork and chicken) and Spanish potato omelette from restaurants were studied to evaluate the incidence of Escherichia coli, E. coli O157:H7,Staphylococcus aureus, Salmonella spp.,Yersinia enterocolitica, enterococci and some micro-organisms that can cause spoilage orcan be usedas indicators for food safety. Escherichia coliand enterococci were harboured with the highest incidence in lettuce, whereas incidence of Staphylococcus aureus was higherin meat than in the other foods studied. Enterobacter cloacae and Klebsiella pneumoniaewere isolated from the three food groups. Chryseomonas luteola, Enterobacter sakazakii, Klebsiella ozaenae, Mo…

Assessment of the microbiological quality and wash treatments of lettuce served in University restaurants

Abstract One hundred and forty-four samples of lettuce from 16 University restaurants were analyzed. The mesophilic aerobic counts of all samples ranged from 3.01 to 7.81 log 10 CFU g −1 . Results of total coliforms ranged from 3.38 log 10 most probable number (MPN) g −1 . Of the lettuce samples, 25.7% harbored Escherichia coli , 22.9% Staphylococcus aureus and 84% group D streptococci. Similarly, 10.4% of the samples harbored Aeromonas hydrophila , 2.8% Pseudomonas aeruginosa , and coliforms such as 14.6% Citrobacter freundii , 8.3% Klebsiella pneumoniae , 4.2% Enterobacter cloacae and 1.4% Providencia spp. Salmonella , Shigella and E. coli O157:H7 were not detected. When sodium hypochlori…

Solid-phase extraction in multi-residue pesticide analysis of water

The determination of pesticides in water is fundamental to the solution of environmental problems as natural waters are usually contaminated with a large number of pesticides. The selection of an isolation and/or concentration technique depends largely on the class of pesticides to be determined. It is often necessary to determine simultaneously a wide variety of compounds in a water sample. Application of solid-phase extraction techniques offers a solution. The mechanisms of solid-phase extraction, types of sorbents and their application to multi-residue pesticide analysis are reviewed.

Ochratoxin A in the morning and afternoon portions of urine from Coimbra and Valencian populations.

Abstract The widespread contamination of foodstuffs and beverages by mycotoxins, such as ochratoxin A (OTA), has made the monitoring of human contamination levels essential. By using a sensitive, accurate and speedy method that combines extraction with 5% NaHCO 3 , immunoaffinity column clean-up and HPLC with fluorescence detection, the human exposure to OTA through urine analysis can be monitored. This method is less invasive than blood monitoring and has the potential to be a good marker of human exposure. The limit of quantification of the method was 0.007 ng/mL of urine, with recoveries of OTA, from urine samples spiked at levels between 0.02 and 0.1 ng/mL, higher than 91% with RSD lowe…

Determination of aflatoxins in peanuts by matrix solid-phase dispersion and liquid chromatography

A new method based on matrix solid-phase dispersion (MSPD) extraction was studied to determine aflatoxin B1, B2, G1 and G2 from peanuts. Optimization of different parameters, such as type of solid supports for matrix dispersion and elution solvents were carried out. The method used 2 g of peanut sample, 2 g of C18 bonded silica as MSPD sorbent and acetonitrile as eluting solvent. Recoveries of each aflatoxin spiked to peanut samples at 2.5 ng/g (5 ng/g for aflatoxin G2) level were between 78 and 86% with relative standard deviations ranging from 4 to 7%. The limits of quantification ranged from 0.125 to 2.5 ng/g for the four studied aflatoxins using liquid chromatography (LC) with fluoresce…

The importance of a registered dietitian in restaurants: a pilot study in Valencia (Spain)

University students have the option to purchase their meals at university restaurants; in general, food eaten away from home has high contents of saturated fat and energy. The aim of this work was to perform a pilot study of the nutritional adequacy of meals served at two university restaurants from Valencia. Energy, macronutrient and micronutrient contents were calculated and compared against the Spanish Recommended Dietary Intake (SRDI). Daily menus provided a high amount of energy; lunch from restaurant 1 provides 60 and 78% of the energetic SRDI for male and female, respectively. In restaurant 2 these values are 49.5 and 64.6%, respectively. Menus from one university restaurant are plan…

Microbial evaluation of Spanish potato omelette and cooked meat samples in University restaurants.

The focus of this study was to evaluate the microbial quality of Spanish potato omelette and cooked meat samples including pork loin, chicken croquettes, long pork sausage, chicken breast, and meatballs from University restaurants. Microbiological analyses of Spanish potato omelette and cooked meat samples resulted in aerobic plate counts from1.00 to 2.90 and from1.00 to 6.04 log10 CFU g(-1), respectively. Total coliforms ranged from3 to 43 most probable number (MPN) g(-1) and from3 to2,400 MPN g(-1) for Spanish potato omelette and meat products, respectively. Escherichia coli, coagulase-positive staphylococci, and Lancefield group-D streptococci were detected in 1.7%, 3.5%, and 12.9% of Sp…

Exposure assessment of fruits contaminated with pesticide residues from Valencia, 2001– 03

A total of 634 samples of oranges, tangerines, peaches, nectarines, khakis and watermelons were collected from an Agricultural Valencia Community Cooperative during the May 2001 to April 2003 campaigns and they were analysed for 15 pesticides among those recommended for pest treatment. A conventional multiresidue analytical procedure based on ethyl acetate extraction was used followed by gas chromatography coupled to a nitrogen phosphorus detector for routine analysis; and mass spectrometry was performed for confirmation. Recovery studies with spiked samples at 0.5 mg kg-1 for each pesticide ranged from 52% for acephate to 87% for fenthion with a standard deviation20%. Limits of quantificat…

A review of the application of the hazard analysis and critical control point system to salads served in the restaurant of Valencia University

Solid-phase extraction of quaternary ammonium herbicides

This paper highlights recent advances in the solid-phase extraction (SPE) of quaternary ammonium herbicides in water, soil, plant and biological samples. After a brief introduction summarizing the properties of quaternary ammonium herbicides and the difficulties involved in measuring them, attention is paid primarily to solid supports used for isolation and concentration, pre-treatments required for the different matrices, and eluents applied for quantitative desorption of these analytes. The determination techniques used after SPE and applications of the proposed SPE methodology are also briefly discussed.

Levels of ochratoxin A in wheat and maize bread from the central zone of Portugal.

Ochratoxigenic fungi are natural contaminants of cereal and the produced toxins are harmful to humans and animals. Ochratoxin A (OTA) is among the most important mycotoxins, and the International Agency for Research on Cancer (IARC) classifies it as possibly carcinogenic to humans (group 2B). A total of 61 samples of bread from the central zone of Portugal were analysed for OTA by liquid chromatography (LC) with fluorescence detection (FD). For confirmation two procedures were applied, methyl ester derivatization with boron trifluoride-methanol and liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI/MS/MS). As far as we know, this is the first report where on-line…

Presence of mycotoxins in sorghum and intake estimation in Tunisia

Sorghum samples (n = 60) from Tunisian markets were analysed for the occurrence of 22 of both traditional and emerging mycotoxins. Samples were extracted with a QuEChERS-like method and mycotoxins were detected by LC-MS/MS. This method was validated and adequate analytical parameters were obtained. All samples had contamination with mycotoxins and several samples had higher contamination levels than European Union legislative limits (MLs). The most frequently found mycotoxins were ENB (100%), OTA (98%), ENA₁ (63%), ENB₁ (56%), BEA (48%), AFB1 (38%) and STG (33%). Mean contaminations were 30.7, 1.93, 33.2, 51.0, 15.4, 1.49 and 20.5 µg kg(-1), respectively. While two samples were contaminated…

Listeria species in raw and ready-to-eat foods from restaurants.

From September 1999 to March 2000, meat (pork, beef, and chicken), fish (salmon, hake, and sole), vegetable (lettuce and spinach), and Spanish potato omelette samples obtained at restaurants were collected and tested for the occurrence of Listeria spp. Listeria monocytogenes was isolated from 3 (2.9%) out of 103 studied samples. Other species isolated were Listeria grayi (13.6%), Listeria innocua (1.9%), Listeria ivanovii (5.8%), Listeria seeligeri (3.9%), and Listeria welshimeri (1.9%). Listeria was neither isolated from beef nor any type of fish.

Simultaneous determination of Fusarium mycotoxins in wheat grain from Morocco by liquid chromatography coupled to triple quadrupole mass spectrometry

Abstract In the present study, eighteen (18) mycotoxin produced by the genus Fusarium (fumonisins (FB1, FB2 and FB3), type-B trichothecenes (NIV, DON, FUS-X, 3Ac-DON and 15Ac-DON), type-A trichothecenes (NEO, DAS, T2 and HT2), zearalenone (ZEA), beauvericin (BEA), and enniatins (ENA, ENA1, ENB and ENB1)) were monitored in different samples of wheat grain commercialized in Morocco. A liquid chromatography coupled to triple quadrupole mass spectrometry method previous matrix solid phase dispersion extraction was used for sample analysis. A total of eighty (80) samples of durum wheat were collected in different local markets from several areas in Morocco. Analytical results showed that 54 out …

Clean-up and confirmation procedures for gas chromatographic determination of pesticide residues in contaminated waters. Part I

The effects of sulphuric acid, potassium hydroxide and chromic acid on eleven organochlorine and ten organophosphorus pesticides were investigated. The treatments destroy some pesticides totally or partially, leave others unaltered and have a clean-up effect. These reactions can be used to confirm the presence of an identified pesticide. The clean-up extracts in the environmental samples facilitate the identification of the organochlorine and organophosphorus pesticides and their quantitative analysis. The results obtained for contaminated surface waters show the usefulness of these methods for multi-residue capillary gas chromatography without the need for other additional separative chrom…

Incidence of Staphylococcus aureus in meals from cafeterias

A study to determine the incidence of Staphylococccus aureus in 705 meals from several cafeterias in Valencia, Spain was undertaken. Out of the 705 studied meals, 81 samples (I I. I %) had coagulase positive staphylococci with a range of S. aureus from 100 to 53000 cfu/g. me four highest values (> l0,ooO S. aureus &/g) were obtained with Russian type salad, meatballs, chicken croquettes and salad. These products involved more handling stages. These data show that food handlers may contribute to food poisoning and that there are some handling practices that require more attention.

Determination of macrolide and lincosamide antibiotics by pressurised liquid extraction and liquid chromatography-tandem mass spectrometry in meat and milk

Abstract A total of 155 samples, including meat and milk, were analyzed using a method developed for determining five macrolide antibiotics: tilmicosin (TILM), tylosin (TS), spiramycin (SPM), erythromycin (ERY), and tulathromycin (TULA) and two lincosamide antibiotics: pirlimycin (PIRL) and lincomycin (LM). The method was performed by pressurised liquid extraction (PLE) coupled to LC–MS/MS using electrospray ionization in positive ion mode. 2.5 mL of milk or 2.5 g of meat were dispersed in ethylenediaminetetraacetic acid sodium salt 2-hydrate (EDTA) and sea sand. The PLE conditions as: solvent, temperature, pressure, static time, and cell size were optimized. The following analytical parame…

Presence of mycotoxins in ready-to-eat food and subsequent risk assessment

Abstract A study on a set of ready-to-eat meals (n = 328) based on cereals, legumes, vegetables, fish and meat was carried out to determine the natural presence of twenty-seven mycotoxins by both liquid chromatography and gas chromatography coupled mass spectrometry in tandem (MS/MS) after QuEChERS extraction. The occurrence of mycotoxins was headed by cereal samples with 35% of samples contaminated by at least one mycotoxin followed by vegetables (32%), legumes (15%) and lastly, 9% of fish and meat samples were contaminated. DON was the most detected mycotoxin in vegetables, meat, fish and cereals with an incidence of 13% 18% 19% and 60%, respectively, and the highest mean levels were foun…

Indirect analysis of urea herbicides from environmental water using solid-phase microextraction.

We described here a solid-phase microextraction procedure used to extract six urea pesticides-- chlorsulfuron, fluometuron, isoproturon, linuron, metobromuron and monuron--from environmental samples. Two polydimethylsiloxanes and a polyacrylate fiber (PA) are compared. The extraction time, pH control, addition of NaCl to the water and the influence of organic matter such as humic acid on extraction efficiency were examined to achieve a sensitive method. Determination was carried out by gas chromatography with nitrogen-phosphorus detection. The proposed method requires the extraction of 2 ml of sample (pH 4, 14.3%, w/v, NaCl) for 60 min with the PA fiber. The limits of detection range from 0…

Influence of the solvent on the gas chromatographic behaviour of urea herbicides

Degradation products of chlorsulfuron, chlortoluron, diuron, fluometuron, isoproturon, linuron, metabenzthiazuron, metobromuron, and monuron formed in the gas chromatographic injector have been used for identification of the respective herbicides. Mass spectra of the derived compounds were obtained with a quadrupole mass spectrometric detector working in scan mode (20–450 amu). The compounds generated often depended on the solvent used for phenylurea herbicide injection (ethanol, methanol, dichloromethane, and acetonitrile). When methanol and ethanol were used as solvents the major products formed from phenylureas were carbamic acid esters. When acetonitrile or dichloromethane were used the…

Occurrence and daily intake of ochratoxin A of organic and non-organic rice and rice products

Abstract Ochratoxin A (OTA) was extracted from 84 rice samples and rice products by using accelerated solvent extraction (ASE) and analysed with liquid chromatography coupled with fluorescence detection. Samples were collected from rice cultivars, local markets and supermarkets; 64 were of non-organic and 20 of organic production. 7.8% of non-organic samples had OTA levels from 4.3 to 27.3 μg/kg and in 30% of organic samples was detected the presence of this mycotoxin varying from 1.0 to 7.1 μg/kg. OTA presence was confirmed by methyl-ester derivatization. Rice and rice products labelled with denomination of origin (DO) were not detected OTA due to the fact that its production has implement…

Matrix effects on solid-phase microextraction of organophosphorus pesticides from water

Abstract This study develops a method for solid-phase microextraction (SPME) of eight organophosphorus pesticides, diazinon, fenthion, fenitrothion (sumithion), methyl-parathion, parathion, methyl-trithion, ethion and triazophos, from water. Determination is carried out by gas chromatography with nitrogen-phosphorus detection. To perform the SPME, poly(dimethylsiloxane) and polyacrylate fibers were initially compared on the basis of their absorption capacities for the selected pesticides, and polyacrylate was selected to accomplish the rest of assays. The main factors affecting the SPME process such as memory effect, stirring rate, extraction temperature and absorption-time profile were stu…

Presence of aflatoxin M1 in pasteurized milk from Morocco

Fifty four samples of pasteurized milk produced by five different dairies from Morocco were surveyed for the presence of aflatoxin M1 (AFM1) using immunoaffinity columns and liquid chromatography coupled to fluorescence detection. Confirmation of AFM1 identity in positive samples was based on the formation of AFM1 hemi-acetal derivative (AFM2a) after derivatization with trifluoracetic acid. Analytical results showed that 88.8% of the samples were contaminated with AFM1; 7.4% being above the maximum level of 0.05 microg/L set by the Moroccan and European regulations for AFM1 in liquid milk. The incidence of AFM1 in milk from these dairies was 100, 92.3, 90, 83.3 and 77.7% respectively, with …

Simple liquid chromatography assay for analyzing ochratoxin A in bovine milk

Abstract Ochratoxin A (OTA) is a mycotoxin with teratogenic and carcinogenic properties. Animal intake of feedstuffs contaminated with OTA may cause that some residues may be found in bovine milk, therefore, its analysis requires a highly sensitive, simple and precise technique. This method is based on a liquid–liquid extraction with methanol, followed by filtration and extract concentration. Liquid chromatography coupled to fluorescence detection was used for OTA analysis. In this way, several impurities are filtered off and OTA is quantified with a mean recovery of 93.0 ± 7.4% and a limit of detection of 0.01 ng mL −1 . Therefore, this methodology allows a simple quantitative extraction o…

Rapid determination of ochratoxin A in cereals and cereal products by liquid chromatography.

A new method based on extraction with octylsilica (C8) followed by liquid chromatography coupled with fluorescence detection (LC-FLD) was studied to determine ochratoxin A (OTA) from cereals and cereal products. Optimization of different parameters, such as type and amount of solid phase, type and volume of eluent and amount of sample were carried out. Recovery of OTA from rice samples spiked at 10 ng/g level was of 86% with relative standard deviation of 5%. The limits of detection and quantification of the proposed method were 0.25 and 0.75 ng/g, respectively. Furthermore, LC-FLD after of OTA methylation and liquid chromatography coupled to mass spectrometry with an electrospray interface…

Application of solid-phase microextraction for determining phenylurea herbicides and their homologous anilines from vegetables.

Abstract Residues of metobromuron, monolinuron and linuron herbicides and their aniline homologous were analyzed in carrots, onions and potatoes by solid-phase microextraction (SPME) performed with a polyacrylate fiber. A juice was obtained from food samples that were further diluted, and an aliquot was extracted after sodium chloride (14%) addition and pH control. At pH 4 only the phenylureas were extracted. A new extraction at pH 11 allowed the extraction of phenylureas plus homologous aniline metabolites. Determination was carried out by gas chromatography with nitrogen–phosporus detection (NPD) the identity of the determined compounds was studied by gas chromatography–mass spectrometry.…

Validation of a confirmatory method for the determination of macrolides in liver and kidney animal tissues in accordance with the European Union regulation 2002/657/EC

Abstract This study proposes a simple multiresidue liquid chromatography–diode array detector (LC–DAD) method capable of determining seven macrolide antibiotics in samples of liver and kidney animals at concentrations lower than those allowed by current legislation. Samples were prepared by homogenizing the tissue with EDTA–McIlvaine's buffer and extracted with an Oasis HLB cartridge. The consumption of organic solvent during extraction was minimum. The analytes were detected by LC–DAD and also by liquid chromatography–mass spectrometry with electrospray ionization (LC–(ESI)MS). The method was specific, stable and robust enough for the required purposes. The DAD method was validated in acco…

Development of a nutritional HACCP plan.

Thermal and non-thermal preservation techniques of tiger nuts' beverage "horchata de chufa". Implications for food safety, nutritional and quality properties.

"Horchata de chufa" is a traditional Spanish beverage produced from tiger nuts (Cyperus esculentus L.). Due to its richness in nutritional compounds, it is highly perishable and its conservation by pasteurization and/or adding preservatives is required. Although efficient, conventional thermal treatment for pasteurization induces changes in the nutritional and sensory properties. Replacing conventional pasteurization by non-thermal technologies such as pulsed electric fields, ultraviolet, and high pressure, combined with moderate temperatures (<40°C) allows a reduction of energy consumption, along with the preservation of the most thermo-sensitive molecules. Accordingly, this review deals w…

Dietary intake of ochratoxin A from conventional and organic bread

Ochratoxin A (OTA) was extracted from 100 bread samples by using accelerated solvent extraction (ASE) and analyzed with liquid chromatography coupled with fluorescence detection. The presence of OTA was confirmed by methyl-ester derivatization. Bread samples were bought from different bakeries and supermarkets, 74 of non-organic and 26 of organic bread. The incidence of OTA varied between 20.3% and 23.0% for non-organic and organic bread, respectively. The highest values were obtained with non-organic versus organic products, five samples exceeded the European maximum permitted limit of OTA (3 ng/g) for this product. Estimated daily intake of OTA in this study was 1.6 ng/kg b.w./day. This v…

Gas chromatographic evaluation of pesticide residue contents in nectarines after non-toxic washing treatments

Washing with aqueous solutions of citric acid, ethanol, glycerol, hydrogen peroxide, potassium permanganate, sodium metabisulfite, sodium laurylsulfate (SLS), sodium hypochlorite, and urea is evaluated for pesticide residue reduction in nectarines and compared with simple tap water washing. Residues of pesticides commonly utilized in nectarines (chlorpyrifos, fenarimol, iprodione, malathion, methidathion, myclobutanil, parathion and pirimicarb) are extracted with ethyl acetate and anhydrous sodium sulfate, extract is concentred and analyzed by GC with nitrogen-phosphorus detection. The formation of possible toxic by-products (chlorpyrifos oxon, malaoxon, methidaoxon and paraoxon methyl) is …

Development of microextraction techniques in combination with GC-MS/MS for the determination of mycotoxins and metabolites in human urine.

Simple and highly efficient sample preparation procedures, namely, dispersive liquid–liquid microextraction and salting-out liquid–liquid extraction for the analysis of ten Fusarium mycotoxins and metabolites in human urine were compared. Various parameters affecting extraction efficiency were carefully evaluated. Under optimal extraction conditions, salting-out liquid–liquid extraction showed a better accuracy (84–96%) and precision (<14%) than dispersive liquid–liquid microextraction. Hence, a multibiomarker method based on salting-out liquid–liquid extraction followed by gas chromatography with tandem mass spectrometry was proposed. Satisfactory results in terms of validation were achiev…

Simple liquid chromatography assay for analyzing ochratoxin a in bovine milk

Limited survey for the occurrence of aflatoxins in cereals and poultry feeds from Rabat, Morocco

Fifty eight (58) samples of cereals for human consumption (20 corn flour, 17 wheat flour) and poultry feeds (n=21) purchased from popular markets of Rabat in Morocco were analyzed for aflatoxins (AF) by HPLC with immunoaffinity column (IAC) clean-up and fluorimetric detection. The incidence of AF in corn, wheat flour and poultry feeds was about 80, 17.6 and 66.6% respectively. High contamination levels were found in corn and poultry feeds samples. Levels of contamination of analyzed samples with AFB1 ranged from 0.23 to 11.2, 0.03 to 0.15 and 0.05 to 5.38 ng/g for corn, wheat and poultry feeds respectively. Results showed also that the contamination of 10% of samples of corn was higher than…

A survey of trichothecenes, zearalenone and patulin in milled grain-based products using GC-MS/MS.

An analytical protocol based on QuEChERS and gas chromatography-tandem mass spectrometry (GC-MS/MS) was successfully applied for the determination of trichothecenes, patulin and zearalenone in 182 milled grain-based samples. The analytical method was validated following the SANCO 1495/2011 document. LOQs were lower than 10μgkg(-1) for the selected mycotoxins. Recoveries of fortified cereals ranged between 76-108% and 77-114% at 20 and 80μgkg(-1), respectively, with relative standard deviation lower than 9%. More than 60% of the samples analysed showed deoxynivalenol contamination, followed by HT-2 toxin and nivalenol with frequencies of 12.1% and 10.4%, respectively. Co-occurrence of mycoto…

Enterotoxigenic staphylococci and their toxins in restaurant foods

Abstract This review presents an overview of the enterotoxigenic staphylococci and their toxins in restaurant foods, with special reference to the characteristics of these micro-organisms and their enterotoxins. Furthermore, this paper reviews the staphylococcal food poisoning outbreaks, principal sources of contamination and food safety measures that can be applied to eliminate the presence of enterotoxigenic staphylococci in restaurant foods.

Improvement of accessibility for the disabled in university restaurants

AMELIORATION DE L’ACCESSIBILITE DE RESTAURANTS UNIVERSITAIRES A DES HANDICAPES Une etude a ete realisee en vue d’ameliorer l’acces des handicapes aux 19 restraurants universitaires de Valence en Espagne, puisque le taux des etudiants handicapes, ces trois dernieres annees universitaires, est de l’ordre de 0,12 a 0,13 %. Au debut de cette etude, 16 etablissements disposaient d’un acces correct avec un pourcentage de 87,5, 25 et 6,3 concernant respectivement les rampes, les ascenseurs et les balustrades. En outre, toutes les portes d´acces de ces etablissements etaient equipees des poignees a leviers, ou etaient concues de sorte qu’une prise serree et qu’une torsion du poignet ne soient pas n…

Monitoring of the pesticide levels in natural waters of the Valencia Community (Spain)

Tiger nut and its by-products valorization: From extraction of oil and valuable compounds to development of new healthy products

Abstract Consumer's growing demand for consumption of “Horchata de chufa”, a Spanish beverage produced from tiger nut tubers, has led to large-scale production of tiger nuts, and its subsequent processing for the food industry. Recent investigations clearly show that tiger nut is a valuable source of stable vegetable oils, rich in monounsaturated fatty acids, and phytosterols as well as high-added value compounds (proteins, carbohydrates, vitamins, minerals and bioactive compounds). Several conventional (Soxhlet) and alternative innovative (SC-CO2, enzyme, high pressure, etc.) extraction methods have been developed for the efficient recovery of tiger nut oil and high-added value compounds. …

Quantitative determination of trichothecenes in breadsticks by gas chromatography-triple quadrupole tandem mass spectrometry.

Breadsticks are pencil-sized sticks of dry bread widely consumed as a pre-meal appetiser. They are basically wheat-based snacks, which makes them a good matrix to evaluate mycotoxin contamination, since wheat is very susceptible to fungal attack. In this sense, the fast, selective and sensitive gas chromatography-triple quadrupole tandem mass spectrometry (GCQqQ- MS/MS) method proposed here allows simultaneous determination of deoxynivalenol (DON), 3-acetyldeoxynivalenol, fusarenon-X, diacetoxyscirpenol, nivalenol, neosolaniol, HT-2 and T-2 toxin in breadsticks after QuEChERS extraction and clean-up. The performance of the method was assessed with respect to European Commission Regulations …

Optimization of a matrix solid-phase dispersion method for the analysis of pesticide residues in vegetables

A multiresidue method based on matrix solid-phase dispersion (MSPD) is studied to determine chlorfenvinfos, chlorpyrifos, fenarimol, iprodione, procimydone, propiconazole, tetradifon, triadimefon and vinclozolin in artichokes, green beans, lettuces and tomatoes. Alumina, silica and Florisil were assessed as extracting phases, and the extracts from Florisil were the cleanest. To facilitate manual extraction, sand was added to the sample together with the dispersing phase. Three eluting systems were then studied, and dichloromethane proved to be the best. Further purification can be performed using solid-phase cleanup after diluting extracts with aqueous solutions. Octyl- and octadecyl-silica…

Determination of trichothecenes in chicken liver using gas chromatography coupled with triple-quadrupole mass spectrometry

Abstract Chicken meat and edible offal are included in a wide number of preparations in the worldwide cuisine. Among the offal, the liver is one of the most consumed in some countries like Egypt since it is rich in proteins and is an economical source of many essential nutrients for humans. Mycotoxins, secondary toxic metabolites produced by fungi, have the potential to enter human food chain not only with cereal consumption but also through edible tissues from animals fed with mycotoxin-contaminated feed. Accordingly, a rapid method for the determination of eight trichothecenes in chicken liver was developed based on a quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction an…

Effect of introduction of HACCP on the microbiological quality of some restaurant meals

The microbial quality of Spanish potato omelette and pork loin before and after implementation of the HACCP system in University restaurants was used as indicator of food safety in this work. The prevalence of aerobic plate counts and incidences of Staphylococcus aureus, Escherichia coli, E. coli O157:H7, Listeria monocytogenes, Salmonella spp. and Clostridium perfringens were analysed. Results of implementation of the HACCP system show a lower incidence of studied microorganisms. On the other hand, a documented training in personal hygiene, good manufacturing practices (GMPs), cleaning and sanitation procedures and personal safety in addition to the rearrangement in the infrastructure of t…

Evaluation of the Fate of Aldicarb and Its Metabolites in Oranges

Abstract The accumulation, persistence and fate of systemic pesticide aldicarb was melencholy evaluated in orange crops. The concentration of this pesticide and its two toxic metabolites, aldicarb sulfoxide and aldicarb sulfone was determined in leaves, rind and pulp of three orange varieties (Satsuma, Navelina and Clemetina de Nules) and in the top soil of the orange groves. The groves were located in two different places in the Valencia Community (Spain). The analysis showed that the aldicarb concentration was lower than those of aldicarb sulfoxide and aldicarb sulfone. In all cases, the residues persisted at least 160 days in vegetable samples and between 157 and 227 days in soil samples…

Development of a GC–MS/MS strategy to determine 15 mycotoxins and metabolites in human urine

The widespread mycotoxins contamination of food commodities has made the monitoring of their levels essential. To overcome the disadvantages of the indirect approach by food analysis, detection of mycotoxin as biomarkers in urine provides a useful and specific data for exposure assessment to these food contaminants. In this work, a sensitive, rapid and accurate method based on gas chromatography-tandem mass spectrometry procedure to determine 15 mycotoxins and metabolites in human urine was optimized and validated taking into consideration the guidelines specified in Commission Decision 2002/657/EC and 401/2006/EC. A salting-out assisted acetonitrile-based extraction was used for sample pre…

Evaluation of Mycotoxins in Infant Breast Milk and Infant Food, Reviewing the Literature Data

In this review, an analysis focusing on mycotoxin determination in infant breast milk and infant food has been summarised for the last fifteen years of research focused on the intended population group of 1–9 months. The objective was to know the level of exposure of the child population to an estimated daily intake (EDI) of mycotoxins from the consumption of habitual foods. The EDI was compared with the tolerable daily intake (TDI) established by EFSA to estimate risk. In breast milk, the high prevalence and levels were for samples from Africa (Egypt and Tanzania) with aflatoxin M1 (1.9 μg/L and 10%), and Asia (Iran) with ochratoxin-A (7.3 μg/L and 100%). In infant formulas, high incidence…

Review on the toxicity, occurrence, metabolism, detoxification, regulations and intake of zearalenone: An oestrogenic mycotoxin

Zearalenone (ZEA) is a mycotoxin produced mainly by fungi belonging to the genus Fusarium in foods and feeds. It is frequently implicated in reproductive disorders of farm animals and occasionally in hyperoestrogenic syndromes in humans. There is evidence that ZEA and its metabolites possess oestrogenic activity in pigs, cattle and sheep. However, ZEA is of a relatively low acute toxicity after oral or interperitoneal administration in mice, rat and pig. The biotransformation for ZEA in animals involves the formation of two metabolites alpha-zearalenol (alpha-ZEA) and beta-zearalenol (beta-ZEA) which are subsequently conjugated with glucuronic acid. Moreover, ZEA has also been shown to be h…

Comparison of different sorbents for on-line liquid-solid extraction followed by high-performance liquid chromatographic determination of nitrogen-containing pesticides

Abstract LiChrolut EN [poly(styrene-divinylbenzene), PSDVB], Carbograph (graphitized carbon black, GCB), Isolute CN (cyanopropylsilica), Isolute C 2 (ethylsilica), and LiChrospher RP18 (octadecylsilica) were studied for on-line solid-phase extraction of twelve nitrogen containing pesticides from water. Determination (UV 210 nm) was performed with a Spherisorb C 8 analytical column and an acetonitrile-water gradient. The mean recoveries from 50 ml ranged from 83% for RP18 to 44% for GCB, and decreased in the following order: RP18, CN, LiChrolut EN, C 2 , and GCB. GCB showed poor recoveries due to incomplete desorption with the acetonitrile-water gradient used, and memory effects were detecte…

Concentration of ochratoxin A in wines from supermarkets and stores of Valencian Community (Spain)

Ochratoxin A (OTA) is a mycotoxin produced by fungi species belonging to the genera Aspergillus and Penicillium being isolated in alcoholic beverages. The aim of this work is developed and applied a procedure for the analysis of OTA in wines. An analytical method based on immunoaffinity column (IAC) for clean-up, liquid chromatography with fluorescence detection (LC-FD), and LC-FD after of OTA methylation was used to determine the occurrence of OTA in wines. Recoveries of this mycotoxin spiked to red wines at 0.5 ng/ml level were >90% with an average of relative standards deviations of 4%. Furthermore, 116 wine samples from designation of origin (DO) and three samples from food stores of Va…

Determination of ochratoxin A in maize bread samples by LC with fluorescence detection.

Ochratoxin A (OTA) is a secondary fungal metabolite produced by several moulds, mainly by Aspergillus ochraceus, A. carbonarius, A. niger and by Penicillium verrucosum. The present work shows the results of comparative studies using different procedures for the analysis of OTA in maize bread samples. The studied analytical methods involved extraction with different volumes of PBS/methanol, different extraction apparatus, and clean-up through immunoaffinity columns. The separation and identification were carried out by high-performance liquid chromatography with fluorescence detection. The optimized method for analysis of OTA in maize bread involved extraction with PBS:methanol (50:50), and …

Solid-Phase Extraction of Organochlorine Pesticides from Water Samples

Abstract A procedure for the accumulation of organochiorine pesticides by reversed-phase adsorption on octadecylsilica glass microcolumns was used for the isolation and concentration from spiked distilled and natural waters. The pesticides were eluted from the octadecylsilica with light petroleum, and analyzed by gas chromatography using an electron capture detector. The average recovery was over 90% in spiked water samples at 0.1 ng/ml. The performance of the octadecylsilica when applied to the analysis of water samples were compared with the Rodier and the APHA solvent extraction methods.

SPME of 52 pesticides and polychlorinated biphenyls: Extraction efficiencies of the SPME coatings poly(dimethylsiloxane), polyacrylate, poly(dimethylsiloxane)-divinylbenzene, Carboxen-poly(dimethylsiloxane), and Carbowax-divinylbenzene

Fiber/water partition coefficients (Kfw) of 52 pesticides, including triazines, organophosphorus pesticides, organochlorine pesticides, and polychlorinated biphenyls (PCBs) were experimentally calculated for the five polymeric coatings poly(dimethylsiloxane) (PDMS), polyacrylate (PA), poly(dimethylsiloxane)-Divinylbenzene (PDMS-DVB), Carboxen-poly(dimethylsiloxane) (CAR-PDMS), and Carbowax-divinylbenzene (CW-DVB) commercially available for solid-phase microextraction coupled to gas chromatography. The equilibrium-time profiles for the five coatings were previously studied in order to establish the time needed for equilibrium. To calculate Kfw the amount of analyte extracted at equilibrium w…

Occurrence of deoxynivalenol and T-2 toxin in bread and pasta commercialised in Spain

Abstract Deoxynivalenol and T-2 toxin were extracted from wheat-based bread ( n  = 75) and pasta ( n  = 75) samples using a mixture of acetonitrile:water (86:14 v/v); for analysis, gas chromatography/mass spectrometry after derivatisation with trifluoroacetic anhydride was utilised. The recovery of deoxynivalenol and T-2 toxin from both food matrixes ranged from 90.1 to 94.0%. The occurrence of these mycotoxins in bread was 28.0% and 2.6% for deoxynivalenol and T-2 toxin, respectively, whereas in pasta, the occurrence of both mycotoxins was higher, varying from 9.3 to 62.7%. The mean content of deoxynivalenol (42.5 μg/kg) in bread was lower than the content of T-2 toxin (68.37 μg/kg), while…

Factors affecting the presence of ochratoxin A in wines.

Ochratoxin A (OTA) are synthesized mainly by different species of Aspergillus and Penicillium being its human toxicological effects reflected in different countries due to the consumption of different foods and beverages such as red, white, rose, and special wines. This review presents an overview of the direct (meteorological conditions, grape cultivation, and wine-making techniques) and indirect (latitude, year of production, use of pesticides, presence of spoilage microorganisms, conditions of storage of the harvested grapes, type of maceration, and conditions of fermentation), factors affecting the presence of OTA in wines.

Pesticide residue determination in fruit and vegetables by liquid chromatography–mass spectrometry

An overview is given of pesticide residue determination in fruit and vegetables by liquid chromatography-mass spectrometry (LC-MS). Emphasis is placed on the thermospray, particle beam and atmospheric pressure ionization interfaces including advantages and drawbacks and typical detection limits. The capacity of each interface to provide useful data for identification/confirmation of analytes and the possibility of obtaining structural information for the identification of target and non-target compounds is discussed. Finally, sample preparation techniques are dealt with in relation to their influence on further LC-MS determination.

Evaluating the impact of supercritical-CO2 pressure on the recovery and quality of oil from “horchata” by-products: Fatty acid profile, α-tocopherol, phenolic compounds, and lipid oxidation parameters

Abstract The effect of supercritical carbon dioxide (SC-CO2) (10–40 MPa) and conventional extraction (CE) to recover oil from by-products obtained during “horchata” production was assessed. To evaluate both extraction techniques, the fatty acid composition, polyphenols, α-tocopherol, antioxidant capacity and lipid oxidation parameters of the extracts obtained were analysed. A linear relationship between extraction pressure and oil yield was observed. However, the highest oil yield was obtained under conventional extraction. The by-products from “horchata” presented a profile where monounsaturated fatty acids (MUFA) were the predominant, representing ≈ 70% of total fatty acids. The amount of…

Determination of triazines and organophosphorus pesticides in water samples using solid-phase extraction.

Abstract Octadecyl (C 18 )-bonded porous silica was evaluated for the extraction of triazine and organophosphorus pesticides from natural water. The extraction results showed an effective performance when 1 l of water was passed through small glass columns containing 500 mg of 50–100-μm C 18 bonded porous silica. The absorbed compounds were removed with ethyl acetate, evaporated to 200 μl and determined by gas chromatography. The overall average recoveries were greater than 85% except for dimethoate and trichlorfon. Application of this procedure to the analysis of natural water samples gave results that agree well with those obtained by solvent extraction methods.

Exposure assessment approach through mycotoxin/creatinine ratio evaluation in urine by GC–MS/MS

Abstract In this pilot survey human urine samples were analyzed for presence of 15 mycotoxins and some of their metabolites using a novel urinary multi-mycotoxin GC–MS/MS method following salting-out liquid–liquid extraction. Fifty-four urine samples from children and adults residents in Valencia were analyzed for presence of urinary mycotoxin and expressed in gram of creatinine. Three out of 15 mycotoxins were detected namely, HT-2 toxin, nivalenol and deoxynivalenol (DON). 37 samples showed quantifiable values of mycotoxins. Co-occurrence of these contaminants was also observed in 20.4% of assayed samples. DON was the most frequently detected mycotoxin (68.5%) with mean levels of 23.3 μg/…

Influence of dissolved humic material and ionic strength on C8 extraction of pesticides from water

A mixture of twelve intermediate polarity pesticides, mostly carbamate-type, have been chromatographied on an octadecyl-silica bonded-phase column using acetonitrile-water gradient mobile phase and UV detection. Pesticides were extracted from aqueous matrix by solid-phase extraction. The extraction system consisted of a glass microcolumn containing octyl-silica solidphase conditioned with methanol and water. The elution was by acetonitrile-dichloromethane (50:50). Studies of extraction factors like volume of sample, addition of 10% sodium chloride and presence of dissolved humic material are investigated.

Determination of ochratoxin A in organic and non-organic cereals and cereal products from Spain and Portugal

The objective of this work was to know the occurrence of OTA in organic and non-organic cereals and cereal products from Spain and Portugal. A method based on extraction with matrix solid phase dispersion (MSPD) using octylsilica (C8) followed by liquid chromatography coupled with fluorescence detection (LC-FD) was used to determine OTA from the selected samples. Recoveries of OTA from the studied samples spiked at 10 ng/g level ranged from 78% to 89% with a standard deviation of 3.66. The limits of detection and quantification of this method were 0.05 and 0.19 ng/g, respectively. Furthermore, LC-FD after OTA methylation was used to confirm the identity of OTA in all positive samples. This …

Accelerated solvent extraction of ochratoxin a from rice samples.

In this paper, accelerated solvent extraction (ASE) for the analysis of ochratoxin A (OTA) is applied for the first time. Optimization of the method is given for the extraction of OTA from rice samples. Several parameters such as type of solvent, temperature, pressure, static time, and cell size were investigated thoroughly to find the optimal extraction conditions. The optimum ASE operating conditions were methanol as extraction solvent, 1500 psi, 40 degrees C, 5 min of static time, 50% flush volume, 60 s of purge, 1 cycle, and 11 mL cell size. The total extraction time was approximately 15 min. OTA was determined by liquid chromatography coupled with a fluorescence detector and confirmed …

Dietary intake and food pattern among university students

Dietary intake and food pattern were determined among university students. Nine hundred-eighteen students (384 males and 534 females) completed a 24 hour recall and a questionnaire. This study showed an average energy intake of 10.3 and 8.0 MJ among male and female university students. The mean intakes of energy and magnesium for males and energy, iron, magnesium and zinc for females were lower to the Spanish Recommended Intakes. For males, breakfast, lunch, dinner and snacks bring about 18, 33, 25 and 27% of total dairy energy, respectively, however, for females a 15, 34, 23 and 27% of total dairy energy were obtained for breakfast, lunch, dinner and snacks, respectively. The university po…

Absence Ochratoxin A in soy sauce

A method is described for the determination of ochratoxin A (OTA) in soy sauce using phosphate-buffered saline (PBS) extraction, an immunoaffinity clean-up, a liquid chromatographic determination with fluorescence detection (LC-FD) and confirmation with LC-FD after methylation of OTA. Recoveries of OTA spiked to soy sauce samples at 0.25 ng/ml level were 90% with relative standard deviations of 4%. The limit of detection was 0.01 ng/ml for OTA using the proposed method. Furthermore, the proposed method was applied to 60 soy sauce samples from China and Japan and none of them were found to contain OTA.

Aldicarb residues in citrus soil, leaves and fruits

Aldicarb was applied to the soil of Late Valencia orange field plots. A comparative study between four analytical methods is reported, the NPD-gas chromatography method being the best choice. The work also reports the study of accumulation and persistence of aldicarb and its biologically active metabolites in the soil, leaves and fruits (rind and pulp, separately). Residue content, at the ppb level, was found in the order leaves much greater than rind greater than pulp. Carbamate was found to accumulate mainly in its oxidized forms. Residues had reached a maximum level in about 90 days after application.

Hazard analysis and critical control points in deep-fat frying

The Hazard Analysis and Critical Control Point (HACCP) system was applied to sunflower oils used for frying in nineteen university restaurants. Guidelines for implementation that include training personnel, flow diagram, identifying hazards, controlling hazards at critical control points (CCP's), monitoring CCP's and measure of action for exceeding limit were developed. Polar compounds were used as a measure for deteriorated sunflower oil and the values obtained from university restaurants before and after personnel training and implementation of HACCP were determined. Implementation of the guidelines produced an improvement in the quality of the frying process, and all establishments reduc…

Gas chromatographic behaviour of urea herbicides

Gas chromatographic conditions for determining eight phenylurea (chlortoluron, diuron, fluometuron, isoproturon, linuron, metabenzthiazuron, metobromuron and monuron) and one sulfonylurea (chlorsulfuron) herbicides were assessed. Degradation products of the herbicides formed in the injector were used for identification. Most phenylureas formed their respective carbamic acid methyl esters, metabenzthiazuron formed an aminobenzothiazol and chlorsulfuron formed an aminotriazine plus a phenylsulfonamide. On-column injection of standards using a BP10 capillary column was evaluated to identify the chromatographic behaviour. Detection limits ranged from 0.05 ng for chlorsulfuron to 3 ng for monuro…

Determination of Urea Pesticide Residues in Vegetable, Soil, and Water Samples

The main physico-chemical, toxicological, and environmental properties of urea pesticides are summarized. General characteristics of analytical methods for residues of phenylurea herbicides (PUHs), sulfonylurea herbicides (SUHs), and Benzoylurea insecticides (BUIs) in crops, soil, and water samples, employed in the last 5 years are reviewed. Provided it is information about liquid-liquid and solid-phase extraction of the samples and clean-up steps. The applications of gas chromatography (GC), liquid chromatography (LC), and capillary electrophoresis (CE) techniques in the analysis of these compounds are exposed in tabular form and commented on. Sensitivity and instrument conditions of liqui…

Exposure to patulin from consumption of apple-based products.

Patulin is a mycotoxin produced by species of Penicillium, Aspergillus and Byssochylamys. Several Scientific Committees classify patulin as mutagenic, embryotoxic and immunotoxic. It has been found as a natural contaminant of processed apple products and its presence may be indicative of the quality of fruit used in production. In this work, a method for the analysis of patulin is described, based on a simple liquid-liquid extraction with acetonitrile; patulin is analyzed using liquid chromatography with UV detection. Patulin identity was confirmed by GC-MS after its reaction with N-methyl-N-(trimethylsilyl)trifluoroacetamide. Fifty-three apple-containing products were analyzed and patulin …

Occurrence of fumonisins B1 and B2 in Portuguese maize and maize-based foods intended for human consumption.

Fumonisin B(1) (FB(1)) and fumonisin B(2) (FB(2)) are mycotoxins mainly produced by Fusarium verticillioides and Fusarium proliferatum, which are field pathogens of maize. A survey was conducted on the incidences of FB(1) and FB(2) in both maize and derived products purchased in Portugal. The analytical method involved extraction with methanol-water, clean-up by immunoaffinity column and derivatization with naphthalene-2,3-dicarboxaldehyde. Determination was carried out by high-performance liquid chromatography (HPLC) with spectrofluorimetric detection, with liquid chromatography/mass spectrometry (LC/MS) confirmation. The presence of FB(1) and FB(2) was determined in 67 samples of maize an…