Determination of type A and type B trichothecenes in paprika and chili pepper using LC-triple quadrupole-MS and GC-ECD.

There is a need to develop sensitive and accurate analytical methods for determining deoxynivalenol (DON), HT-2 toxin and T-2 toxin in paprika to properly assess the relevant risk of human exposure. An optimized analytical method for determination of HT-2 toxin and T-2 toxin using capillary gas chromatography with electron capture detection and another method for determination of DON by liquid chromatography-mass spectrometry in paprika was developed. The method for determination of HT-2 toxin and T-2 toxin that gave the best recoveries involved extraction of the sample with acetonitrile-water (84:16, v/v), clean-up by solid-phase extraction on a cartridge made of different sorbent material…

Electrochemical Characterization of Egyptian Blue Pigment in Wall Paintings Using the Voltammetry of Microparticles Methodology

The solid state voltammetric response of Egypt blue, Han blue and ploss blue pigments upon attachment to graphite electrodes in contact with aqueous phosphate buffer at pH 7.0 is studied by voltammetry of microparticles and scanning electrochemical microscopy. Such voltammetric responses, combined with those for synthetic specimens consisting of binary mixtures of the pigment and SiO2 or CaCO3 as well as ternary ones of CaCO3 and SiO2 mixtures allow for the identification of the pigment and the support in samples from wall paintings using different electrochemical parameters, in particular upon performing the Tafel and modified Tafel analysis of voltammetric peaks. Identification of Egypt b…

Different sample treatment approaches for the analysis of T-2 and HT-2 toxins from oats-based media.

A LC-DAD method is proposed for the determination of the T-2 and HT-2 toxins in cultures of Fusarium langsethiae in oat-based and other in vitro media. Test media consisted of freshly prepared milled oats to which T-2 and HT-2 toxin stock solutions were added. Different mixtures of extraction solvent (acetonitrile:water and methanol water), extraction times (30', 60' or 90') and drying methods were investigated. Results showed that extraction with methanol: water (80:20, v/v) for 90 min, drying with N-2 and subsequent analysis by LC-DAD was the fastest and most user friendly method for detecting HT-2 and T-2 toxins production by F. langsethiae strains grown on oat-based media at levels of 0…

Effect of carbendazim and physicochemical factors on the growth and ochratoxin A production of Aspergillus carbonarius isolated from grapes.

Carbendazim is a systemic fungicide that is commonly used on several crops (tobacco, fruit, vegetables, cereals, etc.). This fungicide is used to control fungal infections in vineyards. It is indicated against Botrytis cinerea, Uncinula necator, Plasmopara viticola and other fungi and can be used either alone or coupled with other fungicides. However, there is a lack of in-depth studies to evaluate its effectiveness against growth of Aspergillus carbonarius isolated from grapes and OTA production. A medium based on red grape juice was used in this study. Preliminary studies were performed at 0.98 a(w) and 25 degrees C using carbendazim concentrations over a wide range (1-2000 ng/ml medium) …

Determination of ochratoxin A in beer marketed in Spain by liquid chromatography with fluorescence detection using lead hydroxyacetate as a clean-up agent

Abstract A new sample treatment for liquid chromatographic analysis of ochratoxin A (OTA) in beer is proposed. Degassed beer is mixed with lead hydroxyacetate, which precipitates some bulk components but does not remove OTA. The precipitate is separated and the acidified liquid is extracted with chloroform. The solvent is evaporated and the residue is dissolved in mobile phase (acetonitrile–water, 40:60, v/v; acidified at pH 3.0 with phosphoric acid) and separated by liquid chromatography using fluorescence detection. The limit of detection was 0.005 ng/ml. The average recovery rate and the average RSD of recovery in the spiking level range 0.01–0.5 ng/ml were 95.5% and about 5%, respective…

Mycobiota and co-occurrence of mycotoxins in Capsicum powder

This study aimed to: (1) determine the mycobiota of Capsicum powder samples, paying a special attention to the mycotoxigenic moulds; (2) evaluate the contamination levels of aflatoxins (AF), ochratoxin A (OTA), zearalenone (ZEA), deoxynivalenol (DON), T2 and HT2 toxins in those samples. Thirty-two samples were obtained through the methods of sampling established by the European Union legislation. Aspergillus and Eurotium were the most frequently found genera. Aspergillus section Nigri had the higher relative frequency in the samples, A. niger aggregate being the most representative group of this section. Other potentially mycotoxigenic Aspergillus, Fusarium and Penicillium species were foun…

Study of Spanish grape mycobiota and ochratoxin A production by Isolates of Aspergillus tubingensis and other members of Aspergillus section Nigri.

ABSTRACT The native mycobiota of five grape varieties grown in Spain has been studied. Four (Bobal, Tempranillo, Garnacha, and Monastrell) were red varieties and one (Moscatel) was white. The main fungal genera isolated were Alternaria , Cladosporium , and Aspergillus . The isolation frequency of Aspergillus spp. section Nigri in contaminated samples was 82%. Ochratoxin A (OTA) production was assessed using yeast extract-sucrose broth supplemented with 5% bee pollen. Cultures of 205 isolates from this section showed that 74.2% of Aspergillus carbonarius and 14.3% of Aspergillus tubingensis isolates produced OTA at levels ranging from 1.2 to 3,530 ng/ml and from 46.4 to 111.5 ng/ml, respecti…

Changes in ochratoxin A and type B trichothecenes contained in wheat flour during dough fermentation and bread baking processes

Ochratoxin A (OTA) and type B trichothecenes are mycotoxins that occur frequently in cereals and thus can be found in cereal by-products such as bread. The aim of this work was to study the variation of the levels of OTA, deoxynivalenol (DON), 3-acetyldeoxynivalenol (3-ADON) and nivalenol (NIV) during the bread-making process. This was done by using wheat flour spiked with different levels of toxins. Mycotoxin levels were controlled after fermentation of the dough with yeasts (Saccharomyces cerevisiae) and after further baking at different temperature-time combinations. Analysis of variance (ANOVA) of the results showed a significant reduction in OTA level (p < 0.05) during fermentation of …

Screening and mapping of pigments in paintings using scanning electrochemical microscopy (SECM)

The use of the scanning electrochemical microscopy (SECM) technique for identifying and mapping of both organic and inorganic pigments in sub-microsamples from pictorial specimens is described. This methodology, inspired by the voltammetry of immobilized particles technique, permits the study of textural properties of paint layers and mapping the distribution of pigment grains upon application of different potentials to the substrate. A combination of the redox competition SECM strategy with voltammetry yields a local identification methodology for different organic and inorganic pigments in paint samples.

Archaeometrical study of paleometallurgical materials from the archaeological site “Cerro de las Balsas — Chinchorro” (La Albufereta, Alacant, Spain)

An Iberian archaeological site located in the east of Spain is one of the most important cupellation centers found in the 4th century b.c. Different metallurgical materials were found in the archaeological site as minerals, cast slags, forged slags, metallic lead, cupella fragments and bronzes. Also was found reverbs remains used for cupper-based materials and cupellation procedure, and hearth forge remains for obtained iron material. The recuperated samples were studied by comparing samples of the same type of material by macroanalysis and microanalysis. The microanalysis and quantitation of the different archaeological materials was carried out by SEM/EDX. The information provides about t…

Optimization of clean-up procedure for patulin determination in apple juice and apple purees by liquid chromatography

Patulin (PAT) is a mycotoxin produced in fruits, mainly in apples, by several fungal species that can be carried into industrial apple juice by-products during factory processing. An analytical method for determination of PAT in apple juice and another one for determination of this compound in apple purees and apple compotes by liquid chromatography are proposed in the present paper. These methods have better precision and sensitivity than previously reported methods and focus mainly on extraction and clean-up. To accomplish analytical methods with higher accuracy, lower limits of detection and simpler procedures for application in quality control of the goods, different extraction and clea…

Isomerization and redox tuning in ‘Maya yellow’ hybrids from flavonoid dyes plus palygorskite and kaolinite clays

Abstract The composition of the organic fraction of organic–inorganic hybrid materials prepared upon attachment of different natural, ‘historical’ flavonoid yellow dyes (zacatlaxcalli, fustic, marigold and cosmos) to palygorskite and kaolinite clays is described. Upon thermal treatment between 100 and 180 °C, significant isomerization and oxidation reactions occur thus resulting in the formation of polyfunctional materials potentially usable for therapeutic, catalytic and art purposes. The dye attachment to the clays would define a ‘Maya chemistry’ whose complexity could explain the versatile use of such materials in the pre-Columbian cultures.

Impact of non-selective fungicides on the growth and production of ochratoxin A byAspergillus ochraceusandA. carbonariusin barley-based medium

The aim of this study was to assess the influence of the non-selective fungicides mancozeb, copper oxychloride, and sulfur on the growth and capability for producing ochratoxin A (OTA) of ochratoxigenic isolates of Aspergillus carbonarius and A. ochraceus in barley-based medium. Lag phases and growth rates were determined for each fungicide at different doses, at 15°C and 25°C and at 0.97 a(w). Mancozeb at 40 mg l(-1 )inhibited fungal growth and provided lag phases24 days at 10-20 mg l(-1) and 15°C. OTA was observed only at 25°C and doses10 mg l(-1). At 15°C, copper oxychloride proved inhibitory at 800 mg l(-1), while at 25°C growth was not delayed and only high doses decreased OTA levels. …

Characterization of Fusarium spp. isolates by PCR-RFLP analysis of the intergenic spacer region of the rRNA gene (rDNA)

In the present study, 44 Fusarium spp. isolates (5 Fusarium culmorum, 7 Fusarium graminearum, 1 Fusarium cerealis, 1 Fusarium poae, 26 Fusarium oxysporum, and 4 Gibberella fujikuroi species complex) were characterized morphologically, physiologically and genetically. All except one (Dutch Collection: CBS 620.72) were isolated from different hosts grown in various Spanish localizations. Morphological characterization was made according to macroscopic and microscopic aspects. Physiological characterization was based on their ability to produce zearalenone (ZEA) and type B trichothecenes (deoxynivalenol, nivalenol and 3-acetyldeoxynivalenol). ZEA was determined by liquid chromatography and tri…

Thermal decomposition of chromite spinel with chlorite admixture

Abstract The behaviour of minerals in a South African chromite ore during the increasing of the temperature has been studied. Firstly, the changes produced during the ignition process have been examined by means of thermal and differential analysis (TGA–DTA) until 1200 °C. The characterization of the initial mineral and those obtained after heating at several temperatures in room atmosphere has been performed by X-ray diffraction (XRD). Moreover, voltammetric analyses have allowed to determine the variation of the iron oxidation degree in the studied materials. Light microscopy was applied to find more information about the different phases by their colour. During the heating, a wide range …

Comparative assessment of solid-phase extraction clean-up procedures, GC columns and perfluoroacylation reagents for determination of type B trichothecenes in wheat by GC–ECD

Abstract Various solid-phase extraction (SPE) procedures for clean-up, two perfluoroacylation reagents (pentafluoropropionic anhydride (PFPA) and heptafluorobutyric anhydride (HFBA)) and two chromatographic columns (HP-1701 and HP-5) have been assessed comparatively to achieve the determination of type B trichothecenes (deoxynivalenol (DON), nivalenol (NIV), 3- and 15-acetyldeoxynivalenol (3- and 15-ADON)) in wheat grain by gas chromatography (GC)–electron-capture detection (ECD). Spiked wheat samples were extracted with acetonitrile–water (84:16, v/v). Tested SPE procedures were MycoSep 225 column, Florisil and different cartridges prepared in the laboratory with mixtures of various sorben…

Composition and Color of Maya Blue: Reexamination of Literature Data Based On the Dehydroindigo Model

[EN] An analysis of literature data studying the composition and color of Maya blue (MB) type materials prepared from indigo, dehydroindigo, and different aluminosilicates, accompanied by new spectral data, is presented. After thermal treatment at above 100 degrees C, indigo-based specimens displayed Raman and UV-vis spectroscopic features common to those of equivalent dehydroindigo-based replicants, thus supporting the socalled dehydroindigo model (J. Phys. Chem. B 2006, 110, 6027-6039) in which the dehydroindigo/indigo ratio, increasing with temperature, is crucial to determine the color of MB and its variability. The current analysis supports the view of MB as a polyfunctional hybrid mat…

Survey of the mycobiota of Spanish malting barley and evaluation of the mycotoxin producing potential of species of Alternaria, Aspergillus and Fusarium

The present work deals with the toxigenic mycobiota occurring in Spanish malting barley and the capability for producing mycotoxins by several important toxigenic fungi. One hundred and eighty seven samples of malting barley were gathered from Spanish breweries before processing. One hundred and fifty kernels per sample were surface-sanitized with a 2% sodium hypochlorite solution and incubated on three culture media. The most abundant fungi were species of Alternaria, Aspergillus, Penicillium and Fusarium, which were present in 93%, 82.3%, 57.8% and 27.8% of the samples, respectively. To evaluate their mycotoxin producing potential a number of isolates belonging to each genus, except Penic…

Voltammetry of microparticles, scanning electrochemical microscopy and scanning tunneling microscopy applied to the study of dsDNA binding and damage by scorpiand-like polyamine receptors

Abstract Microparticulate deposits of scorpiand-like azamacrocyclic receptors (L1–L4) attached to graphite electrodes provide distinctive voltammetric features in contact with aqueous DNA solutions at biological pH, denoting the formation of DNA surface complexes. This voltammetry allows for screening dsDNA, ssDNA and G-Quadruplex DNA using L4-modified electrodes. Scanning electrochemical microscopy and scanning tunneling microscopy examination of dsDNA fibers attached to the substrate electrode in contact with DMSO solutions containing ferrocene and receptor indicate that a synergic effect is exerted between electrochemically generated ferrocenium ion and the receptors so that they increas…

Ochratoxin A removal in synthetic media by living and heat-inactivated cells of Oenococcus oeni isolated from wines

The capacity of Oenococcus oeni to eliminate ochratoxin A (OTA) from synthetic media in different conditions was studied. Ten tested O. oeni strains removed OTA from the medium but with significant differences depending on the strain, incubation period, and initial OTA level in the medium. Mycotoxin reductions higher than 60% were recorded in 14-day cultures spiked with 2 mu g OTA/l. Toxin removal was independent of bacterial viability and culture medium composition. This is the first study carried out to study OTA removal dynamics by living and heat-inactivated cells of O. oeni. The results aim that this bacterium may be a very useful tool to control OTA in food and beverages. (C) 2009 Els…

Presence of trichothecenes and co-occurrence in cereal-based food from Catalonia (Spain)

The most important trichothecenes are HT-2 toxin (HT2) and T-2 toxin (T2) from type A and deoxynivalenol (DON) from type B. Thus, the aim of the current study was to assess the occurrence of these trichothecenes in the Catalonian market. 479 food samples were taken from the most susceptible to trichothecenes contamination and most commonly consumed in Catalonia commodities. DON, T2 and HT2 toxin were determined in breakfast cereals, snacks and pasta samples following extraction, clean-up, derivatization and finally analysis by GC–ECD. Moreover, these mycotoxins were determined in sliced bread, sweet corn and beer by LC–DAD. Our results showed that DON was the main trichothecene present in t…

Influence of nitrogen and carbon sources on the production of ochratoxin A by ochratoxigenic strains of Aspergillus spp. isolated from grapes.

This work studies the influence of nitrogen and carbon source on ochratoxin A production by three Aspergillus isolates A. ochraceus (Aso2), A. carbonarius (Ac25) and A. tubingensis (Bo66), all isolated from grapes. A basal medium (0.01 g/l FeSO4.7H2O, 0.5 g/l MgSO4.7H2O, 0.5 g/l Na2HPO4.2H2O, 1.0 g/l KCl) was prepared. This medium was supplemented with different nitrogen sources, both inorganic [(NH4)3PO(4), 0.3 g/l plus NH4NO3, 0.2 g/l] and organic (histidine, proline, arginine, phenylalanine, tryptophan or tyrosine) at two concentrations (0.05 g/l or 0.3 g/l), and different carbon sources (sucrose, glucose, maltose, arabinose or fructose) at three concentrations (10 g/l, 50 g/l or 150 g/l…

Discovery of indigoid-containing clay pellets from La Blanca: significance with regard to the preparation and use of Maya Blue

Analytical studies using extraction/liquid chromatography, pyrolysis–silylation gas chromatography–mass spectrometry, visible and infrared spectroscopies, solid state voltammetry and electron microscopy on a set of spherical greenish pellets discovered in the Structure 4H1 of the ancient Maya site of La Blanca (Peten Department, Guatemala), dated in the Terminal Classic period, confirm the presence of indigoids (dehydroindigo, indigo) associated to palygorskite. The appearance of such pieces, whose origin and function is uncertain, but most likely correspond to residuals of a decorative plaster, can be considered as indicative of the use of Maya Blue in a quotidian context, thus suggesting …

New method for determination of ochratoxin A in beer using zinc acetate and solid-phase extraction silica cartridges

Abstract A new method for the determination of ochratoxin A (OTA) in beer has been developed. The new method has been compared with a reference method currently accepted as AOAC official first action. The limits of detection and quantification of the proposed method were 0.0008 and 0.0025 ng/ml, respectively, while they were 0.0025 and 0.0075 ng/ml, respectively, in the AOAC method used as reference. The recovery levels in the 0.025–0.40 ng OTA/ml spiking range for the proposed and the reference methods were 80.6–87.6% and 78.2–83.8%, respectively. The relative standard deviations of recoveries were 2.6–7.5% for the proposed method and 0.7–6.1% for the reference method. Passing and Bablok r…

‘Maya chemistry’ of organic–inorganic hybrid materials: isomerization, cyclicization and redox tuning of organic dyes attached to porous silicates

[EN] Association of indigo and lapachol dyes to aluminosilicate clays yields polyfunctional organic – inorganic hybrid materials forming Maya Blue-like systems. Upon partial removing of clay's zeolitic water by moderate thermal treatment, abundant isomerization, cyclicization and oxidation reactions occur defining a‘ Maya chemistry whose complexity could explain the versatile use of such materials in the pre-Columbian cultures and permits the preparation of polyfunctional materials potentially usable for therapeutic and catalytic purposes.

Influence of environmental factors on the biosynthesis of type B trichothecenes by isolates of Fusarium spp. from Spanish crops.

Various species of Fusarium can produce trichothecene mycotoxins that contaminate food commodities and can represent a risk for human and animal health. In this paper, a full factorial design was applied to study the influence of incubation temperature, water activity (a(w)) and type of isolate on the production of deoxynivalenol (DON), nivalenol (NIV) and 3-acetyldeoxynivalenol (3-AcDON) in corn kernel cultures by three isolates of Fusarium graminearum and three isolates of Fusarium culmorum from crops grown in Spain. The tested temperatures were 15, 20, 28 and 32 degrees C. The a(w)-values were 0.960, 0.970 and 0.980. Moisture of cultures (within the studied range) did not affect signific…

MYCOTOXINS | Detection and Analysis by Classical Techniques

This article is a revision of the previous edition article by Imad Ali Ahmed, volume 2, pp. 1526–1532, © 1999, Elsevier Ltd.

On-line database of voltammetric data of immobilized particles for identifying pigments and minerals in archaeometry, conservation and restoration (ELCHER database)

[EN] A web-based database of voltammograms is presented for characterizing artists' pigments and corrosion products of ceramic, stone and metal objects by means of the voltammetry of immobilized particles methodology. Description of the website and the database is provided. Voltammograms are, in most cases, accompanied by scanning electron microphotographs, X-ray spectra, infrared spectra acquired in attenuated total reflectance Fourier transform infrared spectroscopy mode (ATR-FTIR) and diffuse reflectance spectra in the UV-Vis-region. For illustrating the usefulness of the database two case studies involving identification of pigments and a case study describing deterioration of an archae…

Neural network models for prediction of trichothecene content in wheat

Fusarium graminearum is a mould that causes serious diseases in cereals worldwide and that synthesises mycotoxins such as deoxynivalenol (DON), which can seriously affect human and animal health. Predicting the level of mycotoxin accumulation in food is very difficult, because of the complexity of the influencing parameters. In this work, we have studied the possibility of using artificial neural networks (NN) to predict DON level attained in F. graminearum wheat cultures taking as inputs the fungal contamination level of the cereal, the water activity as a measure of the available water for fungal growth in the cereal, the temperature and time. DON analysis was performed by gas chromatogr…

Redox tuning and species distribution in Maya Blue-type materials: a reassessment.

Maya Blue-type specimens prepared from indigo (1 wt %) plus kaolinite, montmorillonite, palygorskite, sepiolite, and silicalite are studied. Liquid chromatography with diode array detection, ultra-performance liquid chromatography coupled with mass spectrometry, and pyrolysis-silylation gas chromatography-mass spectrometry analyses of the extracts from these specimens combined with spectral and solid-state voltammetry, electrochemical impedance spectroscopy, and scanning electrochemical microscopy techniques provide evidence for the presence of a significant amount of dehydroindigo and isatin accompanying indigo and other minority organic compounds in all samples. Solid-state electrochemist…

Fumonisin production in rice cultures of Fusarium verticillioides under different incubation conditions using an optimized analytical method.

Fumonisin B1 (FB1) and fumonisin B2 (FB2) are the main members of a family of mycotoxins produced by various fungal species belonging to the Gibberella fujikuroi complex. The present work shows the results of a comparative study of various clean-up and derivatization procedures for analysis of fumonisins in rice cultures. Fumonisins were extracted from rice with acetonitrile/water (50/50, v/v). For clean-up, three solid-phase extraction procedures were assayed (C18 cartridge, SAX cartridge, and a combination of both). Two reagents (o-phthaldialdehyde and 4-fluoro-7-nitro-benzofurazan) were studied comparatively for formation of fluorescent derivatives. The separation was carried out by LC u…

Analytical Study of a Resinous Material Used as Sealing in Ancient Pottery Found in an Archaeological Site by Thermally Assisted Hydrolysis Methylation–Gas Chromatography–Mass Spectrometry, Vibrational Spectroscopy and Light Microscopy

Abstract A resin sample was found in the archaeological site of Lixus (Morocco), belonging to the second century BC. The resinous material was found inside an amphora containing iron remains used in the plug as sealing material to hermetically close the pottery. The resinous sample was studied by several analytical techniques, as thermally assisted hydrolysis and methylation–gas chromatography–mass spectrometry (THM–GC–MS), Fourier transformed infrared spectroscopy (FTIR), and light microscopy. The material was identified as a Pinaceae resin. Therefore, a modern pine resin was also analyzed to consider the influence of aging in the archaeological sample. The ancient material was found not t…

Comparison of Different Analytical Methods for Determination of Type B Trichothecenes in Wheat and Ochratoxin A in Beer

Determination of the depth profile distribution of guest species in microporous materials using the voltammetry of immobilized particles methodology: application to lapachol attachment to palygorskite and kaolinite.

A model for determining the in-depth profile distribution of electroactive species hosted in inorganic microporous matrixes using the voltammetry of immobilized particles methodology is described. The method, based on the analysis of cyclic voltammetric data at different potential scan rates, allows us to determine the in-depth profile variation of the concentration of electroactive guest species as well as the evaluation of the (oxidized form)/(reduced form) concentration ratio in cases where two oxidation states of the electroactive species coexist. The application to Maya blue-type materials prepared from lapachol, a naphtoquinonic dye, and palygorskite and kaolinite clays is reported. T…

Comparison of different analytical processes for patulin determination in apple juice

F. M. Valle-Algarra, R. Mateo, A. Medina, F. Mateo, E. M. Mateo, E. Sanchis Blanco, J.V. Gimeno-Adelantado, J. Peris-Vicente and M. Jimenez 1 Dpto. de Quimica Analitica, Facultad de Quimica, Universidad de Valencia, Dr. Moliner 50, E-46100 Burjassot, Valencia, Spain 2 Dpto. de Microbiologia y Ecologia, Facultad de Biologia, Universidad de Valencia, Dr. Moliner 50, E-46100 Burjassot, Valencia, Spain 3 Dpto. de Ingenieria Electronica, Universidad Politecnica de Valencia, Camino de Vera 14, E-46022, Valencia, Spain

Archaeopolymetallurgical study of materials from an Iberian culture site in Spain by scanning electron microscopy with X-ray microanalysis, chemometrics and image analysis

Abstract Archaeometallurgical materials from “La Bastida de Moixent”, a site in Valencia (Spain), from the second Iberian iron age (4th Century B.C.) have been studied using metallographic techniques, microanalysis, chemometrics and image analysis. The materials come from various phases of iron production and cupellation of argentiferous lead to obtain silver. Scanning electron microscopy (SEM) is used to determine the morphological, microstructural and topographic characteristics of the samples. Image analysis was used to obtain a numeric estimate of the main components in these materials. X-ray microanalysis (SEM/EDX) provides qualitative and quantitative information about the elements in…