Contribution of critical doses of iprovalicarb, mepanipyrim and tetraconazole to the generation of volatile compounds from Monastrell-based wines.

The individual effects of iprovalicarb, mepanipyrim, and tetraconazole on the volatile composition and aromatic profile of Monastrell-based wines were evaluated. To date, no studies about the effect of these fungicides on Monastrell-based wines are available, and the effect on other grape varieties is also unknown. Fungicides were added separately in the cellar to the grape must at two concentration levels (4 and 10 mg/kg for iprovalicarb and mepanipyrim and 1 and 2.

Applicability of an In-Vitro Digestion Model to Assess the Bioaccessibility of Phenolic Compounds from Olive-Related Products.

The Mediterranean diet includes virgin olive oil (VOO) as the main fat and olives as snacks. In addition to providing nutritional and organoleptic properties, VOO and the fruits (olives) contain an extensive number of bioactive compounds, mainly phenolic compounds, which are considered to be powerful antioxidants. Furthermore, olive byproducts, such as olive leaves, olive pomace, and olive mill wastewater, considered also as rich sources of phenolic compounds, are now valorized due to being mainly applied in the pharmaceutical and nutraceutical industries.

The effect of two antifungal commercial formulations on the metabolism of a commercial Saccharomyces cerevisiae strain and their repercussion on fermentation evolution and phenylalanine catabolism.

The effect of two commercial formulations (incorporating mepanipyrim and tetraconazole as active substances) on the metabolism of Saccharomyces cerevisiae Lalvin T73™, growing on a synthetic grape must, and their influence on the alcoholic fermentation course and the biosynthesis of volatiles derived from phenylalanine catabolism was studied. No relevant effects were observed for mepanipyrim except for glycerol production. On the contrary, in the presence of tetraconazole many genes and some proteins related to cell cycle progression and mitosis were repressed.

Influence of tetraconazole on the proteome profile of Saccharomyces cerevisiae Lalvin T73™ strain.

This work aimed to evaluate the modifications on the proteome profile of Saccharomyces cerevisiae T73™ strain as a consequence of its adaptive response to the presence of tetraconazole molecules in the fermentation medium. Pasteurised grape juices were separately supplemented with tetraconazole or a commercial formulation containing 12.5% w/v of tetraconazole at two concentration levels.

Impact of mepanipyrim and tetraconazole in Mencía wines on the biosynthesis of volatile compounds during the winemaking process.

The impact of fungicides mepanipyrim (Mep) and tetraconazole (Tetra) and their corresponding commercial formulations (Mep-Form and Tetra-Form) on the aroma composition of wines was assessed. Fungicide residues can affect the biotransformation of aroma precursors from grapes and/or the yeast metabolism. The results confirmed that both maximum residue levels (MRL and 2xMRL) of Mep promoted benzyl alcohol and 4-vinylguaiacol contents; while MRL and 2xMRL of Mep-Form promoted benzene derivatives (benzyl alcohol, benzaldehyde, and trans-isoeugenol), 2-phenylethanol and γ-nonalactone.

Dissipation of Three Fungicides and Their Effects on Anthocyanins and Color of Monastrell Red Wines.

The effect of fungicides on fermentation is of paramount importance to control the quality and safety of wines. In this work, the quality (enological parameters, color, phenolic content, antioxidant activity, and fungicide residues) of wines from Monastrell grapes fortified with iprovalicarb, mepanipyrim, and tetraconazole fungicides was evaluated. Along the winemaking process, initial residues of mepanipyrim and tetraconazole were removed in more than 90% while the dissipation of iprovalicarb was around 73%.

Modelling the isothermal degradation kinetics of metrafenone and mepanipyrim in a grape juice analog.

Five photodegradation products of metrafenone (MTF) and six of mepanipyrim (MEP) were identified in synthetic grape juice at 25 °C and the structures of the main reaction products established. The degradation of MTF and MEP was modelled by using three different strategies involving monitoring (a) the disappearance of the parent compound, (b) the conversion of the parent compound into its main structurally related reaction products and (c) the degradation of the parent compound to all intermediates and degradation end-products. The kinetic coefficients of degradation for these fungicides were determined and the corresponding half-lives found to be 20.

Kinetic modelling of mancozeb hydrolysis and photolysis to ethylenethiourea and other by-products in water.

The aim of this study was to propose kinetic models suitable for reproducing and predicting mancozeb (Mz) conversion to by-products as a function of the operational conditions. The main factors (pH, temperature and light) potentially affecting the mancozeb degradation in aqueous models were studied by a multifactorial screening design. In addition, the response surface methodology (RSM) was applied to evaluate the interactive effects of these factors on ethylenethiourea (ETU) formation.

High-throughput HPLC-MS/MS determination of the persistence of neonicotinoid insecticide residues of regulatory interest in dietary bee pollen.

The aim of this work is the development of a simple, fast, quantitative, and economic method for the determination of neonicotinoid insecticide residues in dietary bee pollen. Several parameters of the method, such as extraction solvent, extraction time, and solid-phase extraction sorbents for purification [silica, C18, primary-secondary amine (PSA), and Envi-Carb II/PSA], were studied. The final proposed method based on solid-liquid extraction with hexane, cleanup with Supelclean™ Envi-Carb II/PSA cartridges, and subsequent analysis by high-performance liquid chromatography with tandem mass spectrometry was validated and applied to the analysis of commercial bee pollen samples from different geographical zones.

Effect of two anti-fungal treatments (metrafenone and boscalid plus kresoxim-methyl) applied to vines on the color and phenol profile of different red wines.

The effect of two anti-fungal treatments (metrafenone and boscalid + kresoxim-methyl) on the color and phenolic profile of Tempranillo and Graciano red wines has been studied. To evaluate possible modifications in color and phenolic composition of wines, control and wines elaborated with treated grapes under good agricultural practices were analyzed. Color was assessed by Glories and CIELab parameters.

Wine aroma compounds in grapes: a critical review.

Volatile organic compounds are vital to wine quality, determining their aroma and varietal characteristics. Which are present, and in what quantity, depends on the cultivar, the situation and soil of the vineyard, weather, cultivation methods, and wine-making practices. Here, we review the literature on the development of wine aroma compounds in grapes, and how it is affected by the above-named factors.

A review on the fermentation of foods and the residues of pesticides-biotransformation of pesticides and effects on fermentation and food quality.

Residues of pesticides in food are influenced by processing such as fermentation. Reviewing the extensive literature showed that in most cases, this step leads to large reductions in original residue levels in the fermented food, with the formation of new pesticide by-products. The behavior of residues in fermentation can be rationalized in terms of the physical-chemical properties of the pesticide and the nature of the process.

Effects of sugar concentration processes in grapes and wine aging on aroma compounds of sweet wines—a review.

Dessert sweet wines from Europe and North America are described in this review from two points of view: both their aroma profile and also their sensorial description. There are growing literature data about the chemical composition and sensory properties of these wines. Wines were grouped according to the production method (concentration of sugars in grapes) and to the aging process of wine (oxidative, biological, or a combination of both and aging in the bottle).

Distribution of polychlorinated biphenyls in both products and by-products of a mussel shell incinerator facility.

Purpose: Solid waste incineration has recently attracted much attention because the combustion process involved produces highly toxic organohalogen contaminants such as dioxin-like polychlorinated biphenyls (DL-PCBs) present in fly ash. This has raised the need for simple, rapid, accurate methods for monitoring PCBs in ash samples.

Methods: A method for the simultaneous quantitative determination of indicator, non-ortho and mono-ortho PCBs based on ultrasound-assisted extraction with 50:50 (v/v) n-hexane/acetone was developed, validated, and subsequently applied to real samples from a mussel shell incinerator facility in Galicia.

Influence of soil characteristics on copper sorption from a copper oxychloride fungicide.

The objective of this work was to assess the sorption of copper (Cu) applied as a Cu-oxychloride metalaxyl formulation by soils characterized by anthropogenic accumulation of Cu due to agricultural activity. The methods involved batch incubation of soils with a Cu-oxychloride metalaxy-based fungicide suspended in 0.01 M CaCl(2), phase separation, and determination of the concentration of Cu (Cu) in solution.

Effect of organic matter and iron oxides on quaternary herbicide sorption-desorption in vineyard-devoted soils.

Herbicide soil/solution distribution coefficients (K(d)) are used in mathematical models to predict the movement of herbicides in soil and groundwater. Herbicides bind to various soil constituents to differing degrees. The universal soil colloid that binds most herbicides is organic matter; however metallic hydrous oxides might also have some influence.

Determination of metalaxyl and identification of adjuvants in wettable powder pesticide technical formulas.

Foliar runoff is one of the most important processes affecting off-target movement of fungicides. In this way, Ridomil Gold Plus and Ridomil Gold MZ are two types of wettable powder technical formulations which contain metalaxyl and they are used for such a purpose. A method for quantitative determination of metalaxyl in pesticide formulas has been developed, validated, and subsequently applied to Ridomil Gold Plus and Ridomil Gold MZ.

Detachment of sprayed colloidal copper oxychloride-metalaxyl fungicides by a shallow water flow.

Background: Flow shear stress induced by rainfall promotes the loss of the pesticides sprayed on crops. Some of the factors influencing the losses of colloidal-size particulate fungicides are quantified by using a rotating shear system model. With this device it was possible to analyse the flow shear influencing washoff of a commercial fungicide formulation based on a copper oxychloride-metalaxyl mixture that was sprayed on a polypropylene surface.

Determination of 23 pesticide residues in leafy vegetables using gas chromatography-ion trap mass spectrometry and analyte protectants.

A gas chromatographic method was developed for simultaneously determining residues of 12 insecticides (acrinathrin, bifenthrin, carbofuran, cyfluthrin, lambda-cyhalothrin, cypermethrin, chlorfenvinphos, deltamethrin, esfenvalerate, fenamiphos, methiocarb and tau-fluvalinate) and 11 fungicides (cyprodinil, fludioxonil, iprodione, metalaxyl, penconazole, pyrimethanil, procymidone tebuconazole, triadimefon, triadimenol and vinclozolin) in leafy vegetables. Samples were extracted with acetonitrile and cleaned-up with graphitized carbon black/primary secondary amine (GCB/PSA) solid-phase extraction (SPE) cartridges using acetonitrile:toluene (3:1, v/v) as eluent. The eluate was finally evaporated and redissolved with 0.

Simplifying sample handling for protein identification by peptide mass fingerprint using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

An ultrasonic bath, an ultrasonic probe and a sonoreactor were used to speed up the kinetics of the reactions involved in each step of the sample handling for in-gel protein identification by peptide mass fingerprint, PMF, using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). The following steps were successfully accelerated using ultrasonic energy: gel washing, protein reduction, and protein alkylation. As a result, a reduction comprising 80% to 90% of the total time involved in the classic approach was achieved.

Simultaneous determination of the herbicides diquat and paraquat in water.

A method based on solid-phase extraction (on silica cartridges) and high-performance liquid chromatography (HPLC) followed by diode array UV detection is presented as an analytical tool for screening diquat (DQ) and paraquat (PQ) in drinking waters. The method is useful for quality control laboratories of water companies and beverage industries. Absolute recoveries of DQ and PQ from drinking water (25 mL in all cases), spiked at levels between 0.

Variation in concentrations of the fungicides tebuconazole and dichlofluanid following successive applications to greenhouse-grown lettuces.

Residual levels and degradation rates of tebuconazole and dichlofluanid in lettuce plants grown in a greenhouse under agricultural conditions typical of northwestern Spain were studied. Lettuce plants were sprayed four times with a homogeneous 0.2% aqueous solution of Folicur Combi (wettable powder containing 40% dichlofluanid and 10% tebuconazole) at a rate of 2500 g/ha.

Parameters affecting extraction of selected fungicides from vineyard soils.

This paper describes a sensitive method for the simultaneous quantification of eight commonly used grapevine fungicides in vineyard soils: cyprodinil, fludioxonil, metalaxyl, penconazole, pyrimethanil, procymidone, tebuconazole, and vinclozolin. The fungicides are extracted from the soil sample by sonication with water followed by shaking with ethyl acetate and are quantified by gas chromatography with mass spectrometry. Average extraction efficiencies in a sample of seven spiked, previously fungicide-free soils were > or =79% for all of the analytes, method precisions were > or =17%, and quantification limits were < or =50 microg/kg.

Determination of fungicide residues in white grapes for winemaking by gas chromatography with mass spectrometric detection and assessment of matrix effects.

A new analytical method, based on organic solvent extraction with dichloromethane-acetone (75 + 25, v/v) followed by gas chromatography with mass spectrometric detection, is presented for the determination of residues of 10 fungicides in white grapes for vinification. Some of them (cyprodinil, fludioxonil, and pyrimethanil) have been used for only 2-3 years and, therefore, no methods are available in the scientific literature for such a screening. Quality parameters yielded good precision (relative standard deviation of <10%) and detection limits (ranging between 1 and 18 microg/kg) that are lower than the maximum residue limits (MRLs) set by the 76/895/European Economic Community (EEC) and 90/642/EEC Directives.

Procedure for the measurement of soil inputs of plant-protection agents washed off through vineyard canopy by rainfall.

Soil inputs produced by rainfall waters washed off through a Ribeiro vineyard (Galicia, northwestern Spain) confirmed that levels recovered are <5% of the added fungicides. Laboratory studies showed that some fungicides were degraded in the ODS cartridge used for the collection of fungicides washed off by rainfall. Procymidone wash-off data obtained in the vineyard can be explained by a first-order rate mass transfer model.