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

Int. J. Mol. Sci. 2019, 20(6), 1447

DOI: 10.3390/ijms20061447

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%. Significant statistical differences were found in the presence of iprovalicarb and mepanipyrim residues, especially at the highest concentration assayed. For both fungicides, increases in the volatile acidity (between 4 and 8.6 times), the lactic acid content (between 8.6 and 20.5 times), the percentage of polymeric anthocyanins (between 1.3 and 1.7 times), and also a slight increase of the total phenolic index and the total anthocyanin content determined by spectrophotometry were observed. On the contrary, the total monomeric anthocyanins content decreased about 16.3% and 28.6% in the presence of iprovalicarb and mepanipyrim, respectively. These results could be related to a higher development of acetic acid or lactic bacteria in the presence of these fungicides. The color of the final wines was also different in comparison with the control, with a higher yellow component, color intensity, tonality, and hue angle because of pH changes in the medium. Tetraconazole fermentations had a more similar trend to the control wine, probably due to the lower concentration of this fungicide in the grape must at the initial time. No effects on the antioxidant activity was observed for any of the target fungicides. A multivariate statistical analysis was done to view the interrelationships between different variables (color and anthocyanins profile). The obtained model allowed the wines to be separated according to the fungicide treatment applied.

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

Food Research International, 108, 339-346, 2018

DOI: 10.1016/j.foodres.2018.03.058

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 20.8 h for MFT and 10.1 h for MEP. The proposed models afford reasonably accurate interpretation of the experimental data. Based on the results, modelling the kinetics of disappearance of the parent compound by itself does not ensure the best fit of the degradation behaviour of the fungicides.

Fungicide residues affect the sensory properties and flavonoid composition of red wine

Journal of Food Composition and Analysis, 66 (2018) 185-192

doi.org/10.1016/j.jfca.2017.12.021

The influence of four fungicide treatments [viz., metrafenone, boscalid + kresoxim-methyl, fenhexamid and mepanipyrim, which are typically used to control downy mildew (Plasmopara viticola) and grey mould (Botrytis cinerea)] on the composition of Tempranillo red wines was assessed by examining changes in phenolic composition, colour and aroma profile in wines from pesticide-treated grapes in relation to control wines made from untreated grapes. The results were also compared with those for wine of a previous vintage in order to ascertain whether fungicide-related changes were comparable to vintage-related changes. Only the boscalid + kresoxim-methyl treatment led to significant differences in wine of the 2013 vintage; thus, it increased the contents in monomeric anthocyanins (58%) and flavan-3-ols (36%), and also colour lightness (20%), but decreased the contribution of the ripe (42%) and fresh fruits (59%) odorant series. These results seemingly confirm that the presence of boscalid + kresoxim-methyl residues in must impairs the sensory quality of the resulting wine by diminishing its brightness and aroma. Differences varied markedly between years, which suggests that the course of the fermentation process is influenced not only by the composition of the grapes but also by the presence of the fungicide.

Effects of hydrochemistry variables on the half-life of mancozeb and on the hazard index associated to the sum of mancozeb and ethylenethiourea

Environmental Research, 154, 2017, 253-260

https://doi.org/10.1016/j.envres.2017.01.016

Mancozeb is a dithiocarbamate non-systemic agricultural fungicide with multi-site, protective action. It helps to control many fungal diseases in a wide range of field crops, fruits, nuts, vegetables, and ornamental plants. We have investigated the stability profiles of mancozeb in aqueous solutions to determine the effect of pH, temperature and light on the degradation process of mancozeb. In addition, the toxicological risk for humans associated with the joint intake of mancoze7b and its final degradation product, ethylenethiourea (ETU), was calculated and modelled as a function of the experimental conditions. Stability study results showed a very low stability profile of mancozeb in all the aqueous solutions with rapid degradation that varied with experimental conditions. The process followed first order kinetics. The study of the degradation kinetics showed a significant effect of pH*temperature interaction on the degradation process. The results also expressed that light has a greater impact on the stability of mancozeb and the formation of ETU. The current study concludes that mancozeb is unstable in aqueous solutions, particularly at an acid pH, in addition to presenting both severe light and lower temperature sensitivity. The toxicological risk associated with mancozeb degradation increases with time and temperature, being higher at basic pH and in absence of light.

Rainfall-induced removal of copper-based spray residues from vines

Ecotoxicology and Environmental Safety,132, 2016, 304–310

http://dx.doi.org/10.1016/j.ecoenv.2016.06.020

The continuous use of copper against fungal diseases and off-target effects causes major environmental and agronomic problems. However, the rain-induced removal of Cu-based residues is known only for a limited number of crops. We present the results of rain-induced removal of fungicides from two monitored vineyard plots which were sprayed with two widely used Cu-based formulations: copper-oxychloride (CO) and Bordeaux mixture (BM), respectively. Cu removal per growing season was 0.60±0.12 kg ha−1 (30% of the applied fungicide) for CO and 0.80±0.10 kg ha−1 for BM (70% of the applied fungicide). Fractioning the Cu in soluble (CuS) and particulate fractions (CuP) showed that most of the Cu was removed as CuP, but CuS concentrations found in throughfall collectors exceeded the regulatory threshold for toxicity in surface waters. The first few millimeters of rain caused most of the Cu removal. Our findings agreed with the data reported in the scientific literature, in which a significant fraction of the Cu-based formulation is loosely attached to the plant surfaces. In addition, we found that rainfall energy had a minor influence on the removal.

Biological activities and novel applications of chalcones

Planta Daninha

http://dx.doi.org/10.1590/S0100-83582016340300022

This review provides information on the biological activities of chalcones (whether natural or synthetic derivatives) on different organisms, as well as an overview of the functions and possible new applications of these plant secondary metabolites on crop protection, as eco-friendly pesticides and weed control agents. Naturally occurring chalcones have been used in traditional medicine for many years; however, recent scientific advances have shown that these molecules have a broad range of biological activities in a variety of organisms. A review on the major sources of chalcones and the main molecular events involved in the modes of action of these natural products is achieved. Chalcones are molecules with a broad spectrum of biological activities, which are of great interest in agriculture to control weeds and unwanted pests.

Dissipation of fungicides residues along winemaking, and their effects on fermentation and the volatile composition of wines

Journal of Agricultural and Food Chemistry

The effects of four fungicides commonly used for the control of fungal diseases in vines and grapes in the course of winemaking was tested. The concentration of fungicide residues was monitored throughout the process in order to establish their kinetics of dissipation. In all cases the percentages of dissipation were higher than 68% which shows the detoxificant effect of the winemaking process. On the other hand, the effect of the fungicide residues on the aroma composition of Tempranillo red wines was tested.

Toxicity evaluation of new agricultural fungicides in primary cultured cortical neurons

Environmental Research, 140, 2015, 37-44

doi 10.1016/j.envres.2015.03.013

Fungicides are crucial for food protection as well as for the production of crops of suitable quality and quantity to provide a viable economic return. Like other pesticides, fungicides are widely sprayed on agricultural land, especially in wine-growing areas, from where they can move-off after application. Furthermore, residues of these agrochemicals can remain on crops after harvest and even after some food processing operations, being a major exposure pathway. Although a relatively low toxicity has been claimed for this kind of compounds, information about their neurotoxicity is still scarce.

In the present study, nine fungicides recently approved for agricultural uses in the EU ― ametoctradin, boscalid, cyazofamid, dimethomorph, fenhexamid, kresoxim-methyl, mepanipyrim, metrafenone and pyraclostrobin ― have been evaluated for their toxicity in primary cultured mouse cortical neurons. Exposure to 0.1–100 µM for 7 days in vitro resulted in a dose-dependent toxicity in the MTT cell viability assay. Strobilurin fungicides kresoxim-methyl (KR) and pyraclostrobin (PY) were the most neurotoxic compounds (lethal concentration 50 were in the low micromolar and nanomolar levels, respectively) causing a rapid raise in intracellular calcium [Ca2+]i and strong depolarization of mitochondrial membrane potential. KR- and PY-induced cell death was reversed by the calcium channels blockers MK-801 and verapamil, suggesting that calcium entry through NMDA receptors and voltage-operated calcium channels are involved in KR- and PY-induced neurotoxicity. These results highlight the need for further evaluation of their neurotoxic effects in vivo.