Search Results (20)

The presence of pesticide residues in wine raises concerns about consumer health and regulatory compliance. This study evaluates the behaviour of seven pesticides (boscalid, penconazole, tebufenozide, kresoxim-methyl, trifloxystrobin, chlorpyrifos and lambda-cyhalothrin) during key stages of vinification, including clarification, fermentation, and racking, using liquid chromatography–tandem mass spectrometry. Penconazole, kresoxim-methyl and trifloxystrobin were not detected at the beginning of the vinification stage. Boscalid, chlorpyrifos and lambda-cyalothrin showed a reduction of 100% whit, a concentration below the limit of quantification at the end of the vinification stage. However, tebufenozide showed the lower elimination rate (88.1%), presenting a concentration at the end of the vinification process of 21.71 µg/kg. Experimental data confirm that pesticide concentrations progressively decline due to a combination of physicochemical transformations, adsorption onto solids, and biochemical processes. The clarification and racking stages are particularly important for reducing residues, primarily by removing suspended solids that adsorb pesticides. Fermentation also contributes to this reduction through microbial metabolism and enzymatic hydrolysis. The effectiveness of these stages depends on the pesticide’s solubility, chemical stability, and interactions with components in the wine matrix. Additionally, a risk assessment based on Acceptable Daily Intake and Estimated Daily Intake was performed to evaluate potential consumer exposure, showing lower risk for all pesticides studied. The findings emphasise the importance of optimising clarification and racking procedures, selecting effective fining agents, and refining filtration techniques to further enhance pesticide removal. Full article

To manage the developing resistance of Alternaria spp. [the causal fungi of ginseng Alternaria leaf and stem blight (GALSB)] to QoIs fungicides, the toxicity and biochemical activity of pyrimidine nucleoside antibiotics (PNA) against Alternaria spp., cross-resistance between PNA and eight other fungicides currently used to control GALSB disease, and the efficacy of PNA for controlling GALSB in vitro and in vivo were investigated. The distributions of EC₅₀ values of PNA against the mycelial growth (115 isolates) and conidia germination (89 isolates) of A. alternata were unimodal, with mean EC₅₀ values of 10.192 ± 4.961 μg/mL and 0.828 ± 0.101 μg/mL, respectively. There were no significant correlations between the sensitivity of A. alternata to PNA and eight other fungicides (p < 0.05). PNA caused morphological changes in A. alternata mycelia and germ tubes, increased cell membrane permeability, and reduced intracellular DNA and protein levels. On detached ginseng leaves, 300 μg/mL PNA achieved mean protective and curative effects of 87.93% and 94.77% against A. alternata 7 days post-inoculation, outperforming that of 300 μg/mL kresoxim-methyl. Field trial results showed that PNA (180 g a.i./hm²) achieved mean efficacies of 85.63%, 84.07%, and 72.55% at three sites 7, 15, and 30 days after the last spray, which were 5.28–37.74% higher than those of control fungicides pyraclostrobin, azoxystrobin, and kresoxim-methyl at corresponding time points. Overall, our findings indicate that PNA are effective agents for the management of Alternaria spp. resistance to QoIs fungicides. Full article

Pharmaceutical and Personal Care Products (PPCPs), such as carbamazepine, enter the food chain through wastewater irrigation, posing risks to ecosystems and human health. However, research on the translocation and subcellular distribution of carbamazepine in vegetables is limited. Herein, we used ¹⁴C-labeled carbamazepine as a tracer to investigate its removal, accumulation, and subcellular compartmentalization in hydroponic vegetable systems. Results showed carbamazepine accumulated in Chinese flowering cabbage and water spinach with removal efficiencies of 93.0–93.2%. The compound was absorbed by roots and translocated to aboveground tissues, particularly in bottom leaves, reaching 90.3 μmol/kg after 768 h, as confirmed by autoradiography. Subcellular analysis indicated that carbamazepine is predominantly distributed in root organelles and in the soluble fraction of leaves and stems. A strong correlation (R² > 0.800) was observed between root enrichment coefficients and log K_OW for caffeine, carbamazepine, and kresoxim-methyl. Higher lipid content in water spinach roots (2.07%) significantly enhanced upward transport, underscoring lipid content’s role in translocation. Additionally, a higher xylem content in the plant accelerated the transport of carbamazepine. This study provides key insights into the environmental behavior of organic pollutants, supporting efforts in environmental and health protection. Full article

Consumption of common dandelion (Taraxacum officinale agg.) can pose a risk when foraged in agroecosystems like vineyards where pesticides are frequently used. The aims of our study are to evaluate whether dandelion foraged in vineyards with different management practices (integrated pest management, organic, and biodynamic) in spring is suitable for consumption and to assess whether the contents of selected pesticide residues (PR) in integrated vineyards in dandelion vary throughout the seasons. Young dandelion leaves were sampled in spring, summer, and autumn in integrated vineyards, while in spring also in organic and biodynamic vineyards. The selected PR was analyzed using GC-MS/MS and LC-MS/MS, using extraction with acetonitrile. The method was validated on a dandelion matrix according to international guideline SANTE 11312/2021. Despite the use of many pesticides in integrated vineyards, only tebuconazole was detected in spring in one sample (0.005 mg/kg), while no PR was detected in dandelion from organic and biodynamic vineyards. However, at summer sampling seven different PR were detected, of which the kresoxim-methyl maximum residue limit was exceeded in five samples (0.012–0.029 mg/kg), while in autumn no PR was detected. Based on this study, it seems that dandelion leaves foraged in vineyards in spring could be unproblematic for consumption. Full article

THz waves have garnered significant attention across multiple domains, particularly in high-sensitivity sensing applications. Metamaterials are applicable in THz sensors owing to their exceptional sensitivity, particularly in refractive index measurement and pesticide identification. This paper proposes a THz metamaterial sensor for detecting ether kresoxim-methyl. The sensor comprises a periodic array of silicon cylindrical trimers organized on a silicon substrate. Resonances in the guided mode, dictated by bound states in the continuum spectrum, can be stimulated by meticulously configuring the geometric arrangement of the silicon column trimer. The sensor demonstrates a Q-value of up to 143 at the resonant frequency. The detection of pesticide residues achieved high sensitivity and specificity, with a detection limit of 37.74 μg/cm². This study presents a novel alternative for THz metamaterial sensors characterized by high sensitivity and a broad spectrum of pesticide concentration detection. The sensor platform developed in this paper, utilizing conventional CMOS technology, is posited as a potential detection instrument for herbicide and pesticide residues in agriculture and food. Full article

Antifungals support modern medical and agricultural practices, and extensive screening environmental data are missing. This work aims to survey antifungals for medical and agricultural purposes in surface- and groundwater in Portugal. A passive sampling technique and a high-resolution chromatographic system were used. Antifungals applied in medical practice were not detected as only antifungals for agricultural purposes (fungicides). Thirty-nine different fungicide molecules were found; its detection frequency in surface- and groundwater was dominated by rabenzazole (61%, 92%) and ethoxyquin (54%, 77%); among the five fungicides with similar surface- and groundwater catching rates, ferimzone was the most polluting (54%, 54%); oxadixyl (61%), kresoxim-methyl (61%) and fenamidone (46%) were primarily designated surface water contaminants; for azoles, the occurrence in surface water ranged from a residual (10%) to a moderate detection rate for two compounds (31%—propiconazole and tebuconazole). Surprisingly, only 51% of detected fungicides are authorised. The frequently detected fungicides that are either not authorised (ethoxyquin and its impurity, furmecyclox, oxadixyl), without data in the EU (rabenzazole, ferimzone), or authorised at the national level (fenamidone), should be included in environmental monitoring programmes and followed as emerging (micro)contaminants. Policy makers should gather their efforts to allow the implementation of proper risk management and effective contamination control strategies to achieve Sustainable Development Goals. Full article

Strawberry crown rot poses a significant menace to strawberry production during the seedling stage, and the main pathogen is Colletotrichum spp. Pyraclostrobin is one of the main fungicides that have been registered to control anthracnose caused by Colletotrichum spp. The diversity of pathogens and the risk of fungicide resistance may change from year to year. In order to explore the diversity of pathogens causing crown rot and evaluate the resistance risk of pathogens to pyraclostrobin in different years, crown rot samples were collected in Jiande, Zhejiang Province in 2019 and 2021, and the pathogens were identified. Based on the morphological identification and phylogenetic analysis based on ACT, CAL, CHS, GAPDH, and ITS, all 55 strains were identified as C. gloeosporioides species complexes, including 23 C. siamense isolates and 2 C. fructicola isolates in 2019, and all isolates were identified as C. siamense in 2021. C. siamense was the dominant pathogen of strawberry crown rot in 2019 and 2021. The resistance frequencies of the isolates collected in 2019 and 2021 to pyraclostrobin were 69.57% and 100%, respectively. In general, compared to that in 2019, the resistance frequencies of the pathogen to pyraclostrobin increased in 2021. In terms of fitness, there was no significant difference between resistant strains and sensitive strains in the mycelium growth rate, sporulation and spore germination rate. In addition, the resistant mutants exhibited positive cross-resistance to kresoxim-methyl and azoxystrobin. A sequential analysis of cytochrome b gene showed that C. siamense resistance to pyraclostrobin is linked to the G143A point mutation. Our study indicated that the risk of resistance a fungicide gradually increases with the increase in use years, and in order to reduce the emergence and spread of resistant populations, we should choose fungicides of different mechanisms of action for rotation to reduce the risk of resistance development. Full article

Alfalfa Fusarium Root Rot (AFRR) is a serious soil-borne disease with a complex pathogenicity. Diseased samples suspected of AFRR were collected from Hohhot, Ordos, Hulunbeier, Chifeng, and Bayannur in Inner Mongolia, China, leading to 317 isolates. The isolates were identified as Fusarium acuminatum, F. solani, F. equiseti, F. incarnatum, F. oxysporum, F. avenaceum, F. verticillioides, F. proliferatum, F. falciforme, F. tricinctum, F. virguliforme, and F. redolens, and the results of pathogenicity testing showed that 12 Fusarium species could cause alfalfa root rot. Among these, F. verticillioides, F. falciforme, and F. virguliforme have not previously been reported to cause AFRR in China. Although the population structure of the pathogens differed in different regions, the dominant pathogenic species was F. acuminatum. Fungicide toxicity tests showed that seven fungicides inhibited F. acuminatum, of which fludioxonil, kresoxim-methyl, and triadimefon were found to be strongly toxic towards F. acuminatum with EC₅₀ values of 0.09, 2.28, and 16.37 μg/mL, respectively, suggesting that these could be used as alternative fungicides for the control of AFRR. The results of this study can provide a theoretical basis for exploring the occurrence and epidemiology of alfalfa root rot and strategies for its control. Full article

Pesticides are widely used in agriculture as a pest control strategy. Despite the benefits of pesticides on crop yields, the persistence of chemical residues in soil has an unintended impact on non-targeted microorganisms. In the present study, we evaluated the potential adverse effects of a mixture of fungicides (difenoconazole, epoxiconazole, and kresoxim-methyl) on soil fungal and bacterial communities, as well as the manifestation of wheat diseases. In the fungicide-treated soil, the Shannon indices of both fungal and bacterial communities decreased, whereas the Chao1 indices did not differ compared to the control soil. Among bacterial taxa, the relative abundances of Arthrobacter and Sphingomonas increased in fungicide-treated soil due to their ability to utilize fungicides and other toxic compounds. Rhizopus and plant-beneficial Chaetomium were the dominant fungal genera, with their prevalence increasing by 2–4 times in the fungicide-treated soil. The genus Fusarium, which includes phytopathogenic species, which are notably responsible for root rot, was the most abundant taxon in each of the two conditions but its relative abundance was two times lower in fungicide-treated soils, consistent with a lower level of disease incidence in plants. The prediction of metabolic pathways revealed that the soil bacterial community had a high potential for degrading various pollutants, and the soil fungal community was in a state of recovery after the application of quinone outside inhibitor (Q_oI) fungicides. Fungicide-treated soil was characterized by an increase in soil microbial carbon, compared with the control soil. Collectively, the obtained results suggest that the application of difenoconazole, epoxiconazole, and kresoxim-methyl is an effective approach for pest control that does not pose a hazard for the soil ecosystem in the short term. However, it is necessary to carry out additional sampling to take into account the spatio-temporal impact of this fungicide mixture on the functional properties of the soil. Full article

The search for fungicides of novel classes is the long-standing priority in crop protection due to the continuous development of fungal resistance against currently used types of active compounds. Recently, 4-nitropyrazolin-3-ones were discovered as highly potent fungicides, of which activity was believed to be strongly associated with the presence of a nitro group in the pyrazolone ring. In this paper, a series of 4-substituted pyrazolin-3-ones were synthesized and their fungicidal activity against an important species of phytopathogenic fungi (Venturia inaequalis, Rhizoctonia solani, Fusarium oxysporum, Fusarium moniliforme, Bipolaris sorokiniana, and Sclerotinia sclerotiorum) was tested in vitro. We discovered that 4-mono and 4,4-dihalogenated pyrazolin-3-ones demonstrate fungicidal activity comparable to that of 4-nitropyrazolin-3-ones and other modern fungicides (such as kresoxim methyl). This discovery indicates that NO₂ moiety can be replaced by other groups of comparable size and electronic properties without the loss of fungicidal activity and significantly expands the scope of potent new fungicides based on a pyrazolin-3-one fragment. Full article

Bamboo is rich in starch and sugars and can be infected by mold and stain fungi, degrading its performance, shortening its service life, and reducing its utilization value. It is crucial to investigate how to protect bamboo against mold and stain fungi. The zone of inhibition test was used to evaluate the antifungal activity of azoxystrobin, kresoxim-methyl, pyraclostrobin and 3-iodo-2-propynyl-butylcarbamate (IPBC) against stain fungi (Botryodiplodia theobromae, Fusarium moniliforme, and Alternaria alternate) and mold fungi (Aspergillus niger, Penicillium citrinum, and Trichoderma viride) to develop new chemicals to protect bamboo against stain fungi and molds. The inhibitory activity of the composite pyraclostrobin and IPBC with different ratios was evaluated. Water-based formulations of the fungi were used to treat the bamboo, and the mold and stain resistance of the bamboo was investigated at different chemical retention rates. The results showed that the antifungal activity of pyraclostrobin was significantly higher than that of azoxystrobin and kresoxim-methyl. Different degrees of inhibitory activities against the stain and mold fungi were observed, and the inhibitory activity was higher against stain fungi than against molds. The three stain fungi were completely inhibited at a 7:3 ratio of pyraclostrobin to IPBC and 0.1% concentration. As the ratio increased, the inhibitory effect against mixed mold strains improved. The control efficacy of the pyraclostrobin formulations Str-1 and Str-2 at 0.1% concentration was 100% against Alternaria alternate and 70.8% against Fusarium moniliforme. The control efficacy of the composite formulations SI-1 and SI-2 at 0.1% concentration was 100% against all three stain fungi and greater than 91.8% against the mixed mold strains. This study provides new insights into the utilization of pyraclostrobin and its composite formulations as new bamboo antifungal agents. Full article

Sediment, notothenioid fish, and moss samples were collected from the vicinity of Galindez Island, Antarctic Peninsula during the austral autumn of 2016 and 2017. Pesticide, Polycyclic Aromatic Hydrocarbon (PAH), and dioxin-like Polychlorinated Biphenyl (dl-PCB) concentrations were measured using High-Resolution Gas and Liquid Chromatography. Pollutant concentrations were below detection limits in sediment and moss samples. However, pesticides, PAH, and dl-PCB congeners were detected in the muscle tissue of fishes. Pesticide concentrations varied between 0.46 and 12.2 ng/g-dw, and Mecarbam was the dominant compound. Kresoxim-methyl, Mecarbam, Procymidone, Pyridaben, and Quinoxyfen were reported in the muscle tissue of the fishes, for the first time from the Antarctic. PCB-118, PCB-105, and PCB-156 were dominant dl-PCBs. The ∑12-dl-PCB concentration was 160,929 pg/g-dw, and WHO-TEQ-total dl-PCB was 8.30 pg/g-dw in Trematomus bernachii, over the consumable limit in fishes according to the European Commission. The PCB-126 concentration was 36 pg/g-dw in the muscle tissue of fish, the first reported from the Antarctic. Phenanthrene was the dominant PAH congener. The ∑16-PAH concentration was 22.5 ng/g-dw. PAH sources were local and petrogenic in the fishes, likely after long-term bioaccumulation. The flow rate is rather low around Galindez Island; accordingly, contaminant removal takes time and may demonstrate long-lasting effects including bioaccumulation in the marine food web. Full article

Quinone outside inhibitors (QoI) fungicides group were introduced for commercial use against apple scab (Venturia inaequalis) in Israel in 1997. Unlike other regions in the world, in which resistance of V. inaequalis to QoI fungicides was observed within 3–5 years of use, in Israel it only occurred after 14 years of use. Field trials conducted between 2007 and 2017 showed a significant reduction in susceptibility to QoIs in northern Israel only since 2011. The delay in the development of resistance is related to limited fungicidal sprays resulting from unfavorable conditions for the pathogen. Of the 28 isolates collected from infected leaves or fruits of commercial orchards in northern Israel, 27 were resistant to the QoI fungicide Kresoxim-methyl. Amplification of the CYTB gene and sequencing of the G143A mutation region confirmed the resistance of all 27 isolates to QoIs. Resistance is demonstrated in the orchard, in vitro and molecular-based study, which forced the growers to avoid using QoIs against apple scab. We show that foliar applications of tank mixtures of systemic fungicides plus captan or prepacked fungicidal mixtures improved efficacy and can be used as a strategic approach in fungicide resistance management, including in orchards in which resistance to QoIs has been detected. Full article

Azoxystrobin is one of the most popular strobilurin fungicides, widely used in agricultural fields for decades.Extensive use of azoxystrobin poses a major threat to ecosystems. However, little is known about the kinetics and mechanism of azoxystrobin biodegradation. The present study reports a newly isolated bacterial strain, Ochrobactrum anthropi SH14, utilizing azoxystrobin as a sole carbon source, was isolated from contaminated soils. Strain SH14 degraded 86.3% of azoxystrobin (50 μg·mL⁻¹) in a mineral salt medium within five days. Maximum specific degradation rate (q_max), half-saturation constant (K_s), and inhibition constant (K_i) were noted as 0.6122 d⁻¹, 6.8291 μg·mL⁻¹, and 188.4680 μg·mL⁻¹, respectively.Conditions for strain SH14 based azoxystrobin degradation were optimized by response surface methodology. Optimum degradation was determined to be 30.2 °C, pH 7.9, and 1.1 × 10⁷ CFU·mL⁻¹ of inoculum. Strain SH14 degraded azoxystrobin via a novel metabolic pathway with the formation of N-(4,6-dimethoxypyrimidin-2-yl)-acetamide,2-amino-4-(4-chlorophenyl)-3-cyano-5,6-dimethyl-pyridine, and 3-quinolinecarboxylic acid,6,8-difluoro-4-hydroxy-ethyl ester as the main intermediate products, which were further transformed without any persistent accumulative product. This is the first report of azoxystrobin degradation pathway in a microorganism. Strain SH14 also degraded other strobilurin fungicides, including kresoxim-methyl (89.4%), pyraclostrobin (88.5%), trifloxystrobin (78.7%), picoxystrobin (76.6%), and fluoxastrobin (57.2%) by following first-order kinetic model. Bioaugmentation of azoxystrobin-contaminated soils with strain SH14 remarkably enhanced the degradation of azoxystrobin, and its half-life was substantially reduced by 95.7 and 65.6 days in sterile and non-sterile soils, respectively, in comparison with the controls without strain SH14. The study presents O. anthropi SH14 for enhanced biodegradation of azoxystrobin and elaborates on the metabolic pathways to eliminate its residual toxicity from the environment. Full article

Kresoxim-methyl is a high-efficiency and broad-spectrum fungicide used for the control of rice fungal diseases; however, its residues after application potentially threaten human health. Investigations on the dissipation of kresoxim-methyl residue in rice field systems and dietary risk assessment of kresoxim-methyl in humans are limited. The present study employed the QuEChERS-GC-MS/MS method for residue analysis of kresoxim-methyl in rice plants, brown rice, and rice husks. The samples were extracted with acetonitrile and purified by PSA, C₁₈ column, and GCB. The average recovery of the spiked target compounds in the three matrices was between 80.5% and 99.3%, and the RSD was between 2.1% and 7.1%. The accuracy and precision of the method is in accordance with the requirements of residue analysis methods. Dissipation dynamic testing of kresoxim-methyl in rice plants indicated a half-life within the range of 1.8–6.0 days, and a rapid dissipation rate was detected. Dietary intake risk assessment showed that the national estimated daily intake (NEDI) of kresoxim-methyl in various Chinese subpopulations was 0.022–0.054 μg/(kg bw·days), and the risk quotient (RQ) was 0.0000055–0.00014%. These findings indicate that the risk for chronic dietary intake of kresoxim-methyl in brown rice is relatively low. The present study provides information and theoretical basis for guiding the scientific use of kresoxim-methyl in rice fields and evaluating its dietary risk in brown rice. Full article