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The present study is designed to evaluate whether pretreatment with moringa would have a protective effect on thioacetamide (TAA)-induced liver fibrosis, assessing biochemical and histopathological changes in Wistar male rats. Exposure to TAA induced notable biochemical and histopathological alterations. Liver fibrosis induced by TAA, along with associated biochemical and histological damage, has not been previously investigated in male rats supplemented with moringa oil. The experiment involved forty male rats distributed across four groups, each comprising ten rats. Group 1 served as controls and received intraperitoneal injections of saline solution twice weekly for six weeks. Group 2 rats were injected with 300 mg/kg body weight of TAA (Sigma-Aldrich Corp.) twice weekly for the same duration. Group 3 rats were orally supplemented with moringa oil at 800 mg/kg body weight/day and received intraperitoneal injections of TAA at the same dosage as Group 2 for six weeks. Finally, Group 4 rats were injected with saline solution twice weekly and orally supplemented with moringa oil at 800 mg/kg body weight/day for the same period. At the end of the experiment, we determined body weight and performed liver function analysis. Additionally, we examined the liver histology of the different groups. Results showed that moringa oil treatment protected rat livers from TAA toxicity by improving liver function analysis and preventing liver fibrosis. Moringa oil can be considered a promising agent for protection against TAA toxicity., (© 2023. Pleiades Publishing, Ltd.)

Objective: The aim: Нygienic assessment of labour conditions and risks for the Ukrainian agricultural personnel treating berries and melon crops with fungicides, herbicides and insecticides for justification of their safe use regulations., Patients and Methods: Materials and methods: Natural studies of labour conditions and risk correspond to the acting laws of Ukraine. The results were statistically treated using IBM SPSS StatisticsBase v.22., Results: Results: The natural studies of fungicides, insecticides, used for treatment of berries and melon crops, show that labour air environment corresponds to hygienic standards. The authors have established that the hazard index of complex fungicides effect on spray fueling attendants and tractor drivers is 0.110}0.046 and 0.155}0.071, that of herbicides - 0.34}0.025 and 0.380}0.257, that of insecticides - 0.221}0.111 and 0.222}0.110, respectively; hazard index of combined effect of several acting substances makes up- 0.239}0.088 and 0.336}0.140 for spray fueling attendants and tractor drivers, respectively. The statistical analysis shows that the hazard coefficients of inhalation and percutaneous penetration do not differ statistically between spray fueling attendants and tractor drivers (р>0.05). The percutaneous risk (%) of various pesticide groups for spray fueling attendants ranges 65.74-97.58 %, for tractor drivers - 50.72-95.23 %., Conclusion: Conclusions: The analysis has shown that the professional risk of fungicides, herbicides, insecticides, during agricultural treatment of the berries and melon crops does not exceed standards.

Botrytis cinerea is considered an important plant pathogen and is responsible for significant crop yield losses. With the frequent application of commercial fungicides, B . cinerea has developed resistance to many frequently used fungicides. Therefore, it is necessary to develop new kinds of fungicides with high activity and new modes of action to solve the increasingly serious problem of resistance. During our screening of fungicide candidates, one novel sulfonamide compound, N -(2-trifluoromethyl-4-chlorphenyl)-2-oxocyclohexyl sulfonamide ( L13 ), has been found to exhibit good fungicidal activity against B. cinerea . In this work, the mode of action of L13 against B. cinerea and the field control effect on tomato gray mold was studied. L13 had good control against B. cinerea resistant to carbendazim, diethofencarb, and iprodione commercial fungicides in the pot culture experiments. SEM and TEM observations revealed that L13 could cause obvious morphological and cytological changes to B. cinerea , including excessive branching, irregular ramification or abnormal configuration, and the decomposition of cell wall and vacuole. L13 induced more significant electrolyte leakage from hyphae than procymidone as a positive control. L13 had only a minor effect on the oxygen consumption of intact mycelia, with 2.15% inhibition at 50 μg/mL. In two locations over 2 years, the field control effect of L13 against tomato gray mold reached 83% at a rate of 450 g ai ha -1 , better than the commercial fungicide of iprodione. Moreover, toxicological tests demonstrated the low toxicological effect of L13 . This research seeks to provide technical support and theoretical guidance for L13 to become a real commercial fungicide.

The present study was focused on comparison of four typical fungicides in ginseng field to evaluate the impact of the different fungicides on the soil bacterial and fungal communities' composition and diversity by using high-throughput sequencing. Five treatments were designed comprising carbendazim (D), dimethyl disulfide (E), dazomet (M), calcium cyanamide (S), and control (C). The application of fungicide obviously altered the distribution of dominant fungal and bacterial communities and remarkably decreased the diversity (1099-763 and 6457-2245). The most abundant Proteobacteria obviously degenerate in fungicide-treated soil and minimum in E (0.09%) compared to control (25.72%). The relative abundance of Acidobacteria was reduced from 27.76 (C) to 7.14% after applying fungicide and minimum in E. The phylum Actinobacteria are both decomposers of organic matter and enemies of soil-borne pathogens, elevated from 11.62 to 51.54% and are high in E. The fungi community mainly distributed into Ascomycota that enriched from 66.09 to 88.21% and highin M and E (88.21 and 85.10%), and Basidiomycota reduced from 21.13 to 3.23% and low in M and E (5.27 and 3.23%). Overall, environmentally related fungicides decreased the diversity and altered the composition of bacterial and fungal communities, highest sensitivity present in dimethyl disulfide-treated soil.

The study aims to identify risks of agrochemicals that impact farmworkers, consumers, and ecology in Vietnamese mango cultivation to enhance safety and friendly production. The study finds out the total numbers of root fertilizers (N-P-K) of the noncooperative and cooperative farmers are similar, approximately 1,400 kg/ha/year higher than those in other countries. Excessive fertilizer usage is a potential threat to soil, water, and air pollution. In addition, the findings indicate that the ecology component is undergoing the most negative impact from excessive agrochemical use in mango farming. The vast majority of agrochemicals in mango cultivation are fungicide and paclobutrazol over 90% of the total number of agrochemicals used in both noncooperative and cooperative farmer groups among the three seasons. Total field EIQ of the cooperative grower category is less than that of the noncooperative grower category. These results show that mango cultivation should consider rejecting the banned active ingredients of glyphosate, paraquat, and carbendazim as well as reducing fungicide and paclobutrazol usage and encouraging cooperative participation to safeguard the environment and human health. Moreover, science information needs to be closely linked and fed back to policy development to boost the management of the awareness of the ecological risks for farmers associated with reducing agrochemical use in mango cultivation., Competing Interests: The authors declare that they have no conflicts of interest., (Copyright © 2021 Kiet Hong Vo Tuan Truong et al.)

Background: Wheat is one of the most important cereal crops worldwide, and use of fungicides is an essential part of wheat production. Both prothioconazole and fluoxastrobin give excellent control of important seed and soilborne pathogens. The combination of these two fungicides shows a complementary mode of action and has a wide usage around the world. But the residue levels of these fungicides in the wheat matrix are still unknown., Results: In the current study, a simple, low-cost and highly sensitive method using modified QuECHERS procedure combined with high-performance liquid chromatography-tandem mass spectrometry was developed to simultaneously quantify E- and Z-fluoxastrobin and the main metabolite prothioconazole-desthio of prothioconazole in the wheat matrix. The recoveries of prothioconazole-desthio, E-fluoxastrobin and Z-fluoxastrobin ranged from 84% to 101%, with relative standard deviation of less than 13.2%. The terminal residues of prothioconazole-desthio and E- and Z-fluoxastrobin were studied in wheat grain and straw under field conditions. The results showed that the terminal residue of the target compounds ranged from <0.01 to 0.029 mg kg -1 and <0.05 to 7.6 mg kg -1 in wheat grain and straw (expressed as dry weight), respectively. The risk quotients of prothioconazole-desthio and fluoxastrobin were 0.2% and 3.2%., Conclusions: The residue levels of the target analytes in wheat grain were lower than the maximum residue limits recommended by the Chinese Ministry of Agriculture. And the calculated risk quotient values were far below 100%, indicating a low dietary intake health risk to consumers. © 2021 Society of Chemical Industry., (© 2021 Society of Chemical Industry.)

Ziram, a zinc dithiocarbamate is widely used worldwide as a fungicide in agriculture. In order to investigate ziram-induced changes in macrophage functions and polarization, human monocytes-derived macrophages in culture were treated with ziram at 0.01-10 μmol.L -1 for 4-24 h. To characterize zinc involvement in these changes, we also determined the effects of disulfiram alone (dithiocarbamate without zinc) or in co-incubation with ZnSO 4 . We have shown that ziram and disulfiram at 0.01 μmol.L -1 increased zymosan phagocytosis. In contrast, ziram at 10 μmol.L -1 completely inhibited this phagocytic process, the oxidative burst triggered by zymosan and the production of TNF-α, IL-1β, IL-6, and CCL2 triggered by LPS. Disulfiram had the same effects on these macrophages functions only when combined with zinc (10 μmol.L -1 ). In contrast, at 10 μmol.L -1 ziram and zinc associated-disulfiram induced expression of several antioxidants genes HMOX1, SOD2, and catalase, which could suggest the induction of oxidative stress. This oxidative stress could be involved in the increase in late apoptosis induced by ziram (10 μmol.L -1 ) and zinc associated-disulfiram. Concerning gene expression profiles of membrane markers of macrophage polarization, ziram at 10 μmol.L -1 had two opposite effects. It inhibited the gene expression of M2 markers (CD36, CD163) in the same way as the disulfiram-zinc co-treatment. Conversely, ziram induced gene expression of other M2 markers CD209, CD11b, and CD16 in the same way as treatment with zinc alone. Disulfiram-zinc association had no significant effects on these markers. These results taken together show that ziram via zinc modulates macrophages to M2-like anti-inflammatory phenotype which is often associated with various diseases.

Plant breeding and disease management practices have increased the grain yield of hard winter wheat (Triticum aestivum L.) adapted to the Great Plains of the United States during the last century. However, the effect of genetic gains for seed yield and the application of fungicide on the micronutrient and cadmium (Cd) concentration in wheat grains is still unclear. The objectives of this study were to evaluate the effects of fungicide application on the productivity and nutritional quality of wheat cultivars representing 80 years of plant breeding efforts. Field experiments were conducted over two crop years (2017 and 2018) with eighteen hard winter wheat genotypes released between 1933 and 2013 in the presence or absence of fungicide application. For each growing season, the treatments were arranged in a split-plot design with the fungicide levels (treated and untreated) as the whole plot treatments and the genotypes as split-plot treatments in triplicate. The effects on seed yield, grain protein concentration (GPC), micronutrients, phytic acid, and Cd in grains were measured. While the yield of wheat was found to increase at annualized rates of 26.5 and 13.0 kg ha-1 yr-1 in the presence and absence of fungicide (P < 0.001), respectively, GPC (-190 and -180 mg kg-1 yr-1, P < 0.001), Fe (-35.0 and -44.0 μg kg-1 yr-1, P < 0.05), and Zn (-68.0 and -57.0 μg kg-1 yr-1, P < 0.01) significantly decreased during the period studied. In contrast to the other mineral elements, grain Cd significantly increased over time (0.4 μg kg-1 yr-1, P < 0.01) in the absence of fungicide. The results from this study are of great concern, as many mineral elements essential for human nutrition have decreased over time while the toxic heavy metal, Cd, has increased, indicating modern wheats are becoming a better vector of dietary Cd., Competing Interests: The authors have declared that no competing interests exist.

Aspergillus fumigatus is the main cause of invasive aspergillosis (IA) with a high annual global incidence and mortality rate. Recent studies have indicated an increasing prevalence of azole-resistant A. fumigatus (ARAF) strains, with agricultural use of azole fungicides as a potential contributor. China has an extensive agricultural production system and uses a wide array of fungicides for crop production, including in modern growth facilities such as greenhouses. Soils in greenhouses are among the most intensively cultivated. However, little is known about the occurrence and distribution of ARAF in greenhouse soils. Here, we investigated genetic variation and triazole drug susceptibility in A. fumigatus from greenhouses around metropolitan Kunming in Yunnan, southwest China. Abundant allelic and genotypic variations were found among 233 A. fumigatus strains isolated from nine greenhouses in this region. Significantly, ∼80% of the strains were resistant to at least one medical triazole drug, with >30% showing cross-resistance to both itraconazole and voriconazole. Several previously reported mutations associated with triazole resistance in the triazole target gene cyp51A were also found in our strains, with a strong positive correlation between the frequency of mutations at the cyp51A promoter and that of voriconazole resistance. Phylogenetic analyses of cyp51A gene sequences showed evidence for multiple independent origins of azole-resistant genotypes of A. fumigatus in these greenhouses. Evidence for multiple origins of azole resistance and the widespread distributions of genetically very diverse triazole-resistant strains of A. fumigatus in greenhouses calls for significant attention from public health agencies. IMPORTANCE The origin and prevalence of azole-resistant Aspergillus fumigatus have been attracting increasing attention from biologists, clinicians, and public health agencies. Current evidence suggests agricultural fungicide use as a major cause. In southwest China, greenhouses are used to produce large amounts of fruits, flowers, and vegetables for consumers throughout China as well as those in other countries, primarily in southeast Asia. Here, we found a very high frequency (∼80%) of triazole-resistant A. fumigatus in our sample, the highest reported so far, with a significant proportion of these strains resistant to both tested agricultural fungicides and medical triazole drugs. In addition, we found novel allelic and genotypic diversities and evidence for multiple independent origins of azole-resistant genotypes of A. fumigatus in greenhouse populations in this region. Our study calls for a systematic evaluation of the effects of azole fungicide usage in greenhouses on human health., (Copyright © 2021 Zhou et al.)

Avocados (Persea americana) are a fruit, whose shelf-life is jeopardized by rapid ripening and fungal diseases, which heighten the necessity for postharvest treatments. The use of refrigeration during storage and transport helps delay the ripening process and phytopathogen growth but it is not enough to attenuate the problem, especially once avocados are placed in ambient temperatures. Fungicides are effective in controlling fungal prevalence, but their possible adverse environmental and human health effects have spurred interest in finding safer, natural substitutes. The objective of this paper is to review recent advances and trends in the use of edible coatings as a safe alternative to preserve and extend avocados shelf-life. Edible biopolymer coatings have gained considerable attention due to their ability to extend fruit and vegetable shelf-life. These coatings are a novel type of biodegradable primary packaging made from biological compounds like polysaccharides, proteins, lipids, and other polymers. Coatings are considered nonactive if they only form a physical barrier, separating avocados from their immediate environment, controlling gas and moisture transfer. Active coatings can contain supplementary ingredients with additional properties like antioxidant and antifungal activity. The application of edible coatings shows promising potential in extending avocado shelf-life, replacing synthetic fungicides and reducing economic losses from avocado spoilage., (© 2020 Institute of Food Technologists®.)

The fungal pathogen Pyrenophora teres f. sp. maculata (Ptm), responsible for spot-form of net blotch (SFNB), is currently the most significant disease of barley in Australia and a major disease worldwide. Management of SFNB relies heavily on fungicides and in Australia the demethylase inhibitors (DMIs) predominate. There have been sporadic reports of resistance to DMIs in Ptm but the mechanisms remain obscure. Ptm isolates collected from 1996 to 2019 in Western Australia were tested for fungicide sensitivity levels. Decreased sensitivity to DMIs was observed in isolates collected after 2015. Resistance factors to tebuconazole fell into two classes; moderate resistance (MR; RF 6-11) and high resistance (HR; RFs 30-65). Mutations linked to resistance were detected in the promoter region and coding sequence of the DMI target gene Cyp51A. Solo-LTR insertion elements were found at 5 different locations in the promoter region. Three different non-synonymous mutations encoded an altered protein with a phenylalanine to leucine substitution at position 489, F489L (F495I in the archetype CYP51A of Aspergillus fumigatus). F489L mutations have also been found in DMI-resistant strains of P. teres f. sp. teres. Ptm isolates carrying either a LTR insertion element or a F489L allele displayed the MR1 or MR2 phenotypes, respectively. Isolates carrying both an insertion element and a F489L mutation displayed the HR phenotype. Multiple mechanisms acting both alone and in concert were found to contribute to DMI resistance in Ptm. Moreover, these mutations have emerged repeatedly in Western Australian Ptm populations by a process of parallel evolution., (Crown Copyright © 2020. Published by Elsevier Inc. All rights reserved.)

Chlorothalonil (CT) is a commonly used fungicide and its excessive application seriously threatens aquatic life and human health. Resveratrol (RSV) is a natural polyphenol and can be used as a therapeutic and preventive agent for the treatment of various diseases. To explore the toxic mechanism of CT exposure on fish kidney cell, as well as the alleviation effect of RSV, we established CT poisoning and/or RSV treatment fish kidney cell models. Ctenopharyngodon idellus kidney (CIK) cell line was treated with CT (5 μg/L) and/or RSV (10 μM) for 48 h. The results showed that CT exposure activated cytochromeP450s (CYPs) including CYP1A1, CYP1B1 and CYP1C, caused malondialdehyde (MDA) accumulation, inhibited glutathione (GSH) levels and glutathione peroxidase (GPX) activities, increased the expression of miR-15a and downregulated BCL2 and TNFα-induced protein 3 (TNFAIP3, A20), triggered mitochondrial pathway mediated apoptosis and receptor interacting serine/threonine kinase (RIP)-dependent necroptosis in CIK cells. However, cell death under CT exposure could be relieved by RSV treatment through inhibiting the expression of CYP1 family genes and restoring miR-15a/BCL2-A20 axis disorders. Overall, we conclude that RSV could relieve CT-induced apoptosis and necroptosis through miR-15a/Bcl2-A20 axis in CIK cells. These results enrich the toxicological mechanisms of the CT and confirm that RSV can be used as a potential antidote for CT poisoning., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

We showed the results of the first long-term analysis (1987-2019) of pesticide (herbicides, fungicides and insecticides) impact in the Rolling Pampa, one of the main agricultural areas of Argentina. Using a clear and meaningful tool, based not only on acute toxicity but also on scaling up the results to total sown area, we identified time trends for both pesticide impact and the ecoefficiency of modal pesticide profiles. By the end of the time series, soybean showed a pesticide impact four times greater than maize crop in the studied area. However, the time trend in the subperiod (2012-2019) showed a sustainable pattern of pesticide use in soybean crop, with an improvement in its ecoefficiency. Oppositely, maize showed a relatively constant ecoefficiency value during most of the time series, suggesting a possible path towards an unsustainable cropping system. Findings from this study suggest that some efforts have to be made to improve the pest management decisions towards a more efficient pesticide profiles in maize crop and to keep improving the ecotoxicity pesticide profile in soybean crops because of its large sown area in the studied area., Competing Interests: The authors have declared that no competing interests exist.

Objective: This research was performed to evaluate the effect of tebuconazole (TBZ) on reproductive organs of male rats and to assess the protective role of combined essential trace elements in alleviating the detrimental effect of TBZ on male reproductive function., Methods: For this purpose, 48 rats were exposed to 100 mg/kg TBZ, TBZ supplemented with zinc (Zn), selenium (Se), copper (Cu), and iron (Fe), TBZ + (Se + Zn); TBZ + Cu; or TBZ + Fe. The experiment was conducted for 30 consecutive days., Results: TBZ caused a significant perturbation in mineral levels and reduction in reproductive organs weights, plasma testosterone level, and testicular antioxidant enzyme activities. The TBZ-treated group also showed a significant increase in sperm abnormalities (count, motility, and viability percent), plasma follicle-stimulating hormone and luteinizing hormone concentrations, lipid peroxidation, protein oxidation, and severe DNA degradation in comparison with the controls. Histopathologically, TBZ caused testis impairments. Conversely, treatment with trace elements, in combination or alone, improved the reproductive organ weights, sperm characteristics, TBZ-induced toxicity, and histopathological modifications in testis., Conclusion: TBZ exerts significant harmful effects on male reproductive system. The concurrent administration of trace elements reduces testis dysfunction, fertility, and toxicity induced by TBZ., (Copyright © 2020 The Editorial Board of Biomedical and Environmental Sciences. Published by China CDC. All rights reserved.)

Excessive use of fungicides in agriculture may result in substantial accumulation of active residues in soil, which affect crop health and yield. We investigated the response of Raphanus sativus (white radish) to fungicides in soil and potential beneficial interactions of radish plants with fungicide-tolerant plant growth-promoting rhizobacteria (PGPR). The PGPR were isolated from cabbage and mustard rhizospheres. Morphological and biochemical characteristics measured using standard methods, together with analysis of partial 16S rRNA gene sequences, revealed that fungicide-tolerant PGPR, isolates PS3 and AZ2, were closely related to Pseudomonas spp. These PGPR survived in the presence of high fungicide concentrations i.e., up to 2400 μg mL -1 carbendazim (CBZM) and 3200 μg mL -1 hexaconazole (HEXA). Bacterial isolates produced plant growth stimulants even under fungicide stress, though fungicides induced surface morphological distortion and alteration in membrane permeability of these bacteria, which was proved by a set of microscopic observations. Fungicides considerably affected the germination efficiency, growth, and physiological development of R. sativus , but these effects were relieved when inoculated with PGPR isolates. For instance, CBZM at 1500 mg kg -1 decreased whole dry biomass by 71%, whole plant length by 54%, total chlorophyll by 50%, protein content by 61%, and carotenoid production by 29%. After applying isolate AZ2 for white radish grown in CBZM (10 mg kg -1 )-amended soil, it could improve plant growth and development with increased whole plant dry weight (10%), entire plant length (13%) and total chlorophyll content (18%). Similarly, isolate PS3 enhanced plant survival by relieving plant stress with declined biomarkers, i.e., proline (12%), malondialdehyde (3%), ascorbate peroxidase (6.5%), catalase (18%), and glutathione reductase (4%). Application of isolates AZ2 and PS3 could be effective for remediation of fungicide-contaminated soil and for improving the cultivation of radish plants while minimizing inputs of fungicides.

The fungicide Mancozeb is an endocrine-disrupting chemical and the mode of action of Mancozeb on embryo implantation is largely unknown. Mancozeb (1 and 3 μg/ml) significantly reduced Jeg-3 trophoblastic spheroids attachment to endometrial epithelial Ishikawa cells. Mancozeb treatment from gestation day (GD) 1 to GD8 or from GD4 to GD8 significantly lowered the number of implantation sites with higher incidence of morphological abnormalities in the reproductive tissues. However, these were not seen in the treatment from GD1 to GD4. Mancozeb at 30 mg/kg BW/d did not alter the expression of p53, COX-2, or PGFS transcripts in the uterus, but down-regulated the PGES transcript and protein. Mancozeb treatment in human endometrial stromal cells did not alter the decidualization response, but the morphological transformation was impaired. Taken together, exposure to Mancozeb affected embryo implantation probably through the modulation of decidualization and to delineate the exact mode of action needs further investigations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Honeybees ensure a key ecosystem service by pollinating many agricultural crops and wild plants. However, in the past few decades, managed bee colonies have been declining in Europe and North America. Researchers have emphasized both parasites and pesticides as the most important factors. Infection by the parasite Nosema ceranae and exposure to pesticides can contribute to gut dysbiosis, impacting the honeybee physiology. Here, we examined and quantified the effects of N. ceranae, the neonicotinoid thiamethoxam, the phenylpyrazole fipronil and the carboxamide boscalid, alone and in combination, on the honeybee gut microbiota. Chronic exposures to fipronil and thiamethoxam alone or combined with N. ceranae infection significantly decreased honeybee survival whereas the fungicide boscalid had no effect on uninfected bees. Interestingly, increased mortality was observed in N. ceranae-infected bees after exposure to boscalid, with synergistic negative effects. Regarding gut microbiota composition, co-exposure to the parasite and each pesticide led to decreased abundance of Alphaproteobacteria, and increased abundance of Gammaproteobacteria. The parasite also induced an increase of bacterial alpha-diversity (species richness). Our findings demonstrated that exposure of honeybees to N. ceranae and/or pesticides play a significant role in colony health and is associated with the establishment of a dysbiotic gut microbiota., (Copyright © 2020 Elsevier Inc. All rights reserved.)

The rapid development of electrochemical sensors holds great promise to serve as next generation point-of-care safety devices. However, the practical performances of electrochemical sensors are cruelly limited by stability, selectivity, and sensitivity. These issues have been well addressed by introducing rational designs into the modified electrode for achieving the required performances. Herein, we demonstrate the gadolinium oxide nanorods embedded on the graphene aerogel (GdO NRs/GA) for a highly selective electrochemical detection of carbendazim (CDM). The GdO NRs/GA nanocomposite was characterized using X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, field emission gun scanning electron microscopy, transmission electron microscopy with elemental mapping, and energy-dispersive spectrometry. The GdO NRs/GA-modified electrode shows a much improved electrochemical performance compared to other electrodes. Interestingly, the GdO NRs are strongly anchored in the GA matrix, which provides a more sufficient pathway for the rapid electron and ion transportation. On the basis of these findings, our proposed sensor achieves a wide detection range from 0.01 to 75 μM with a correlation coefficient of 0.996 and a low detection limit of 3.0 nM. Most markedly, the real-time monitoring of the proposed electrochemical sensor was proved by the successful determination of CDM in environmental samples. Our research work has opened a novel way to the rationale for the construction of highly efficient practical electrochemical sensors.

Understanding the effect of pesticides on the survival of honeybee colonies is important because these pollinators are reportedly declining globally. In the present study, we examined the changes in the head proteome of nurse honeybees exposed to individual and combined pesticides (the fungicide pyraclostrobin and the insecticide fipronil) at field-relevant doses (850 and 2.5 ppb, respectively). The head proteomes of bees exposed to pesticides were compared with those of bees that were not exposed, and proteins with differences in expression were identified by mass spectrometry. The exposure of nurse bees to pesticides reduced the expression of four of the major royal jelly proteins (MRJP1, MRJP2, MRJP4, and MRJP5) and also several proteins associated with carbohydrate metabolism and energy synthesis, the antioxidant system, detoxification, biosynthesis, amino acid metabolism, transcription and translation, protein folding and binding, olfaction, and learning and memory. Overall, when pyraclostrobin and fipronil were combined, the changes in protein expression were exacerbated. Our results demonstrate that vital proteins and metabolic processes are impaired in nurse honeybees exposed to pesticides in doses close to those experienced by these insects in the field, increasing their susceptibility to stressors and affecting the nutrition and maintenance of both managed and natural colonies.

Background: Few published studies are reported for neurobehavioral toxicity of combined exposure to fungicides in mammals. This study was aimed to evaluate reproductive and neurobehavioral effects of maternal exposure to combined fungicides in mice., Methods: Imazalil (IMZ) and thiabendazole (TBZ) were given in the diet to provide levels of 0/0% (control), 0.0015/0.006% (IMZ/TBZ), 0.006/0.018%, and 0.024/0.054% during the gestation and lactation periods. Selected reproductive and neurobehavioral parameters were measured in the F 1 generation., Results: No adverse effect of IMZ/TBZ was observed in litter size, litter weight, or sex ratio at birth. The average body weight of male and female offspring was increased significantly in treatment groups during the lactation period. With respect to behavioral developmental parameters, the swimming head angle on PND 7 of male offspring was significantly accelerated in the treatment groups. After weaning, the movement time of exploratory behavior shortened in a significant dose-related manner in adult males of the F 1 generation. In adult females, the rearing time of exploratory behavior lengthened in a significant dose-related manner in the F 1 generation. Spontaneous behavior examination indicated that longitudinal patterns of each of the total distance and number of rearing were different during the control and treatment groups in the F 1 -generation females. Parallel width of the control and treatment groups was significantly different in the average time of movement and rearing in the F 1 -generation females., Conclusions: The high-dose level of IMZ/TBZ in the present study produced several adverse effects in neurobehavioral parameters after weaning without concurrent chemical administration in mice., (© 2019 Wiley Periodicals, Inc.)

Food poisoning and environmental pollution are products of excessive chemical usage in Agriculture. In Nigeria, cocoa farmers apply fungicides frequently to control black pod disease (BPD), this practice is life threatening and lethal to the environment. The development of a warning system to detect BPD outbreak can help minimize excessive usage of fungicide by farmers. 8 models (MRM1-MRM8) were developed and 5 (MRM1-MRM5) selected for optimization and performance check. MRM5 (ETAPOD) performed better than the other forecast models. ETAPOD had 100% performance rating for BPD prediction in Ekiti (2009, 2010, 2011 and 2015) with model efficiency of 95-100%. The performance of the model was rated 80% in 2010 and 2015 (Ondo) with model efficiency of 85-90%, 70% in 2011 (Osun) with model efficiency of 81-84%, 60% in 2010 (Ondo and Osun) and 2015 (Osun) with model efficiency of 75-80%, 40% in 2009 (Osun) with model efficiency of 65-69% and 0% 1n 2011 (Ondo) with model efficiency between 0 and 49%. ETAPOD is a simplified BPD detection device for the past, present and future., Competing Interests: The authors have declared that no competing interests exist.

Ortho-phenylphenol (OPP), as an active ingredient of disinfectants, has been worldwide utilized as fungicides and antibacterial agents in hospital, agriculture, wood preservation, and veterinary products. However, little is known about the toxic effects of OPP on male reproduction, especially sperm motility, and the underlying mechanisms. In this study, we chose porcine sperms as in vitro model to investigate the effects and mechanisms of OPP exposure on sperm motility. Our results indicated that porcine sperm motility decreases significantly in a dose-dependent manner after exposed to OPP. Additionally, ATP synthesis deficiency was revealed by downregulation of ATP synthase subunit beta and adenosine 5'-monophosphate-activated protein kinase expression. Furthermore, OPP disturbed the expression of TP53 and PTEN, which contributed to AKT pathway deactivation. OPP exposure also disrupted platelet-derived growth factor receptor A expression, which further inhibited 3-phosphoinositide-dependent protein kinase 1 activation, resulting in protein kinase B and pyruvate dehydrogenase phosphatase catalytic subunit 1 deactivation. In conclusion, these observations suggest that OPP exposure decreases porcine sperm motility by disturbing the AMPK/AKT signaling pathway. Environ. Mol. Mutagen. 2019. © 2019 Wiley Periodicals, Inc., (© 2019 Wiley Periodicals, Inc.)

Carbendazim (CBZ) is a widely used, systemic, broad-spectrum benzimidazole fungicide. It is used worldwide against fungal diseases on a wide range of agricultural products and in domestic gardens. The activities of brain oxidative stress biomarkers and acetylcholinesterase (AChE) in juvenile African Catfish Clarias gariepinus exposed to CBZ were investigated. Juveniles were exposed to sublethal concentrations of 0.22, 0.43, and 0.64 mg/L CBZ, which corresponded to 5, 10, and 15% of the 96-h LC50 (the concentration that was lethal to 50% of the test organisms over the first 96 h) of CBZ fungicide for 21 d. Individuals were allowed an extra 7-d recovery period. The brain tissues were sampled and analyzed on days 1, 7, 14, 21, and 28 (including the 7-d recovery period). The results indicated significant concentration-dependent inhibition of the brain AChE activities in all exposed groups. The lipid peroxidation was significantly elevated while the antioxidant enzymes and protein values were significantly inhibited by CBZ exposure. However, the values of catalase on days 7, 14, and 21 were significantly higher than day 1 values. Overall, CBZ altered brain oxidative stress parameters and led to the inhibition of AChE. This fungicide should be used with utmost caution to protect and safeguard fish, ensuring that fish production and survival in the environment remain unaffected., (© 2019 American Fisheries Society.)

This study was planned to investigate TD (Tibial dyschondroplasia) on the potential MAPK signaling pathway and angiogenesis related genes. Forty-eight broilers were allotted into control (C) and treatment (T) groups of 2, 6 and 15 days as C1, C2, C3, T1, T2 and T3. The histopathology results revealed that tibiotarsus bone of chickens had more lesions on day 6 (T2 group). The chondrocytes were disordered, and the size, shape and proliferation were affected. Transcriptome results revealed that differentially expressed genes (DEGs) identified were 63, 1026, 623, 130, 141 and 146 in C1 (2 days control vs 6 days control); C2 (2 days control vs 15 days control); C3 (6 days control vs 15 days control); T1 (2 days treatment vs 6 days treatment); T2 (2 days treatment vs 15 days treatment) and T3 (6 days treatment vs 15 days treatment) groups respectively. Whereas, 10 angiogenesis related-genes RHOC, MEIS2, BAIAP2, TGFBI, KLF2, CYR61, PTPN11, PLXNC1, HSPH1 and NRP2 were downregulated on day 6 in the treatment group. The pathway which was found enriched in the control and treatment groups was MAPK signaling pathway. Therefore selected 10 MAPK signaling pathway-related genes RAC2, MAP3K1, PRKCB, FLNB, IL1R1, PTPN7, RPS6KA, MAP3K6, GNA12 and HSPA8 which were found significantly downregulated in the treatment group on day 6. It is concluded that angiogenesis and MAPK signaling pathway related genes has an essential role in TD, as those top screened genes found downregulated in the thiram fed chickens when TD observed severed on day 6., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Selective inhibition (SI) has been routinely used to differentiate the contributions of bacteria and fungi to soil ecological processes. SI experiments typically measured rapid responses within hours since the addition of inhibitor, but the long-term effects of selective biocides on microbial community composition and function were largely unknown. In this study, a microcosm experiment was performed with an agricultural soil to explore the effectiveness of two bactericides (bronopol, streptomycin) and two fungicides (cycloheximide, captan), which were applied at two different concentrations (2 and 10 mg g -1 ). The microcosms were incubated for 6 weeks. A radiolabeled substrate, [1,2,3,4,4a,9a- 14 C] anthracene, was spiked to all microcosms, and the derived CO 2 was monitored during the incubation. The abundance and composition of bacteria and fungi were assessed by qPCR and Miseq sequencing of ribosomal rRNA genes. It was demonstrated that only 2 mg g -1 bronopol and cycloheximide significantly changed the bacteria to fungi ratio without apparent non-target inhibition on the abundances; however, community shifts were observed in all treatments after 6 weeks incubation. The enrichment of specific taxa implicated a selection of resistant or adapted microbes by these biocides. Mineralization of anthracene was continuingly suppressed in all SI microcosms, which may result in biased estimate of bacterial and fungal contributions to pollutant degradation. These findings highlight the risks of long-term application of selective inhibition, and a preliminary assessment of biocide selection and concentration is highly recommended.

The widespread use of engineered nanomaterials (ENMs) in consumer products and the overwhelming uncertainties in their ecological and human health risks have raised concerns regarding their safety among industries and regulators. There has been an ongoing debate over the past few decades on ways to overcome the challenges in assessing and mitigating nano-related risks, which has reached a phase of general consensus that nanotechnology innovation should be accompanied by the application of the precautionary principle and best practice risk management, even if the risk assessment uncertainties are large. We propose a quantitative methodology for selecting the optimal risk control strategy based on information about human health and ecological risks, efficacy of risk mitigation measures, cost and other contextual factors. The risk control (RC) methodology was developed in the European FP7 research project SUN and successfully demonstrated in two case studies involving real industrial nano-enabled products (NEPs): nano-scale copper oxide (CuO) and basic copper carbonate (Cu 2 (OH) 2 CO 3 ) used as antimicrobial and antifungal coatings and impregnations for the preservation of treated wood, and two nanoscale pigments used for colouring plastic automotive parts (i.e. red organic pigment and carbon black). The application of RC for human health risks showed that although nano-related risks could easily be controlled in automotive plastics case study with modifications in production technology or specific type of engineering controls, nano-related risks due to sanding and sawing copper oxide painted wood were non-acceptable in the use lifecycle stage and would need the identification of a more effective risk control strategy., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Fludioxonil is fungicide used in agriculture, which is present in fruits and vegetables. In this study, the effects of fludioxonil on human immune cell viability, apoptosis, cell cycle arrest, and mitochondrial membrane potential were examined in human immune cells, such as Jurkat T cells and Ramos B cells. To examine the cell viability, Jurkat T cells and Ramos B cells were treated with fludioxonil (10 -9 -10 -5 M) for 24 h and 48 h. Water soluble tetrazolium salt assay showed that fludioxonil decreased Jurkat T cell and Ramos B cell viability. Jurkat T cell viability decreased at 24 and 48 h, but Ramos B cell viability decreased only at 48 h. JC-1 dye revealed decreased mitochondrial membrane potential in fludioxonil-treated Jurkat T cells and Ramos B cells. To evaluate apoptosis, annexin-V conjugated FITC, AF488, and propidium iodide (PI) were used and to evaluate cell cycle arrest PI was used. Apoptosis and cell cycle arrest were induced by fludioxonil (10 -7 -10 -5 M) in the Jurkat T cells at 24 and 48 h and Ramos B cells at 48 h. Moreover, the protein levels of pro-apoptotic proteins, such as p53, BAX, and cleaved caspase 3, were increased and anti-apoptotic protein Bcl-2 was decreased by fludioxonil. Expression of the Fas receptor related to the extrinsic apoptosis pathway was increased by fludioxonil. Additionally, cyclin D1 and cyclin E1 were decreased by fludioxonil. In the present study, fludioxonil induced immunotoxicity in human T cells and B cells through apoptosis and cell cycle arrest. Therefore, the present study suggests that fludioxonil induces the cellular toxicity in immune cells.

Cu(OH) 2 nanopesticides and organic insecticides are continuously applied to soil at a temporal interval, while knowledge about the impact of Cu(OH) 2 nanopesticides on organic insecticides degradation is currently scarce, resulting in poorly comprehensive evaluation of the potential environmental risks of Cu(OH) 2 nanopesticides. Herein, a commercial Cu(OH) 2 nanopesticide formulation (NPF), the active ingredient of NPF (AI-NPF), the prepared Cu(OH) 2 nanotubes (NT) with comparable morphology and size to AI-NPF, and CuSO 4 were respectively applied to soil at normal doses (0.5, 5 and 50 mg/kg), followed by an application of neonicotinoid thiacloprid after an interval of 21 d, showing that NPF at doses of 5 and 50 mg/kg significantly (p < 0.05) mitigated thiacloprid degradation compared to control and CuSO 4 . Furthermore, AI-NPF was the primary component that contributed to the mitigation effect of NPF, which was also validated by the NT. Large differences in the degradation efficiency of thiacloprid in sterilized and unsterilized soils with Cu(OH) 2 nanopesticides suggested that biodegradation was the primary process responsible for thiacloprid degradation, especially as chemical degradation was negligible. Besides a decrease of thiacloprid bioavailability due to adsorption by Cu(OH) 2 nanopesticides, we demonstrated that Cu(OH) 2 nanopesticides changed soil microbial communities, reduced nitrile hydratase activity and down-regulated thiacloprid-degradative nth gene abundance, which thus mitigated thiacloprid biodegradation. Clearly, this study shed light on the potential environmental risks of Cu(OH) 2 nanopesticide., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Fungal parasites of the phylum Chytridiomycota (chytrids) are increasingly recognized as potent control agents of phytoplankton, including toxic bloom-forming cyanobacteria. We experimentally tested whether agricultural fungicides can interfere with natural epidemics caused by parasitic chytrid fungi and thereby favor cyanobacterial bloom formation. Specifically, we exposed the toxic bloom-forming cyanobacterium Planktothrix and its chytrid parasite Rhizophydium megarrhizum to different concentrations of the widely used agricultural fungicides tebuconazole and azoxystrobin, as well as the medical fungicide itraconazole (the latter was included to test its potential to suppress infection in vitro). Environmentally relevant concentrations of tebuconazole (20-200 μg/L) and azoxystrobin (1-30 μg/L) significantly decreased infection prevalence over a timespan of seven days, while not affecting the growth of uninfected cyanobacteria. Itraconazole suppressed infection completely. Our findings demonstrate that agricultural fungicide run-off has the potential to inhibit natural chytrid epidemics and, thereby, to promote the proliferation of toxic cyanobacteria., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Copper-based fungicides have been used for a long time in viticulture and have accumulated in many vineyard soils. In this study, incrementing Cu(OH) 2 -based fungicide application from 0.05 to 5 g Cu kg -1 on two agricultural soils (an acidic sandy loam (L, pH 4.95) and an alkaline silt loam (D, pH 7.45)) resulted in 5 times more mobile Cu in the acidic soil. The most sensitive parameters of alfalfa (Medicago sativa) growing in these soils were the root nodule number, decreasing to 34% and 15% of the control at 0.1 g Cu kg -1 in soil L and at 1.5 g Cu kg -1 in soil D, respectively, as well as the nodule biomass, decreasing to 25% and 27% at 0.5 g Cu kg -1 in soil L and at 1.5 g Cu kg -1 in soil D, respectively. However, the enzymatic N 2 -fixation was not directly affected by Cu in spite of the presence of Cu in the meristem and the zone of effective N 2 -fixation, as illustrated by chemical imaging. The strongly different responses observed in the two tested soils reflect the higher buffering capacity of the alkaline silt loam and showed that Cu mitigation and remediation strategies should especially target vineyards with acidic, sandy soils.

The aim of this study was to investigate the effect of 3-chloro-5-trifluoromethylpyridine-2-carboxylic acid (PCA), a metabolite of the fungicide fluopyram, on grapevine. During spring and summer 2015, grapevine growth disorders were observed in several countries in Europe. An unprecedented herbicide-like damage was diagnosed on leaves and flowers, causing significant loss of harvest. This study proposes PCA as the causing agent of the observed growth disorders. PCA was shown to cause leaf epinasty, impaired berry development that leads to crop loss, and root growth anomalies in Vitis vinifera similar to auxin herbicides in a dose-dependent manner. Using both field trials and greenhouse experiments, the present study provides first evidence for a link between the application of fluopyram in vineyards 2014, the formation of PCA, and the emergence of growth anomalies in 2015. Our data could be useful to optimize dosage, application time point, and other conditions for an application of fluopyram without phytotoxic effects.

Chlorothalonil is a commonly used fungicide to control the karnal bunt caused by Tilletia indica Mitra in wheat production from the Yaqui Valley, Mexico. Here, the effect of Chlorothalonil on the growth of 132 bacterial strains associated with wheat rhizosphere from the Yaqui Valley was evaluated, as well as their ability to produce indoles. Thirty-three percent of the evaluated strains were inhibited by Chlorothalonil, being Bacillus and Paenibacillus the most inhibited genera, observing an inhibition >50% of their strains. In addition, 49% of the inhibited strains showed the ability to produce indoles (>5 μg/mL), where the genus Bacillus was the most abundant (80%). The remaining strains (67%) were tolerant to the evaluated fungicide, but only 37% of those showed the ability to produce indoles, which could be considered as Plant Growth Promoting Rhizobacteria (PGPR). These results showed that Chlorothalonil is not only an antifungal compound but also inhibits the growth of bacterial strains with the ability to produce indoles. Thus, the intensive application of fungicides to agro-systems needs more validation in order to develop sustainable agricultural practices for food production.

Whether now or in the foreseeable future, agricultural production cannot do without chemical pesticides. Strobilurin fungicides, including mitochondrial inhibitors, can easily enter the soil environment and causing pollution. Fluoxastrobin is one of the top-selling strobilurin fungicides. Limited information can be found in the literature on the environmental toxicity of fluoxastrobin in soil. It is essential to understand the effects of fluoxastrobin on microorganisms in fluvo-aquic soil. The present study used a Biolog-EcoPlate method to analyze the effects of fluoxastrobin on soil microbial diversity in groups exposed to 0.1, 1.0, and 2.5 mg/kg fluoxastrobin and in control groups at exposure and on days 7, 14, 21, 28, and 48. The effects of fluoxastrobin on enzyme activities (β-glucosidase, dehydrogenase, and urease) in the soil were also evaluated. The results indicated that the three tested enzyme activities were lower at each dose to a varying degree than those of the controls. The soil microbial diversity was shown to be affected according to the results of average well color development (AWCD) experiments. The present study aimed to assess environmental risks to terrestrial ecosystems under the stress of pesticide use. These results also enrich the basic data on fungicide toxicity to the soil environment and have a guiding significance for the rational use of pesticides and the sustainable utilization of resources., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Background: An increasing widespread use of Pesticides is as an issue in the agricultural sector. Pesticides use is one of the occupational risks in farmers of low-income countries including Nepal. Objective of this study was to explore the health effects of Pesticides among agricultural farmers of Sunsari., Methods: A community based cross sectional study was carried out in Duhabi-Bhaluwa of Sunsari District, Nepal from September 2015 to February 2016. Non-probability sampling technique was used to enroll the total 300 study participants. Data were collected by face to face interview with farmers using pre-tested semi structured questionnaire. Data were recorded by reading the original container of the Pesticides., Results: Fungicides (60.3%), Herbicides (56.3%), pyrethrum (35.3%) and Organophophate (11.6%) Pesticides were commonly used by the agricultural farmers in their farms. The health problem within 48 hours after application of pesticides was reported by more than one-sixth (17%) of the farmers. Dizziness (74.5%) and headache (58.8%) were the most common health problems found among the farmers. Skin irritation (19.6%), nausea (13.7%), paraesthesia (9.8%), restlessness (5.8%), eye irritation (5.8%) and vomiting (1.9%) were also reported by pesticides handlers. Factors associated with health problems were hazardous pesticides use (AOR=26.95, CI 6.15 - 118.0), good knowledge on impacts of pesticides (AOR=3.16, CI 1.09-9.13), determination of wind direction first and spray (AOR=2.25, CI 1.08-4.67), working experience of 20-29 years on farm (AOR=3.38, CI 1.05-10.83)., Conclusions: One-sixth of the farmers reported health problems. Farmers working with hazardous Pesticides were in need of special attention in terms of safe handling, determing the wind direction and spray.

Fludioxonil is a phenylpyrrole pesticide that is applied to fruit and vegetable crops post-harvest to minimize losses to mold, both during transport and at point of sale. Its effectiveness is reflected in the dramatic increase in its production/usage since its introduction in 1994, an increase that has peaked in recent years as it became licenced for use abroad. Recently, doubts as to the nature of its mechanism of action have been raised. Given that the pesticide has long been known to induce stress intermediates in target and non-target organisms alike, the lack of a firmly established mechanism might be cause for concern. Troubling reports further delineate a capacity to disrupt hepatic, endocrine and neurological systems, indicating that fludioxonil may represent a health threat to consumers. In the absence of a clear, safe mechanism of action, fludioxonil should be re-evaluated for its potential to impact human health., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Penconazole (PEN) and tebuconazole (TEB) are fungicides widely used in vineyards. The aim of this the study was to assess the suitability of hair to assess long-term exposure to PEN and TEB. Hair samples of agricultural workers exposed to PEN (AW-PEN, 18 subjects) or TEB (AW-TEB, 2 subjects) during the application of fungicides, agricultural workers relatives (AR, 4 subjects), and research staff technicians (RS, 5 subjects) were collected before (PRE-EXP) and after (POST-EXP) the application season. PEN in PRE-EXP samples was quantifiable in all AW and AR (medians from 1.4 to 7.9 pg/mg hair) and in one RS (1.4 pg/mg hair); PEN in POST-EXP samples was always quantifiable (medians from 2.6 to 23.7 pg/mg hair), with higher levels in AW. Comparing PRE- vs. POST-EXP samples, an increase in PEN level in AW and RS was found. TEB in PRE-EXP samples was quantifiable in most AW and AR (median from 2.1 to 15.5 pg/mg hair), but not in RS; TEB in POST-EXP samples was similarly quantifiable in AW and AR, and was quantifiable also in RS (from 1.4 to median of 141.3 pg/mg hair). Comparing PRE- vs. POST-EXP samples, an increase in TEB level in AW and RS was found. In AW, a positive correlation between the number of PEN treatments during the season and the POST-EXP level of PEN in hair was found (N = 8, Spearman rho = 0.794, p = 0.019). Our results suggest that PEN and TEB accumulate in hair during the agricultural season and that hair is a promising matrix for biomonitoring long-term exposure., (Copyright © 2018 Elsevier B.V. All rights reserved.)

For the medical practice, our manuscript acts as a signal, despite only presenting three cases which feature the association between hepatocytolysis, haemolysis and hypermagnesaemia. This clinical-biologic triad was highlighted with the workers who through the nature of their profession were exposing themselves periodically to vapours which contained copper sulphate neutralised with calcium hydroxide, a fungicide used for fruit trees. We are exclusively assessing the haematological perturbation. In this aetiological context, the generating mechanism for haemolysis is very probable biochemical, where hypercupraemia interferes with cellular antioxidant defence mechanisms. Hypothetically, the role of the redox homeostasis disorder in the intravascular destruction of erythrocytes is sustained, and particularly the coexistence of cell cytolysis in the medullary erythroid compartment, which can be assimilated with a possible ineffective erythropoiesis.

Young children differ from adults in their exposure and susceptibility to environmental chemicals (e.g. pesticides) because of various factors such as behavior, diet and physiology. Their heightened vulnerability to environmental stressors makes it important to obtain appropriate urine samples for exposure characterization. However, collecting urine from non-toilet-trained children has been shown to be methodologically and practically challenging. Four urine collection approaches were tested: a disposable diaper, a urine bag, a collection pad and the clean catch. The success rate and the user rating of each method was evaluated. The success rates were 67%, 21%, 17% and 4% for the disposable diaper, urine bag, collection pad and clean catch, respectively. The average user ratings on a 0-10 (0 = inconvenient, 10 = convenient) scale were 9.0, 4.7, 7.3 and 2.5, respectively. Subsequently, the best rated method, the disposable polyacrylate diaper was tested with hydroxy-tebuconazole as an exposure biomarker for the fungicide tebuconazole and creatinine for urine density adjustment. After LC-MS/MS analysis, the recoveries of hydroxy-tebuconazole in the range of 0.05-25 ng/mL were on average 106%, and for creatinine 87%. Precisions (relative standard deviation) were for both 3%. The overall procedure including collection and extraction was assessed, resulting in three out of seven positive samples. Based on this study, the disposable diaper is a suitable method for urine collection of non-toilet-trained children for biomonitoring of tebuconazole. This method can serve as a basis for extension to other substances of interest., (Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.)

Despite the efforts of the European Commission to implement measures that offset the detrimental effects of agricultural intensification, farmland bird populations continue to decline. Pesticide use has been pointed out as a major cause of decline, with growing concern about those agro-chemicals that act as endocrine disruptors. We report here on the effects of flutriafol, a ubiquitous systemic fungicide used for cereal seed treatment, on the physiology and reproduction of a declining gamebird. Captive red-legged partridges (Alectoris rufa; n = 11-13 pairs per treatment) were fed wheat treated with 0%, 20% or 100% of the flutriafol application rate during 25 days in late winter. We studied treatment effects on the reproductive performance, carotenoid-based coloration and cellular immune responsiveness of adult partridges, and their relationship with changes in oxidative stress biomarkers and plasma biochemistry. We also studied the effect of parental exposure on egg antioxidant content and on the survival, growth and cellular immune response of offspring. Exposed partridges experienced physiological effects (reduced levels of cholesterol and triglycerides), phenotypical effects (a reduction in the carotenoid-based pigmentation of their eye rings), and most importantly, severe adverse effects on reproduction: a reduced clutch size and fertile egg ratio, and an overall offspring production reduced by more than 50%. No effects on body condition or cellular immune response of either exposed adult or their surviving offspring were observed. These results, together with previous data on field exposure in wild partridges, demonstrate that seed treatment with flutriafol represents a risk for granivorous birds; they also highlight a need to improve the current regulation system used for foreseeing and preventing negative impacts of Plant Protection Products on wildlife., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Hydroxypropyltrimethyl ammonium chitosan halogenated acetates were successfully synthesized from six different haloacetic acids and hydroxypropyltrimethyl ammonium chloride chitosan (HACC) with high substitution degree, which are hydroxypropyltrimethyl ammonium chitosan bromacetate (HACBA), hydroxypropyltrimethyl ammonium chitosan chloroacetate (HACCA), hydroxypropyltrimethyl ammonium chitosan dichloroacetate (HACDCA), hydroxypropyltrimethyl ammonium chitosan trichloroacetate (HACTCA), hydroxypropyltrimethyl ammonium chitosan difluoroacetate (HACDFA), and hydroxypropyltrimethyl ammonium chitosan trifluoroacetate (HACTFA). These chitosan derivatives were synthesized by two steps: first, the hydroxypropyltrimethyl ammonium chloride chitosan was synthesized by chitosan and 3-chloro-2-hydroxypropyltrimethyl ammonium chloride. Then, hydroxypropyltrimethyl ammonium chitosan halogenated acetates were synthesized via ion exchange. The structures of chitosan derivatives were characterized by Fourier transform infrared spectroscopy (FTIR), ¹H Nuclear magnetic resonance spectrometer (¹H NMR), 13 C Nuclear magnetic resonance spectrometer ( 13 C NMR), and elemental analysis. Their antifungal activities against Colletotrichum lagenarium , Fusarium graminearum , Botrytis cinerea , and Phomopsis asparagi were investigated by hypha measurement in vitro. The results revealed that hydroxypropyltrimethyl ammonium chitosan halogenated acetates had better antifungal activities than chitosan and HACC. In particular, the inhibitory activity decreased in the order: HACTFA > HACDFA > HACTCA > HACDCA > HACCA > HACBA > HACC > chitosan, which was consistent with the electron-withdrawing property of different halogenated acetates. This experiment provides a potential idea for the preparation of new antifungal drugs by chitosan.

Strobilurins is the most widely used class of fungicides, but is reported highly toxic to some aquatic organisms. In this study, zebrafish embryos were exposed to a range concentrations of three strobilurins (pyraclostrobin, trifloxystrobin and picoxystrobin) for 96 h post-fertilization (hpf) to assess their aquatic toxicity. The 96-h LC 50 values of pyraclostrobin, trifloxystrobin and picoxystrobin to embryos were 61, 55, 86 μg/L, respectively. A series of symptoms were observed in developmental embryos during acute exposure, including decreased heartbeat, hatching inhibition, growth regression, and morphological deformities. Moreover, the three fungicides induced oxidative stress in embryos through increasing reactive oxygen species (ROS) and malonaldehyde (MDA) contents, inhibiting superoxide dismutase (SOD) activity and glutathione (GSH) content as well as differently changing catalase (CAT) activity and mRNA levels of genes related to antioxidant system (Mn-sod, Cu/Zn-sod, Cat, Nrf2, Ucp2 and Bcl2). In addition, exposure to the three strobilurins resulted in significant upregulation of IFN and CC-chem as well as differently changed expressions of TNFa, IL-1b, C1C and IL-8, which related to the innate immune system, suggesting that these fungicides caused immunotoxicity during zebrafish embryo development. The different response of enzymes and genes in embryos exposed to the three fungicides might be the cause that leads to the difference of their toxicity. This work made a comparison of the toxicity of three strobilurins to zebrafish embryos on multi-levels and would provide a better understanding of the toxic effects of strobilurins on aquatic organisms., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Background: Exposure to endocrine-disrupting chemicals (EDCs) during gestation influences development of the F1 generation offspring and can result in disease and dysfunction in adulthood. Limited evidence suggests consequences on the F2 generation, exposed as germ cells within the F1 fetus. These F2s provide a unique window into the programming effects of EDCs., Objective: This study assessed intergenerational effects of EDC exposure on adult physiology and behavior in Sprague-Dawley rats., Methods: Pregnant rats were exposed to either a polychlorinated biphenyl (PCB) mixture, Aroclor 1,221 (A1221), the fungicide vinclozolin (VIN), or the vehicle (VEH) (6% dimethylsulfoxide in sesame oil) alone. A1221 is weakly estrogenic, while VIN is antiandrogenic, enabling us to compare different classes of EDCs. The F1 male and female offspring were bred to generate the paternal- and maternal-lineage F2 generation. This F2 generation was assessed for physiological outcomes, ultrasonic vocalizations (USVs), and sexual behavior in adulthood., Results: Each EDC caused phenotypic effects in a sex- and lineage-dependent manner. The most robustly affected group was the paternal-lineage males. F2 VIN paternal male descendants had increased body weight throughout the lifespan, lower concentrations of circulating estradiol, and lower adrenal and testicular indices. Both VIN and A1221 paternal-lineage males also exhibited the greatest number of changes in the characteristics of USVs in response to an opposite-sex animal and changes in sexual behaviors in a mating test., Conclusion: Exposure of rats to EDCs at the germ cell stage led to differences in the physiological and behavioral phenotype later in life, especially in males. This finding has implications for multigenerational physiological and reproductive health in wildlife and humans. https://doi.org/10.1289/EHP3550.

Pollinators in agroecosystems are often exposed to pesticide mixtures. Even at low concentrations, the effects of these mixtures on bee populations are difficult to predict due to potential synergistic interactions. In this paper, we orally exposed newly emerged females of the solitary bee Osmia bicornis to environmentally realistic levels of clothianidin (neonicotinoid insecticide) and propiconazole (fungicide), singly and in combination. The amount of feeding solution consumed was highest in bees exposed to the neonicotinoid, and lowest in bees exposed to the pesticide mixture. Ovary maturation and longevity of bees of the neonicotinoid and the fungicide treatments did not differ from those of control bees. By contrast, bees exposed to the pesticide mixture showed slow ovary maturation and decreased longevity. We found a synergistic interaction between the neonicotinoid and the fungicide on survival probability. We also found an interaction between treatment and emergence time (an indicator of physiological condition) on longevity. Longevity was negatively correlated to physiological condition only in the fungicide and the mixture treatments. Delayed ovary maturation and premature death imply a shortened nesting period (highly correlated to fecundity in Osmia ). Our findings provide a mechanism to explain the observed dynamics of solitary bee populations exposed to multiple chemical residues in agricultural environments., (© 2018 The Author(s).)

Mancozeb (MZ), a manganese- and zinc-containing ethylene-bis-dithiocarbamate, is a broad-spectrum fungicide. Harmful effects of this fungicide have been reported in nontarget organisms via a not fully understood mechanism. Drosophila melanogaster has provided remarkable contributions for toxicological studies. This work was aimed at evaluating the biochemical targets and implication of oxidative stress in MZ-mediated toxicity in drosophilas. Exposure of flies for fifteen days to MZ at 5 and 10 mg/mL through the diet impaired locomotor performance and induced fly mortality. In parallel, it caused lipid peroxidation and reactive oxygen species (ROS) formation and Mn overload. MZ inhibited superoxide dismutase and inducted catalase and glutathione S-transferase activities. Nitric oxide and reduced glutathione levels were significantly decreased by MZ. Heat shock proteins (HSP70 and HSP83) and Nrf2 mRNA levels were significantly augmented in MZ-exposed flies. Our study reinforced the use of Drosophila melanogaster as a reliable model for the study of biochemical targets of pesticides, and based on our data, MZ induced oxidative damage and Mn accumulation in a concentration-dependent manner. An adaptative cellular state was inducted by the lower concentration of pesticide, possibly contributing to the slighter damage observed.

Carbendazim is nowadays widely used to control fungus in various nectariferous crops. Little is known about how honey bees, Apis mellifera L. (Hymenoptera: Apidae), respond to carbendazim exposure. In this study, the effects of field-realistic concentrations of carbendazim (4.516, 0.4516, and 0.04516 ppm) on the survival, biomarker enzyme activity (AChE, GST, CarE, and P450), and four antimicrobial peptide gene expression (hymenoptaecin, defensin, apidaecin, and abaecin) in forager honey bees were evaluated. The forager bees were fed with the pesticides for 10 d. The results showed that the field-realistic concentrations of carbendazim did not affect survival; activities of AChE, GST, and CarE; and expression levels of defensin and abaecin in forager bees. However, 4.516, 0.4516, and 0.04516 ppm of carbendazim all significantly inhibited the expression of hymenoptaecin and apidaecin (P < 0.01), while P450 (7-ethoxycoumarin-O-deethylase) activity was downregulated by 4.516 ppm of carbendazim (P < 0.05). Our results indicate that the field-realistic concentrations of carbendazim may alter the immune response and P450-mediated detoxification of honey bees. Thus, carbendazim should be discreetly used on nectariferous crops during florescence.

Temperature is expected to modulate the responses of organisms to stress. Here, we aimed to assess the influence of temperature on the interaction between parasitism and fungicide contamination. Specifically, using the cladoceran Daphnia as a model system, we explored the isolated and interactive effects of parasite challenge (yeast Metschnikowia bicuspidata) and exposure to fungicides (copper sulphate and tebuconazole) at two temperatures (17 and 20 °C), in a fully factorial design. Confirming a previous study, M. bicuspidata infection and copper exposure caused independent effects on Daphnia life history, whereas infection was permanently suppressed with tebuconazole exposure. Here, we show that higher temperature generally increased the virulence of the parasite, with the hosts developing signs of infection earlier, reproducing less and dying at an earlier age. These effects were consistent across copper concentrations, whereas the joint effects of temperature (which enhanced the difference between non-infected and infected hosts) and the anti-parasitic action of tebuconazole resulted in a more pronounced parasite × tebuconazole interaction at the higher temperature. Thus, besides independently influencing parasite and contaminant effects, the temperature can act as a modulator of interactions between pollution and disease.

Silkworm cocoon production has been reduced due to a number of problems other than those inherent in sericulture, such as diseases, malnutrition, and inappropriate management. The use of pesticides in areas surrounding mulberry fields can contaminate these plants and consequently harm caterpillars. The aim of this study was to evaluate whether the application of the fungicide pyraclostrobin in mulberry plants interferes with the mitochondrial bioenergetics and the productive performance of silkworms. Mulberry plants were treated with pyraclostrobin (0, 100, 200, and 300 g ha-1). After 30 d of fungicide application, fifth instar caterpillars were fed with leaves from the treated plants. We evaluated in vitro and in vivo mitochondrial bioenergetics of mitochondria from the head and intestines, as well as the feed intake and mortality rate of the caterpillars and the weight of fresh cocoons and cocoons shells. At doses of 50 µM (in vitro) and 200 g ha-1 (in vivo), pyraclostrobin inhibited oxygen consumption in state 3, dissipated membrane potential, and inhibited ATP synthesis in mitochondria. Pyraclostrobin acted as a respiratory chain inhibitor, affecting mitochondrial bioenergetics. The fungicide did not interfere with food consumption but negatively affected mortality rate and weight of cocoons. Mulberry leaves contaminated with pyraclostrobin negatively impact the mitochondrial bioenergetics of silkworms and cocoon production.

Methyl benzimidazole carbamate (MBC) fungicides are fungicidal compounds that exert their biological activities by preventing cell division through the inhibition of tubulin polymerization, which is the major component of microtubules. Several mutations in the β-tubulin gene contribute to MBC resistance, the most common and significant of which occur at residues 198 and 200. Despite nearly 50 years of agricultural use, the binding site of MBCs and the precise mechanism by which those mutations affect fungicide efficacy have not been determined. The aim of this work was to clarify the mode of action and the mechanism of resistance to MBC fungicides in Podosphaera xanthii, the primary causal agent of cucurbit powdery mildew, using a combination of biochemical, biophysical and computational approaches. The results allow us to propose an MBC binding site in β-tubulin that lies close to the GTP binding site and does not include residue 198 involved in MBC resistance.

In this study, the effects of oligochitosan treatment on controlling postharvest diseases in Dongxue peach ( Prunus Persica L. Batsch, cv Dongxuemi) were examined and the possible underlying mechanisms were discussed. Results showed that the disease incidence and lesion area in peach fruit inoculated with Monilinia fructicola and Penicillium expansum were all remarkably reduced by oligochitosan treatment. Oligochitosan treatment inhibited spore germination and mycelial growth of the two fungi in vitro. Oligochitosan treatment also induced upregulation of the salicylic acid signalling pathway-related genes (NPR1, PR1 and phenylalanine ammonia lyase) and enhanced the levels of total phenolics, flavonoids and lignin in peach. Meanwhile, enzymatic activities of superoxide dismutase, catalase, polyphenoloxidase, ascorbate peroxidase and phenylalanine ammonia lyase also increased. These findings suggest that the effects of oligochitosan on the disease control of peach fruit may be associated with its direct antimicrobial effects as well as increasing antioxidant, phenylpropanoid metabolism and accumulating antifungal compounds by activating the salicylic acid-dependent pathway.