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Ecotoxicology and Environmental Safety Jan 2020Pesticides have been extensively produced and used to help the agricultural production which leads to the contamination of the environment, soil, groundwater sources,...
Pesticides have been extensively produced and used to help the agricultural production which leads to the contamination of the environment, soil, groundwater sources, and even foodstuffs. Fungicides carbendazim (CBZ) and chlorothalonil (Chl) are widely applied in agriculture and other aspects. CBZ or Chl have been reported to disrupt spermatogenesis and decrease semen quality. However, it is not understood the effects of pubertal exposure to low doses of CBZ and Chl together, and the underlying mechanisms. Therefore, the aim of current investigation was to explore the negative impacts of pubertal exposure to low doses of CBZ and Chl together on spermatogenesis and the role of epigenetic modifications in the process. We demonstrated that CBZ and Chl together synergize to decrease sperm motility in vitro (CBZ 1.0 + Chl 0.1, CBZ 10.0 + CHl 1.0, CBZ 100.0 + Chl 10 μM in incubation medium for 24 h) and sperm concentration and motility in vivo with ICR mice (CBZ 0.1 + Chl 0.1, CBZ 1.0 + CHl 1.0, CBZ 10.0 + Chl 10 mg/kg body weight; oral gavage for five weeks). CBZ + Chl significantly increase reactive oxygen species (ROS) and apoptosis by the increase in the protein level of caspase 8 in vitro. Moreover, CBZ + Chl synergized to disrupt mouse spermatogenesis with the disturbance in sperm production proteins and sperm proteins (VASA, A-Myb, STK31, AR, Acrosin). CBZ + Chl synergized to decrease the protein level of estrogen receptor alpha and the protein level of DNA methylation marker 5 mC in Leydig cells, and to increase the protein levels of histone methylation marker H3K9 and the methylation enzyme G9a in germ cells. Therefore, greater attention should be paid to the use of CBZ and Chl as pesticides to minimise their adverse impacts on spermatogenesis.
Topics: Animals; Benzimidazoles; Carbamates; Drug Synergism; Epigenesis, Genetic; Estrogen Receptor alpha; Fungicides, Industrial; Male; Methylation; Mice; Mice, Inbred ICR; Nitriles; Signal Transduction; Spermatogenesis; Spermatozoa
PubMed: 31706243
DOI: 10.1016/j.ecoenv.2019.109908 -
Biomaterials Advances Dec 2023The synergy between eco-friendly biopolymeric films and printed devices leads to the production of plant-wearable sensors for decentralized analysis of pesticides in...
The synergy between eco-friendly biopolymeric films and printed devices leads to the production of plant-wearable sensors for decentralized analysis of pesticides in precision agriculture and food safety. Herein, a simple method for fabrication of flexible, and sustainable sensors printed on cellulose acetate (CA) substrates has been demonstrated to detect carbendazim and paraquat in agricultural, water and food samples. The biodegradable CA substrates were made by casting method while the full electrochemical system of three electrodes was deposited by screen-printing technique (SPE) to produce plant-wearable sensors. Analytical performance was assessed by differential pulse (DPV) and square wave voltammetry (SWV) in a linear concentration range between 0.1 and 1.0 μM with detection limits of 54.9 and 19.8 nM for carbendazim and paraquat, respectively. The flexible and sustainable non-enzymatic plant-wearable sensor can detect carbendazim and paraquat on lettuce and tomato skins, and also water samples with no interference from other pesticides. The plant-wearable sensors had reproducible response being robust and stable against multiple flexions. Due to high sensitivity and selectivity, easy operation and rapid agrochemical detection, the plant-wearable sensors can be used to detect biomarkers in human biofluids and be used in on-site analysis of other hazardous chemical substances.
Topics: Humans; Pesticides; Paraquat; Wearable Electronic Devices; Food Safety; Agriculture; Water
PubMed: 37944446
DOI: 10.1016/j.bioadv.2023.213676 -
Environment International Jan 2023As an indispensable type of pesticide, fungicides have been somewhat neglected compared to insecticides and herbicides. Heavy fungicide application in agricultural...
As an indispensable type of pesticide, fungicides have been somewhat neglected compared to insecticides and herbicides. Heavy fungicide application in agricultural regions may generate downstream ecological concerns via in-stream transport, and the reservoir complicates the process. Monitoring fungicide exposure and exploring reservoir effect on fungicide transport is the key to develop the downstream strategies of agricultural diffusion pollution control. Here, we investigated the exposure, spatiotemporal dynamics, and ecological risk of fungicides in a reservoir-regulated agricultural basin, located in the middle of the Yangtze River Basin, China. Seven fungicides were preliminarily identified and exhibited high detection frequencies (>85 %) in subsequent quantification of water samples from three sampling activities. The total concentration of fungicides ranged from 2.47 to 560.29 ng/L, 28.35 to 274.69 ng/L, and 13.61 to 146.968 ng/L in April, September, and November, respectively. Overall, the contamination levels of fungicides were in the ascending order of April < November < September. The spatial distribution of fungicides was closely associated with the dense of cultivated land, supporting its agricultural source. Furthermore, the reservoir plays a retention role in fungicides, alleviating ecological pressure downstream during the water storage period. Yet, due to the alternation of "source" and "sink" function of the reservoir, the contribution of Zijiang River to the fungicide load in the Yangtze River Basin still needs further attention. Although there is no acute risk posed by fungicides, even in the high-exposure scenario, the chronic ecological risk could not be ignored. Agricultural intensive regions, coupled with the reservoir, provide rather substantial chronic ecological concerns. Carbendazim has been designated as a priority pollutant that contributes significantly to cumulative chronic risk. Thus, we emphasize strengthening the supervision of fungicides in surface water and rationally restricting the use of carbendazim in agricultural operations.
Topics: Fungicides, Industrial; Water Pollutants, Chemical; Environmental Monitoring; Water; China; Risk Assessment
PubMed: 36535191
DOI: 10.1016/j.envint.2022.107697 -
Food Chemistry Aug 2023Carbendazim (CBZ), a well-known benzimidazole pesticide, is utilized in agriculture to prevent and cure plant diseases caused by fungi. Residual CBZ in food poses...
Carbendazim (CBZ), a well-known benzimidazole pesticide, is utilized in agriculture to prevent and cure plant diseases caused by fungi. Residual CBZ in food poses serious threat to human health. Herein, a fluorescent two-dimensional terbium-based metal-organic framework (2D Tb-MOF) nanosheet sensor was developed for the rapid and ultrasensitive detection of CBZ. The 2D Tb-MOF nanosheets, prepared with Tb ions and 5-borono-1,3-benzenedicarboxylic acid (BBDC) as the precursors, exhibited excellent optical properties. Upon the addition of CBZ, the fluorescence of Tb-MOF nanosheets was quenched because of the inner filter effect (IFE) and dynamic quenching. The fluorescence sensor offered two linear ranges of 0.06-4 and 4-40 µg/mL with a low detection limit of 17.95 ng/mL. Furthermore, the proposed sensing platform was successfully applied to assay CBZ in apples and tea, and satisfactory results were obtained. This study provides an effective alternative strategy for the qualitative and quantitative determination of CBZ to ensure food safety.
Topics: Humans; Metal-Organic Frameworks; Terbium; Benzimidazoles; Coloring Agents; Food Safety
PubMed: 36893637
DOI: 10.1016/j.foodchem.2023.135853 -
Pesticide Biochemistry and Physiology Mar 2021Nano-fungicides are expected to play an important role in future plant disease management. Their unique properties include a broad antimicrobial action, increased...
Nano-fungicides are expected to play an important role in future plant disease management. Their unique properties include a broad antimicrobial action, increased effectiveness in lower doses, slower a.i. release and/or enhanced drug delivery and an ability to control drug-resistant pathogens, which makes them appealing candidates for use as eco-friendly antifungal alternatives to counter fungicides resistance. Copper nanoparticles (Cu-NPs) could suppress mycelial growth in both sensitive (BENS) and resistant (BEN-R) Monilinia fructicola isolates harboring the E198A benzimidazole resistance mutation, more effectively than copper oxide NPs (CuO-NPs) and Cu(OH). A significant synergy of Cu-NPs with thiophanate methyl (TM) was observed against BEN-S isolates both in vitro and when applied on plum fruit suggesting enhanced availability or nanoparticle induced transformation of TM to carbendazim. ATP-dependent metabolism is probably involved in the mode of fungitoxic action of Cu-NPs as indicated by the synergy observed between Cu-NPs and the oxidative phosphorylation-uncoupler fluazinam (FM). Copper ion release contributed in the toxic action of Cu-NPs against M. fructicola, as indicated by synergism experiments with ethylenediaminetetraacetic acid (EDTA), although the lack of correlation between nano and bulk/ionic copper forms indicate an additional nano-property mediated mechanism of fungitoxic action. Results suggested that Cu-NPs can be effectively used in future plant disease management as eco-friendly antifungal alternatives to counter fungicides resistance and reduce the environmental footprint of synthetic fungicides.
Topics: Ascomycota; Benzimidazoles; Copper; Drug Resistance, Fungal; Nanoparticles
PubMed: 33771267
DOI: 10.1016/j.pestbp.2021.104796 -
Food Additives & Contaminants. Part B,... Oct 2023The occurrence of pesticide residues, their metabolites and degradation products in 49 edible mushrooms (fresh, dried, canned and frozen) was investigated. Using...
The occurrence of pesticide residues, their metabolites and degradation products in 49 edible mushrooms (fresh, dried, canned and frozen) was investigated. Using QuEChERS extraction, followed by liquid and gas chromatography coupled with tandem mass spectrometry, the samples collected from Czech markets were tested for 427 analytes. A total of 21 pesticide residues, their metabolites and pesticide synergists were found in quantifiable concentrations. The most frequently detected pesticide residues included prochloraz and its metabolites, metrafenone and carbendazim. Two mushroom samples were found to be in violation of the maximum residue level. In addition, the fate of 13 pesticides during the processing of fresh mushrooms was investigated. The processing factors calculated from the data ranged from 6.0 to 12.3 for drying and from 0.3 to 1.3 for deep-freezing. The results showed that most of the pesticide residues tested were stable under the conditions of mushroom processing.
PubMed: 37830121
DOI: 10.1080/19393210.2023.2259867 -
Molecules (Basel, Switzerland) Oct 2023Herein, ZIF-67-derived Co and N-doped carbon (Co/NC) particle-modified multilayer MXene (MXene@Co/NC) was developed as remarkable electrode material for carbendazim...
Herein, ZIF-67-derived Co and N-doped carbon (Co/NC) particle-modified multilayer MXene (MXene@Co/NC) was developed as remarkable electrode material for carbendazim (CBZ) detection. MXene as a substrate provides an excellent conductive framework and plentiful accessibility sites. Co/NC particles embedding in MXene can not only prevent the interlayer stacking of MXene but also contribute a great deal of metal catalytic active sites and finally improve the adsorption and catalytic properties of the composite. Accordingly, the MXene@Co/NC electrode displays excellent electrocatalytic activity toward CBZ oxidation. Experimental parameters such as pH value, accumulation time, MXene@Co/NC modification volume and constituent materials' mass ratios were optimized. Under optimal conditions, the as-prepared sensor based on MXene@Co/NC holds a broad linearity range from 0.01 μM to 45.0 μM with a low limit of detection (LOD) of 3.3 nM (S/N = 3, S means the detection signal, while N represents the noise of the instrument). Moreover, the proposed sensor displays excellent anti-interference ability, superior reproducibility, excellent stability, and successfully achieves actual applications for CBZ detection in a lettuce sample.
PubMed: 37959766
DOI: 10.3390/molecules28217347 -
Environmental Research Aug 2021Residential exposure to pesticides may occur via inhalation of airborne pesticides, direct skin contacts with pesticide-contaminated surfaces, and consumption of food...
BACKGROUND
Residential exposure to pesticides may occur via inhalation of airborne pesticides, direct skin contacts with pesticide-contaminated surfaces, and consumption of food containing pesticide residues. The aim was to study the association of dermal exposure to pesticides between the use and non-use periods, between farmer and non-farmer families and between dermal exposure and the excretion of metabolites from urine in residents living close to treated agricultural fields.
METHODS
In total, 112 hand wipes and 206 spot urine samples were collected from 16 farmer and 38 non-farmer participants living within 50 m from an agricultural field in the Netherlands. The study took place from May 2016 to December 2017 during the use as well as the non-use periods of pesticides. Hand wipes were analysed for the parent compound and urines samples for the corresponding urinary metabolite of five applied pesticides: asulam, carbendazim (applied as thiophanate-methyl), chlorpropham, prochloraz and tebuconazole. Questionnaire data was used to study potential determinants of occurrence and levels of pesticides in hand wipes according to univariate and multivariate analysis.
RESULTS
Carbendazim and tebuconazole concentrations in hand wipes were statistically significantly higher in the pesticide-use period compared to the non-use period. In addition, especially during the use periods, concentrations were statistically significantly higher in farmer families compared to non-farmer families. For asulam, chlorpropham and prochloraz, the frequency of non-detects was too high (57-85%) to be included in this analysis. The carbendazim contents in urine samples and hand wipes were correlated on the first and second day after taking the hand wipe, whereas chlorpropham was only observed to be related on the second day following the spray event.
CONCLUSIONS
Concentrations in hand wipes were overall higher in pesticide use periods compared to non-use periods and higher in farmer families compared to non-farmer families. Only for carbendazim a strong correlation between concentrations in hand wipes and its main metabolite in urine was observed, indicating dermal exposure via contaminated indoor surfaces. We expect this to be related to the lower vapour pressure and longer environmental lifetime of carbendazim compared to the other pesticides studies.
Topics: Biomarkers; Environmental Exposure; Environmental Monitoring; Hand; Humans; Netherlands; Pesticide Residues; Pesticides
PubMed: 34015296
DOI: 10.1016/j.envres.2021.111282 -
The Science of the Total Environment Feb 2020Combating drug-resistance is a daunting task, especially due to the shortage of available drug alternatives with multisite modes of action. In this study, the potential...
Combating drug-resistance is a daunting task, especially due to the shortage of available drug alternatives with multisite modes of action. In this study, the potential of copper nanoparticles (Cu-NPs) to suppress 15 Botrytis cinerea isolates, which are sensitive or resistant to fungicides, alone or in combination with conventional fungicides, was tested in vitro and in vivo. Sensitivity screening in vitro revealed two fungicide resistance phenotypes, resulting from target site mutations. DNA sequencing revealed three B. cinerea isolates highly resistant to benzimidazoles (BEN-R), thiophanare methyl (TM), and carbendazim, bearing the E198A resistance mutation in the β-tubulin gene, and four isolates highly resistant to the QoI pyraclostrobin (PYR-R) with a G143A mutation in the cytb gene. Cu-NPs were equally effective against sensitive and resistant isolates. An additive/synergistic effect was observed between Cu-NPs and TM in the case of BEN-S isolates both in vitro and when applied in apple fruit. A positive correlation was observed between TM and TM + Cu-NPs treatments, suggesting that an increased TM availability in the target site could be related with the observed additive/synergistic action. No correlation between Cu(OH) and Cu-NPs sensitivity was found, indicating that different mechanisms govern the fungitoxic activity between nano and bulk counterparts. A synergistic profile was observed between Cu-NPs and fluazinam (FM) - an oxidative phosphorylation inhibitor - in all isolates regardless of resistance phenotype, suggesting that ATP metabolism could be involved in the mode of action of Cu-NPs. Furthermore, the observed cross sensitivity and antagonistic action between Cu-NPs and NaCl also provided evidence for copper ions contribution to the fungitoxic action of Cu-NPs. The results suggested that Cu-NPs in combination with conventional fungicides can provide the means for an environmentally safe, sustainable resistance management strategy by reducing fungicide use and combating resistance against B. cinerea.
Topics: Benzimidazoles; Botrytis; Carbamates; Copper; Drug Resistance, Fungal; Metal Nanoparticles; Phenotype; Plant Diseases
PubMed: 31767318
DOI: 10.1016/j.scitotenv.2019.135557 -
Chemosphere Apr 2022The widespread use of methyl parathion (MP) and carbendazim (CBZ) as pesticide molecules for controlling pests and protect crops has added pollution issues; excess usage...
The widespread use of methyl parathion (MP) and carbendazim (CBZ) as pesticide molecules for controlling pests and protect crops has added pollution issues; excess usage of these can lead to atmospheric pollution through contaminating water and soil sources. In the present study, detection of these compounds at the trace level was achieved by employing graphene oxide (GO) and graphitic carbon nitride (g-CN) nanohybrid electrode assembly (GO/g-CN/GCE). The X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), and Atomic Force Microscopy (AFM) techniques were also used to characterize the materials developed to reveal their purity, crystal structure, and morphology. The complete voltammetric behavior of these analytes was investigated using cyclic voltammetic (CV) and square wave voltammetry (SWV) techniques. The influence of pH was studied and it was noticed that electrochemical response was the highest at pH 7.0 for MP and at pH 4.2 for CBZ. Density Functional Theory (DFT) calculations could help us to understand the adsorption behavior of MP and CBZ onto the GO and g-CN before their degradation due to the electrochemical reactions. SWV technique was helpful in the trace level detection of MP and CBZ. Linearity plots were obtained in the range of concentration from 8.0 × 10 M to 1.0 × 10 M with a limit of detection 0.824 nM for MP and 1.0 × 10 M to 2.5 × 10 M for CBZ with the detection limit of 2.82 nM. Significance of the developed method in the field of agricultural and environmental domains was successfully investigated by monitoring MP and CBZ in water and soil samples, and the obtained results suggested the selectivity, stability, and reproducibility of the newly developed GO/g-CN/GCE electrode assembly.
Topics: Benzimidazoles; Carbamates; Electrochemical Techniques; Electrodes; Graphite; Methyl Parathion; Nanocomposites; Nitriles; Reproducibility of Results
PubMed: 34979209
DOI: 10.1016/j.chemosphere.2021.133450