Determinants of pesticides use among tomato farmers in the Bono and Ahafo regions of Ghana.

Tomato production plays a crucial role in the livelihoods of farmers and agricultural households in the forest savanna transitional belt of Ghana. However, the success of tomato cultivation is hindered by the presence of insect pests and diseases, necessitating the use of agricultural inputs. This study aimed to identify the pesticides used in tomato farming, assess their World Health Organization (WHO) active ingredient hazard class, determine the precautionary behaviour associated with pesticide use by tomato farmers, and elucidate the socio-economic factors influencing pesticide usage in the Bono and Ahafo regions of Ghana. A multistage sampling procedure was employed to select 1009 respondents, who were administered a structured questionnaire. Descriptive statistics and logistic regression models were used to analyse the collected data. The results revealed that tomato farmers utilized 15 types of insecticides (e.g., lambda and chlorpyrifos ethyl based), 8 types of fungicides (e.g., mancozeb and sulphur + copper based), and 6 types of weedicides (mostly glyphosate based) on their crops. Notably, four insecticides and two fungicides types were found to be unregistered products. Lambda-cyhalothrin-based insecticides and mancozeb-based fungicides were predominantly used by the farmers. The assessed pesticides exhibited varying levels of hazard, ranging from slight to moderate. The study found that farmer training was a significant driver influencing insecticide use, while the educational level of farmers and average yield played important roles in determining fungicide use. Socio-economic factors such as being the head of the household, employing farm workers, the cultivated tomato variety, and farmer training influenced weedicide use. The type of tomato variety cultivated emerged as the primary socio-economic driver of pesticide use. The study recommended the establishment and implementation of a systematic monitoring regime for pesticide product marketing and use, with the aim of reducing the utilization of unregistered products by farmers. Implementing these measures supports sustainable tomato farming in the Bono and Ahafo regions of Ghana.

Fungicide ingestion reduces net energy gain and microbiome diversity of the solitary mason bee.

Fungicides are frequently used during tree fruit bloom and can threaten insect pollinators. However, little is known about how non-honey bee pollinators such as the solitary bee, Osmia cornifrons, respond to contact and systemic fungicides commonly used in apple production during bloom. This knowledge gap limits regulatory decisions that determine safe concentrations and timing for fungicide spraying. We evaluated the effects of two contact fungicides (captan and mancozeb) and four translaminar/plant systemic fungicides (cyprodinil, myclobutanil, penthiopyrad, and trifloxystrobin) on larval weight gain, survival, sex ratio, and bacterial diversity. This assessment was carried out using chronic oral ingestion bioassays where pollen provisions were treated with three doses based on the currently recommended field use dose (1X), half dose (0.5X), and low dose (0.1X). Mancozeb and penthiopyrad significantly reduced larval weight and survival at all doses. We then sequenced the 16S gene to characterize the larvae bacteriome of mancozeb, the fungicide that caused the highest mortality. We found that larvae fed on mancozeb-treated pollen carried significantly lower bacterial diversity and abundance. Our laboratory results suggest that some of these fungicides can be particularly harmful to the health of O. cornifrons when sprayed during bloom. This information is relevant for future management decisions about the sustainable use of fruit tree crop protection products and informing regulatory processes that aim to protect pollinators.

Identification and Fungicide Screening of Fungal Species Associated with Walnut Anthracnose in Shaanxi and Liaoning Provinces, China.

Walnut is cultivated around the world for its precious woody nut and edible oil. Recently, walnut infected by Colletotrichum spp. resulted in a great yield and quality loss. In August and September 2014, walnut fruits with anthracnose were sampled from two commercial orchards in Shaanxi and Liaoning provinces, and five representative isolates were used in this study. To identify the pathogen properly, four genes per region (internal transcribed spacer, glyceraldehyde-3-phosphate dehydrogenase, actin, and chitin synthase) were sequenced and used in phylogenetic studies. Based on multilocus phylogenetic analysis, five isolates clustered with Colletotrichum fioriniae, including its ex-type, with 100% bootstrap support. The results of multilocus phylogenetic analyses, morphology, and pathogenicity confirmed that C. fioriniae was one of the walnut anthracnose pathogens in China. All 13 fungicides tested inhibited mycelial growth and spore germination. Flusilazole, fluazinam, prochloraz, and pyraclostrobin showed the strongest suppressive effects on the mycelial growth than the others, the average EC50 values ranged from 0.09 to 0.40 µg/ml, and there was not any significant difference (P < 0.05). Pyraclostrobin, thiram, and azoxystrobin were the most effective fungicides on spore germination (P < 0.05), and the EC50 values ranged from 0.01 to 0.44 µg/ml. Pyraclostrobin, azoxystrobin, fluazinam, flusilazole, mancozeb, thiram, and prochloraz exhibited a good control effect on walnut anthracnose caused by C. fioriniae, and preventive activities were greater than curative activities. Pyraclostrobin at 250 a.i. µg/ml and fluazinam at 500 a.i. µg/ml provided the highest preventive and curative efficacy, and the values ranged from 81.3 to 82.2% and from 72.9 to 73.6%, respectively. As a consequence, mancozeb and thiram could be used at the preinfection stage, and pyraclostrobin, azoxystrobin, flusilazole, fluazinam, and prochloraz could be used at the early stage for effective prevention and control of walnut anthracnose caused by C. fioriniae. The results will provide more significant instructions for controlling the disease effectively in northern China.

Low concentrations of ethylene bisdithiocarbamate pesticides maneb and mancozeb impair manganese and zinc homeostasis to induce oxidative stress and caspase-dependent apoptosis in human hepatocytes.

The worldwide and intensive use of phytosanitary compounds results in environmental and food contamination by chemical residues. Human exposure to multiple pesticide residues is a major health issue. Considering that the liver is not only the main organ for metabolizing pesticides but also a major target of toxicities induced by xenobiotics, we studied the effects of a mixture of 7 pesticides (chlorpyrifos-ethyl, dimethoate, diazinon, iprodione, imazalil, maneb, mancozeb) often detected in food samples. Effects of the mixture was investigated using metabolically competent HepaRG cells and human hepatocytes in primary culture. We report the strong cytotoxicity of the pesticide mixture towards hepatocytes-like HepaRG cells and human hepatocytes upon acute and chronic exposures at low concentrations extrapolated from the Acceptable Daily Intake (ADI) of each compound. Unexpectedly, we demonstrated that the manganese (Mn)-containing dithiocarbamates (DTCs) maneb and mancozeb were solely responsible for the cytotoxicity induced by the mixture. The mechanism of cell death involved the induction of oxidative stress, which led to cell death by intrinsic apoptosis involving caspases 3 and 9. Importantly, this cytotoxic effect was found only in cells metabolizing these pesticides. Herein, we unveil a novel mechanism of toxicity of the Mn-containing DTCs maneb and mancozeb through their metabolization in hepatocytes generating the main metabolite ethylene thiourea (ETU) and the release of Mn leading to intracellular Mn overload and depletion in zinc (Zn). Alteration of the Mn and Zn homeostasis provokes the oxidative stress and the induction of apoptosis, which can be prevented by Zn supplementation. Our data demonstrate the hepatotoxicity of Mn-containing fungicides at very low doses and unveil their adverse effect in disrupting Mn and Zn homeostasis and triggering oxidative stress in human hepatocytes.

Evaluation of the acute and sublethal toxicity of Mancozeb in Pacamã (Lophiosilurus alexandri).

The toxic potential of dithiocarbamates fungicides widely used in world agriculture is well known, among which Mancozeb is one of the most used. This study aimed to evaluate the toxicity of Mancozeb, determining the LC50% of the product and the behavioral and histological changes observed in fish of the Pacamã species through acute and sublethal toxicity tests. The first experiment was carried out on Pacamã fingerlings exposed to dosages of 0.5, 1, 2, 4, and 8mg/L of Mancozeb under the form ManzateWG®, for a total period of 96 hours in the acute experiment, and in the second experiment, fish were subjected to concentrations of 1/10 of those used in the acute experiment (0.05, 0.1, 0.2, 0.4 and 0.8mg/L, respectively), for 15 days in total. The 50% lethal concentration of ManzateWG® was calculated at the end of the acute experiment, presenting a value of 2.29mg/L at 96h for Pacamã fingerlings. A behavioral assessment was carried out through daily observation of the fish during both experiments, and an increase in mucus production was observed, as well as atypical social behavior in those exposed to the toxic agent. Histopathological evaluation was performed on livers collected after the end of the sublethal experiment, and the main hepatic alterations observed were cytoplasmic vacuolization, inflammatory infiltrate, and necrosis. Mancozeb has toxic potential and is capable of generating behavioral changes, as well as increasing the risk of liver damage in Pacamãs exposed to this compound.

A novel bidirectional regulation mechanism of mancozeb on the dissemination of antibiotic resistance.

The high abundance of antibiotic resistance genes (ARGs) in the fungicide residual environment, posing a threat to the environment and human health, raises the question of whether and how fungicide promotes the prevalence and dissemination of antibiotic resistance. Here, we reported a novel mechanism underlying bidirectional regulation of a typical heavy-metal-containing fungicide mancozeb on the horizontal transfer of ARGs. Our findings revealed that mancozeb exposure significantly exerted oxidative and osmotic stress on the microbes and facilitated plasmid-mediated ARGs transfer, but its metallic portions (Mn and Zn) were potentially utilized as essential ions by microbes for metalating enzymes to deal with cellular stress and thus reduce the transfer. The results of transcriptome analysis with RT-qPCR confirmed that the expression levels of cellular stress responses and conjugation related genes were drastically altered. It can be concluded mancozeb bidirectionally regulated the ARGs dissemination which may be attributed to the diverse effects on the microbes by its different portions. This novel mechanism provides an updated understanding of neglected fungicide-triggered ARGs dissemination and crucial insight for comprehensive risk assessment of fungicides.

Pre-imaginal exposure to mancozeb induces morphological and behavioral deficits and oxidative damage in Drosophila melanogaster.

Mancozeb (MZ), a manganese/zinc containing ethylene-bis-dithiocarbamate, is a broad-spectrum fungicide. Chronic exposure to MZ has been related to several organisms' neurological, hormonal, and developmental disorders. However, little is known about the post-natal effects of developmental exposure to MZ. In this study, Drosophila melanogaster was subjected to a pre-imaginal (eggs-larvae-pupae stage) model of exposure to MZ at 0.1 and 0.5 mg/mL. The emergence rate, body size, locomotor performance, sleep patterns, and molecular and biochemical parameters were evaluated in post-emerged flies. Results demonstrate that pre-imaginal exposure to MZ significantly impacted early emerged flies. Additionally, reduced progeny viability, smaller body size and delaying in emergence period, locomotor impairment, and prolonged sleep time were observed. Content of glucose, proteins, and triglycerides were altered, and the bioenergetics efficiency and oxidative phosphorylation at complex I were inhibited. mRNA stade state levels of genes responsive to stress, metabolism, and regulation of circadian cycle (Nrf2, p38, Hsp83, Akt1, GPDH, tor, per, tim, dILP2, and dILP6) were augmented, pointing out to stimulation of antioxidant defenses, insulin-dependent signaling pathway activation, and disruption of sleep regulation. These data were followed by increased lipid peroxidation and lower glutathione levels. In addition, the activity of catalase and glutathione-S-transferase were induced, whereas superoxide dismutase was inhibited. Together, these results demonstrate that developmental exposure to MZ formulation led to phenotype and behavioral alterations in young flies, possibly related to disruption of energetic metabolism, oxidative stress, and deregulation of genes implied in growth, sleep, and metabolism.

Mancozeb induces nephrotoxicity by impairing the oxidative phosphorylation pathway: A transcriptome study.

This study analyzed the mechanism underlying mancozeb (MCZ)-induced kidney injury by detecting kidney function indicators, combined with transcriptome and metabolome sequencing. Twenty mice were randomly assigned into two groups (control and MCZ groups) to explore the MCZ-induced kidney toxicity. The control group was gavaged with 0.2 mL of deionized water, and the MCZ group with 0.2 mL of 100 mg/kg MCZ for 30 days. The kidney structure of the MCZ group was damaged, with slight hyaline degeneration in the kidney tubular epithelial envelope. The creatinine (CRE) and uric acid (UA) were significantly increased in the MCZ group than in the control group. Moreover, the reactive oxygen species (ROS) significantly accumulated in the MCZ group kidneys. Compared to the control group, superoxide dismutase (SOD) and glutathione peroxidase (GSH-PX) were significantly decreased in the MCZ group, while the MDA content was substantially increased. The differentially expressed genes (DEGs) in the MCZ group were mainly enriched in the oxidative phosphorylation pathway. Besides, in the MCZ group, ndufs1 and ndufab1 genes were significantly up-regulated, while cox5b, ndufa5, and ndufa6 genes were significantly down-regulated, consistent with the PCR verification results. The metabolomic analysis identified cGMP-PKG signaling pathway of MCZ-induced nephrotoxicity, with Guanosine monophosphate and Adenosine 5'-monophosphate as the main altered metabolites. These results indicated that MCZ impairs the mice kidneys by obstructing the oxidative phosphorylation pathway, which increases oxidative stress in the kidneys, resulting in kidney injury.

Foliar application of three dithiocarbamates inhibits the absorption and accumulation of Cd in wheat.

In cadmium (Cd) contaminated farmland soil, antagonism between elements can be used to control the absorption and accumulation of Cd in crops through the external application of zinc (Zn) and manganese (Mn). Dithiocarbamates (DTCs) are highly effective fungicides commonly used in farmlands, and DTCs are rich in Zn and Mn. We selected three representative DTCs (propineb, mancozeb, and zineb) for a field experiment in Henan province, China. The effects of DTC on Cd absorption and accumulation in wheat and the interaction of Zn, Mn, and Cd in wheat after spraying of DTC were studied using different application times at the heading stage. The results showed that after foliar spraying of DTCs according to pesticide application requirements, wheat yield was not affected. The Zn and Mn contents in grains increased, with the highest increases being 19.2% and 12.4%, respectively. Zn and Cd as well as Mn and Cd were antagonistic in wheat, and the transport of Cd from soil to root and from husk to grain was inhibited. The bioconcentration factor (grains/soil) decreased from 1.3 to 0.68 and the translocation factor (grains/husks) decreased from 0.76 to 0.35. The Cd content in grains decreased by 60.4%, 52.8%, and 25.6% with mancozeb, propineb, and zineb applications, respectively, and the Cd reduction effect of spraying DTCs twice was better than that of spraying DTCs once and thrice. The results show that DTCs application could reduce the Cd content in wheat grains and realize the dual effects of crop disease prevention and Cd reduction.

Assessment of Mancozeb Exposure, Absorbed Dose, and Oxidative Damage in Greenhouse Farmers.

Mancozeb (MNZ) is a fungicide commonly employed in many countries worldwide. This study assesses MNZ absorption dynamics in 19 greenhouse farmers, specifically following dermal exposure, aiming to verify the efficacy of both preventive actions and protective equipment. For data collection, a multi-assessment approach was used, which included a survey to record study population features. MNZ exposure was assessed through the indirect measurement of ethylene thiourea (ETU), widely employed as an MNZ biomarker. The ETU concentration was measured with the patch method, detecting environmental ETU trapped in filter paper pads, applied both on skin and working clothes, during the 8 h work shift. Urine and serum end-of-shift samples were also collected to measure ETU concentrations and well-known oxidative stress biomarkers, respectively, namely reactive oxygen metabolites (ROMs), advanced oxidation protein products (AOPPs), and biological antioxidant potential (BAP). It was observed that levels of ETU absorbed and ETU excreted were positively correlated. Additionally, working clothes effectively protected workers from MNZ exposure. Moreover, following stratification of the samples based on the specific working duty (i.e., preparation and spreading of MNZ and manipulation of MNZ-treated seedlings), it was found that the spreading group had higher ETU-related risk, despite lower chronic exposure levels. AOPP and ROM serum levels were higher in MNZ-exposed subjects compared with non-exposed controls, whereas BAP levels were significantly lower. Such results support an increase in the oxidative stress upon 8 h MNZ exposure at work. In particular, AOPP levels demonstrated a potential predictive role, as suggested by the contingency analysis results. Overall, this study, although conducted in a small group, confirms that ETU detection in pads, as well as in urine, might enable assessment of the risk associated with MNZ exposure in greenhouse workers. Additionally, the measurement of circulating oxidative stress biomarkers might help to stratify exposed workers based on their sensitivity to MNZ. Pivotally, the combination of both ETU measurement and biological monitoring might represent a novel valuable combined approach for risk assessment in farmhouse workers exposed to pesticides. In the future, these observations will help to implement effective preventive strategies in the workplace for workers at higher risk, including greenhouse farmers who are exposed to pesticides daily, as well as to clarify the occupational exposure levels to ETU.

Transcriptomics and metabolomics revealed the molecular mechanism of the toxic effect of mancozeb on liver of mice.

Mancozeb (MCZ), a broad-spectrum fungicide, has been widely used in crops (tomatoes and potatoes) in the past few decades, resulting in its bioaccumulation in the food web. However, the mechanism of MCZ on liver injury has not been reported yet. This study combined transcriptomics and metabolomics to explore the potential mechanism of MCZ on liver injury. MCZ group was given 100 mg/kg MCZ every day, and the C group was given 0.2 mL of deionized water every day. One hundred mg/kg MCZ led to unclear hepatocyte structure and hemorrhagic inflammatory cell infiltration. Transcriptomics and metabolomics analyses showed that the MCZ group resulted in 326 differentially expressed genes (DEGs) and 179 differential metabolites. Joint analysis showed that DEGs and differential metabolites were mainly enriched in the adenosine monophosphate (AMP)-activated protein kinase (AMPK) signaling pathway. We found that MCZ could increase the content of reactive oxygen species (ROS) and reduce the activities of superoxide dismutase (SOD) and catalase (CAT). The contents of DNA methyltransferases (DNMT1, DNMT3A, and DNMT3B) in the liver decreased significantly, and the state of DNA methylation was significantly higher than the control (C) group (p < 0.05). Our results suggest that AMPK and mitogen­activated protein kinase (MAPK) signaling pathways play an important role in MCZ-induced liver injury and are the key mechanisms for understanding the hepatotoxicity of MCZ.

Nematode Community of a Natural Grassland Responds Sensitively to the Broad-Spectrum Fungicide Mancozeb in Soil Microcosms.

Fungicides make up the largest part of total pesticide use, with the dithiocarbamate mancozeb being widely applied as a nonsystemic contact pesticide to protect a wide range of field crops against fungal diseases. Although nematodes are key drivers of soil functioning, data on effects of fungicides, and especially mancozeb, on these nontarget organisms are scarce. Therefore, the effects of mancozeb on a soil nematode community from a natural grassland were assessed in small-scale soil microcosms. Nematodes were exposed to mancozeb-spiked soil in six nominal concentrations (7-133 mg/kg dry soil) and analyzed after 14, 56, and 84 days in terms of densities, genus composition, and functional traits. Because this fungicide is known to quickly degrade in soils (50% degradation time <1 day), mancozeb concentrations were analyzed for all sampling occasions. Chemical analysis revealed considerably lower measured concentrations compared with the aimed nominal soil concentrations at the beginning of the exposure (1-18 mg/kg dry soil), suggesting fast degradation during the spiking process. Nevertheless, the native nematode community responded sensitively to the fungicide mancozeb, revealing lower no-observed-effect concentration and 10% effect concentration (EC10) values than reported for other soil invertebrates such as springtails and earthworms. Using the EC10 for the most sensitive nematode community endpoint (percentage of predators and omnivores: 1.2 mg/kg dry soil), the risk assessment exhibited a toxicity exposure ratio of 0.66 and, thus, a high risk of mancozeb for soil nematodes. Keeping in mind their abundance and their central roles in soil food-web functioning, the demonstrated sensitivity to a widely applied fungicide underscores the relevance of the inclusion of nematodes into routine risk-assessment programs for pesticides. Environ Toxicol Chem 2022;41:2420-2430. © 2022 SETAC.

High tolerance and degradation of fungicides by fungal strains isolated from contaminated soils.

The aim of this work was to isolate fungal strains from phytotoxic agricultural soils, screen them, categorize the most tolerant fungi to three fungicides, and identify them by a molecular approach. In this study, 28 fungal strains were isolated from phytotoxic agricultural soil with intensive use of pesticides. The capacity of fungi to resist and degrade different concentrations of carbendazim, captan, and zineb was determined by an exploratory multivariate analysis. Actinomucor elegans LBM 239 was identified as the most tolerant fungus to these fungicides, degrading a 86.62% of carbendazim after 7 days of treatment. In conclusion, A. elegans LBM 239 demonstrated the highest tolerance and capacity to biodegrade carbendazim, becoming a potential candidate for bioremediation of contaminated soils with carbendazim, captan, or zineb.

Interaction of mancozeb with human hemoglobin: Spectroscopic, molecular docking and molecular dynamic simulation studies.

Mancozeb is a broad-spectrum fungicide used extensively in agriculture to protect plants from numerous diseases. Hemolysis of human erythrocytes on exposure to mancozeb has been reported. In the present study, we investigated the interaction of mancozeb with human hemoglobin (Hb) using multi-spectroscopic techniques, molecular docking and molecular dynamic simulation. UV-visible spectroscopy studies suggested intimate binding of mancozeb to Hb. Mancozeb quenched the intrinsic fluorescence of Hb and Stern-Volmer plots revealed that the quenching mechanism was of static type. Evaluation of thermodynamic parameters indicated that the binding of Hb to mancozeb was spontaneous, with van der Waals forces and hydrogen bonding being the key contributors in the binding reaction. Synchronous fluorescence experiments demonstrated that mancozeb altered the microenvironment around tryptophan residues, whereas polarity around tyrosine residues was not changed. Circular dichroism studies showed a decrease in the α helical content of Hb upon interaction with mancozeb. The inhibition of esterase activity showed that mancozeb can impair the enzymatic functions of Hb. Molecular docking study revealed that strong binding affinity existed between mancozeb and Hb, with hydrophobic forces playing a crucial role in the interaction. Molecular dynamic simulation showed that mancozeb formed a stable complex with Hb resulting in slight unfolding of the protein. To sum up, the results of this study show that mancozeb binds strongly to Hb, induces conformational changes in Hb and adversely affects its function.

Histopathological, immunohistochemical and biochemical alterations in liver tissue after fungicide-mancozeb exposures in Wistar albino rats.

PURPOSE: To evaluate the histopathological, immunohistochemical, and biochemical effects of liver changes after mancozeb administration. METHODS: Rats were divided into groups-the control group (n=7) and the mancozeb group (n=7)-, given 500 mg/kg mancozeb dissolved in corn oil daily for four weeks by an orogastric tube. Caspase-3 and tumor necrosis factor-alpha (TNF-α) primary antibodies were used for immunohistochemical analysis. RESULTS: Serum aspartate aminotransferase (AST) and alanine aminotransferase (ALT) values of the mancozeb group increased significantly than ones of the control group. Venous dilatation, inflammation, hepatocyte degeneration, TNF-α, and caspase-3 expression scores increased significantly in the mancozeb group. In the mancozeb group, intensive caspase-3 expression was observed in hepatocyte cells around the central vein in the center of the liver lobule, and there was an increase in TNF-α expression in the inflammatory cells around the enlarged central vein and Kupffer cells and apoptotic hepatocyte cells. CONCLUSIONS: Subacute mancozeb exposure in rats leads to elevated toxicity with impaired liver function, increased inflammation in tissue and increased apoptosis due to cellular damage in the liver, and decreased liver regeneration ability due to congestion and degeneration of blood vessels.

Low level of mancozeb exposure affects ovary in mice.

Mancozeb (MCZ) is widely used as a protective fungicide. This study aimed to explore the effects of low level MCZ exposure on ovary in mice. Twenty Kunming mice were randomly divided into control and MCZ groups (10 mice each). The mice in the MCZ group were given 100 mg/kg MCZ daily via gavage. The mice were sacrificed to collect serum and ovaries on day 31. The experimental indicators were then assessed. The weight of MCZ-exposed mice significantly reduced while ovarian index significantly increased compared with the control group. The FSH, LH, E2, P, CAT, SOD and MDA contents in the serum were significantly decreased and the content of estradiol significantly increased after MCZ exposure. Histological observation showed that the ovarian structure of mice exposed to MCZ was damaged, and the apoptosis was increased. Immunohistochemistry and RT-qPCR showed that the expression of Bax, caspase-3 and caspase-9 significantly increased in the MCZ- group. Conversely, Bcl-2 expression significantly decreased. Transcriptome sequencing showed that the expression of NADH dehydrogenase ND3, ND4L, ND6 subunits, Cyt b, and SDHC genes in mitochondria were down-regulated after MCZ exposure, similar to real-time PCR analysis. These results collectively indicate that the MCZ can affect the abnormal function of mitochondrial respiratory chain, lead to oxidative phosphorylation decoupling, produce oxidative stress, and finally cause ovarian injury and apoptosis in mice.

Determination of propineb in vegetable samples after a coprecipitation strategy for its separation-preconcentration prior to its indirect determination by FAAS.

In the presented work, a coprecipitation method was developed for separation-preconcentration, and determination of trace quantities of propineb in vegetable samples. Propineb was coprecipitated by using Al(OH)3. The zinc contents in complex structure of propineb was determined by flame atomic absorption spectrometry (AAS). The propineb concentration was calculated by using stoichiometric relationship between the zinc and propineb. Several parameters including the amount of aluminum(III) as carrier element and hydroxide concentration and sample volume were examined. The effects of matrix ions were also investigated. The preconcentration factor was calculated as 15. The limit of detection (LOD) value for propineb was calculated as 15.2 µg L-1. The presented coprecipitation procedure was successfully applied to determination of propineb in vegetable samples.

The ethylene bisdithiocarbamate fungicides mancozeb and nabam alter essential metal levels in liver and kidney and glutathione enzyme activity in liver of Sprague-Dawley rats.

Mancozeb is a fungicide of the ethylene bisdithiocarbamate (EBDC) class complexed to the metals manganese and zinc. Nabam is the sodium salt of the EBDC backbone. The purpose of this study was to determine if these EBDC compounds alter essential metal homeostasis and glutathione status in Sprague-Dawley rats. Our findings indicate EBDCs caused accumulation of copper in kidneys, but not liver. EBDC compounds also increased glutathione reductase activity in liver, but not kidneys, whereas only mancozeb increased glutathione peroxidase activity in the liver. Mancozeb and nabam increased total glutathione in liver, but only mancozeb increased total glutathione in the kidney. Neither mancozeb nor nabam altered glutathione ratio in either liver or kidney compared to control. Our data suggest that the EBDC backbone of mancozeb, and not the zinc or manganese moieties, is responsible for changes in glutathione status and alteration of essential metal homeostasis in rat liver and kidney.

Electrochemical quantification of mancozeb through tungsten oxide/reduced graphene oxide nanocomposite: A potential method for environmental remediation.

The extensive use of pesticides for better yield of crops have become major human concern over the decades. Pesticides are widely used in the fields to kill weeds and pests on the vegetable and crops to improve the quality and yield of the food knowing the fact that pesticides residue in food are very lethal for human being. Amongst, the hazardous pesticides, mancozeb is widely applied in the protection of crops. Thus the quantification of mancozeb residue is of great importance. This study reports the electrochemical monitoring of mancozeb through tungsten oxide reduced graphene oxide (WO3/rGO) nanocomposite. The engineered nanocomposite was characterized though different analytical tools such as FTIR, XRD and TEM to examine crystallinity, internal texture and the size. The FTIR result confirm the functionalities of GO and WO3/rGO nanocomposite in finger print and functional group region. Through XRD analysis, the size of the WO3/rGO nanocomposite was calculated as 31.6 nm. While the TEM analysis was also exploited to examine the 2D texture of GO and nanometric size of the WO3/rGO. To ensure the conductive nature of the WO3/rGO nanocomposite, the glassy carbon electrode was modified and exploited for cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Under the optimal conditions, the modified sensor showed exceptional response for mancozeb. The linear dynamic range was set from 0.05 to 70 µM in BRB buffer of pH 4. The LOD and LOQ for proposed method was calculated as 0.0038 and 0.0115 µM. The analytical applicability of chemically modified sensor was investigated in real matrix of different vegetable samples and the recovery values were observed in acceptable range. The electrochemical examination of present work reveals that WO3/rGO nanocomposite can be an exceptional aspirant for the determination of mancozeb at commercial level.

A novel validated simple derivatization liquid chromatographic method with diode array detection for the simultaneous determination of mancozeb, azoxystrobin and difenoconazole in pesticide dosage form.

A novel, rapid and simple reverse-phase high performance liquid chromatography (RP-HPLC) method for the simultaneous determination of three pesticides - mancozeb, azoxystrobin and difenoconazole by derivatization with ethyl iodide is presented. Analysis was performed on a C18 column (Agilent Eclipse plus, 150 mm × 4.6 mm; 5 µ) with the mobile phase consisting of acetonitrile + methanol (90 + 10 v/v) - water (0.1% v/v trifluoroacetic acid) (60 : 40, v/v) pumped isocratically at a flow rate of 1.0 mL min-1 and detection wavelength of 205 nm and 272 nm. The factors affecting the derivatization reaction and separation conditions were carefully evaluated and optimized. The method was linear over the concentration range of 3.50 mg L-1 to 31.48 mg L-1 for mancozeb, 0.32 mg L-1 to 2.85 mg L-1 for azoxystrobin and 0.32 mg L-1 to 2.89 mg L-1 for difenoconazole. The new method was successfully applied for the analysis of mancozeb, azoxystrobin and difenoconazole in the pesticide formulation with range recoveries of 99.46% to 100.76%, 99.07% to 101.09% and 98.59% to 101.59%, respectively. The present method is suitable and favorable for the simultaneous separation and analysis of tertiary mixture analytes on account of its sensitivity, rapidity and cost-effectiveness. In addition, it could have excellent application prospects for the simultaneous determination of all three pesticides in other formulated products.