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Carbofuran is a broad‐spectrum synthetic pesticide. Its exposure to non‐target mammals affects the biological system through the induction of oxidative stress. Since oxidative stress is a major contributing factor to cellular autophagy and senescence, our present investigation determined the impacts of carbofuran‐induced oxidative stress on cellular autophagy and senescence. A transmembrane protein, Spinster homolog 1 (Spns1), is involved in autophagic lysosomal metabolism. Its mutation accelerates the cellular senescence and shortens the lifespan. Using a transgenic zebrafish line, expressing fluorescent microtubules‐associated protein 1 light chain 3 (EGFP‐LC3) at the membrane of the autophagosome, we found that carbofuran affects autophagic lysosomal biogenesis in wild‐type zebrafish and exacerbates autophagic defect in spns1‐mutant zebrafish. In real‐time mortality study, carbofuran has shortened the lifespan of wild‐type fish. Nrf2 is a stress‐responsive transcription factor that regulates the expression of antioxidant genes (such as gstp1) in the prevention of oxidative stress‐mediated cellular damage. To assess the effect of carbofuran on Nrf2 signalling, we established a dual‐monitoring transgenic zebrafish line, expressing gstp1 promoter‐driven EGFP and mCherry‐tagged Neh2 domain of Nrf2. Our results suggested that the exposure of carbofuran has down‐regulated both Nrf2 and Gstp1 expressions. Overall, carbofuran affects cellular autophagy and accelerates senescence by enervating the Nrf2 signalling.

BACKGROUND Inoculation of arbuscular mycorrhizal (AM) fungi in soil can promote the uptake of nutrients and xenobiotics by plants. In this study, the effects of arbuscular mycorrhizal fungi (including Glomus intraradices and Glomus mossea) on the growth of maize, the uptake of carbosulfan and the control efficacy on Spodoptera frugiperda were investigated through maize seed coating. RESULTS Results from the pot experiment showed that carbofuran reduced the mycorrhizal colonization of AM fungi in the early stage of the experiment. The inhibiting effect disappeared in 21-49 DAP, whereas the mycorrhizal colonization rate under the G. intraradices treatment was maintained at ≈90%. Compared with noninoculated treatment, the fresh weights of roots in G. intraradices and G. mosseae treatments increased by 20-41% and 10-23%, respectively. Mycorrhizal treatment could significantly increase the transmission rates (root/soil and leaf/stem) and the carbosulfan accumulation in maize. During the harvest period, the control efficacy against S. frugiperda in mycorrhizal treatment was significantly higher than that in noninoculated treatments (P

BACKGROUND Coating seed with pesticides is an effective way to control plant pests, however, factory-based coating processes may carry a potential risk to operational workers of chemical exposure. To study the risk, carbofuran and tebuconazole were used to coat corn seed and their subsequent distribution on the bodies of workers was measured at manufacturers XFS and LS (Shanxi, China). Clothing was collected from workers during operations and analyzed using high-performance liquid chromatography. RESULTS At XFS, dermal exposure to carbofuran was 4.83, 3.31 and 1.48 mg kg-1 , and exposure to tebuconazole was 6.88, 5.16 and 1.72 mg kg-1 for coating, packing and transport workers, respectively. At LS, dermal exposure to carbofuran was 2.32, 0.46 and 0.55 mg kg-1 , and exposure to tebuconazole was 1.69, 0.46 and 0.70 mg kg-1 , for coating, packing and transport workers, respectively. The level of pesticide exposure was significantly higher for seed-coating workers than for packing and transport workers. The main area of exposure was the hands for all workers and the lower limbs for packers; exposure was relatively uniform for pesticide handlers. Occupational risk was assessed based on margin of exposure (MOE). In seed-coating, the MOE was greater than 100 for tebuconazole, indicating no potential risk, but ranged from 0.25 to 2.88 for carbofuran, indicating the risk of a health impact. CONCLUSION The level of exposure varied depending on type of operation undertaken and body parts of workers' body, but the risk of a health impact was highly associated with pesticide toxicity. This provides a guideline for workers in pesticide manufacturing to ensure safe operation of the seed-coating process. © 2021 Society of Chemical Industry.

Carbofuran is a carbamate pesticide, widely used in agricultural practices to increase crop productivity. In mammals, carbofuran is known to cause several untoward effects, such as apoptosis in the hippocampal neuron, oxidative stress, loss of memory and chromosomal anomalies. Most of these effects are implicated with cellular senescence. Therefore, the present study aimed to determine the effect of carbofuran on cellular senescence and biological ageing. Spinster homolog 1 (Spns1) is a transmembrane transporter, regulates autolysosomal biogenesis and plays a role in cellular senescence and survival. Using senescence‐associated β‐galactosidase staining, we found that carbofuran accelerates the cellular senescence in spns1 mutant zebrafish. The yolk opaqueness, a premature ageing phenotype in zebrafish embryos, was accelerated by carbofuran treatment. In the survival study, carbofuran shortened the life span of spns1 mutant zebrafish. Autophagy is the cellular lysosomal degradation, usually up‐regulated in the senescent cells. To know the impact of carbofuran exposure on autophagy progress, we established a double‐transgenic zebrafish line, harbouring EGFP‐tagged LC3‐II and mCherry‐tagged Lamp1 on spns1 mutant background, whereas we found, carbofuran exposure synergistically accelerates autolysosome formation with insufficient lysosome‐mediated degradation. Our data collectively suggest that carbofuran exposure synergistically accelerates the cellular senescence and affects biological ageing in spns1 defective animals.

In this study, porous sandwich structure Fe3 O4 nanoparticles coated by polyhedral oligomeric silsesquioxanes and β-cyclodextrin were prepared by surface polymerization and were used as the magnetic solid phase extraction adsorbent for the extraction and determination of carbaryl and carbofuran. The Fe3 O4 nanoparticles coated with polyhedral oligomeric silsesquioxanes and β-cyclodextrin were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, vibrating sample magnetometry, and scanning electron microscopy. After optimizing the extraction conditions, a method that combined magnetic solid phase extraction with high-performance liquid chromatography was developed for the determination of carbaryl and carbofuran in apple. The method exhibited a good linearity in the range of 2-400 μg/kg for carbaryl and carbofuran (R2 = 0.9995), respectively. The limits of detection were 0.5 μg/kg of carbaryl and 0.7 μg/kg for carbofuran in apple, respectively. Extraction recoveries ranged from 94.2 to 103.1% with the preconcentration factor of 300 and the relative standard deviations were less than 5.9%. These results indicated that the method combined magnetic solid phase extraction with high-performance liquid chromatography and was promising for the determination of carbaryl and carbofuran at trace amounts.

The greater cane rat, as it is commonly known, is often called grasscutter (in Ghana, Nigeria and other regions of West Africa). Even though is highly patronized as a delicacy by a majority of Ghanaians (akrantie—Twi language) mostly in the rural areas, the persistent reports on people being poisoned as a result of eating food prepared with grasscutter which has been captured/killed by the use of poison are deterring people from consuming the grasscutter meat despite its high protein content. The objective of this study was, therefore, to investigate the actual ingredients that are used in the formulation of poison to capture grasscutter for human consumption. Questionnaires were administered to participants (farmers) who are involved in grasscutter hunting to solicit the ingredient they formulate to poison the grasscutter in their hunting. To prove the activeness of these ingredients, the main ingredient used in formulating the poison to capture the grasscutters were tested on two male grasscutters and these were yellow oleander root (Cascabela thevetia; syn: Thevetia peruviana) powder and carbofuran. The findings of the experimental trial revealed that the grasscutter that was fed with yellow oleander root powder did not die but showed some signs of intoxication and staggered each time it tried to move. However, the grasscutter fed with carbofuran died within 10 hr of being poisoned. Majority of the participants attested to the fact that the use of poison increases their chance of capturing the grasscutter, especially in the dry season since the poison is not washed away by the rainwater. However, consuming grasscutter poisoned with either yellow oleander root power or carbofuran could be detrimental to human health., Consuming grasscutter poisoned with either yellow oleander root power or carbofuran could be detrimental to our health. There is a need to increase public awareness.

Carbofuran residue in vegetables is a concern to human health. Direct competitive enzyme-linked immunosorbent assay (dcELISA) and dipstick immunoassay were developed in the present study. The dcELISA showed a 50% inhibition concentration (IC50 ) and working range of 1.3 and 0.2 to 7.5 ng/mL, respectively, while the cutoff value of dipstick immunoassay was 20 ng/mL. Applying the two immunoassays, we achieved the goal of rapid screening of carbofuran residue in commercial vegetables with a simple sample processing method. Among 46 leek, 39 potato, and 39 sweet potato samples, carbofuran residue was detected in 22% of the leek samples, and two samples exceeded the maximum residue limit of China (0.02 mg/kg). In addition, carbofuran residue was found at less than 2.5 ng/g in one potato and one sweet potato samples. The residual level of carbofuran measured by immunoassays agreed well with those determined by ultra-performance liquid chromatography tandem mass spectrometry. To ensure food safety and human health, it is greatly necessary and meaningful to monitor carbofuran residue in commercial vegetables. PRACTICAL APPLICATION: Rapid monitoring of carbofuran residue in vegetables is very necessary and important for consumers, regulatory agencies, and food industry.

Background Many insect cytochrome P450 proteins (CYPs) are involved in the metabolic detoxification of exogenous compounds such as plant toxins and insecticides. Tribolium castaneum, the red flour beetle, is a major agricultural pest that damages stored grains and cereal products. With the completion of the sequencing of its genome, two T. castaneum species-specific CYP genes, CYP4BN6, and CYP6BQ11, were identified. However, it is unknown whether the functions of most CYPs are shared by TcCYP4BN6 and TcCYP6BQ11, and the upstream regulatory mechanism of these two CYPs remains elusive. Results QRT-PCR analysis indicated that TcCYP4BN6 and TcCYP6BQ11 were both most highly expressed at the late pupal stage and were mainly observed in the head and gut, respectively, of adults. Moreover, the transcripts of these two CYPs were significantly induced by dichlorvos and carbofuran, and RNA interference (RNAi) targeting of each of them enhanced the susceptibility of beetles to these two insecticides. Intriguingly, knockdown of the latrophilin (lph) gene, which has been reported to be related to the insecticide susceptibility, reduced the expression of TcCYP4BN6 and TcCYP6BQ11 after insecticide treatment, suggesting that these two CYP genes are regulated by lph to participate in insecticide susceptibility in T. castaneum. Conclusion These results shed new light on the function and mechanism of CYP genes associated with insecticide susceptibility and could facilitate research on appropriate and sustainable pest control management. © 2019 Society of Chemical Industry.

Background Within its natural habitat, Croton ehrenbergii exhibits an innate defense mechanism that is not seen in other plants; it grows unharmed amidst predators and nature, while other species perish. In light of its capacity for defense, C. ehrenbergii was evaluated to better understand the scope of its phytotoxic and nematicide properties. To assess this, fractions obtained by bipartition of a hydro-alcoholic extract, and l-quebrachitol, the main constituent of C. ehrenbergii, were evaluated on Lactuca sativa (dicotyledon) and Lolium perenne (monocotyledon) seeds. Additionally, bipartition fractions and l-quebrachitol were evaluated on a population of Meloidogyne incognita for their nematicide activity. Results From this phytochemical research, l-quebrachitol (1), phenylalanine (2), trans-4-hydroxy-N-methylproline (3) and the flavonoids: kaempferol (4), tiliroside (5), nicotiflorine (6) and rutin (7) were identified by spectroscopic analysis. Both methanol and hexane fractions from aerial parts of the plant inhibited the germination and elongation of roots and stems in L. sativa, but not in Lolium perenne, showing that these fractions mostly inhibit the dicotyledon species used in this research. l-Quebrachitol showed slightly higher seed germination inhibition for Lolium perenne in comparison with L. sativa. Three of the fractions evaluated showed nematicide activity against Meloidogyne incognita larvae (J2) at the 48 h benchmark, compared with carbofuran. l-Quebrachitol shows higher mortality after 48 h exposure at a lower concentration than carbofuran. Conclusion A variety of compounds were isolated from this research, some were common within the Croton genus (4-7), whereas others were not (1-3). This is the first phytochemical, phytotoxic and nematicide report on C. ehrenbergii. Methanol and hexane fractions from the aerial parts of C. ehrenbergii and l-quebrachitol could be used as alternative natural herbicides, predominantly against dicotyledon weed seeds. All fractions had a good mortality percentage against J2 Meloidogyne incognita larvae. © 2019 Society of Chemical Industry.

BACKGROUND Resistance to pesticides is an evolutionary process that entails, in most cases, substantial consequences to the biology of the resistant populations. In this study we focus on the life history traits of the potato tuber moth Tecia solanivora, an invasive and voracious pest for which resistance to pyrethroid insecticides was recently reported. Marginally resistant and multiple-resistant populations were selected from eight sampled localities in Colombia; the use of a fully susceptible population was not possible since none was recognized in the laboratory or field. The multiple-resistant Siachoque population exhibited a 42-fold resistance to the carbamate insecticide carbofuran, and low levels of resistance to chlorpyrifos, a trend observed in six of the eight tested populations. This population also exhibits 24-fold resistance to permethrin. The marginally resistant population of Gualmatan showed 4-fold resistance to chlorpyrifos. RESULTS The multiple-resistant population exhibited a 3.8-day shorter developmental time than the susceptible population, but with higher larval mortality. The peak of egg-laying was delayed in the resistant population in 9 days and the population growth rate was lower than that of the susceptible population. CONCLUSION We hypothesize that the short developmental time of the multiple-resistant population may be an adaptation to minimize exposure to insecticides, which are applied to the soil. This adaptation is likely to require the surviving adults to compensate for the smaller nutrient amounts accumulated by the larvae in investing part of its adult life in securing the necessary resources for late-life egg production. © 2018 Society of Chemical Industry.

In this work, the uncertainty estimation for the determination of ametryn, carbofuran, atrazine, carbaryl, and methyl parathion in papaya and avocado is presented, along with other validation parameters. The analytical method was developed using Quick, Easy, Cheap, Effective, Rugged, and Safe extraction and ultrahigh performance liquid chromatography coupled to a triple quadrupole mass detector. The method validation showed that the linear correlation coefficients were higher than 0.99 for both fruits. The limits of detection for avocado and papaya were in the range of 0.022 to 0.46 and 0.003 to 0.109 μg/g, respectively. Intermediate precision varied from 5.3% to 13.0% in papaya, and from 4.8% to 20.2% in avocado. Recoveries obtained for each pesticide in both matrices ranged between 61.3% and 119.0%. Matrix effect was calculated for all compounds in both fruits. Finally, the overall uncertainty was lower than 36% for both fruits. The present analytical method could be used for pesticides determination in different kind of fruits as papaya and avocado and as a practical guide for uncertainty and matrix effect determination.

Background The dissipation behavior, pre-harvest interval and dietary risk of carbosulfan, dimethoate, and their relevant metabolites were investigated in greenhouse cucumber in Tianjin, northern China, to ensure raw consumption safety. Results Carbosulfan was metabolized to carbofuran, dibutylamine, 3-hydroxycarbofuran and 3-ketocarbofuran, and dimethoate was degraded to omethoate in cucumber fruits and leaves. The dissipation of carbosulfan, carbofuran, 3-hydroxycarbofuran and dimethoate fitted first-order kinetics well, with R2 ranging from 0.912 to 0.992, and their half-lives were 2.6, 2.7, 2.4 and 5.2 days in cucumber fruits and 2.8, 3.0, 4.6 and 2.5 days in leaves, respectively. The estimated daily intakes of the active ingredients and their relevant metabolites were 0.1-4% of the corresponding acceptable daily intakes. Acute oral exposure to carbofuran (a metabolite of carbosulfan) represented 367% of the acute reference dose (ARfD) for 1-6-year-old Chinese children and 227% for the general Chinese population. Conclusion A minimum pre-harvest interval of 12 days for carbosulfan is proposed to ensure safe consumption of cucumber. The slow dissipation rate of omethoate in cucumber reveals that a longer pre-harvest interval (≥ 27 days) is necessary to prevent dietary risk when dimethoate is applied to cucumber. © 2018 Society of Chemical Industry.

BACKGROUND Insecticides are extensively used in China and may leach to groundwater, which is used as a source of drinking water in Northern China. However, the risk of insecticide leaching to groundwater and the subsequent risk to human health caused by the consumption of insecticide-contaminated drinking water remain unclear. RESULTS A total of 336 predicted environmental concentrations (PECs) were simulated for 32 commonly used insecticides, and 171 PECs were calculated for 20 metabolites in six agricultural dry-land scenario locations of Northern China with eight target crops. In 264 of the 336 cases, the PEC in groundwater is ≤0.1 µg L−1. Carbofuran, imidacloprid, trichlorfon and oxidative metabolites of aldicarb are the most leached chemicals in groundwater. The most vulnerable crop is cotton, whereas soil treatment is the most vulnerable application type. Urumqi and Weifang are the most vulnerable among the six scenario locations. Less than 3% of 336 cases show unacceptable risk of insecticide-contaminated groundwater, thereby requiring higher risk assessment and risk mitigation. The unacceptable cases are the leaching of carbofuran for cotton growing in Urumqi and Weifang, and leaching of metabolites of aldicarb in cotton and tobacco scenarios. CONCLUSION Popular insecticides used in Northern China are generally safe to groundwater. © 2017 Society of Chemical Industry

We describe a new methodology for the simultaneous determination of the endocrine-disrupting herbicides (acetochlor, alachlor, amitrole and atrazine), fungicides (carbendazim, triadimefon, penconazole and propiconazole) and insecticides (carbaryl and carbofuran) in fish samples followed by high-performance liquid chromatography with tandem mass spectrometry. Samples were extracted and purified using the pass-through cleanup approach. The recoveries of the pesticides were in the range 71.8–116.5%, with relative standard deviations lower than 15.28%. Limits of quantitation were 0.03–2.50 μg/kg. Validation results on linearity, accuracy and precision, as well as on application to the analysis of the endocrine-disrupting pesticides in 20 fish samples demonstrated the applicability to screen the presence of pesticides in fish. This article is protected by copyright. All rights reserved

Summary Carbofuran-mineralizing strain Novosphingobium sp. KN65.2 produces the CfdJ enzyme that converts the N-methylcarbamate insecticide to carbofuran phenol. Purified CfdJ shows a remarkably low KM towards carbofuran. Together with the carbaryl hydrolase CehA of Rhizobium sp. strain AC100, CfdJ represents a new protein family with several uncharacterized bacterial members outside the proteobacteria. Although both enzymes differ by only four amino acids, CehA does not recognize carbofuran as a substrate whereas CfdJ also hydrolyzes carbaryl. None of the CfdJ amino acids that differ from CehA were shown to be silent regarding carbofuran hydrolytic activity but one particular amino acid substitution, i.e., L152 to F152, proved crucial. CfdJ is more efficient in degrading methylcarbamate pesticides with an aromatic side chain whereas CehA is more efficient in degrading the oxime carbamate nematicide oxamyl. The presence of common flanking sequences suggest that the cfdJ gene is located on a remnant of the mobile genetic element Tnceh carrying cehA. Our results suggest that these enzymes can be acquired through horizontal gene transfer and can evolve to degrade new carbamate substrates by limited amino acid substitutions. We demonstrate that a carbaryl hydrolase can gain the additional capacity to degrade carbofuran by a single nucleotide transversion.

The present article describes a miniaturized potentiometric carbofuran chemical sensor on graphene nanosheets with incorporated lipid films. The graphene electrode was used for the development of a very selective and sensitive chemical sensor for the detection of carbofuran by immobilizing an artificial selective receptor on stabilized lipid films. The artificial receptor was synthesized by transformation of the hydroxyl groups of resorcin[4]arene receptor into phosphoryl groups. This chemical sensor responded for the wide range of carbofuran concentrations with fast response time of ca. 20 s. The presented potentiometric carbofuran chemical sensor is easy to construct and exhibits good reproducibility, reusability, selectivity, rapid response times, long shelf life and high sensitivity of ca. 59 mV/decade over the carbofuran logarithmic concentration range from 10−6 to 10−3 M.

To improve the analysis of pesticides in complex food matrices with economic importance, alternative chromatographic techniques, such as supercritical fluid chromatography, can be used. Supercritical fluid chromatography has barely been applied for pesticide analysis in food matrices. In this paper, an analytical method using supercritical fluid chromatography coupled to a photodiode array detection has been established for the first time for the quantification of pesticides in papaya and avocado. The extraction of methyl parathion, atrazine, ametryn, carbofuran, and carbaryl was performed through the quick, easy, cheap, effective, rugged, and safe methodology. The method was validated using papaya and avocado samples. For papaya, the correlation coefficient values were higher than 0.99; limits of detection and quantification ranged from 130-380 and 220-640 μg/kg, respectively; recovery values ranged from 72.8-94.6%; precision was lower than 3%. For avocado, limit of detection values were ˂450 μg/kg; precision was lower than 11%; recoveries ranged from 50.0-94.2%. Method feasibility was tested for lime, banana, mango, and melon samples. Our results demonstrate that the proposed method is applicable to methyl parathion, atrazine, ametryn, and carbaryl, toxics pesticides used worldwide. The methodology presented in this work could be applicable to other fruits.

Lipids regulate a wide range of biological activities. Since their local concentrations are tightly controlled in a spatiotemporally specific manner, the simultaneous quantification of multiple lipids is essential for elucidation of the complex mechanisms of biological regulation. Here, we report a new method for the simultaneous in situ quantification of two lipid pools in mammalian cells using orthogonal fluorescent sensors. The sensors were prepared by incorporating two environmentally sensitive fluorophores with minimal spectral overlap separately into engineered lipid-binding proteins. Dual ratiometric analysis of imaging data allowed accurate, spatiotemporally resolved quantification of two different lipids on the same leaflet of the plasma membrane or a single lipid on two opposite leaflets of the plasma membrane of live mammalian cells. This new imaging technology should serve as a powerful tool for systems-level investigation of lipid-mediated cell signaling and regulation.

Pesticides cause oxidative stress and adversely influence Na(+)-K(+)-ATPase activity in animals. Since impact of carbofuran has not been properly studied in the mammalian brain, the ability of carbofuran to induce oxidative stress and modulation in Na(+)-K(+)-ATPase activity and its amelioration by vitamin E was performed. The rats divided into six groups received two different doses of carbofuran (15% and 30% LD50) for 15 days. The results suggested that the carbofuran treatment caused a significant elevation in levels of malonaldehyde and reduced glutathione and sharp inhibition in the activities of super oxide dismutase, catalase, and glutathione-S-transferase; the effect being dose dependent. Carbofuran at different doses also caused sharp reduction in the activity of Na(+)-K(+)-ATPase. The pretreatment of vitamin E, however, showed a significant recovery in these indices. The pretreatment of rats with vitamin E offered protection from carbofuran-induced oxidative stress.

Ten systemic pesticides, comprising methomyl, thiamethoxam, acetamiprid, carbofuran, fosthiazate, metalaxyl, azoxystrobin, diethofencarb, propiconazole, and difenoconazole, were detected in 13 baby foods (cereals, boiled potatoes, fruit and milk) using QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) for sample preparation and liquid chromatography tandem mass spectrometry for analysis. The matrix-matched calibration curves showed good linearity with determination coefficients (R 2 )>0.992. The limits of detection and quantitation were 0.0015-0.003 and 0.005-0.01 mg/kg, respectively. The mean recoveries of three different concentrations ranged from 69.2 to 127.1% with relative standard deviations

BACKGROUND Over 1000-fold carbofuran resistance has been observed in Chilo suppressalis (Walker) collected from the Changhua (CH) and Chiayi (CY) prefectures of Taiwan. An understanding of the pertinent mechanisms will benefit effective insecticide resistance management of C. suppressalis. RESULTS Among the five amino acid substitutions of acetylcholinesterase (AChE) identified in C. suppressalis, A314S and H668P had been reported and E101D, F402V and R667Q were novel. Substitution frequencies in AChE of CH and CY populations were much higher than in the susceptible Hsinchu (HC) population. Significantly negative correlations were observed between the frequencies of E101D, A314S and R667Q and the kinetic parameters of AChEs in these populations. AChE from the resistant CH population was less susceptible to the inhibition of carbofuran, with an I50 that was 3.6-fold higher than that of the susceptible HC population. Although Km and Vmax of AChE from the CH and CY populations were reduced to 72–87% of those from the HC population, the overall catalytic efficiency (Vmax/Km) remained constant for all three populations. CONCLUSION Amino acid substitutions identified in the AChE of C. suppressalis are associated with changes in AChE kinetics and its insensitivity to carbofuran. These observations are helpful for rapid monitoring, prediction and management of OP and CB resistance in the field. © 2014 Society of Chemical Industry

Organophosphates and carbamates are major agrochemicals that strongly affect different neuroenzymes and the growth of various fish species. Here, we study the effect of sublethal concentrations of profenofos and carbofuran on the activity of acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE) and the associated health risk in fish. Labeo rohita fingerlings were exposed to three sublethal concentrations of profenofos and carbofuran. The minimum cholinesterase activities in the brain, gills, muscle, kidney, liver, and blood were after exposure to profenofos (0.06 mg/L). The minimum AChE and BuChE activities in the brain, gills, muscle, kidney, liver, and blood were after exposure to carbofuran (0.28 and 0.198 mg/L). Exposure to both types of pesticides affected the functions of these organs, including metabolism and neurotransmission, to various extents at different exposure concentrations. These findings suggest that they are required to be properly monitored in the environment, to reduce their toxic effects on nontarget organisms.

RATIONALE Direct analysis in real time (DART) is a new ion source technique, which is conducted in the open air under ambient conditions, applied to the rapid and direct analysis of any material (gases, liquids, and solids) with minimal or no sample preparation. In order to take advantage of the capacity of DART mass spectrometry for the real-time analysis of hazardous ingredients in commercial agrochemicals, a pilot study of rapid qualitative determination of hazardous pesticides was performed. METHODS Highly hazardous pesticides were identified by DART ionization coupled to a single-quadrupole mass spectrometer (DART-MS). Acetonitrile was chosen for dissolving samples prior to the analysis. Samples were analyzed by this technique in as little as 5 s. RESULTS Phorate, carbofuran, ethoprophos and fipronil were be detected directly from commercial agrochemicals. The ionization-related parameters (DART temperature, grid voltage and MS fragment) of these compounds were optimized to obtain highly response. Isotope patterns were taken into consideration for qualitative identification. Relative standard deviations (RSDs, n = 5) of 2.3–15.0% were obtained by measuring the relative abundance of selected isotopes. CONCLUSIONS This study showed that DART-MS technology was able to qualitatively determine the existence of highly hazardous pesticides in commercial pesticide formulations. It is suggested that this technology should be applied for routine monitoring in the market. Copyright © 2012 John Wiley & Sons, Ltd.

We developed an analytical method for the detection and quantitation of five pesticides and some of their metabolites - 3-hydroxycarbofuran, 3-ketocarbofuran, carbofuran, carbosulfan, and isoprocarb - using micellar electrokinetic chromatography coupled with a UV-Vis detector. The optimum separation conditions were 20 mM phosphate buffer (pH 8.0) containing 15 mM sodium dodecyl sulfate. The detection wavelength was set at 200 nm and the applied voltage was 12.5 kV. Under these conditions, baseline separation of five pesticides was achieved in 15 min, and the detection limits (S/N = 3) of 3-hydroxycarbofuran, 3-ketocarbofuran, carbofuran, carbosulfan, and isoprocarb were 0.3, 0.3, 0.3, 4.0, and 0.3 μM, respectively. The linear ranges for 3-hydroxycarbofuran, 3-ketocarbofuran, carbofuran, and isoprocarb were between 1.0 and 50.0 μM and that for carbosulfan was between 10.0 and 100.0 μM, with R(2) larger than 0.995. When applied to the analysis of a carbofuran-spiked rice sample, this approach yielded results with excellent repeatability (3.3%, n = 5), reproducibility (4.5%, n = 5), separation efficiency (>2.1 × 10(4) theoretical plates), and recovery (95.5 ± 1.4%, n = 5).

Anticholinesterase pesticides are widely used, and as a result they are involved in numerous acute and even fatal poisonings. The aim of this study was the development, optimization, and validation of a simple, rapid, specific, and sensitive gas chromatography-mass spectrometry method for the determination of 11 anticholinesterase pesticides (aldicarb, azinphos methyl, carbofuran, chlorpyrifos, dialifos, diazinon, malathion, methamidophos, methidathion, methomyl, and terbufos) in blood. Only 500 μL of blood was used, and the recoveries after liquid-liquid extraction (toluene/chloroform, 4:1, v/v) were more than 65.6%. The calibration curves were linear (R(2) ≥ 0.996). Limit of detections and limit of quantifications were found to be between 1.00-10.0 and 3.00-30.0 μg/L, respectively. Accuracy expressed as the %E(r) was found to be between -11.0 and 7.8%. Precision expressed as the percent relative standard deviation was found to be

The aim of the present study is to contribute an ecologically relevant assessment of the ecotoxicological effects of pesticide applications in agricultural areas in the tropics, using an integrated approach with information gathered from soil and aquatic compartments. Carbofuran, an insecticide/nematicide used widely on sugarcane crops, was selected as a model substance. To evaluate the toxic effects of pesticide spraying for soil biota, as well as the potential indirect effects on aquatic biota resulting from surface runoff and/or leaching, field and laboratory (using a cost-effective simulator of pesticide applications) trials were performed. Standard ecotoxicological tests were performed with soil (Eisenia andrei, Folsomia candida, and Enchytraeus crypticus) and aquatic (Ceriodaphnia silvestrii) organisms, using serial dilutions of soil, eluate, leachate, and runoff samples. Among soil organisms, sensitivity was found to be E. crypticus < E. andrei < F. candida. Among the aqueous extracts, mortality of C. silvestrii was extreme in runoff samples, whereas eluates were by far the least toxic samples. A generally higher toxicity was found in the bioassays performed with samples from the field trial, indicating the need for improvements in the laboratory simulator. However, the tool developed proved to be valuable in evaluating the toxic effects of pesticide spraying in soils and the potential risks for aquatic compartments. published

An electrically heated microelectrode chip (HMEC) was designed and the Ru(bpy)32+/carbofuran electrochemiluminescence (ECL) systems were applied to characterize the performance of the HMEC. The ECL intensities increase at elevated electrode temperature, and the detection limit at 60°C (electrode surface temperature) was about 10 times lower than that at 30°C. The results indicate that new heated electrode can be handled easily and can be mass produced, the difference between the electrodes was little. The stability of the HMEC was good since the electrode surface can hardly be destroyed during detection and storage.

BACKGROUND: Carbofuran is a carbamate insecticide that inhibits AChE. Although toxic by ingestion in mammals, it has low dermal toxicity, with relatively few confirmed worker illnesses. This risk assessment describes its time of onset, time to peak effect and time to recovery in rats using brain AChE inhibition in acute and 21 day dermal studies; in vitro rat/human relative dermal absorption for granular (5G) and liquid (4F) formulations; occupational exposure estimates using the Pesticide Handlers' Exposure Database and Agricultural Handlers' Exposure Database (PHED/AHED). RESULTS: The point of departure for acute risk calculation (BMDL10) was 6.7 mg kg−1 day−1 for brain AChE inhibition after 6 h exposure. In a 21 day study, the BMDL10 was 6.8 mg kg−1 day−1, indicating reversibility. At 75 mg kg−1 day−1, time of onset was ⩽30 min and time to peak effect was 6–12 h. Rat skin had ca tenfold greater dermal absorption of carbofuran (Furadan® 5G or 4F) than human skin. Exposure estimates for 5G in rice and 4F in ten crops had adequate margins of exposure (>100). CONCLUSION: Rat dermal carbofuran toxicity was assessed in terms of dose and time-related inhibition of AChE. Comparative dermal absorption in rats was greater than in humans. Worker exposure estimates indicated acceptable risk for granular and liquid formulations of carbofuran. Copyright © 2011 Society of Chemical Industry

The effect of nonionic and anionic micelles upon the stability of 3-hydroxy-carbofuran in basic media has been studied. The presence of micelles in the reaction medium implies a large inhibition of the basic hydrolysis of 3-hydroxy-carbofuran, due to the association of 3-hydroxy-carbofuran with the micellar core. The kinetic constants for the basic hydrolysis in these microheterogeneous media have been obtained on the basis of a micellar pseudophase model. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 402–408, 2011

This paper described a simple, rapid and efficient method for the determination of N-methyl carbamate pesticides in tomato, cucumber, carrot and lettuce samples by dispersive liquid-liquid microextraction coupled with HPLC-diode array detection. Some experimental parameters that influenced the extraction efficiency, such as types and volumes of extraction and disperser solvents, extraction time and salt effect were examined and optimized. Under optimum conditions, the LOD of the method were 0.5-3.0 μg/kg depending on the compounds and the kind of vegetables. The linearities of the method were obtained in the range of 10.0-300 μg/kg for aldicarb, MTMC, carbofuran and carbaryl, and 20.0-600 μg/kg for isoprocarb, with the correlation coefficients ranging from 0.9921 to 0.9993. The RSD varied from 2.9 to 7.5% (n=5). The recoveries of the method for the five carbamates from vegetable samples at two different spiking levels were ranged from 77.8 to 98.2%. Results showed that the method we proposed can meet the requirements for the determination of N-methyl carbamate in vegetable samples and was finally applied to the analysis of target pesticides in vegetable samples taken from local markets.

In the present study, acetylcholinesterase (AChE) from the brain of the Amazonian fish tambaqui (Colossoma macropomum) was partially characterized and its activity was assayed in the presence of five organophosphates (dichlorvos, diazinon, chlorpyrifos, and tetraethyl pyrophosphate [TEPP]) and two carbamates (carbaryl and carbofuran) insecticides. Optimal pH and temperature were 7.0 to 8.0 and 45°C, respectively. The enzyme retained approximately 70% of activity after incubation at 50°C for 30 min. The insecticide concentration capable of inhibiting half of the enzyme activity (IC50) for dichlorvos, chlorpyrifos, and TEPP were calculated as 0.04 µmol/L, 7.6 µmol/L, and 3.7 µmol/L, respectively. Diazinon and temephos did not inhibit the enzyme. The IC50 values for carbaryl and carbofuran were estimated as 33.8 µmol/L and 0.92 µmol/L, respectively. These results suggest that AChE from the juvenile C. macropomum brain could be used as an alternative biocomponent of organophosphorus and carbamate biosensors in routine pesticide screening in the environment.

BACKGROUND:Informationontheinsecticidesusceptibilityofstripedstemborer,Chilosuppressalis(Walker),isessentialforan effective pest management programme. An early detection of resistance development can prompt the modification of current control methods and increase the lifespan of insecticides through the rotation of chemicals with different modes of action. In this study, the susceptibility of this pest in Taiwan to four classes of insecticides has been examined. RESULTS: Over 1000-fold resistance to carbofuran was detected in C. suppressalis collected from Chiayi and Changhua prefectures, with estimated LC50 values of > 3mgc m −2 . In addition, 61-fold resistance to cartap was found in the Chiayi population. On theother hand,alltested populations of rice stem borer were stillrelatively susceptible to chlorpyrifos,fipronil and permethrin, with LC50 values ranging from 30 to 553 ng cm −2 . Chilo suppressalis populations collected from the central parts of Taiwan have a higher degree of resistance to the tested insecticides than those from northernareas. CONCLUSION: The occurrence of high resistance to carbofuran in the Chiayi and Changhua areas suggests that this compound should be replaced with chemicals having a different mode of action, such as chlorpyrifos, fipronil and permethrin, to which low cross-resistance has been detected. c � 2010 Society of Chemical Industry

A 3-year study was conducted in ‘Washington’ navel orange orchards to investigate the utility and efficacy of applying insecticides under citrus tree canopies for control of the citrus thrips, Scirtothrips citri (Moulton). Both flowable and emulsifiable concentrates of O-P's and carbamates were significantly more effective than their granular formulation. Fonofos 4E, FMC 35001 4EC, carbofuran 4F, chlorpyrifos 4EC and 50 % weed oil were proven to be thripicidally active for > 4–5 wks when used as a canopy ground cover application. The use of visual sampling of pre-bloom terminal foliage or developing fruitlets and/or monitoring emergence traps for 1st and 2nd generation S. citri is central to the successful implementation of this IPM cultural tactic. Zusammenfassung Ausbringung von Insektiziden auf den Boden zur Bekampfung des Citrus-Blasenfuses, Scirtothrips citri (Moulton) (Thysanopt., Thripidae) In 3jahrigen Studien wurde in den “Washington Navelorangen-Plantagen” die Brauchbarkeit und Wirkung einer Ausbringung verschiedener Insektizide am Boden unter den Citrus-Baumen zu Ende der Blutezeit zwecks Bekampfung des sich zu dieser Zeit im Boden zu Adulten umwandelnden Blasenfuses, Scirtothrips citri, untersucht. Dabei ergab sich dieuberlegenheit von Suspensions- und Emulsions-Formulierungen von P-Estern und Carbamaten gegenuber den Granulaten. Fonofos 4 E, FMC 35001 4 EC, Carbofuran 4 F, Chlorpyrifos 4 EC sowie 50 %iges “weed oil” erwiesen sich 4 bis 5 Wochen lang wirksam gegen die Blasenfusschaden, wenn sie gegen Ende der Blutezeit auf den Boden ausgebracht wurden. Terminale Blattproben vor der Baumblute (zur Bestimmung der Blasenfusdichte), Proben sich entwickelnder Fruchte und Schlupffallen fur die 1. und 2. Generation bildeten die Voraussetzung fur eine Beurteilung der Wirkung dieser Art von Bekampfung.

Laboratory studies on the influence of soil treatments with Diazinon, Chlormephos, Terbuphos, Chlorfenvinphos, Lindane, Carbofuran, Aldicarb and Atrazine on egg and larval stages of Poecilus cupreus L. and P. sericeus Fischer d. W. (Col., Carabidae) Alle larval stages of P. cupreus were killed within a week by Diazinon, Chlormephos, Terbuphos and Lindane even if dosage was markedly reduced. These larvae showed no burrowing behaviour and built no cavities under the soil surface in contrast to untreated check and the other tested pesticides. Aldicarb and Carbofuran killed the 1st and 2nd larval instar completely and the 3rd instar to 80%. Chlorfenvinphos and the herbicid Atrazine caused no statistical significant increase of mortality in any larval instar. 2nd instar of P. sericeus reacted as sensible upon an aldicarb treatment as the same stage of P. cupreus but much more sensible upon an chlorfenvinphos treatment. All tested insecticides had an ovicidal effect on eggs of P. cupreus. This effect was most distinct after a soil treatment with Diazinon, Terbuphos, Chlormephos and Lindane and less distinct after Carbofuran and Aldicarb treatments. Ovicidal action decreased with increasing egg-age or decreasing dosage. Zusammenfassung In Laborversuchen wurde der Einflus einer Bodenbehandlung mit Diazon, Chlormephos, Lindan, Carbofuran, Chlorfenvinphos, Terbuphos, Aldicarb und Atrazin auf die Jugendstadien von Poecilus cupreus L. und P. sericeus Fischer d. W. untersucht. Alle 3 Larvenstadien von P. cupreus wurden durch Diazion, Chlormephos, Terbuphos und Lindan, selbst bei stark reduzierten Aufwandmengen, innerhalb einer Woche abgetotet. Der Bau eines unterirdischen Ganges durch die Larven unterblieb in den meisten Fallen, im Gegensatz zur unbehandelten Kontrolle und den ubrigen Varianten. Durch Aldicarb und Carbofuran wurden die L1 und L2 vollig, die L3 zu 80% abgetotet. Chlorfenvinphos und das Herbizid Atrazin bewirkten gegenuber der unbehandelten Kontrolle bei keinem Larvenstadium einen statistisch signifikanten Mortalitatsanstieg. In diesen 3 Versuchsvarianten verringerte sich auch die Mortalitatsrate von L1 zu L3. Das 2. Larvenstadium von P. sericeus reagierte gegenuber Aldicarb gleich, gegenuber Chlorfenvinphos empfindlicher als das entsprechende Stadium von P. cupreus. Alle getesteten Insektizide entwickelten eine ovizide Wirkung gegenuber Eiern von P. cupreus. Am starksten ausgepragt war diese Wirkung bei Diazinon, Terbuphos, Chlormephos und Lindan, etwas geringer bei Carbofuran und Aldicarb. Mit Zunahme des Ei-Alters bzw. bei Reduktion der Aufwandmenge nahm der ovizide Einflus ab.

In the present work we report a novel procedure for in-capillary microextraction using a monolithic polymeric sorbent. In the proposed methodology, sample treatment takes place in the CE instrument but in a different capillary from that used for the electrophoretic separation. Polymers based on butyl methacrylate and divinylbenzene formed in situ inside a capillary column were assayed. The best results were found with the divinylbenzene-based polymers. The usefulness of the proposed procedure was checked for the determination of carbamate pesticides (Methomyl, Asulam, Carbendazim, Aldicarb, Carbetamide, Propoxur, Pirimicarb, Carbaryl, Carbofuran and Methiocarb) and three of their degradation compounds (Aldicarb sulphoxide, 2-isopropoxyphenol and alpha-naphthol) using MEKC. The optimization of the MEKC is reported, a good separation of the 13 analytes being obtained in less than 6 min. The analytical method using in-capillary microextraction was validated in terms of linearity, repeatability, precision (RSD< or =18% for 50 microg/L), and LODs (1-16 microg/L), and it revealed the usefulness of this in-capillary preconcentration procedure for the determination of analytes of intermediate polarity.

A mouse hybrid hybridoma (tetradoma) was derived from fusing hybridomas producing monoclonal antibody to N-methylcarbamate pesticide carbofuran with hybridomas producing monoclonal antibody to organophosphorus pesticide Triazophos. The prepared tetradoma line (12C1 to 2H12) secreted hybrid immunoglobulin exhibiting parental and bispecific binding characteristics. The effect of relevant physicochemical factors on the immunoassay based on the 12C1 to 2H12 bispecific monoclonal antibody had been studied to optimize the ELISA performance. The developed immunoassay showed that the detection limit (I(20)) were 0.36 and 1.89 ng/mL for triazophos and carbofuran, respectively, without obvious cross-reactivity to other related compounds. Water samples spiked with triazophos at 0.5, 1, and 5 ng/mL or carbofuran at 5, 10, and 20 ng/mL were directly analyzed by the developed ELISA format. The mean recovery of triazophos and carbofuran were 108.1% and 107.5%, with variation coefficient of 15.9% and 17.7%, respectively.

Flowing afterglow atmospheric pressure glow discharge tandem mass spectrometry (APGD-MS/MS) is used for the analysis of trace amounts of pesticides in fruit juices and on fruit peel. The APGD source was rebuilt after Andradeet al. (Andradeetal.,Anal.Chem. 2008; 80: 2646–2653; 2654–2663) and mounted onto a hybrid quadrupole time-of-flight mass spectrometer. Apple, cranberry, grape and orange juices as well as fruit peel and salad leafs were spiked with aqueous solutions containing trace amounts of the pesticides alachlor, atrazine, carbendazim, carbofuran, dinoseb, isoproturon, metolachlor, metolcarb, propoxur and simazine. Best limits of determination (LODs) of pesticides in the fruit juices were achieved for metolcarb (1 mg/L in apple juice), carbofuran and dinoseb (2 mg/L in apple juice); for the analysis of apple skin best LODs were 10 pg/cm 2 of atrazine, metolcarb and propoxur which corresponds to an estimated concentration of 0.01 mg/kg apple, taking into account the surface area and the weight of the apple. The measured LODs were within or below the allowed maximum residue levels (MRLs) decreed by the European Union (1–500 mg/kg for pesticides in fruit juice and 0.01–5 mg/kg for apple skin). No sample pretreatment (extraction, pre-concentration, chromatographic separation) was necessary to analyze these pesticides by direct desorption/ionization using APGD-MS and to identify them using MS/MS. This makes APGD-MS a powerful highthroughput tool for the investigation of very low amounts of pesticides in fruit juices and on fruit peel/vegetable skin. Copyright # 2008 John Wiley & Sons, Ltd.