The SPEC model (Predicted Environmental Concentrations in agricultural Soils) was developed and improved for the simulation of pesticide runoff. The model was applied to the Sakaecho upland bare soil field (Tokyo, Japan) to predict runoff water, sediment concentration in runoff water, pesticide concentrations in runoff water, and runoff sediment (clothianidin and imidacloprid) under artificial rainfall conditions. The results showed that the simulated time to first runoff agreed very well with the observed data. The simulated cumulative runoff, sediment yield, and imidacloprid concentration in sediment agreed well with the observed data (Nash–Sutcliffe Efficiency (NSE)>0.75). The simulated runoff rate agreed reasonably well with the observed data (NSE >0.5). The predicted clothianidin concentrations in sediment and in runoff water had acceptable agreement with the observed data (NSE >0). The results implied the model’s potential to predict runoff water, sediment yield, and pesticide runoff.
A direct competitive enzyme-linked immunosorbent assay (dc-ELISA) was developed for determination of anilinopyrimidine fungicide mepanipyrim in vegetables. Two derivatives of mepanipyrim and mepanipyrim propanol type metabolite which carried carboxy acid were synthesized and conjugated with keyhole limpet hemocyanin. BALB/c mice were immunized to prepare anti-mepanipyrim monoclonal antibodies (MoAbs) by obtained conjugates. The dc-ELISAs based on the prepared MoAbs, MPP107 and MPP204, showed working ranges between 0.12 and 1.8 ng/mL with mepanipyrim for MPP107, 0.12 and 2.4 ng/mL with mepanipyrim for MPP204, and 0.2 ng/mL and 5.7 ng/mL with the mepanipyrim propanol type for MPP204. The dc-ELISAs showed the sufficient sensitivity to determine the mepanipyrim residues for the MRLs of 1–15 mg/kg among the majority of vegetables and fruits in Japan. Recovery and/or correlation results from HPLC suggested that the dc-ELISAs would be applicable to the residue analysis of mepanipyrim and its propanol type in vegetables.
To estimate the influence of sample processing with a blender, we conducted a homogeneity test using a bulk sample of pre-harvest grapes. Relative standard deviations (RSDs) were calculated from the concentrations of pesticides in the portions from the top, middle, and bottom of the homogenate with fine and rough particles. The results from adequate sample processing showed that the RSDs of the residue levels of all five pesticides in the fine-particle homogenate were lower than 10%. In contrast, the results under problematic conditions such as short blending times and long standing times after blending showed higher RSDs (>15%). The RSDs of nonpolar pesticides showed greater variabilities under the problematic conditions than those of polar pesticides. Separate analyses of the precipitate and supernatant phases suggested that the distribution bias of skin particles in the homogenate has a major effect on the concentration of nonpolar pesticides because of weighing errors in the extracted portions.
The substrate range of Nocardioides sp. strain PD653, capable of mineralizing hexachlorobenzene, was investigated based on the dissipation of substrates and the liberation of halogen ions. Strain PD653 dehalogenated 10 out of 18 halophenol congeners; however, it could dehalogenate only hexachlorobenzene out of seven halobenzene congeners tested. Moreover, dehalogenation activities were shown for chloronitrobenzenes, along with an increase in the number of substituted chlorine atoms except for 2,3,4,5-tetrachloro-1-nitrobenzene. These results suggested that this strain might be applicable to remediate soil contaminated with these persistent chloroaromatic compounds.
The peach-potato aphid, Myzus persicae, is a serious crop pest that has developed imidacloprid resistance, mainly through overexpression of CYP6CY3. Here, we established a metabolic assay using Drosophila S2 cells that stably expressed CYP6CY3. We found that CYP6CY3 showed metabolic activity against imidacloprid, as well as acetamiprid, clothianidin, and thiacloprid, but had no activity against dinotefuran. Our study suggested that stable gene expression in Drosophila S2 cells is useful for examining which insecticide is metabolized by P450 monooxygenases.
Two series of novel cuminaldehyde derivatives containing pyrazoline and isoxazoline moieties have been designed and synthesized. All of the compounds were characterized via1H-NMR,13C-NMR, and HRMS. The antifungal activities were evaluated against six plant-pathogenic fungi. 3-(2-Fluorophenyl)-5-(4-isopropylphenyl) isoxazoline (2d) and 1-acetyl-3-(2-fluorophenyl)-5-(4-isopropylphenyl)-2-pyrazoline (3d) displayed higher antifungal activities than commercial fungicides against Sclerotinia sclerotiorum, Physalospora piricola and Pyricularia oryzae. The title compounds (2d and 3d) with strong antifungal activities are worth being further evaluated in vivo and in the field.
A micro liquid–liquid extraction has been applied to sample preparation in the current authorized method for clopyralid in compost. The method rendered matrix effects practically negligible during determination with ultraperformance liquid chromatography-electrospray ionization tandem mass spectrometry with an improved limit of quantification of 0.7 µg/kg dry weight. Moreover, it had good accuracy and reproducibility. Therefore, the method is proposed as a highly effective routine analytical technique for investigating the actual status of clopyralid residue in compost.
From 2012 to 2018, proficiency testings (PTs) were carried out to support the analytical skill development of participants. Grains were sprayed with various target pesticides and used as material samples for PTs. It was found that 27–56% and 10–43% of participants used the Japanese official multiresidue method and a solid-phase extraction technique with the Quick, Easy, Cheap, Effective, Rugged, and Safe (modified QuEChERS, known as “STQ” in Japan) method, respectively. Reported results were evaluated using two types of z-scores: one was based on consensus values calculated from the analytical results reported by the participants, and the other was based on values obtained by the National Metrology Institute of Japan (NMIJ). Acceptable z-scores based on the consensus values and NMIJ reference values were achieved by 78–95% and 67–94% of the participants, respectively. Many laboratories improved their z-scores by continuing participation in our PT.
Microorganisms produce and secrete a variety of secondary metabolites including fatty acids, polyketides, terpenoids, alkaloids, and peptides. Among them, many molecules act as chemical signals that play important roles in inter-/intra-species microbial communication or the interaction with host organisms. In this review, I focus on our recent reports of the microbial signaling molecules involved in bacterium–fungus, bacterium–plant, and fungus–plant interactions. Their potential contribution to pest management is also discussed.
Tolprocarb developed by Mitsui Chemicals Agro, Inc. (Tokyo, Japan) was discovered as a new oomycete fungicide. However, its antifungal spectrum and action mechanisms against fungi are completely different from those of the original compound, iprovalicarb. Tolprocarb has a potent and highly controlled effect on a rice blast fungus Magnaporthe grisea, and its mode of action was revealed to be the inhibition of polyketide synthase in the melanin biosynthesis pathway. In addition, tolprocarb induced systemic acquired resistance in Arabidopsis thaliana and rice (Oryza sativa L.). Owing to these double modes of action, tolprocarb can effectively control not only rice blast but also bacterial diseases, and has a low risk of developing fungicide-resistant isolates. Tolprocarb also provides long-term residual activity. A meta-analysis was performed in order to demonstrate tolprocarb’s superior control against panicle blast in paddy fields. In addition, tolprocarb did not show cross-resistance against the fungi that are resistant to dehydratase inhibitor in melanin biosynthesis (Melanin Biosynthesis Inhibitor-Dehydratase; MBI-D) or respiratory complex III: cytochrome bc1 at Quinone outside site inhibitor (Quinone outside Inhibitor; QoI). Owing to its stable effects, tolprocarb appears to be a suitable choice for practical use against fungi in the rice production field.