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1.
Chemosphere ; 359: 142343, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38754491

RESUMO

The current research highlights the fabrication of a novel SnS2/CO32-@Ni-Co LDH (SnS2/NCL) by precipitating Ni-Co LDH over hydrothermally synthesized SnS2 nanoparticles for the enhanced degradation of thiamethoxam (THM) insecticide through the advanced oxidation process. The effect of several reaction parameters was optimized, and a maximum degradation of 98.1 ± 1.2 % with a rate constant of 0.0541 min-1 of 10 ppm THM was reached at a catalyst loading of 0.16 gL-1 using 0.3 mM of H2O2 within 70 min of visible light irradiation. The effect of metal cations, inorganic anions, dissolved organic matter, organic compounds and water samples on the photodegradation performance of SnS2/NCL nanocomposite was also examined to evaluate the prepared photocatalyst's suitability for use in actual wastewater conditions. The metal cations blocked the active sites of the photocatalyst and reduced the degradation efficiency except for Fe2+ ions, since it is a Fenton reagent and increased the production of hydroxyl radicals. Inorganic anions are the scavengers of hydroxyl radicals and hinder photocatalytic activity. Meanwhile, lake water containing varying degrees of co-existing ions shows the lowest degradation efficiency among other water samples. The SnS2/NCL nanocomposite could be reused for five cycles while maintaining a photocatalytic efficiency of 83.6 ± 0.3 % in the fifth run. The prepared SnS2/NCL nanocomposite also showed excellent photodegradation of several other emerging organic pollutants with an efficiency of over 80 % under optimum conditions. Incorporating Ni-Co LDH with SnS2 helped to delocalize photoinduced charges, leading to increased photocatalytic activity and a slower electron-hole recombination rate. The present research highlights the photocatalytic activity of SnS2/NCL photocatalysts for the photocatalytic degradation of emerging contaminants from wastewater.


Assuntos
Inseticidas , Fotólise , Tiametoxam , Compostos de Estanho , Poluentes Químicos da Água , Catálise , Tiametoxam/química , Inseticidas/química , Poluentes Químicos da Água/química , Compostos de Estanho/química , Sulfetos/química , Oxirredução , Nanocompostos/química , Níquel/química , Cobalto/química , Águas Residuárias/química , Luz , Peróxido de Hidrogênio/química
2.
Environ Sci Pollut Res Int ; 31(19): 28578-28593, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38558333

RESUMO

The application of perovskite lanthanum ferrite (LaFeO3) as a photocatalyst has shown significant potential in the removal of persistent organic and inorganic contaminants. In the present research, LaFeO3 and various composites consisting of LaFeO3 and TiO2 were prepared. The photocatalytic efficiency of the produced catalysts was assessed by measuring their effectiveness in degrading thiamethoxam, a pesticide belonging to the second generation of neonicotinoids. Experimental investigations were carried out to examine the impact of various factors on the degradation process, including variables like concentration of thiamethoxam, catalyst amount, and pH level. The produced catalysts were characterized by various techniques, including field emission scanning electron microscopy (FESEM), Brunauer-Emmett-Teller (BET) analysis, X-ray diffraction (XRD), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), photoluminescence (PL), and X-ray photoelectron spectroscopy (XPS). The highest degradation rates were observed when using the synthesized catalyst, 1% LaFeO3/TiO2 (LFTO1), under both UV-C and direct sunlight conditions. This performance outperformed TiO2 and bare LaFeO3. When exposed to ultraviolet (UV-C) radiation at an intensity of 15 W m-2 and under neutral pH conditions, LFTO1 achieved approximately 97% degradation, while under direct sunlight, the LFTO1 photocatalyst exhibited a degradation rate of 79% within a 120-min reaction period. The enhanced activity of LFTO1 could be attributed to its increased surface area, reduced bandgap, and lower electron-hole recombination. The investigation of reaction kinetics showed that the degradation of thiamethoxam followed a pseudo-first-order rate law. Furthermore, LFTO1 can be employed up to 5 times without experiencing any loss in its catalytic activity, thus confirming its long-term utility.


Assuntos
Tiametoxam , Titânio , Titânio/química , Tiametoxam/química , Catálise , Compostos Férricos/química , Lantânio/química , Neonicotinoides/química , Compostos de Cálcio/química
3.
Pest Manag Sci ; 79(10): 3570-3580, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37160655

RESUMO

BACKGROUND: Thiamethoxam (TMX) is insecticidal, but also can trigger physiological and metabolic reactions of plant cycles. The objective of this work was to evaluate the physiological and metabolic effect of TMX on tea plants and its potential benefits. RESULTS: In this study, dose of TMX (0.09, 0.135 and 0.18 kg a.i./ha) were tested. Except for peroxidase (POD) and glutathione S-transferase (GST), chlorophyll, carotenoid, catalase (CAT) and malondialdehyde (MDA) were significantly affected compared with the controls. The CAT activity was increased by 3.38, 1.71, 2.91 times, respectively, under three doses of TMX treatment. The metabolic response between TMX treatment and control groups on the third day was compared using a widely targeted metabolomics. A total of 97 different metabolites were identified, including benzenoids, flavonoids, lipids and lipid-like molecules, organic acids and derivatives, organic nitrogen compounds, organic oxygen compounds, organoheterocyclic compounds, phenylpropanoids and polyketides, and others. Those metabolites were mapped on the perturbed metabolic pathways. The results demonstrated that the most perturbation occurred in flavone and flavonol biosynthesis. The beneficial secondary metabolites luteolin and kaempferol were upregulated 1.46 and 1.31 times respectively, which protect plants from biotic and abiotic stresses. Molecular docking models suggest interactions between TMX and flavonoid 3-O-glucosyltransferase. CONCLUSION: Thiamethoxam spray positively promoted the physiological and metabolic response of tea plants. And this work also provided the useful information of TMX metabolism in tea plants as well as rational application of insecticides. © 2023 Society of Chemical Industry.


Assuntos
Camellia sinensis , Inseticidas , Tiametoxam/química , Inseticidas/farmacologia , Simulação de Acoplamento Molecular , Chá/metabolismo
4.
J Sci Food Agric ; 102(1): 417-424, 2022 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-34143904

RESUMO

BACKGROUND: Thiamethoxam is widely used to control pests in Chinese kale, popularly consumed leafy vegetables. The potential risk to the environment and human health has aroused much public concern. Therefore, it is important to investigate the degradation behavior, residue distribution and dietary risk assessment of thiamethoxam in Chinese kale. RESULTS: A sensitive analytical method for determination of thiamethoxam and its metabolite clothianidin residue in Chinese kale was established and validated through a quick, easy, cheap, effective, rugged, and safe (QuEChERS) technique with ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS). The recoveries were 85.4-101.2% for thiamethoxam and 79.5-108.1% for clothianidin, with the relative standard deviations (RSDs) of 0.9-10.2% and 1.8-6.0%, respectively. For the dissipation kinetics, the data showed that thiamethoxam in Chinese kale was degraded with the half-lives of 4.1 to 4.5 days. In the terminal residue experiments, the residues of thiamethoxam were 0.017-0.357 mg kg-1 after application 2-3 times with a preharvest interval (PHI) of 7 days under the designed dosages. The chronic and acute dietary exposure assessment risk quotient (RQ) values of thiamethoxam in Chinese kale for different Chinese consumers were 0.08-0.19% and 0.05-0.12%, respectively, and those of clothianidin were 0.01-0.04% and 0.02-0.04%, respectively, all of the RQ values were lower than 100%. CONCLUSION: Thiamethoxam in Chinese kale was rapidly degraded following first-order kinetics models. The dietary risk of thiamethoxam and clothianidin through Chinese kale was negligible to consumers. The results from this study are important reference for Chinese governments to developing criteria for the safe and rational use of thiamethoxam, setting maximum residue levels (MRLs), monitoring the quality safety of agricultural products and protecting consumer health. © 2021 Society of Chemical Industry.


Assuntos
Brassica/química , Cromatografia Líquida/métodos , Guanidinas/metabolismo , Neonicotinoides/metabolismo , Resíduos de Praguicidas/química , Resíduos de Praguicidas/metabolismo , Espectrometria de Massas em Tandem/métodos , Tiametoxam/química , Tiametoxam/metabolismo , Tiazóis/metabolismo , Adolescente , Adulto , Idoso , Idoso de 80 Anos ou mais , Brassica/metabolismo , Criança , Pré-Escolar , China , Exposição Dietética/efeitos adversos , Exposição Dietética/análise , Feminino , Contaminação de Alimentos/análise , Humanos , Cinética , Masculino , Pessoa de Meia-Idade , Medição de Risco , Verduras/química , Verduras/metabolismo , Adulto Jovem
5.
Food Chem ; 354: 129360, 2021 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-33735697

RESUMO

In this study, effects of low-intensity electrical currents (200, 800 and 1400 mA), ultrasound frequencies (24 and 40 kHz) and their combinations were applied at the duration period of 2, 4, 6, 8, and 10 min for the degradation of captan, thiamethoxam and metalaxyl residues in lettuce samples. Residues of the pesticides were determined by gas chromatography with tandem mass spectrometry and electron capture detector. The results indicated that the combination of low-intensity electrical current and ultrasound was found to be effective for the reduction of the pesticides. The most effective combination was obtained to be current of 1400 mA and ultrasound frequency of 24 kHz at 10 min. Under this circumstance, 92.57, 81.99 and 93.09% of captan, thiamethoxam and metalaxyl residues were decreased, respectively. The findings suggest that the combination of low-intensity electrical current and ultrasound applications has an important potential for the degradation of pesticide residues.


Assuntos
Contaminação de Alimentos/análise , Lactuca/química , Resíduos de Praguicidas/análise , Alanina/análogos & derivados , Alanina/análise , Alanina/química , Captana/análise , Captana/química , Eletricidade , Cromatografia Gasosa-Espectrometria de Massas/métodos , Lactuca/metabolismo , Resíduos de Praguicidas/química , Sonicação , Tiametoxam/análise , Tiametoxam/química
6.
Ecotoxicol Environ Saf ; 207: 111280, 2021 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-32937227

RESUMO

As a top-selling neonicotinoid insecticide widely used in the field, thiamethoxam is an environmental pollutant because of the accumulation in ecosystem and has also been reported that it has potential risks to the health of mammals even humans. In order to understand the binding mechanism of thiamethoxam with biological receptors, spectroscopic techniques and theoretical simulations was used to explore the specific interactions between thiamethoxam and proteins. Interestingly, the results indicated that hydrophobic interaction as the main driving force, thiamethoxam formed a single binding site complex with proteins spontaneously, resulting in a decrease in the esterase-like activity of human serum albumin. The results of computer simulation showed that there were hydrophobic, electrostatic and hydrogen bonding interactions between thiamethoxam and receptors. The results of experiment and computer simulation were mutually confirmed, so a model was established for the interaction between the two which uncovered the structural characteristics of the binding site. This research provided new insights for the structure optimization of thiamethoxam, as well as gave an effective reference for evaluating the risk of thiamethoxam systemically in the future.


Assuntos
Inseticidas/química , Modelos Químicos , Soroalbumina Bovina/química , Albumina Sérica Humana/química , Tiametoxam/química , Animais , Sítios de Ligação , Ligação Competitiva , Simulação por Computador , Ecossistema , Esterases/química , Esterases/metabolismo , Humanos , Interações Hidrofóbicas e Hidrofílicas , Ligantes , Simulação de Acoplamento Molecular , Simulação de Dinâmica Molecular , Ligação Proteica , Soroalbumina Bovina/metabolismo , Albumina Sérica Humana/metabolismo , Espectrometria de Fluorescência , Varfarina/química
7.
Food Chem ; 344: 128650, 2021 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-33229159

RESUMO

Zirconium(Ⅳ)-based metal-organic framework (MOF)-UiO-66-NH2 was fabricated to adsorb the imidacloprid and thiamethoxam in fruit samples before analysis using UPLC-MS/MS. The UiO-66-NH2 was confirmed by SEM, FTIR, and XRD. Key experimental parameters were investigated by response surface methodology (RSM). The desirability recovery of imidacloprid was 94.52% under optimum conditions (mount of adsorbent = 52.48 mg, volume of eluent = 5.18 mL, pH = 9, extraction time = 15 min). The desirability recovery of thiamethoxam was 93.57% under optimum conditions (mount of adsorbent = 50.58 mg, volume of eluent = 2.6 mL, pH = 5.65, extraction time = 11.94 min). Under the optimal conditions, the actual recovery of imidacloprid and thiamethoxam was 92.39% and 94.37%, respectively. Besides, the method was applied successfully to detect imidacloprid and thiamethoxam in different fruit samples. The results demonstrated that the UiO-66-NH2 is an excellent adsorbent for the extraction imidacloprid and thiamethoxam from fruit samples.


Assuntos
Análise de Alimentos/métodos , Frutas/química , Estruturas Metalorgânicas/química , Neonicotinoides/análise , Nitrocompostos/análise , Resíduos de Praguicidas/análise , Tiametoxam/análise , Zircônio/química , Adsorção , Cromatografia Líquida de Alta Pressão , Contaminação de Alimentos/análise , Neonicotinoides/química , Nitrocompostos/química , Resíduos de Praguicidas/química , Espectrometria de Massas em Tandem , Tiametoxam/química
8.
J Agric Food Chem ; 68(8): 2329-2339, 2020 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-32011126

RESUMO

The heavy application of neonicotinoid insecticides in agricultural production has burdened the environment. In the present study, interactions of two neonicotinoid insecticides imidacloprid and thiamethoxam with dissolved organic matter (DOM) were investigated by spectroscopic techniques, molecular modeling, and density functional theory (DFT) calculations. The static mechanism of imidacloprid and thiamethoxam quenching the endogenous fluorescence of DOM was assessed through time-resolved analyses. During the binding process, a protein-like substance binds imidacloprid and thiamethoxam later than a humic-like substance, as analyzed by two-dimensional correlation spectroscopy, but more strongly than the humic-like substance, as suggested by molecular modeling and DFT calculations. The conformational changes of DOM are attributed to imidacloprid and thiamethoxam, as assessed with three-dimensional spectra. Fourier transform infrared spectroscopy indicated that DOM binds imidacloprid and thiamethoxam by hydroxyl, aliphatic C-H, amide I, and carboxyl to form stable DOM-imidacloprid and DOM-thiamethoxam complexes. Understanding the changes in the structural conformation of humic-like and protein-like substances with imidacloprid and thiamethoxam helps further understand the fate of the neonicotinoids in the environment.


Assuntos
Inseticidas/química , Neonicotinoides/química , Nitrocompostos/química , Compostos Orgânicos/química , Tiametoxam/química , Teoria da Densidade Funcional , Interações Medicamentosas , Modelos Moleculares , Espectroscopia de Infravermelho com Transformada de Fourier
9.
J Environ Sci Health B ; 55(4): 342-354, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-31790325

RESUMO

Using beeswax as wrapping matrix, two types of release-controlled TM (thiamethoxam)/BK(beeswax-kaolin) microcapsules were prepared by adsorbing TM on kaolin and then encapsulated with beeswax, or directly wrapping TM with beeswax. The structure and morphology of the TM/BK microcapsules were characterized. The effects of different preparation methods, the particle size, pH conditions and different additives on the release property of the TM/BK microcapsules were investigated in water and soil column to compare the advantages of the two approaches. Finally, the insecticidal effect of the TM/BK microcapsules against sugarcane borer and rice planthopper was tested. The results show that the TM/BK microcapsules have a better sustained-release in both water and soil, and the release rate is different under different pH conditions. In addition, the releasing time of the TM/BK microcapsules can be modified by different preparation methods and combination of different additives. In the field applications, the insecticidal activity of the TM/BK microcapsules was better than that of non-sustained control group. Especially in the rice field test, 45 days after the application, the control group lost the activity against rice planthopper because of drug loss, whereas the TM/BK microcapsule group still retained about 90% of the insecticidal activity. The results suggest that the microcapsules have better agricultural application for insect control.


Assuntos
Inseticidas/química , Inseticidas/farmacocinética , Tiametoxam/química , Tiametoxam/farmacocinética , Ceras/química , Cápsulas , Preparações de Ação Retardada/química , Concentração de Íons de Hidrogênio , Inseticidas/farmacologia , Caulim/química , Tamanho da Partícula , Saccharum , Solo , Tiametoxam/farmacologia , Água
10.
J Hazard Mater ; 390: 121749, 2020 05 15.
Artigo em Inglês | MEDLINE | ID: mdl-31818655

RESUMO

Information about the effect of biochar on the environmental fate of pesticide thiamethoxam (THI) in soil-vegetable ecosystems is limited. Therefore, the influence of a wood-derived biochar produced at 450 °C (BC450) on the uptake of THI by Chinese chive (Allium tuberosum) and its dissipation in soil was investigated using a 42-day pot experiment. BC450 addition decreased THI uptake and its metabolite clothianidin (CLO) by 22.8 % and 37.6 %, respectively. However, the half-life of THI in soil rose from 89.4-120 days, indicating that BC450 increased soil THI's persistence. The decreased bioavailability and increased persistence of THI resulted mainly from the higher sorption capacity of BC450 to THI and CLO, which, in turn, enhanced the soil sorption capacity. Consequently, the application of BC450 increased the soil microbial diversity and altered the structure of the microbial community. Although the abundance of Actinobacteria associated with the biodegradation of THI, increased the persistence of THI in the BC450-amended soil, mainly due to the decrease in bioavailable THI. Our findings provide valuable information about the effect of biochar on the fate of THI and its metabolites in agricultural soil and will help to guide the practical application of biochar to remediate soils contaminated with neonicotinoid pesticides.


Assuntos
Carvão Vegetal/administração & dosagem , Cebolinha-Francesa/metabolismo , Inseticidas/metabolismo , Poluentes do Solo/metabolismo , Tiametoxam/metabolismo , Adsorção , Agricultura , Guanidinas/química , Guanidinas/metabolismo , Inseticidas/química , Microbiota , Neonicotinoides/química , Neonicotinoides/metabolismo , Solo/química , Microbiologia do Solo , Poluentes do Solo/química , Tiametoxam/química , Tiazóis/química , Tiazóis/metabolismo
11.
J Agric Food Chem ; 67(43): 11848-11859, 2019 Oct 30.
Artigo em Inglês | MEDLINE | ID: mdl-31600442

RESUMO

To decrease the application dose of thiamethoxam (TMX) to control the pepper whitefly (Bemisia tabaci Q), the deposition, dissipation, metabolism, and field efficacy of TMX were investigated in a pepper (Capsicum annuum var. grossum)-planted ecosystem using eight types of nozzles at six concentrations (56.25, 41.25, 26.25, 21.0, 15.75, and 10.5 g a.i./hm2). The initial deposition amount of TMX in the pepper plant first increased and then decreased with increasing application dose. The optimum spray conditions of TMX were found to be a droplet size of 200 µm volume median diameter and a spray volume of 350 L/hm2. Moreover, three metabolites, TMX-dm, clothianidin (CLO), and C5H8O2N3SCl, were detected in the pepper-planted system. The dissipation rate of TMX in the pepper-field ecosystem was leaves > stems > fruits > roots > soils. The results revealed the deposition and fate of TMX in the pepper-field ecosystem, and the application dose could be reduced by 20% based on the minimum recommended dose for controlling pepper whitefly.


Assuntos
Capsicum/química , Inseticidas/química , Tiametoxam/química , Animais , Capsicum/metabolismo , Ecossistema , Frutas/química , Frutas/metabolismo , Inseticidas/metabolismo , Cinética , Folhas de Planta/química , Folhas de Planta/metabolismo , Raízes de Plantas/química , Raízes de Plantas/metabolismo , Caules de Planta/química , Caules de Planta/metabolismo , Solo/química , Tiametoxam/metabolismo
12.
J Environ Sci Health B ; 54(8): 665-675, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31343381

RESUMO

The insecticide thiamethoxam (TMX) is one of the most important neonicotinoid pesticides. The chromatographic methods currently employed to detect TMX require multiple operational steps. This study proposes a simple method that detects TMX via surface-enhanced Raman scattering (SERS) spectroscopy with Ag nanoparticles (NPs) as the SERS active substrate. Density functional theory (DFT) was used to calculate the structures and vibrational modes of the Ag- and Ag3-TMX complexes at the B3LYP/6-311++G(d,p)(C,H,N)/LanL2DZ(Ag) level of theory. The results reveal that the atoms in the thiazole ring all lie in the same plane, while the six-membered ring is perpendicular to the thiazole ring. Data from both Ultraviolet-visible and Raman spectroscopy indicated that TMX bonds to Ag through its nitro group, vertically. A weak intramolecular (N22-O23…H26) hydrogen bonding and Ag-O bands shift N-O symmetrical vibration to down to lower wavenumber. This was supported by the appearance of a strong 866 cm-1 band in the SERS spectrum assigned to the N-O symmetrical vibration coupled with the N-N stretching vibrational mode of different excitation wavelength. Notably, a good linear relationship was observed in the TMX concentration range 1.0 × 10-6-1.0 × 10-4 mol·L-1 (R2 = 0.9667). SERS is an extremely simple and rapid technique that requires little sample for analysis.


Assuntos
Prata/química , Análise Espectral Raman/métodos , Tiametoxam/química , Ligação de Hidrogênio , Inseticidas/química , Nanopartículas Metálicas , Modelos Químicos , Espectrofotometria Ultravioleta , Vibração
13.
Sci Rep ; 9(1): 9416, 2019 07 01.
Artigo em Inglês | MEDLINE | ID: mdl-31263121

RESUMO

The Thaumastocoris peregrinus spread to eucalyptus plantations in many countries. Chemical control is a questionable measure, mainly due to the environmental impact, high cost and moreover has the use restricted by the forest certifications. Bio-insecticides may have similar efficiency to chemical products to control T. peregrinus. The chemical thiamethoxam, thiamethoxam + lambda-cyhalothrin, acephate and the microbial Beauveria bassiana and Metarhizium anisopliae insecticides were tested at different doses to manage T. peregrinus. The products were sprayed on eucalyptus plants using aircraft and populations of this insect were counted before application and at 1, 14 and 21 days afterwards (DAA). Ten eucalyptus trees were evaluated per plot, with the collection of ten leaves from the middle third of the crown of each tree, and the number of T. peregrinus nymphs and adults obtained per leaf was determined. All the chemical insecticides had similar control at 1 DAA for T. peregrinus nymphs and adults. At 14 DAA, the number of T. peregrinus nymphs and adults on eucalyptus leaves was similar for the chemical and microbial insecticide treatments. At 21 DAA the control efficiency of T. peregrinus nymphs and adults was higher than 80% with all insecticides. The entomopathogenic insecticides have potential for aerial application to control T. peregrinus nymphs and adults and provide viable and environmentally-friendly alternative to manage this pest.


Assuntos
Eucalyptus/parasitologia , Hemípteros/crescimento & desenvolvimento , Inseticidas/química , Controle Biológico de Vetores/métodos , Animais , Beauveria/fisiologia , Hemípteros/efeitos dos fármacos , Hemípteros/microbiologia , Inseticidas/toxicidade , Metarhizium/fisiologia , Nitrilas/química , Ninfa/efeitos dos fármacos , Ninfa/microbiologia , Folhas de Planta/parasitologia , Piretrinas/química , Tiametoxam/química , Tiametoxam/toxicidade
14.
Environ Toxicol Chem ; 38(10): 2111-2120, 2019 10.
Artigo em Inglês | MEDLINE | ID: mdl-31211447

RESUMO

The use of neonicotinoids in agriculture is a critical environmental protection issue. Although there has been considerable research on pollinator exposure and aquatic toxicological effects, few studies have investigated the chronic impacts on soil-dwelling species. Given the application of neonicotinoids into soil systems, there is the potential for risk to soil invertebrates. The toxicity of 2 commercial formulations containing the active ingredients (a.i.) thiamethoxam (Actara® 240SC) or clothianidin (Titan™) was investigated using 3 soil invertebrate species: Oppia nitens, Eisenia andrei, and Folsomia candida. No adverse effects were observed for O. nitens at the highest tested concentrations (≥92 mg a.i./kg dry soil) after a 28-d exposure. Exposure to clothianidin resulted in a 28-d median inhibitory concentration (IC50) of 0.069 (95% confidence limits: 0.039-0.12) mg/kg dry soil for F. candida, and a 56-d IC50 of 0.26 (0.22-3.2) mg a.i./kg dry soil for E. andrei. Exposure to thiamethoxam was less toxic, with IC50s of 0.36 (0.19-0.66) and 3.0 (2.2-4.0) mg a.i./kg dry soil for F. candida and E. andrei reproduction, respectively. The observed toxicity for F. candida adult survival and reproduction and for E. andrei reproduction occurred at environmentally relevant concentrations. However, because clothianidin is a degradation product of thiamethoxam, and detection of clothianidin rose to levels of concern in the thiamethoxam-amended soils over time, the observed toxicity may be partly attributed to the presence of clothianidin. Environ Toxicol Chem 2019;38:2111-2120. © 2019 Crown in the right of Canada. Published by Wiley Periodicals Inc. on behalf of SETAC.


Assuntos
Guanidinas/toxicidade , Neonicotinoides/toxicidade , Poluentes do Solo/toxicidade , Tiametoxam/toxicidade , Tiazóis/toxicidade , Animais , Artrópodes/efeitos dos fármacos , Artrópodes/crescimento & desenvolvimento , Guanidinas/química , Inseticidas/química , Inseticidas/toxicidade , Neonicotinoides/química , Oligoquetos/efeitos dos fármacos , Oligoquetos/crescimento & desenvolvimento , Reprodução/efeitos dos fármacos , Poluentes do Solo/química , Tiametoxam/química , Tiazóis/química , Testes de Toxicidade
15.
J Agric Food Chem ; 67(26): 7538-7546, 2019 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-31180663

RESUMO

Thiamethoxam (TMX) has already been proven to have a physiological effect in plant tissue or cell expect for the insecticidal activity. In our previous study, TMX was verified to be metabolized by tea cells in either a suspension culture or tea plant into several metabolites. Here, tea cell suspension cultures were treated for 45 days to investigate the metabolite effects in both the tea cells and the culture supernatants by nontargeted metabolomics. Using multivariate analysis (PCA and OPLS-DA), all treatment and control groups could be clearly separated. Inside the cells, 113 metabolites were found to be up-regulated while 122 were down-regulated, when compared with untreated cells. In the culture supernatant, there were 128 up-regulated and 35 down-regulated metabolites, compared to untreated cultures. KEGG searches revealed that the alanine, aspartate, and glutamate metabolic pathways were strongly affected by TMX metabolism within the tea cell. Molecular docking models showed that (i) 4-aminobutyrate aminotransferase may be related to the formation of 2-chloro-thiazole-5-carboxylic acid and (ii) 3'(2'),5'-bisphosphate nucleotidase may be able to interact with TMX. This study can help us to understand the interaction mechanism of pesticides with plant cells.


Assuntos
Camellia sinensis/química , Camellia sinensis/metabolismo , Inseticidas/metabolismo , Tiametoxam/metabolismo , Células Cultivadas , Inseticidas/química , Redes e Vias Metabólicas , Metabolômica , Simulação de Acoplamento Molecular , Tiametoxam/química
16.
Environ Sci Pollut Res Int ; 26(15): 15458-15466, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-30941712

RESUMO

External feather rinses and homogenized whole-carcass tissue matrix from two hummingbird species found in California (Calypte anna and Archilochus alexandri) were analyzed for the presence of nine insecticides commonly used in urban settings. Using a liquid chromatography-high-resolution mass spectrometry (LC-HRMS) analytical method, samples were quantitatively tested for the following neonicotinoids: dinotefuran, nitenpyram, thiamethoxam, acetamiprid, thiacloprid, clothianidin, imidacloprid, and sulfoxaflor. This analytical method was also used to qualitatively screen for the presence of approximately 150 other pesticides, drugs, and natural products. Feather rinsates from both hummingbird species had detectable concentrations of carbamate and neonicotinoid classes of insecticides. Combined results of the rinsate and homogenized samples (n = 64 individual hummingbirds) showed that 44 individuals (68.75%) were positive for one to four target compounds. This study documented that hummingbirds found in California are exposed to insecticides. Furthermore, feather rinsates and carcass homogenates are matrices that can be used for assessing pesticide exposure in small bird species. The small body size of hummingbirds limits traditional sampling methods for tissues and whole blood to evaluate for pesticide exposure. Thus, utilization of this analytical method may facilitate future research on small-sized avian species, provide insight into pesticide exposure, and ultimately lead to improved conservation of hummingbirds.


Assuntos
Cromatografia Líquida/métodos , Inseticidas/análise , Espectrometria de Massas em Tandem/métodos , Animais , Aves , California , Plumas/química , Guanidinas/química , Neonicotinoides/química , Nitrocompostos/química , Piridinas/química , Compostos de Enxofre/química , Tiametoxam/química , Tiazinas/química , Tiazóis
17.
J Sci Food Agric ; 99(9): 4407-4413, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-30860596

RESUMO

BACKGROUND: Thiamethoxam (3-[(2-chloro-5-thiazolyl)methyl]tetrahydro-5-methyl-N-nitro-4H-1,3,5-oxadiazin-4-imine) belongs to a relatively new class of insecticides known as neonicotinoids, which can block irreversibly nicotinic acetylcholine receptors of the nervous system of insects. Its determination at trace levels is an acute analytical problem. Therefore, chromatography, spectroscopy, and electrochemical technics were reported. These last have several advantages (simple sensitive and less expensive). This work investigated the electro-reduction of Thiamethoxam using simple and rapid method in real samples using metallic silver electrode. RESULTS: Silver particles, known as effective catalysts in the reduction of nitro groups, were studied to explore their roles in the shift of thiamethoxam peak potential. Cyclic voltammetry, Tafel plot and electrochemical impedance spectroscopy analysis suggest that metallic silver electrodes have a significantly greater electrocatalytic activity in thiamethoxam electroreduction than glassy carbon electrodes and carbon paste electrodes. The electrocatalytic activity of metallic silver electrodes in thiamethoxam reduction was investigated by cyclic voltammetry and chronoamperometry. A linear variation in cathodic current with the square root of the scan rate was observed, suggesting that the process is diffusion controlled. Several supporting electrolytes were tested, and the best results were obtained with Britton-Robinson (BR) buffer, pH 10.4. A linear relationship between peak current and concentration was found in the range from 1.0 × 10-5 to 1.0 × 10-4  mol L-1 using square wave voltammetry (SWV) with a correlation coefficient of 0.994. The detection limit and quantification limit were 5.49 × 10-6 and 1.83 × 10-5  mol L-1 , respectively. CONCLUSION: Silve metallic electrode exhibits efficient catalytic activity towards the Thiamethoxam reduction. The proposed electrode was then used for the determination of thiamethoxam in tomato anad orage juice samples. © 2019 Society of Chemical Industry.


Assuntos
Citrus sinensis/química , Técnicas Eletroquímicas/métodos , Inseticidas/química , Solanum lycopersicum/química , Tiametoxam/química , Catálise , Técnicas Eletroquímicas/instrumentação , Eletrodos , Eletrólitos/química , Contaminação de Alimentos/análise , Sucos de Frutas e Vegetais/análise , Limite de Detecção , Neonicotinoides/química , Prata/química
18.
Bull Environ Contam Toxicol ; 102(4): 550-554, 2019 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-30778615

RESUMO

The adsorption and desorption behaviors of carbendazim (CBD) and thiamethoxam (TMX) were systematically studied in five different agricultural soils. The adsorption and desorption isotherms of CBD and TMX in the five different soils were fitted well by the Freundlich model. The Freundlich adsorption coefficient (Kfads) and Freundlich desorption coefficient (Kfdes) of CBD in the five different soils were 1.46-19.53 and 1.81-3.33, respectively. The corresponding values of TMX were 1.19-4.03 and 2.07-6.45, respectively. The adsorption affinity and desorption ability of the five different soils for CBD and TMX depended mainly on soil organic matter content (OMC) and cation exchange capacity (CEC). Desorption hysteresis occurred in the desorption process of CBD and TMX in the five different agricultural soils, especially for TMX. It is concluded that the adsorption-desorption ability of CBD was much higher than that of TMX in the five different agricultural soils, which was attributed to soil OMC and CEC.


Assuntos
Agricultura , Benzimidazóis/química , Carbamatos/química , Fungicidas Industriais/química , Inseticidas/química , Solo/química , Tiametoxam/química , Adsorção , Poluentes do Solo/análise
19.
Pest Manag Sci ; 75(1): 63-78, 2019 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-30094905

RESUMO

BACKGROUND: The route and rate of degradation of thiamethoxam in the laboratory and field was investigated. The effect of dark incubation versus light/dark cycles, seed treatment versus spray, and watering-in for spray application was explored in side-by-side trials. RESULTS: Geometric mean DT50 values were 75.4 days in OECD307 studies, and 18.3 (spray) and 16.5 (seed treatment) days in the field. In laboratory soil core studies DT50 values were 24.9 to 43.5 days, with the lowest value from the light/dark incubated soil core. Mean clothianidin formation was 19.7% applied thiamethoxam [mol/mol] in OECD307 studies and 17.5 (spray) and 3.4% (seed) in field trials. CONCLUSION: Soil DT50 values decreased with increasingly realistic tests (laboratory OECD307 to soil cores to soil cores with a light/dark cycle to field trials). The majority of the differences were associated with the soil treatment in OECD307 studies which destroys soil structure and retards the degradation rate; and from the impact on soil pore water movement in light/dark conditions. Degradation rates in the field were comparable between spray application and seed treatments. Maximum clothianidin concentrations were four-fold lower for seed treatments than for spray application in field studies. © 2018 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.


Assuntos
Inseticidas/química , Poluentes do Solo/química , Solo/química , Tiametoxam/química
20.
Appl Spectrosc ; 73(3): 313-319, 2019 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-30421982

RESUMO

Advanced gold (Au) and silver (Ag) nanostructures were produced by laser techniques on printer paper substrate. Surface-enhanced Raman spectroscopy (SERS) analyses of the fungicide mancozeb (Dithane DG) and insecticide thiamethoxam (Aktara 25 BG) in quantities smaller than usually applied in agricultural medicine were performed for the first time assisted by the structures fabricated. The investigations and results show an easy alternative and cheap way to detect small amounts or residue of harmful environmental pollutants, which has a direct bearing on food quality and thus on human health.


Assuntos
Poluentes Ambientais/análise , Fungicidas Industriais/análise , Inseticidas/análise , Maneb/análise , Análise Espectral Raman/métodos , Tiametoxam/análise , Zineb/análise , Poluentes Ambientais/química , Análise de Alimentos , Fungicidas Industriais/química , Ouro/química , Inseticidas/química , Maneb/química , Nanopartículas Metálicas/química , Prata/química , Tiametoxam/química , Zineb/química
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