Enhancing soil health, microbial count, and hydrophilic methomyl and hydrophobic lambda-cyhalothrin remediation with biochar and nano-biochar.

Pesticide contamination and soil degradation present significant challenges in agricultural ecosystems, driving extensive exploration of biochar (BC) and nano-biochar (NBC) as potential solutions. This study examines their effects on soil properties, microbial communities, and the fate of two key pesticides: the hydrophilic methomyl (MET) and the hydrophobic lambda-cyhalothrin (LCT), at different concentrations (1%, 3%, and 5% w w-1) in agricultural soil. Through a carefully designed seven-week black bean pot experiment, the results indicated that the addition of BC/NBC significantly influenced soil dynamics. Soil pH and moisture content (MC) notably increased, accompanied by a general rise in soil organic carbon (SOC) content. However, in BC5/NBC5 treatments, SOC declined after the 2nd or 3rd week. Microbial populations, including total plate count (TPC), phosphate-solubilizing bacteria (PSB), and nitrogen-fixing bacteria (NFB), showed dynamic responses to BC/NBC applications. BC1/NBC1 and BC3/NBC3 applications led to a significant increase in microbial populations, whereas BC5/NBC5 treatments experienced a decline after the initial surge. Furthermore, the removal efficiency of both MET and LCT increased with higher BC/NBC concentrations, with NBC demonstrating greater efficacy than BC. Degradation kinetics, modeled by a first-order equation, revealed that MET degraded faster than LCT. These findings underscore the profound impact of BC/NBC on pesticide dynamics and microbial communities, highlighting their potential to transform sustainable agricultural practices.

Rhamnolipids-based bio-supramolecular solvents as green and sustainable media for extraction of pyrethroid insecticides in water and food matrices.

A novel bio-supramolecular solvent (bio-SUPRAS) based on rhamnolipids (RLs) was designed for efficient extraction of pyrethroid insecticides in water and food matrices. Benefiting from RLs as amphiphiles equipped with the attractive properties of bio-degradable, low toxicity and high stability, bio-SUPRAS was spontaneously generated through salt induced coagulation. The bio-SUPRAS was characterized by cryo-scanning electron microscope and main factors influencing the extraction performance were investigated in detail. Under the optimized conditions, the method was found to have desirable limits of detection (5∼10 µg l-1), good precision (RSDs<16.9 %) and satisfactory recovery (75.2 %∼94.3 %). More importantly, the extraction mechanism was studied by density functional theory systematically. Following greenness assessment, the technique was successfully used for enrichment of pyrethroid pesticides in real samples before HPLC-UV analysis. Thus, the method showed the outstanding merits of eco-efficient, green, time-saving, and had favorable application prospect to remove trace analytes from intricate sample matrices.

Causal inference and mechanism for unraveling the removal of four pesticides from lettuce (Lactuca sativa L.) via ultrasonic processing and various immersion solutions.

This study explores the reduction of carbamates (CAs) and pyrethroids (PYs) - commonly used pesticides - in lettuce using various immersion solutions and ultrasonic processing. It also examines the role of machine learning and molecular docking in understanding the mechanisms of pesticide reduction. The results revealed that the highest reduction of both CAs and PYs exceeded 80 % on lettuce leaves. In most samples, the reduction increased with the power of ultrasonic processing and processing time. The results of machine learning models (XGBoost and SHAP) showed that during the immersion cleaning of CAs and PYs, as well as during both immersion cleaning and ultrasonic processing of CAs + PYs, the reduction was most influenced by the initial pesticide levels and immersion time. Gas Chromatography-Mass Spectrometry (GC-MS) analysis of lettuce's wax layer identified 24 compounds, including fatty alcohols, fatty acids, fatty acid esters, and triterpenoids. Despite the absence of active sites, the lipophilic nature of long-chain aliphatic compounds aids in pesticide binding, while triterpenoids form strong hydrogen bonds with pesticides, indicating a robust adsorption on the lettuce surface. This study aims to offer insights into the efficient removal of chemical pesticide residues from fruits and vegetables, addressing critical concerns for food safety and human health.

COF-SiO2@Fe3O4 Composite for Magnetic Solid-Phase Extraction of Pyrethroid Pesticides in Vegetables.

Pyrethroid pesticides (PYRs) have found widespread application in agriculture for the protection of fruit and vegetable crops. Nonetheless, excessive usage or improper application may allow the residues to exceed the safe limits and pose a threat to consumer safety. Thus, there is an urgent need to develop efficient technologies for the elimination or trace detection of PYRs from vegetables. Here, a simple and efficient magnetic solid-phase extraction (MSPE) strategy was developed for the simultaneous purification and enrichment of five PYRs in vegetables, employing the magnetic covalent organic framework nanomaterial COF-SiO2@Fe3O4 as an adsorbent. COF-SiO2@Fe3O4 was prepared by a straightforward solvothermal method, using Fe3O4 as a magnetic core and benzidine and 3,3,5,5-tetraaldehyde biphenyl as the two building units. COF-SiO2@Fe3O4 could effectively capture the targeted PYRs by virtue of its abundant π-electron system and hydroxyl groups. The impact of various experimental parameters on the extraction efficiency was investigated to optimize the MSPE conditions, including the adsorbent amount, extraction time, elution solvent type and elution time. Subsequently, method validation was conducted under the optimal conditions in conjunction with gas chromatography-mass spectrometry (GC-MS). Within the range of 5.00-100 µg·kg-1 (1.00-100 µg·kg-1 for bifenthrin and 2.5-100 µg·kg-1 for fenpropathrin), the five PYRs exhibited a strong linear relationship, with determination coefficients ranging from 0.9990 to 0.9997. The limits of detection (LODs) were 0.3-1.5 µg·kg-1, and the limits of quantification (LOQs) were 0.9-4.5 µg·kg-1. The recoveries were 80.2-116.7% with relative standard deviations (RSDs) below 7.0%. Finally, COF-SiO2@Fe3O4, NH2-SiO2@Fe3O4 and Fe3O4 were compared as MSPE adsorbents for PYRs. The results indicated that COF-SiO2@Fe3O4 was an efficient and rapid selective adsorbent for PYRs. This method holds promise for the determination of PYRs in real samples.

High selectivity molecularly imprinted polymer based on short amylose as bio-based functional monomers for selective extraction of λ-cyhalothrin.

Nowadays, the development of sustainable molecularly imprinted polymers (MIPs) with high selectivity is still challenging due to the limitations of bio-based functional monomers. In this study, the highly selective and porous MIPs (LC-TMIPs) were designed and prepared on short amylose (SAM) as bio-based functional monomers, λ-cyhalothrin (LC) as a template molecule, and tetrafluoroterephthalonitrile as a rigid crosslinking agent. Static, dynamic, and selective adsorption experiments were conducted to investigate the adsorption performance. The results indicated that, compared to MIPs prepared using epichlorohydrin as flexible crosslinking agents, LC-TMIPs exhibited higher imprinting factor (3.93), selectivity (5.78), and adsorption capacity (35.79 mg g-1), as well as faster adsorption/desorption kinetics. The LC-TMIPs were used as sorbents for the selective determination of LC in both apple and cucumber samples by high-performance liquid chromatography. Under the optimal extraction conditions, the recoveries of the method reached 92.1-106.1 %, with a linear range of 1.5-30 ng g-1 and a detection limit of 0.5 ng g-1. The proposed preparation method of LC-TMIPs is expected to open a new way to prepare highly selective and sustainable MIPs for hydrophobic compounds.

Consecutive high-performance removal of Cu2+ metal ions and Deltamethrin using multifunctional pyrolysis cuttlebone/cotton fabric nanocomposite.

A simple technique was developed for the modification of cotton materials that is inexpensive, environmentally friendly, and very effective. Waste Cotton fabrics (WCFs) are loaded with propolis extract (PE) for Cu2+ removal. Then, Cu2+ underwent a pyrolysis process with modified cuttlebone (CB) at 900 °C for 5 h. The surface of the prepared materials was characterized using X-ray diffraction (XRD), scanning electron microscopy with energy-dispersive X-ray (SEM-EDX), Fourier transform infrared (FTIR), BET, particle sizes, thermogravimetric analysis (TGA) and zeta potential analysis. The Cu2+ metal ions from an aqueous solution were removed using WCFs/PE, and DLM was subsequently removed using pyro WCFs/PE/Cu/CB. The as-prepared NPs exhibited the face-centered cubic structure of WCFs/PE/Cu/CB with crystallite sizes ranging from 386.70 to 653.10 nm. FTIR spectra revealed that CB was present on the surface of the resulting WCFs/PE/Cu. SEM revealed the dispersion of a uniformly flower-like morphology over a large area. Sorption studies were performed based on parameters that included pH, dose, contact time, and initial concentration. The adsorption isotherm and the kinetic studies of the DLM adsorption process were applied at a pH of 5.0 and a temperature of 25 °C using several isotherms and kinetic models. The results revealed qmax (20.51 mg/g) with R2 = 0.97, the Langmuir isotherm that best matches the experimental data. Hence, the Langmuir isotherm suggests that it is the model that best describes sorption on homogenous surfaces or surface-supporting sites with various affinities. The correlation coefficient R2, χ2, adjusted correlation coefficient, and error functions like root mean square (RMSE), normalized root mean square error (NRMES), and mean absolute error (MAE) were used to evaluate the best-fit models to the experimental adsorption data. Moreover, cost estimation for the prepared adsorbent WCFs/PE/Cu showed that it costs approximately 3 USD/g, which is a cheap adsorbent compared to other similar adsorbents reported in the literature. The examined WCFs/PE have significant applicability potential for Cu2+-laden wastewater treatment due to their superior Cu2+ metal ions adsorption capability and reusability. The cytotoxicity and safety study showed that at higher concentrations, it resulted in much less cell viability. Additionally, the removal efficiency of Cu2+ metal ions from synthetic, realistic industrial wastewater using WCFs/PE reached up to 96.29 %, demonstrating good adsorption capability. Thus, there is a huge possibility of accomplishing this and performing well. This study paves the way for the reuse and valorization of selected adsorbents following circular economy principles. Two green metrics were applied, the Analytical Eco-scale and the Analytical GREEnness Calculator (AGREE).

Innovative detection mechanism for deltamethrin based on a dual-emitting Fluoroprobe and its application in a smartphone-based photoelectric conversion device.

Pyrethroids are widely used insecticides worldwide, while their on-site and rapid detection still faces technological challenges. Herein, an innovative detection mechanism was designed for deltamethrin, a typical kind of type II pyrethroids, based on a dual-emitting fluoroprobe consisting of NH2-SiQDs and Eu3+. Deltamethrin can rapidly hydrolyze into 3-phenoxybenzaldehyde (3-PBD) and react specifically with fluoroprobe, causing fluorescence quenching of SiQDs while maintaining the fluorescent stability of Eu3+. Building upon the above fluorescence-responsive principle, SiQDs@Eu3+ provided satisfactorily dual-emitting signals, realizing the highly-selective and sensitive detection of deltamethrin. Correlation between the surface structure of SiQDs and their absorption spectra was in-depth unraveled by TD-DFT calculation and FT-IR analysis. As for the analytical performance, the recovery and LOD of deltamethrin in lettuce, provided by SiQDs@Eu3+, were comparable or even superior over conventional chromatographic analysis. Meanwhile, an innovative smartphone-based optical device was developed, which greatly decreased errors caused by the previously reported smartphone-based fluorescence detection.

Mechanistic insight into the impact of interaction between goethite and humic acid on the photooxidation and photoreduction of bifenthrin.

Numerous application of pyrethroid insecticides has led to their accumulation in the environment, threatening ecological environment and human health. Its fate in the presence of iron-bearing minerals and natural organic matter under light irradiation is still unknown. We found that goethite (Gt) and humic acid (HA) could improve the photodegradation of bifenthrin (BF) in proper concentration under light irradiation. The interaction between Gt and HA may further enhance BF degradation. On one hand, the adsorption of HA on Gt may decrease the photocatalytic activity of HA through decreasing HA content in solution and sequestering the functional groups related with the production of reactive species. On the other hand, HA could improve the photocatalytic activity of Gt through extending light absorption, lowing of bandgap energy, hindering the recombination of photo-generated charges, and promoting the oxidation and reduction reaction on Gt surface. The increased oxygen vacancies on Gt surface along with the reduction of trivalent iron and the nucleophilic attack of hole to surface hydroxyl group contributed to the increasing photocatalytic activity of Gt. Electron paramagnetic resonance and quenching studies demonstrated that both oxidation species, such as hydroxyl radical (•OH) and singlet oxygen (1O2), and reducing species, such as hydrogen atoms (H•) and superoxide anion radical (O2•-), contributed to BF degradation in UV-Gt-HA system. Mass spectrometry, ion chromatography, and toxicity assessment indicated that less toxic C23H22ClF3O3 (OH-BF), C9H10ClF3O (TFP), C14H14O2 (OH-MBP), C14H12O2 (MBP acid), C14H12O3 (OH-MBP acid), and chloride ions were the main degradation products. The production of OH-BF, MPB, and TFP acid through oxidation and the production of MPB and TFP via reduction were the two primary pathways of BF degradation.

Efecto del tipo y del número de lavados en la eficacia de mosquiteros tratados con deltametrina de larga duración para el control de Aedes aegypti en Girardot, Colombia / Effect of the type and number of washes in the efficacy of long lasting insecticidal nets for Aedes aegypti control in Girardot, Colombia

Resumen Introducción. El uso de mosquiteros tratados con insecticida en fórmulas de larga duración ha demostrado resultados prometedores en el control de Aedes aegypti. Objetivo. Evaluar la eficacia de mosquiteros impregnados con deltametrina en una fórmula de larga duración para el control de A. aegypti en Girardot, Colombia, después de tres lavados. Materiales y métodos. Se hicieron bioensayos de eficacia de los mosquiteros contra A. aegypti silvestres después de utilizar los siguientes tres productos de lavado, siguiendo la metodología de la Organización Mundial de la Salud: detergente en polvo, detergente en polvo y blanqueador, y jabón de barra, todos utilizados hasta en 20 lavados. Resultados. El tipo de producto de lavado y el número de lavados afectaron significativamente la eficacia de los mosquiteros impregnados con deltametrina. El lavado con jabón de barra presentó el mayor efecto, pues en tan solo seis lavados la mortalidad bajó a 50 % (25/50), en contraste con 66 % (33/50 de mortalidad después del lavado con detergente en polvo y de 84 % (42/50) después del lavado con detergente y blanqueador. En cuanto al número de lavados, el jabón en barra también causó una mayor reducción de la eficacia: a 68 % con solo tres lavados. Conclusión. La eficacia de los mosquiteros impregnados con deltametrina de larga duración en el control de A. aegypti varió con el tipo de producto de lavado y el número de lavados, siendo el jabón en barra el que redujo su eficacia en mayor medida. Se requieren nuevos estudios para establecer la disminución en la concentración del insecticida entre lavados.

Abstract Introduction: The use of long lasting insecticidal materials has shown promising results in the control of Aedes aegypti. Objective: To evaluate the efficacy of long-lasting insecticidal nets (PermaNet®) for Aedes aegypti control after three washing treatments in the city of Girardot, Colombia. Materials and methods: Standard bioassays were conducted with the nets following the World Health Organization protocols using wild A. aegypti after three washing treatments: (1) Detergent powder, (2)detergent powder and bleach, and (3) bar soap, until completing 20 washes. Results: The type and number of wash treatments had a significant effect on net efficacy. Greater effects in the insecticide bioavailability were seen for the bar soap treatment. After six washes, mortality decreased by 50% (25/50), vs 66% (33/50) for the detergent powder and 84% (42/50) for the detergent powder and bleach treatments. Regarding the number of washes, the bar soap treatment reduced the efficacy to 68% after only three washes. Conclusion: The effectiveness of long-lasting insecticidal nets (PermaNet 2.0) for A. aegypti control varied in relation to the treatment and number of washes. The bar soap treatment resulted in the greatest reduction of mortality. Further studies on insecticidal reductions are needed under local conditions.

Evaluación de la B-cipermetrina para el control de Triatoma infestans / Evaluation of -cypermethrin for control of Triatoma infestans

This study assessed the insecticidal effect in the laboratory and in the field of the new pyrethroid -cypermethrin against Triatoma infestans, the vector of Chagas' disease, and compared it with that of deltamethrin. Comparison of the 50% lethal dosis (LD50) of both pyrethroids showed that -cypermethrin is more effective against the nymphs and that deltamethrin is more effective against the adults. Evaluation of the 50% lethal concentration (LC50) of the flowable formulations of both insecticides, placed on different surfaces, showed that their effectiveness on glass is similar, while on a ceramic surface deltamethrin is slightly more effective. The flowable formulations of the two insecticides were tested in 100 infested homes in the province of Santiago del Estero, Argentina. Deltamethrin was applied at a surface concentration of 25 mg/m2 and -cypermethrin at 50 mg/m2. The real surface concentrations of these products were analyzed from filter paper samples placed on walls and ceilings. Gas chromatography revealed good agreement with the target concentrations. In addition, entomological assessments were carried out 60, 90, 180, and 365 days after the treatments. Infestations were found only during the last assessment: in the peridomiciliary area of 10% of the houses treated with -cypermethrin and in 7% of the houses treated with deltamethrin (6% in the peridomiciliary area and 1% inside the house). The results indicate that -cypermethrin's effectiveness in controlling T. infestans when applied at a concentration of 50 mg/m2 is similar to that of deltamethrin applied at a concentration of 25 mg/m2

En este estudio se evaluó en el laboratorio y en el campo el efecto insecticida sobre Triatoma infestans, vector de la enfermedad de Chagas, del nuevo piretroide ß-cipermetrina, y se comparó con el de la deltametrina. La comparación de las dosis letales 50 (DL50) de ambos piretroides indicó que la ß-cipermetrina es más efectiva en ninfas y la deltametrina, en adultos. La evaluación de la concentración letal 50 (CL50) de las dos formulaciones floables de ambos insecticidas depositados sobre distintos soportes mostró que su efectividad en vidrio es similar. En cerámica, la deltametrina es ligeramente más efectiva. Los dos insecticidas floables se evaluaron en 100 viviendas infestadas de la provincia de Santiago del Estero, Argentina. La deltametrina floable se aplicó a una concentración superficial de 25 mg/m2 y la ß-cipermetrina, de 50 mg/m2. Las concentraciones superficiales reales de ambos productos se analizaron por medio de papeles de filtro colocados en paredes y techos. El análisis por cromatografía de gases mostró buena coincidencia con las concentraciones previstas. Asimismo, se realizaron evaluaciones entomológicas 60, 90, 180 y 365 días después de los tratamientos. Solo en la última evaluación se encontró 10% de infestación en peridomicilios de viviendas tratadas con ß-cipermetrina y 7% en las viviendas tratadas con deltametrina (6% en el peridomicilio y 1% en el domicilio). Los resultados indican que la efectividad de la ß-cipermetrina para controlar a T. infestans cuando se aplica a una concentración de 50 mg/m2 es similar a la de la deltametrina cuando esta se administra a una concentración de 25 mg/m2

Aspectos relevantes dos inseticidas piretróides: II. Poder inseticida, metabolismo, análise / Important aspects of pyrethroid insecticides: II. Insecticide power, metabolism, analysis

Nesta segunda parte da revisäo bibliográfica, procurou-se abordar as propriedades dos piretróides naturais e sintéticos com referência ao poder inseticida à luz das suas estruturas moleculares. Também säo apresentadas algumas consideraçöes sobre o metabolismo desses inseticidas, focalizando quais grupos dos ésterespiretróides sofrem açäo química de degradaçäo, quais as técnicas analíticas mais usuais para quantificaçäo e finalmente conclui-se sobre a importância de seu emprego em funçäo do baixo risco de contaminaçäo do meio ambiente

Aspectos relevantes dos inseticidas piretróides: I. Origem, composiçäo química, extraçäo, emprego / Important aspects of pyrethroid insecticides: I. Source, chemical composition, extraction, use

Nesta revisäo bibliográfica apresentam-se algumas informaçöes sobre a origem e o cultivo das flores do gênero crisântemo, a fonte natural de obtençäo dos piretróides. Em seguida, comenta-se a respeito da extraçäo, da composiçäo química dos piretróides existentes nas flores do crisântemo e no advento dos piretródes sintéticos. E, finalmente conclui-se com algumas consideraçöes sobre a baixa toxicidade e grande eficácia destes pesticidas naturais e artificiais. Estas qualidades sugerem que o produto, tanto os piretróides sintéticos como os extraídos do crisântemo, deva ser empregado com mais freqüência, sobretudo no armazenamento de gräos comestíveis

Evaluation of different Cypermethrin formulations and concentrations in the control of Musca domestica

Cypermethrin (4 g/l, 5 g/l wettable powder and 7 ml/l, 10 ml/l emulsifiable concentrate) was tested, under laboratory conditions, against the adult Musca domestica. As a standard for comparison, a 6 ml/l concentrate suspension formulation of deltamethrin was used. One and twenty-four hours after application, mortality counts showed that the substances under test killed, respectively, more than 80% and 85% of the exposed insects. Under the conditions of the test, cypermethrin was considered effective in the control of the house fly.