Eco-friendly chitosan microspheres as a novel one-step sorbent for the rapid purification and determination of pesticides and veterinary drug multi-residues in aquatic products with HPLC-MS/MS.

A modified QuEChERS method was developed to determine multi-class pesticide and veterinary residues in aquatic products. Chitosan microspheres were conveniently synthesized and utilized as the cleanup adsorbent in the QuEChERS procedure, showcasing rapid filtration one-step pretreatment ability for the determination of drug multi-residues in aquatic products. Compared to conventional synthetic sorbents, chitosan microspheres not only have good purification performance, but also have renewable and degradable properties. This novel sorbent worked well in the simultaneous determination of 95 pesticides and veterinary drug residues in aquatic products after being combined with an improved one-step vortex oscillating cleanup method. We achieved recoveries ranging from 64.0% to 115.9% for target drugs in shrimp and fish matrix. The limits of detection and quantification were 0.5-1.0 and 1.0-2.0 µg kg-1, respectively. Notably, hydrocortisone was detected with considerable frequency and concentration in the tested samples, underscoring the necessity for stringent monitoring of this compound in aquatic products.

Toxicity Potential of Nutraceuticals.

During the past few decades and especially during and after the COVID-19 pandemic, the use of nutraceuticals has become increasingly popular in both humans and animals due to their easy access, cost-effectiveness, and tolerability with a wide margin of safety. While some nutraceuticals are safe, others have an inherent toxic potential. For a large number of nutraceuticals, no toxicity/safety data are available due to a lack of pharmacological/toxicological studies. The safety of some nutraceuticals can be compromised via contamination with toxic plants, metals, mycotoxins, pesticides, fertilizers, drugs of abuse, etc. Knowledge of pharmacokinetic/toxicokinetic studies and biomarkers of exposure, effect, and susceptibility appears to play a pivotal role in the safety and toxicity assessment of nutraceuticals. Interaction studies are essential to determine efficacy, safety, and toxicity when nutraceuticals and therapeutic drugs are used concomitantly or when polypharmacy is involved. This chapter describes various aspects of nutraceuticals, particularly their toxic potential, and the factors that influence their safety.

Alcohol-based hydrophobic deep eutectic solvents and ultrasound-assisted liquid phase microextraction followed by GC-MS for the extraction and analysis of organophosphorus pesticides in the blood of farmers.

Organophosphorus pesticides (OPPs) are a group of pesticides that are most widely used in the agricultural sector, and farmers are exposed to these chemicals more than other members of society. In this work, an environmentally friendly, simple, and safe ultrasound-assisted dispersive liquid-liquid microextraction (USA-DLLME) method using alcohol-based hydrophobic deep eutectic solvents (HDESs) followed by gas chromatography-mass spectroscopy (GC-MS) was developed for the extraction and determination of OPPs in the blood of farmers studied in Ravansar cohort. DESs synthesized from thymol as hydrogen bond donor (HBD) and aliphatic alcohols as hydrogen bond acceptor (HBA) have been used as extractants. Under optimal experimental conditions, the reproducibility of the method based on 7 replicate measurements of 10 µg L-1 of OPPs in blood samples was in the range of 1.4-3.8%. The method showed a linearity in the range of 0.01-150 µg L-1. The limits of detection and limits of quantification were between 0.003 and 0.02 µg L-1 and 0.01-0.05 µg L-1, respectively. The matrix effect and accuracy of the method were confirmed by spiking different amounts of OPPs in real blood samples and obtaining relative recoveries in the range of 91-112%. The results showed that the concentration of OPPs in the case group was significantly higher than in the control group, which is because the case group was exposed to OPPs during the spraying of agricultural products.

Prenatal exposure to persistent organic pollutants and its impact on the ovarian reserve at 12 years old in the PELAGIE mother-child cohort.

Although the ovarian reserve is constituted in utero, the literature on the effects of persistent organic pollutants (POPs) during this vulnerable period on the ovarian reserve later in life is limited. We investigated whether cord blood concentrations of POPs were associated with decreased anti-Müllerian hormone (AMH, a marker of the ovarian reserve) levels in girls at the age of 12. We included 239 girls from the French mother-child PELAGIE cohort. POP concentrations of 14 organochlorine pesticides, 17 polychlorinated biphenyls (PCBs), 5 polybrominated diphenyl ethers, and 9 per-polyfluoroalkyl substances were measured on cord blood sampled at birth. During a follow-up study at 12 years old, blood samples were collected to measure AMH levels. Single-exposure associations were examined with multivariable linear regression models adjusted a priori for potential confounders. Stratification on menarche status was also performed. Mixture effects were investigated using quantile g-computation and Bayesian kernel machine regression. Overall, 16 POPs were measured in at least 30% of samples. No significant associations were found in multivariable linear regressions, except for the third tercile of exposure to PCB 180 which was statistically significantly associated with an increase in AMH levels at 12 years old (Tercile 2 v. Tercile 1: 0.13 ng/mL, 95% CI = -0.29, 0.56; Tercile 3 v. Tercile 1: 0.51 ng/mL, 95% CI = 0.02, 0.99). Additionally, in post-menarcheal girls (N = 104) only, the second tercile of p,p'-DDE was statistically significantly associated with decreased AMH levels at 12 years old (Tercile 2 v. Tercile 1: -0.61 ng/mL, 95% CI = -1.16, -0.05, Tercile 3 v. Tercile 1: 0.02 ng/mL, 95% CI = -0.51, 0.54). Both mixture models returned null associations. Despite the limited associations observed in this study, we recommend exploring these associations in larger mother-child cohorts and at older ages.

Emerging hazardous chemicals and biological pollutants in Canadian aquatic systems and remediation approaches: A comprehensive status report.

Emerging contaminants can be natural or synthetic materials, as well as materials of a chemical, or biological origin; these materials are typically not controlled or monitored in the environment. Canada is home to nearly 7 % of the world's renewable water supply and a wide range of different kinds of water systems, including the Great Lake, rivers, canals, gulfs, and estuaries. Although the majority of these pollutants are present in trace amounts (µg/L - ng/L concentrations), several studies have reported their detrimental impact on both human health and the biota. In Canadian aquatic environments, concentrations of pharmaceuticals (as high as 115 µg/L), pesticides (as high as 1.95 µg/L), bioavailable heavy metals like dissolved mercury (as high as 135 ng/L), and hydrocarbon/crude oil spills (as high as 4.5 million liters) have been documented. Biological threats such as genetic materials of the contagious SARS-CoV-2 virus have been reported in the provinces of Québec, Ontario, Saskatchewan and Manitoba provinces, as well as in the Nunavut territory, with a need for more holistic research. These toxins and emerging pollutants are associated with nefarious short and long-term health effects, with the potential for bioaccumulation in the environment. Hence, this Canadian-focused report provides the footprints for water and environmental sustainability, in light of this emerging threat to the environment and society. Several remediation pathways/tools that have been explored by Canadian researchers, existing challenges and prospects are also discussed. The review concludes with preventive measures and strategies for managing the inventory of emerging contaminants in the environment.

The role of efflux transporters in cytotoxicity and intracellular concentration of chlorpyrifos and chlorpyrifos oxon in human cell lines.

In this study, we investigated the role of two efflux transporters, p-glycoprotein (P-gp) and breast cancer resistance protein (BCRP), in the cytotoxicity and intracellular accumulation of the organophosphate pesticide chlorpyrifos (CPF) and its active metabolite, CPF-oxon (CPFO), in a human-derived liver cell line (HepG2) and kidney epithelial cell line (HK-2). The cytotoxicity to CPF and CPFO differed between cell lines where HK-2 had lower IC50 values which could be attributed to lower basal expression and inducibility of metabolizing enzymes, transporters, and nuclear receptors in HK-2 cells. In HepG2 cells, co-exposure of CPF with a specific inhibitor of either P-gp or BCRP enhanced the cytotoxicity of CPF while co-exposure of CPFO with VRP enhanced the cytotoxicity of CPFO, suggesting the role of these transporters in the elimination CPF and CPFO. Inhibition of efflux transporters did not affect the cytotoxicity of CPF and CPFO in HK-2 cells. Co-incubation of CPF with P-gp and BCRP inhibitors increased the intracellular concentration of CPF in HepG2 cells suggesting that both transporters play a role in limiting the cellular accumulation of CPF in HepG2 cells. Our results provide evidence that inhibition of efflux transporters can enhance CPF-induced toxicity through enhanced cellular accumulation and raises additional questions regarding how pesticide-transporter interactions may influence toxicity of mixtures containing pesticides and other environmental chemicals.

The association of organochlorine pesticides and polychlorinated biphenyls exposure with dyslipidemia and blood lipids: The mediating effect of white blood cell counts.

Epidemiological evidence regarding the associations of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) with lipid metabolism and its potential biological mechanisms remain largely unknown. We intended to explore the associations of OCPs and PCBs with dyslipidemia and blood lipid levels, and further evaluate the mediating role of total and differential white blood cell (WBC) counts. We measured the blood lipid levels, the concentration of OCPs/PCBs and WBC counts in serum among 2036 adults in Wuhan city, China. In the multiple-pollutant models, the results showed that ß-hexachlorocyclohexane (HCH), p,p'-dichlorodiphenyldichloroethylene (DDE), and PCB-153 were positively correlated with increased odds of dyslipidemia. p,p'-DDE and PCB-153 were correlated with elevated triglyceride (TG) and lowered high-density lipoprotein cholesterol (HDL-c). A positive relationship was observed between p,p'-DDE and total cholesterol (TC) as well. Meanwhile, weighted quantile sum (WQS) regression analyses revealed that PCB and OCP mixtures were positively related to dyslipidemia risk and TG and negatively associated with HDL-c, to which p,p'-DDE was the major contributor. BMI, gender and age might modify the associations of OCPs and PCBs with dyslipidemia and TG. Furthermore, we found that WBC counts were significantly associated with dyslipidemia and blood lipid levels, and a positive correlation was also found between p,p'-DDE and lymphocyte count. Mediation analysis further indicated that lymphocyte count might mediate the associations of p,p'-DDE with dyslipidemia, TG, and TC. Accordingly, our results showed that OCPs and PCBs were related to abnormal lipid metabolism, which was partially mediated by WBC counts.

Maternal exposure to pesticides induces perturbations in the gut microbiota and blood-brain barrier of dams and the progeny, prevented by a prebiotic.

Exposure to pesticide residues during the first 1000 days of life can disrupt body homeostasis and contribute to chronic metabolic diseases. Perinatal chlorpyrifos (CPF) exposure alters gut microbiota (GM) balance, potentially affecting offspring's health. Given the GM influence on brain function, the primary aim is to determine if pesticide-induced dysbiosis (microbial imbalance) affects indirectly other organs, such as the blood-brain barrier (BBB). The secondary objective is to evaluate the prebiotics protective effects, particularly inulin in promoting microbial balance (symbiosis), in both mothers and offspring. A total of 15 or more female rats were divided in 4 groups: control, oral CPF-exposed (1 mg/kg/day), exposed to inulin (10 g/L), and co-exposed to CPF and inulin from pre-gestation until weaning of pups. Samples from intestines, spleen, liver, and brain microvessels underwent microbiological and biomolecular analyses. Bacterial culture assessed GM composition of living bacteria and their translocation to non-intestinal organs. RT qPCR and Western blotting detected gene expression and protein levels of tight junction markers in brain microvessels. CPF exposure caused gut dysbiosis in offspring, with decreased Lactobacillus and Bifidobacterium and increased Escherichia coli (p < 0.01) leading to bacterial translocation to the spleen and liver. CPF also decreased tight junction's gene expression levels (50 to 60% decrease of CLDN3, p < 0.05). In contrast, inulin partially mitigated these adverse effects and restored gene expression to control levels. Our findings demonstrate a causal link between GM alterations and BBB integrity disruptions. The protective effects of inulin suggest potential therapeutic strategies to counteract pesticide-induced dysbiosis.

Biosensing strategies using recombinant luminescent proteins and their use for food and environmental analysis.

Progress in synthetic biology and nanotechnology plays at present a major role in the fabrication of sophisticated and miniaturized analytical devices that provide the means to tackle the need for new tools and methods for environmental and food safety. Significant research efforts have led to biosensing experiments experiencing a remarkable growth with the development and application of recombinant luminescent proteins (RLPs) being at the core of this boost. Integrating RLPs into biosensors has resulted in highly versatile detection platforms. These platforms include luminescent enzyme-linked immunosorbent assays (ELISAs), bioluminescence resonance energy transfer (BRET)-based sensors, and genetically encoded luminescent biosensors. Increased signal-to-noise ratios, rapid response times, and the ability to monitor dynamic biological processes in live cells are advantages inherent to the approaches mentioned above. Furthermore, novel fusion proteins and optimized expression systems to improve their stability, brightness, and spectral properties have enhanced the performance and pertinence of luminescent biosensors in diverse fields. This review highlights recent progress in RLP-based biosensing, showcasing their implementation for monitoring different contaminants commonly found in food and environmental samples. Future perspectives and potential challenges in these two areas of interest are also addressed, providing a comprehensive overview of the current state and a forecast of the biosensing strategies using recombinant luminescent proteins to come.

Mobility and persistence of pesticides and emerging contaminants in age-dated and redox-classified groundwater under a range of land use types.

Understanding groundwater contamination patterns is hampered by the heterogeneous groundwater age and redox status over the depth range typically sampled for identifying pesticides and emerging contaminants threats. This study explores depth patterns of groundwater age and redox status across various land use types, unraveling spatial and temporal trends of pesticides and emerging contaminants using data from groundwater quality monitoring in the south of the Netherlands. The Netherlands is an ideal testing ground due to its high population density and widespread groundwater contamination from multiple sources. 146 multi-level observation wells were age-dated using 3H/3He, and contaminant concentrations were analyzed based on recharge year, land use type, and redox conditions, mitigating uncertainties from spatial and depth-dependent variations in both groundwater age and redox status. Redox-recharge year diagrams were developed to visually evaluate contaminant patterns in relation to these factors and to assess concentration patterns in relation to contamination history. Most detections of pesticides, metabolites, and emerging contaminants occurred in the youngest recharge periods (2000-2010 and 2010-2020) and in agricultural areas. However, certain contaminants, including BAM, desphenyl-chloridazon, short-chain PFCAs, PFOA, and EDTA, were consistently found in older water and Fe- or SO4-reduced conditions, indicating their mobility and persistence in the regional groundwater system. Comparing the presence of contaminants in specific redox classes and recharge periods with known application or leaching history provides insights into retardation (e.g., PFOS) and degradation (e.g., 2-hydroxy-atrazine, benzotriazole), explaining lower detection frequencies in earlier recharge periods. Identifying recharge years from age-dated groundwater helps relate contaminants to farmland application or river water recharge periods, revealing leaching history and contamination origins. The presented framework has the potential to enhance the interpretation of large groundwater datasets from dedicated, short-screened observation wells, such as those from the Danish GRUMO network, the Dutch monitoring networks, and parts of the US National Water Quality Program.

Species Sensitivity Distribution (SSD) profiles towards λ-cyhalothrin for key ecosystem service provider (ESP) species across five European countries representing different pedoclimatic zones.

Although our understanding of the dramatic worldwide loss of biodiversity in recent decades is far from adequate, one of the main factors in areas dominated by agriculture is undoubtedly the widespread use of synthetic pesticides. Unfortunately, the ecological risk assessment (EcoRA) for pesticides is based on a few single-species bioassays which do not allow for the evaluation of risks to whole communities. Here we present the results of an experimental assessment of the risk to the ecosystem service provider (ESP) communities - pest control agents - from exposure to the commonly used pyrethroid insecticide, λ-cyhalothrin. The study was performed in five European countries (Germany, Poland, Portugal, Spain, United Kingdom) representing different pedoclimatic zones. Representatives of the most common species of the ESP communities in each country were exposed in a standardized insecticide-coated glass vials bioassay to five doses of λ-cyhalothrin: 0.8 %, 4 %, 20 %, 100 %, and 200 % of the recommended field dose (RFD) plus an untreated control. Based on the calculated LD50s, species sensitivity distributions (SSDs) were estimated for each country and on combined data. In all five countries, the estimated hazardous concentration for 5 % of the species (HD5) was between 0.23 % and 1.67 % RFD, with HD5 = 0.44 % RFD based on combined data. At the RFD = 7.5 g a.i./ha (active ingredient per hectare), the predicted affected fraction of the ESP communities was between 96.4 % and 99.9 % of the species (98.5 % for combined data). The results indicate an extremely high risk to ESP communities across Europe associated with the use of λ-cyhalothrin at the recommended doses when these species are exposed to insecticide treatment. We recommend that EcoRA should include multi-species approaches, such as SSD, to better protect entire ESP communities from the negative impacts of pesticides.

Assessment of persistent and emerging pollutants levels in marine bivalves in the Gulf of Suez, Egypt.

Bivalves possess important ecological and economic values. They have been extensively used as bioindicators for both emerging and classical pollutants in the aquatic environment. This study investigates the levels of trace metals, polycyclic aromatic hydrocarbons (PAHs), and organochlorine pesticides (OCPs), alongside microplastic (MPs), in Tridacna maxima, Paphia textile, and Paratapes undulatus, collected from the Gulf of Suez. This work represents the first investigation of MPs in marine bivalves from the Gulf of Suez. MPs were detected in 72% of the specimens examined and four types of MPs were identified. The metal pollution index indicated that bivalves may have long-term toxic effects on human consumers. The results showed minimal hydrocarbon pollution. Diagnostic ratios indicated a combination of pyrolytic and petrogenic sources, with a notable influence from pyrolytic origins. The risk assessment reflected that the levels of certain trace metals, PAHs, and OCP contaminants could present a low risk to human health.

Adoption status of integrated pest management (IPM) practices among vegetable growers of Lamjung district of Nepal.

The widespread use of highly toxic pesticides for agricultural purposes has raised concerns about their hazardous impact on both human health and the environment. Integrated pest management (IPM) is a strategy designed to tackle pest problems and reduce pesticide use, with the aim of protecting both human health and the environment. This study was conducted in Besishahar, Sundarbazar, Rainas, and Madhyenepal municipalities of the Lamjung district of Nepal in the year 2023 with a sample of 100 vegetable-growing farmers to assess the adoption of IPM practices in vegetable cultivation. Descriptive and inferential statistics were used to analyze the data, and the logit model was used to identify the factors affecting the adoption of IPM practices in vegetable cultivation among farmers. Respondents were grouped into two categories, adopter and non-adopter, based on the extent of adoption of IPM practices. The findings revealed that only 37 % of the total respondents adopted IPM practices for vegetable cultivation. The easy availability of chemical pesticides and lack of bio-pesticides were the major constraints for the adoption of IPM practices in the study area. The output of the binary logit model indicated that greater participation in training, higher education levels, and increased contact with extension agents significantly influence the adoption of IPM practices in vegetable cultivation. The findings could be used to formulate better policies towards increasing the adoption of sustainable approaches in agriculture and regulation.

Electrochemiluminescence sensor for organophosphorus pesticides based on the regulation of resonance energy transfer between negative charged gold nanorods and Ru(bpy)32.

Combined the electrostatic interaction of the negatively charged gold nanorods (AuNRs) (as acceptor) and Ru(bpy)32+ (as donor), an electrochemiluminescence resonance energy transfer (ECL-RET) sensor was constructed and applied for the detection of organophosphorus pesticides (OPs). Negatively charged AuNRs were synthesized by modifying AuNRs with polystyrene sulfonate (PSS) firstly, which can bind to Ru(bpy)32+ through electrostatic interaction so that the luminophore was absorbed by the acceptor, the resonance energy transfer occurred and only low ECL signal had been detected. Thiocholine can be produced by the hydrolysis process of acetylthiocholine (ATCh) with the help of acetylcholinesterase (AChE), which can bond with PSS-modified AuNRs (PSS-AuNRs) through gold-sulfur interaction, this caused the releasing of the adsorbed Ru(bpy)32+ into the solution and resulting in the restoration of the ECL intensity. However, the activity of AChE was inhibited by OPs, and the recovery process of the ECL signal was thus suppressed as well. In this study, chlorpyrifos was chosen as model target, the results indicated that the correlation between the ECL intensity and the logarithm of chlorpyrifos concentration showed remarkable linearity across 1 ng/mL to 1 mg/mL, achieving a detection limit of 0.51 ng/mL. The proposed system has been utilized for detecting OPs in real samples with satisfied results.

The adsorption of chlorpyrifos and malathion under environmentally relevant conditions using biowaste carbon materials.

Water bodies face persistent contamination from organophosphorus pesticides like chlorpyrifos and malathion, which pose substantial environmental and health hazards due to their toxicity and resilience in ecosystems. This study explores the potential of spent coffee grounds, a common agricultural byproduct, as an eco-friendly adsorbent for eliminating these pesticides from polluted water. Spent coffee grounds underwent carbonization at 400 °C and various activation treatments using KOH, H3PO4, CO2, and their combinations. The impact of these activation methods on the adsorption capacity of carbonized materials was assessed under environmentally relevant conditions (25 °C, pH=6, and typical pesticide concentrations in wastewater). Results revealed that the physical and chemical properties of biowaste-derived materials significantly influence their adsorption efficiency, with KOH-activated adsorbents exhibiting the highest capacities ((16.1 ± 0.8) mg g-1 for chlorpyrifos and (11.2 ± 0.2) mg g-1 for malathion). Spent coffee grounds carbonized at 400 °C without additional activation demonstrated similar adsorption performance to the best-performing material ((19.4 ± 0.4) mg g-1 for chlorpyrifos and (10.6 ± 0.4) mg g-1 for malathion), with notably lower economic and environmental costs. Given its straightforward preparation and significant adsorption capacity, this material stands out as a sustainable solution for treating agrochemical wastewater containing chlorpyrifos and malathion.

Residential proximity to agricultural herbicide and fungicide applications and dust levels in homes of California children.

BACKGROUND: Few studies of the relationship between residential proximity to agricultural pesticide applications and pesticide levels in the home have incorporated crop location or wind direction. We evaluated the relationship between agricultural pesticide applications using the California Pesticide Use Reporting (CPUR) database and pesticide concentrations in carpet dust accounting for land use and wind direction. METHODS: We measured concentrations (ng/g) of seven herbicides and two fungicides in carpet dust samples from 578 California homes (2001-2007). We created three metrics by computing the density (kg/km2) of use of each pesticide reported in CPUR within 0.5-, 1-, 2-, and 4-km buffers around homes 180- and 365-days before sampling (CPUR metric). We apportioned applications to the crop area within the buffers (CROP-A metric) and weighted CPUR applications by the proportion of days that the home was within ±45° of the downwind direction (W-CPUR metric). We modeled natural-log concentrations (Tobit regression) and dust detections (logistic regression) adjusting for season/year, occupation, and home/garden use. RESULTS: Detections were >90 % for glyphosate, 2,4-D, and simazine. Detection rates and dust concentrations increased with increasing CPUR densities for all herbicides and one fungicide. Compared to homes without applications within 4 km, the highest tertile of 365-day glyphosate use was associated with ∼100 % higher concentrations (CPURT3>9.2kg/km2 %change = 110, 95 %CI = 55, 183; CROP-AT3>13.4kg/km2 %change = 144, 95 %CI = 81, 229; and W-CPURT3>2.1kg/km2 %change = 102, 95 %CI = 50, 171). The highest density tertiles of 2,4-D, simazine, and trifluralin were associated with 2- to 6-times higher concentrations, respectively; that was similar across metrics. Across all metrics, agricultural use of dacthal, dicamba, and iprodione were associated with 5- to 10-times higher odds of dust detections. Associations were unclear for 2-methyl-4-chlorophenoxyacetic acid and null for chlorothalonil. CONCLUSIONS: Agricultural herbicide and fungicide use was an important determinant of indoor contamination within 4 km of homes. Accounting for crops and wind direction did not substantially change these relationships.

Advancements in SERS based systematic evolution of ligands by exponential enrichment for detection of pesticide residues in fruits and vegetables.

Fruits and vegetables with pesticide residues pose a serious public health risk. Since 2022, 3 million people worldwide have been poisoned by pesticides annually, with a 20 % fatality rate. This review provides an overview of current research on detecting pesticide residues in produce, focusing on the potential of SERS-based aptasensor. These sensors offer improved efficiency and accuracy in pesticide analysis, ensuring the safety of fruits and vegetables. The review also discusses essential techniques for efficient aptamer production, highlighting their advantages and disadvantages. It emphasizes the benefits and challenges of using SERS-based aptasensor, particularly the need for enhanced anti-interference capabilities and the development of intelligent sensors for on-site detection without extensive sample preparation. This comprehensive review is a great resource that can help with future developments in pesticide residue analysis, food safety, and consumer health protection in contemporary agriculture.

Radiometric approaches with carbon-14-labeled molecules for determining herbicide fate in plant systems.

Weeds cause economic losses in cropping systems, leading to the use of 1.7 million tons of herbicides worldwide for weed control annually. Once in the environment, herbicides can reach non-target organisms, causing negative impacts on the ecosystem. Herbicide retention, transport, and degradation processes determine their environmental fate and are essential to assure the safety of these molecules. Radiometric strategies using carbon-14 herbicides (14C) are suitable approaches for determining herbicide absorption, translocation, degradation, retention, and transport in soil, plants, and water. In this work, we demonstrate how 14C-herbicides can be used from different perspectives. Our work focused on herbicide-plant-environment interactions when the herbicide is applied (a) through the leaf, (b) in the soil, and (c) in the water. We also quantified the mass balance in each experiment. 14C-mesotrione foliar absorption increased with oil and adjuvant addition (5-6 % to 25-46 %), and translocation increased only with adjuvant. More than 80 % of 14C-quinclorac and 14C-indaziflam remained in the soil and cover crops species absorbed less than 20 % of the total herbicides applied. In water systems, Salvinia spp. plants removed 10-18 % of atrazine from the water. Atrazine metabolism was not influenced by the presence of the plants. The radiometric strategies used were able to quantify the fate of the herbicide in different plant systems and the mass balance varied from 70 % to 130 %. Importantly, we highlight a critical and practical view of tracking herbicides in different matrices. This technique can aid scientists to explore other pesticides as environmental contaminants.

Design and Synthesis of Novel Indole-Derived N-Methylcarbamoylguanidinyl Chitinase Inhibitors with Significantly Improved Insecticidal Activity.

Chitinases play an important role in the molting process of insects and are potential targets for the development of green insecticides. Based on the feature that the +1/+2 sites in OfChtI, OfChtII, and OfChi-h have tryptophan residues in mismatch-parallel position, a strategy to introduce indole scaffold into chitinase inhibitors was proposed, and multitarget chitinase inhibitors containing N-methylcarbamoylguanidinyl and indole scaffold were successfully synthesized. The inhibitory activity showed that compound 8u exhibited significant inhibitory activity against OfChtI, OfChtII, and OfChi-h, with IC50 values of 0.7, 0.79, and 0.58 µM, and Ki values of 0.05 ± 0.005, 0.065 ± 0.004, and 0.025 ± 0.006 µM, respectively. In vivo insecticidal activity showed that compounds 8a and 8g exhibited excellent insecticidal activity against Plutella xylostella and Mythimna separata, with LC50 values of 0.79 and 9.17 mg/L against P. xylostella, respectively, and 3.58 and 83.09 mg/L against M. separata, respectively, making them the most potent chitinase inhibitors with in vivo insecticidal activity discovered to date. The inhibition mechanism and binding free energy results suggested that N-methylcarbamoylguanidinyl binds to the -1 catalytic site, while additional interactions acquired by π-π stacking and hydrophobic interactions of the indole scaffold with tryptophan increase the binding affinity of the targets to chitinases. This work provides a new direction for the development of chitinase inhibitors with compounds 8a and 8g potentially serving as promising candidates for pesticide development.

Influence of Pesticide Application Method, Timing, and Rate on Contamination of Nectar with Systemic and Nonsystemic Pesticides.

Exposure to pesticides is one potential factor contributing to the recent loss of pollinators and pollinator diversity. Few studies have specifically focused on the relationship between pesticide management during ornamental plant production and contamination of nectar. We evaluated contamination of nectar in Salvia 'Indigo Spires' (Salvia longispicata M. Martens & Galeotti × S. farinacea Benth.) associated with applications of the systemic insecticide thiamethoxam, and the nonsystemic fungicides boscalid and pyraclostrobin. Applications were made at the labeled rates for the commercially available products, and we compared the influence of application method (drench vs. spray), timing (relative to flowering), and rate (low vs. high) for each pesticide. Nectar was sampled using 50-µL microcapillary tubes and analyzed by liquid chromatography-tandem mass spectrometry. The results indicate that concentrations from the spray application resulted in the least contamination of nectar with the systemic thiamethoxam, with lower concentrations occurring when thiamethoxam was applied before blooming at the lowest rate. Concentrations of thiamethoxam and its metabolite clothianidin were detected in nectar in all treatments (regardless of the method, timing, or rate of application), and ranged from 3.6 ± 0.5 ng/mL (spray-applied before blooming, low rate) to 1720.0 ± 80.9 ng/mL (drench-applied after blooming, high rate). Residues of clothianidin in nectar ranged from below quantification limits (spray-applied before blooming, low rate) to 81.2 ± 4.6 ng/mL (drench-applied after blooming, high rate). Drench applications resulted in the highest levels of nectar contamination with thiamethoxam, and exceeded published median lethal concentrations (LC50s/median lethal doses for native bees and/or honeybees in all cases). Spray treatments resulted in nectar concentrations exceeding published LC50s for some bee species. In comparison, all nonsystemic treatments resulted in concentrations much lower than the published no-observable-effect doses and sublethal toxicity values, indicating low risks of toxicity. Environ Toxicol Chem 2024;001:1-12. © 2024 SETAC.