Ti3C2 MXene/MoS2@AuNPs ternary nanocomposite for highly sensitive electrochemical detection of phoxim residues in fruits.

Phoxim, extensively utilized in agriculture as an organothiophosphate insecticide, has the potential to cause neurotoxicity and pose human health hazards. In this study, an electrochemical enzyme biosensor based on Ti3C2 MXene/MoS2@AuNPs/AChE was constructed for the sensitive detection of phoxim. The two-dimensional multilayer structure of Ti3C2 MXene provides a robust framework for MoS2, leading to an expansion of the specific surface area and effectively preventing re-stacking of Ti3C2 MXene. Additionally, the synergistic effect of self-reduced grown AuNPs with MoS2 further improves the electrical conductivity of the composites, while the robust framework provides a favorable microenvironment for immobilization of enzyme molecules. Ti3C2 MXene/MoS2@AuNPs electrochemical enzyme sensor showed a significant response to phoxim in the range of 1 × 10-13 M to 1 × 10-7 M with a detection limit of 5.29 × 10-15 M. Moreover, the sensor demonstrated excellent repeatability, reproducibility, and stability, thereby showing its promising potential for real sample detection.

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.

[Review and prospects of pesticide use and residues in cultivation of medicinal and food homologous substances].

As people's living standards and awareness of health care are increasing in recent years, the demand for the medicinal and food homologous substances is rising. Promoting the healthy development of this industry to meet people's growing demand and popularizing the TCM concept of preventive treatment of diseases are essential for building a healthy China. The abuse of pesticides by some growers in the one-sided pursuit of economic benefits causes serious pesticide residue, which affects the safety and effectiveness of the medicinal and food homologous substances. Since pesticide residues has received increasing attention, the reasonable control of pesticide residues becomes an important part of the research on these herbs, which, however, is rarely studied. This paper reviewed the publications involving pesticide residues in the cultivation of medicinal and food homologous substances that were published in the last two decades, and put forward the problems faced by the cultivation. According to the current situation of this industry, this paper proposed the management suggestions for the control of pesticide residues in the cultivation. This review will provide the government with data and references for formulating relevant policies and standards to promote the high-quality development of the industry of medicinal and food homologous substances and guarantee the development of TCM and the building of a healthy China.

Dissipation Kinetics, Decontamination and Safety Evaluation of Quinalphos Residues in Cauliflower Curd.

A field experiment was conducted to study the persistence and reduction of quinalphos residues in cauliflower curd by applying quinalphos 25 EC twice at 250 g a.i./ha at 10 days intervals. The limit of quantification (LOQ) was 0.05 µg/g, recovery ranged from 97 to 113%, and the relative standard deviation was less than 7%. The initial deposition of quinalphos residues in cauliflower curd was 1.72 µg/g and reached below LOQ level after 15 days of application. Dissipation of the residue followed first-order kinetics with a half-life of 2.32 days. The reduction of quinalphos residue was evaluated using various household processes. The greatest reduction (82%) was observed when washing was followed by cooking or boiling, while the smallest reduction (55.8%) was found when washing alone was performed. A waiting period of 9 days is recommended for safe consumption of cauliflower based on the FSSAI MRL value of 0.1 µg/g.

Bioaccessibility and bioavailability of exogenous and endogenous toxic substances in traditional Chinese medicine and their significance in risk assessment.

Scientific risk assessment of exogenous and endogenous toxic substances in traditional Chinese medicine (TCM) is of great significance. The present review comprises a comprehensive summary of progress in the health risk assessment of harmful exogenous substances in TCMs. Such substances include heavy metals, pesticide residues, biotoxins, and endogenous toxic components involving pyrrolizidine alkaloids. The review also discusses the strengths and weaknesses of various bioaccessibility and bioavailability models, and their applications in risk assessment. Future avenues of risk assessment research are highlighted, including further exploration of risk assessment parameters, innovation of bioaccessibility and bioavailability techniques, enhancement of probabilistic risk assessment combined with bioavailability, improvement of cumulative risk assessment strategies, and formulation of strategies for reducing relative bioavailability (RBA) values in TCMs. Such efforts represent an attempt to develop a risk assessment system that is capable of evaluating the exogenous and endogenous toxic substances in TCMs to ensure its safe use in clinics, and to promote the sustainable development of the TCM industry.

Mapping pesticide residues in soil for China: Characteristics and risks.

The widespread application of pesticides in China has led to the accumulation of residues in soil. However, few regional studies have fully elucidated the characteristics of pesticide residues in soil (PRS) and the associated risks to the ecosystem and human health on a national level. Therefore, this study aims to compile a dataset on PRS in China from 2006 to 2020 and analyze the interactions and impacts between PRS and the environment. The average concentration of PRS in China was 243.96 µg/kg which was lower than the levels reported in Euro-Americans and other nations. This study revealed PRS in China predominantly originates from organochlorine pesticide residues, with DDTs and HCHs being significant contributors. Despite the high intensity of pesticide application in the Southeast China, PRS concentrations were comparable to those in the Northeast, due to environmental factors that favor pesticide degradation in the Southeast. Both legacy and in-use pesticides were transported by surface runoff or air current, resulting in their accumulation in soil of the lower Yangtze River basin or the piedmont soil of Qinling Mountains, respectively. The average soil environment carrying capacity of PRS in China was -69.5 kg. The ecological risk contributed by PRS in China was mainly at a negligible level. Carcinogenic risks of PRS to adults (4.6 ×10-4) and children (6 ×10-4) exceeded the tolerable thresholds (10-5) by a small margin.

Novel Ultrasensitive Fluorescent Probe for Bioimaging Carboxylesterase and Detecting Pesticide Residues in Foods.

Pesticide residues pose a significant threat to food safety and human health, necessitating the development of novel detection tools. Pesticides can inhibit the activity of certain biological enzymes, so enzyme inhibition is one of the methods of pesticide detection. In this study, we developed a novel near-infrared fluorescent probe named TCFCl-CES based on the tricyanofuran structure, for ultrasensitive detection of carboxylesterase (CES). TCFCl-CES exhibits strong and stable fluorescence, excellent specificity. Notably, the fluorescence intensity of TCFCl-CES shows a linear relationship with CES concentration, achieving an exceptionally low detection limit of 4.41 × 10-5 u/mL. This ultrasensitive probe can also effectively detect pesticide residues in vegetables and monitor CES activity in cells and liver tissues. TCFCl-CES stands out for its rapid and accurate detection capabilities, making it an essential tool for accurately monitoring pesticide residue. It also has great potential for tracking CES activity in biological systems. Additionally, it offers a robust solution for food safety and improving pesticide residue analysis.

Decline pattern and dietary risk assessment of spinetoram in grapes under Egyptian field conditions.

Spinetoram is one of the most extensively used insecticides globally and is a new spinosyn-based insecticide registered for direct treatment of Egyptian grapes. This work established and validated a developed method for determining spinetoram in grape berries and leaves using the QuEChERS coupled LC-MS/MS technique. The average recoveries ranged between 98.52-101.19% and 100.53-104.93%, with RSDs of 2.74-6.21% and 2.79-7.26% for grape berries and leaves, respectively. Spinetoram residues degraded in grape berries and leaves through a first-order kinetic, with an estimated half-life (t1/2) of 4.3 and 2.8 days in grape berries and leaves, respectively, and significant degradation (91.4-97.5%, respectively) after 14 days. Besides, the terminal residues of spinetoram detected in grape berries and leaves samples ranged between 0.017-0.077 mg‧kg-1 and 0.79-0.023 mg·kg-1, respectively, when applied two to three times at a single recommended rate, while it was varied between 0.026-0.44mg‧kg-1 and 0.79-0.023mg‧kg-1 when applied two to three times at a double recommended rate, respectively. A dietary risk assessment was conducted using scientific data from field trials, acceptable daily intake (ADI), and food consumption. It was determined that no noteworthy health hazards were connected to eating grape berries and leaves that had been treated with spinetoram since the risk quotients (RQs) were ≤ 0.4.

Pesticide residues in European sediments: A significant concern for the aquatic systems?

The presence of pesticide residues in waterbed sediments poses a significant concern for aquatic ecosystems' health. This study examined pesticide contamination in sediments of 38 water bodies, embedded in agricultural-dominated regions, across eight European countries. Three indicators were targeted: occurrence, type, and concentrations of multiple pesticide residues in sediments. 196 pesticide residues (including degradation products) were tested in the sediment samples. The analytical results showed that only one sample was 'pesticide-free', three samples contained a single pesticide residue, and the remaining 34 samples contained mixtures of residues. Overall, 99 different residues were found in the sediments, with a maximum of 48 in a single sample. Twenty-seven out of the 99 detected residues were not approved for agricultural use at the time of sampling. The numbers of detected residues and pesticide levels varied among countries. AMPA, glyphosate and DDTs were the most common residues in sediment samples with frequencies of 76, 61, and 52%, respectively. The sediments from the Czech Republic had the highest pesticide concentrations, with total pesticide concentrations ranging between 600 and 1200 µg kg-1. The lowest total pesticide concentrations were found in Slovenia, Switzerland, Croatia, and Denmark, ranging between 80 and 120 µg kg-1. Sediments presented a mix of non-persistent and persistent compounds. Twelve of the detected pesticides are very persistent/stable in sediments, raising concerns about the long-term impacts of pesticides. Our study on the distribution of pesticide residues in European sediments provides valuable insights into the extent of pesticide contamination and possible risks of pesticides to water bodies' health. It also underlines the need for monitoring, research, and policy efforts to mitigate the impacts of pesticides, and to evaluate potential risks of re-use of dredged sediments.

Advances on multiclass pesticide residue determination in citrus fruits and citrus-derived products - A critical review.

The application of agrochemicals in citrus fruits is widely used to improve the quality of crops, increase production yields, and prolong post-harvest life. However, these substances are potentially toxic for humans and the ecosystem due to their widespread use, high stability, and bioaccumulation. Conventional techniques for determining pesticide residues in citrus fruits are chromatographic methods coupled with different detectors. However, in recent years, the need for analytical strategies that are less polluting for the environment has encouraged the appearance of new alternatives, such as sensors and biosensors, which allow selective and sensitive detection of pesticide residues in real time. A comprehensive overview of the analytical platforms used to determine pesticide residues in citrus fruits and citrus-derived products is presented herein. The review focuses on the evolution of these methods since 2015, their limitations, and possible future perspectives for improving pesticide residue determination and reducing environmental contamination.

Pesticide residues and polyphenols in urine - A combined LC-HRMS screening to reveal intake patterns.

Human exposure to pesticides in the general population occurs mainly through food consumption. However, specific dietary habits or food products that contribute to pesticide exposure are often unknown. In this study, we propose a combined screening for polyphenols and pesticide residues by liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS) to assess the diet and the associated pesticide exposure. We measured 587 urine samples from women around the 34th week of pregnancy of a prospective mother-child cohort. A non-targeted screening for flavonoid-like compounds related to fruit and vegetable consumption was performed, prioritizing 164 features and identifying a total of 46 features by spectral library search. Based on a subset of markers, k-means clustering was performed, leading to four clusters with presumably similar dietary habits. The clusters were compared against food questionnaire data collected within the period of sample collection. Suspect screening of more than 500 pesticide residues including metabolites was performed, with a total of 40 residues being reported for 27 different pesticides. The detection of pesticide residues was compared across the different clusters of dietary habits. Indications were found that pyrimethanil metabolites might be associated with the consumption of citrus fruits or derivate products. We demonstrate that the method used has the potential to reveal patterns of pesticide intake from specific food commodities.

Dissipation Kinetics and Residue Distribution of Imazethapyr in Urdbean (Vigna mungo (L.) Hepper) and Urdbean Field soil and its Effect on soil Microbial Population.

Imazethapyr is the most common herbicide used for weed management in pulses. A field trial was carried out with imazethapyr 10% SL formulation at 100 and 150 g a.i./ha application rates, as pre-and post-emergence, to study dissipation of imazethapyr in soil, persistence in urdbean plant, terminal residues in urdbean grains and effect on soil microbes. An acetate buffered- quick, easy, cheap, effective, rugged, and safe (QuEChERS) method in combination with high-performance liquid chromatography (HPLC) was validated for imazethapyr residue analysis. The half-life of imazethapyr in soil ranged from 15.12 to 18.02 days. The residues of imazethapyr persist up to 60 days in soil and up to 7-15 days in urdbean plant. Residues were not detected in grains at the time of harvest. Persistence of imazethapyr residues in soil significantly impact soil microbial populations depending on herbicide application rates and timing.

Pesticides and winemaking: A comprehensive review of conventional and emerging approaches.

The use of pesticides in viticulture may play a crucial role in ensuring the health and quality of grapes. This review analyzes the most common pesticides used, illustrating their classification and toxicity, and their variations throughout the winemaking process. Fungicides are generally harmless or mildly toxic, whereas insecticides are classified as either highly or moderately hazardous. Potential alternatives to synthetic pesticides in wine production are also reviewed, thereby including biopesticides and biological agents. Analytical methods for detecting and quantifying pesticide residues in wine are then described, including liquid chromatography and gas chromatography coupled with mass spectrometry. This review also discusses the impact of the winemaking process on pesticide content. Pesticides with strong hydrophobicity were more likely to accumulate in solid byproducts, whereas hydrophilic pesticides were distributed more in the liquid phase. Grape's skin contains lipids, so hydrophobic pesticides adsorb strongly on grape surfaces and the clarification has been shown to be effective in the reduction of hydrophobic compounds. Therefore, the final wine could have more quantities of hydrophilic pesticides. Alcoholic fermentation has been shown to be crucial in pesticide dissipation. However, pesticide residues in wine have been shown an antagonistic effect on yeasts, affecting the safety and quality of wine products. Therefore, proteomic and genomic analyses of yeast growth are reviewed to understand the effects of pesticides on yeast during fermentation. The last section describes new effective methods used in removing pesticides from grapes and wine, thereby improving product quality and reducing harmful effects.

Dietary Exposure to Pesticide and Veterinary Drug Residues and Their Effects on Human Fertility and Embryo Development: A Global Overview.

Drug residues that contaminate food and water represent a serious concern for human health. The major concerns regard the possible irrational use of these contaminants, since this might increase the amplitude of exposure. Multiple sources contribute to the overall exposure to contaminants, including agriculture, domestic use, personal, public and veterinary healthcare, increasing the possible origin of contamination. In this review, we focus on crop pesticides and veterinary drug residues because of their extensive use in modern agriculture and farming, which ensures food production and security for the ever-growing population around the world. We discuss crop pesticides and veterinary drug residues with respect to their worldwide distribution and impacts, with special attention on their harmful effects on human reproduction and embryo development, as well as their link to epigenetic alterations, leading to intergenerational and transgenerational diseases. Among the contaminants, the most commonly implicated in causing such disorders are organophosphates, glyphosate and antibiotics, with tetracyclines being the most frequently reported. This review highlights the importance of finding new management strategies for pesticides and veterinary drugs. Moreover, due to the still limited knowledge on inter- and transgenerational effects of these contaminants, we underlie the need to strengthen research in this field, so as to better clarify the specific effects of each contaminant and their long-term impact.

Analysis of Flutianil and OC56635 Residues in Hemp Cannabis Matrices by LC-MS/MS.

In this paper, we present analytical methodologies for the determination of the thiazolidine fungicide flutianil (trade name GATTEN) and its primary metabolite OC56635 in hemp cannabis matrices. A total of nine crop matrices were tested: whole seed, fiber, flower buds, hemp hearts, hemp seed oil, hemp meal, hemp flour, ethanol extracted CBD resin (CBD-E), and supercritical CO2 extracted CBD resin (CBD-C). Processing of the CBD-E and CBD-C crop fractions was carried out in-house using methods detailed herein. Field sample analysis utilized sequential extractions, stacked solid phase extraction (SPE) column cleanups, and evaporation to prepare the samples for LC-MS/MS quantitation. Method validations for each fraction were carried out using untreated hemp matrices over a minimum of three levels, with lowest levels of method validation (LLMV) of 0.010 µg/g for all fractions except the CBD resins, for which LLMV was 0.020 µg/g. Flutianil-treated samples from nine field sites were collected from several crop production regions and analyzed to determine the distribution of incurred flutianil and OC56635 residues within the different hemp matrices. This data was generated in support of nationwide registration with the United States Environmental Protection Agency (USEPA).

Pesticide safety practice and its public health risk in African regions: systematic review and meta-analysis.

BACKGROUND: Although pesticides play an integral role in food security and preventing public health from vector-borne diseases, inappropriate handling and continual use of restricted organochlorine pesticides pose short- and long-term adverse effects and become public health concerns in the African region. This study aimed to determine the combined level of protective equipment use, management of empty pesticide containers, and leftover pesticide residues in the African region. METHODS: The preferred reporting items for systematic reviews and the meta-analysis protocol were used to carry out this study. The Scopus, PubMed, Web of Science, Google Scholar, DOAJ, and National Repository databases were searched for articles published between November 12, 2023, and January 2, 2024. The meta-analysis data were visualized using a forest plot. A random-effects model was applied when heterogeneity existed in pooled studies. Subgroup analysis of the data was performed based on the location where the study was conducted and the publication year. Meta-regression and sensitivity analysis were performed to evaluate the robustness of the pooled prevalence of studies. Publication bias was assessed using a funnel plot. The authors used the Joanna Briggs Institute Critical Assessment tool to determine the quality of the studies. RESULTS: In this review, 2174 articles were identified from the included electronic databases, 24 of which were included in the present study. The study revealed that the combined mean prevalence of wearing a mask, glove, boot/safety shoes, overall wear, and head cover accounted for 18% (95% CI: 11.9 to 26.1%, p < 0.001), 18% (95% CI: 11.7 to 26.9%, p < 0.001), 23% (95% CI: 15.7 to 33.3%, p < 0.001), 26% (95% CI: 16.2 to 38.7%, p < 0.001), and 14% (95% CI: 8.90 to 22.0%, p < 0.001), respectively. The prevalence of pesticides stored in the living room and pesticide containers used for different purposes was 51% and 26%, respectively. CONCLUSIONS: Poor pesticide safety practices were identified. A substantial proportion of the respondents reported storing pesticide residues in their living rooms, and the reuse of pesticide empty containers. Regional institutions should lead the designing of safety strategies to reduce the public health risks of pesticide exposure.

Determination of hexachlorophene residue in fruits and vegetables by ultra-high performance liquid chromatography-tandem mass spectrometry.

A modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) -LC-MS/MS method was developed for the determination of hexachlorophene in fruits and vegetables. Samples were extracted by acetonitrile and then salted with an acetate buffer system. Extractants neutral alumina (Al-N), strong cation exchange silica gel bonded adsorbent (SCX) and graphitized carbon black (GCB) were used for sample purification. The method demonstrates excellent accuracy and reproducibility. Under optimized conditions, the correlation coefficients of hexachlorophene were higher than 0.995 in the range of 0.5-20 ng/mL. The limit of quantification (LOQ) was 2.0 µg/kg. The average recoveries, assessed at three spiked levels (2.0, 4.0, and 20.0µg/kg) across various matrices including cabbage, celery, tomato, eggplant, potato, radish, cowpea, chives, apple, peach, grape, citrus, bitter melon, banana and hami melon ranged from 72.0 to 100.5% with relative standard deviations from 3.2 to 9.8% (n = 6).

Novel electrochemiluminescence sensing platform for ultrasensitive detection of malathion residue in tea based on SiO2NSs doped Luminol/AgNPs as a signal amplification strategy.

To address the potential hazards of organophosphorus pesticides (OPs) residues in tea, an electrochemiluminescence (ECL) aptasensor based on functionalized nanomaterials was constructed in this work. Firstly, gold nanoparticles (AuNPs) were attached on the surface of multi-walled carbon nanotubes (MWCNTs) by the constant potential electrodeposition to form a compound, and it was utilized to provide excellent immobilization sites for complementary DNA (cDNA). Subsequently, composite nanomaterials were synthesized by a one-pot method with aminated Luminol/silver nanoparticles@silica nanospheres (NH2-Luminol/Ag@SiO2NSs). Finally, NH2-Luminol/Ag@SiO2NSs was combined with a malathion aptamer (Apt) to obtain signal probes (SPs) for the construction of an aptasensor. The aptasensor had a wide linear range (1×10-3-1×103 ng/mL) and a low limit of detection (LOD) (0.3×10-3 ng/mL). It had the virtues of high sensitivity, wonderful stability and excellent specificity, which could be used for the detection of malathion residue in tea. The work provides a proven way for the construction of a rapid and ultrasensitive aptasensor with low-cost.

Sensitive extraction of seven pesticide residues from environmental water with magnetic graphene oxide-based covalent organic framework.

The use of pesticides has increased with the development of agriculture. However, due to the trace content and the matrix's inherent complexity in environmental water, development of rapid and sensitive detection method present significant challenges in the analysis of pesticide residues. The study synthesized magnetic graphene oxide (MGO) by combining superparamagnetic nanoparticles with the easy modification of graphene oxide (GO). Covalent organic frameworks (COFs) were then modified to have a large specific surface area. Finally, magnetic graphene oxide-based covalent organic frameworks, namely MGO-COFs, were obtained with a spherical structure and used as magnetic solid-phase extraction materials, which was successfully used to determine the seven pesticide residues in environmental samples in conjunction with high performance liquid chromatography. The method has a wide linear range for the tested pesticides, with satisfactory correlation coefficients (R ≥ 0.099) and low detection limits (0.3-1.21 µg L-1). The correlation coefficients for all seven pesticides were high (R2 ≥ 0.9996). The spiked recoveries, exhibiting a range of 91.3 to 109 %, demonstrated that the developed MGO-COF-MSPE-HPLC-UV method is simple, efficient, and suitable for the analysis and detection of seven pesticide residues in environmental water.

Safety evaluation of Indocalamus Iatifolius McClure leaves based on acute toxicity, harmful metals, and 9 organochlorine residue determination.

To investigate the safety of Indocalamu Iatifolius McClur leaves sold in the market, a study was conducted using Indocalamu Iatifolius McClur leaves randomly collected from an online store and a large supermarket. Acute toxicity experiments were performed on mice, and their body weight was monitored for 14 days after administration. After the observation period, blood samples were collected for biochemical analysis, and organ pathology was examined. Then, the content of copper (Cu), lead (Pb), cadmium (Cd), mercury (Hg), arsenic (As), and the residues of nine organochlorine pesticides in Indocalamu Iatifolius McClur leaves were measured according to the National Food Safety Standard (GB/T5009-2003) and the pesticide residue determination methods in the 2020 edition of the Chinese Pharmacopoeia. The results showed that the mice in the Indocalamu Iatifolius McClur leaves (online store) group experienced mortality and severe liver and lung damage. The levels of lead, cadmium, mercury, arsenic, and the nine organochlorine pesticides met the relevant standards and regulations. However, the copper content in the Indocalamu Iatifolius McClur leaves (online store) group was nearly 80 times higher than that in the supermarket group. Mice in the Indocalamu Iatifolius McClur leaves (supermarket) group remained healthy without any abnormalities, and the levels of harmful metals and organochlorine pesticides complied with the standards and regulations. The study suggests the need for regulatory policies and safety standards for the sale of Indocalamu Iatifolius McClur leaves.