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A universal, green, and rapid lignin-based emulsive liquid-liquid microextraction (ELLME) method was established to detect nine triazole fungicides in water, juice, vinegar, and alcoholic beverages via UHPLC-MS/MS. By employing an environmentally friendly emulsifier (lignin), the proposed ELLME was compatible with more extractants, and not restricted to fatty acids. Due to the high amphiphilic properties and three-dimensional structure of lignin, the emulsion was quickly formed through several aspirate-dispense cycles of the green extractant (guaiacol) and lignin solution. And a micropipette was used for rapid microextraction. The limit of detection was 0.0002-0.0057 μg L -1 . The extraction recoveries and relative standard deviation were 81.7%-102.0% and 0.9%-7.1%, respectively. Finally, three green metric tools were used to verify the greenness of the whole procedure. The proposed lignin-based ELLME successfully emulsified green solvents, indicating that emerging solvents may be excellent alternatives as extractants in ELLME for pesticide residue analysis in food samples., Competing Interests: Declaration of competing interest The authors declare no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Benzothiazoles (BTHs), benzotriazoles (BTRs), and benzotriazole ultraviolet absorbers (BUVs) have garnered significant attention owing to their persistent nature in the environment and adverse impacts on aquatic organisms. However, there remains a dearth of investigations and studies conducted in tropical marine environments. In this study, we undertook the inaugural distributional survey and ecotoxicological relevance of BTHs, BTRs, and BUVs in seawater and sediments of the western South China Sea (WSCS). Elevated concentrations of BTHs, BTRs, and BUVs in the seawater and suspended particulate matter (SPM) were primarily observed in the Pearl River Estuary (PRE) and the western region of the WSCS, attributed to terrestrial runoff and hydrodynamic processes. Moreover, the transport of these compounds at the seawater-SPM interface was influenced by both the intrinsic properties of the contaminants and temperature variations. Spatially, concentrations of BTHs, BTRs, and BUVs in surface sediments exhibited a diminishing trend with increasing distance from the coast to offshore areas, reflecting notable anthropogenic impacts. Concentration profiles of these compounds in sediment cores displayed a bottom-up increasing trend, with total organic carbon (TOC) identified as the primary determinant governing their accumulation within sediment cores in the WSCS. Terrestrial runoff inputs and atmospheric deposition as major contributors to the occurrence of BTHs, BTRs, and BUVs in the WSCS. Simultaneously, the study underscores the non-negligible moderate mixture risk quotient associated with BTHs, BTRs, and BUVs in the sediments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Benzotriazoles (BTRs) and bisphenols (BPs), categorized as contaminants of emerging concern (CECs), pose significant risks to human health and ecosystems due to their endocrine-disrupting properties and environmental persistence. This study investigates the occurrence and behavior of nine BTRs and ten BPs in wastewater generated in a large-scale meat processing plant, evaluating the effectiveness of a modern mechanical-biological industrial on-site treatment plant in removing these contaminants, and based on the concentration levels from eleven sampling points at different stages of the treatment process. The method used to determine these micropollutants' concentration was ultrasound-assisted emulsification-microextraction for analytes isolation and gas chromatography-mass spectrometry for detection (USAEME-GC/MS). The results indicate that the rigorous quality control processes in the meat processing facility effectively limit the presence of these micropollutants, especially concerning BPs, which are absent or below detection limits in raw wastewater. While the concentrations of some of these micropollutants increased at different points in the treatment process, these values were relatively low, typically below one microgram per liter. Among the compounds analyzed, the only one present after completing the treatment was 5Cl-BTR (maximum concentration: 3007 ng/L), and these contamination levels are around seven times lower than the reference value associated with non-cancer health risk for drinking water. This study contributes to understanding these CECs in industrial wastewater and highlights the importance of effective treatment systems for environmental protection., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

In this work, 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole (AHMT) was pre-doped into agarose hydrogels; consequently, sustained hydrogel systems with modulated release performance were constructed for simple operation and recyclability in point-of-care detection of formaldehyde (FA). With the increase in FA concentrations, the absorbance response of the supernatant solutions showed linear relationships and the color of the reaction mixtures gradually increased. The detection limit was calculated to be 0.013 μg mL -1 . To verify its practical application, a simple, rapid and low-cost FA detection platform was built on the basis of the optimized conditions, and the method shows the merits of simplicity, high sensitivity and selectivity. More importantly, the developed hydrogels are recyclable and can be used at least five times without any loss in sensing performance. Significantly, the sensory hydrogels can be employed by non-skilled people for monitoring food safety and applied for the practical detection of FA in foods.

In the current study, a new magnetic sorbent (Fe 3 O 4 @2,6-diamino-4-(3,4-dihydroxyphenyl) pyridine-3,5-dicarbonitrile) was prepared as a new and efficient sorbent to be used in the magnetic solid-phase extraction method to extract tebuconazole and propiconazole as model compounds. In this regard, effective parameters such as pH of the sample solution, desorption volume, ionic strength, extraction time, desorption time, and amount of the magnetic sorbent were optimized using experimental design. In the optimal condition, the linear dynamic ranges for tebuconazole and propiconazole were between 0.5 and 200.0 µg/L. Also, the limits of detection, limits of quantification, and relative standard deviations were 0.21-0.14 µg/L, 0.49-0.45 µg/L, and 1.3%-4.6%, respectively. The estimated enrichment factors for tebuconazole and propiconazole were 22 and 28, respectively. The absolute recovery (AR%) values for tebuconazole and propiconazole were also 67% and 84%, respectively. Finally, the proposed method was used for determination of tebuconazole and propiconazole in cucumber, tomato, orange, and lemon fruits. The obtained result confirmed that the presented method is capable for the analysis of the selected analytes in complicated matrices. In addition, the ARs% were in the range of 67%-84%. The result proved that the presented method can be an alternative to the extraction process of various pesticides., (© 2024 Wiley‐VCH GmbH.)

Triazoles, due to their high bactericidal performance, have been widely used in the agricultural, clinical, and chemical industry. However, triazoles have been proven to cause endocrine-toxic and organ impairment in humans as a potentially toxic substance. Besides, because of the improper use and difficulty of degradation, triazoles pesticide residues left in the environment could pose a threat to the environment. Therefore, the rapid, reliable, accurate, and high-sensitivity triazoles analysis methods are significantly essential to effectively monitor their presence in various samples and safeguard human health. This review aims to summarize and update the progress of the pretreatment and analytical methods of triazole fungicides in environmental samples from 2012 to 2024. Common pretreatment methods used to extract and purify targets include simple steps (e.g., protein precipitation and coated blade spray), liquid-liquid extraction, solid-phase extraction, and various microextraction methods such as liquid-phase microextraction and solid-phase microextraction, among others. Detection methods mainly include liquid chromatography-mass spectrometry, gas chromatography-mass spectrometry, supercritical fluid chromatography, sensing methods, and capillary electrophoresis. In addition, we elaborate and compare the advantages and disadvantages of different pretreatment and analytical methods, and their development prospects are discussed., Competing Interests: Declaration of Competing Interest The authors declared that they have no conflicts of interest to this work., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Benzotriazoles are a class of ultraviolet absorbents which absorb UV ranging from 280 to 400 nm and are widely used in personal care products and industrial production. Their residues in environmental matrices have received great concern in recent years, but most studies have focused on pollution in water and few have examined BUVs in marine sediments. In this study, we investigated the occurrence, potential sources, and ecological risk of 15 types of BUVs in the sediments of Bohai Sea in China for the first time. The total concentrations of the 15 BUVs ranged from 0.139 to 4.125 ng/g dw with a median concentration of 0.340 ng/g. UV-327 and UV-360 were predominant among the BUV congeners, accounting for 22.6% and 17.7% of the total concentration of Σ 15 BUVs, respectively. The detection frequencies of the BUV congeners generally exceeded 95%, reflecting the wide use and persistence of these chemicals. The concentrations of the BUV congeners in this study were one order of magnitude lower than those in other areas. Moreover, the distributions of BUVs presented a decreasing gradient from nearshore to offshore, indicating that coastal input was the main influencing factor. Two potential primary sources, plastic manufacturing and domestic wastewater, were identified via principle component analysis. The ecological risks of BUVs to aquatic organisms in the sediments were evaluated using the risk quotient (RQ) method. Generally, the risk to aquatic organisms from exposure to BUVs in Bohai Sea could be considered low at the measured concentrations. While our study provides important new insight into the ecological risks of BUVs in the estuary, further research on the pollution levels and toxicity risks of BUVs in Bohai Sea should be conducted to better understand the ecological effect of these pollutants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Objective: The objective of this work is to develop a stability-indicating HPLC method for the quantification of posaconazole (PCZ) in tablet formulation using an Analytical Quality by Design (AQbD) approach., Materials and Methods: The development process involved the Design of Experiments (DOE) utilizing distinctive constraints mixture design for mobile phase ratio optimization and a 2-level factorial design for selection of extraction diluent compositions. Key responses measured included % assay and system suitability parameters. Method operable design regions (MODR) were determined, and final optimum conditions were selected. Forced degradation studies were conducted to assess method stability., Results: The optimized HPLC method employed a Zorbax C18 column with a mobile phase consisting of pH 3.5 10mM phosphate buffer, acetonitrile, and methanol in a ratio of 30:53:17% v/v/v. The method demonstrated stability-indicating capabilities, with PCZ degradation observed in acidic and oxidative environments, while remaining stable in alkali. Peak purity analysis from Empower software confirmed the absence of interaction with degradants. Validation according to ICH Q2 (R2) guidelines showed precision, linearity over the range of 0.25 to 376μg/mL, and accuracy demonstrated through recovery studies from 50 to 150%., Conclusion: The developed HPLC method utilizing AQbD approach is specific, robust, precise, and accurate for the quantification of PCZ in tablet formulations, thus suitable for routine analysis., (Copyright © 2024. Published by Elsevier Masson SAS.)

Efforts to regulate and monitor emerging contaminants are insufficient because new chemicals are continually brought to market, and many are unregulated and potentially harmful. Domestic wastewater treatment plants are not designed to remove micropollutants and are important sources of emerging contaminants in the aquatic environment. In this study, non-target screening, an unbiased method for analyzing compounds without prior information, was used to identify compounds that may be emitted in wastewater treatment plant effluent and should be monitored. Nine wastewater treatment plants using different treatment methods were studied, and a non-target screening data-processing method was used. The frequencies at which the contaminants were detected and contaminant persistence through the treatment processes were considered, and then the contaminants were prioritized. The predicted no-effect concentration of each prioritized contaminant was used to determine whether further analysis and monitoring of the contaminant was necessary. Quantitative analyses of five compounds (amantadine, atenolol, benzotriazole, diphenhydramine, and sulpiride) were performed using reference standards. Probable molecular formulae and structures were proposed for 17 contaminants, and the risks posed by the contaminants were estimated using predicted no-effect concentrations. The results provide valuable insights into how unregulated micropollutants can be identified and prioritized for monitoring in future studies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Avian droppings (combination of fecal matter and urates) provide a non-lethal and non-invasive matrix for measuring pesticide exposures. In the field, droppings may be collected days or weeks after excretion and the persistence of pesticide residues in weathered droppings is not known. Thus, we studied the effects of weathering on pesticide residues in droppings. Domestic chicken (Gallus gallus domesticus) hens were used as a representative species for Order Galliformes. We collected droppings from hens before they were exposed to the pesticides (reference or pre-dose droppings ). Thereafter, the hens were orally administered encapsulated wheat seeds coated with Raxil® PRO Shield (containing the active ingredients imidacloprid, prothioconazole, metalaxyl, and tebuconazole) for consecutive 7 days. During this time, their droppings were collected on days 3, 5, and 8 from the start of the exposure period (post-dose droppings ). The pre-dose and post-dose droppings were weathered for up to 30 days in autumn and spring in shrubsteppe habitat. Droppings were analyzed using HPLC coupled to triple quad LC/MS for parent compound and metabolite residues. No pesticide or its metabolite residues were detected in the weathered reference droppings. No parent pesticide compounds were detected in weathered post-dose droppings but imidacloprid metabolites, imidacloprid-5-hydroxy and imidacloprid-olefin, and the prothioconazole metabolite, desthio-prothioconazole, were detected in all post-dose weathered samples from both seasons. The active ingredients metalaxyl and tebuconazole and their metabolites were not detected in any of the samples. Our results suggest that, depending on the pesticide, its concentration, and the environmental conditions, residues of some pesticides can be detected in droppings weathered for at least 30 days. Knowledge of pesticide persistence in weathered droppings can help refine the quality and quantity of fecal samples that are collected for monitoring pesticide exposures to birds., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Nimish B. Vyas reports statistical analysis and writing assistance were provided by Fulbright Senior Award. Nimish B. Vyas reports administrative support and writing assistance were provided by US Fish and Wildlife Service. Nimish B. Vyas reports writing assistance was provided by Washington Department of Fish and Wildlife. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Published by Elsevier Inc.)

The environmental pollution and health effects caused by pesticide production have consistently garnered considerable research interest. In the present study, the concentrations of five triazole fungicides (TFs) in air, indoor dust, and diet were monitored around a pesticide factory in eastern China from November 2020 to May 2021. The levels of five TFs in each sample were determined via UPLC‒MS/MS. For a health risk assessment, the United States Environmental Protection Agency's deterministic method was applied. The findings revealed that the total concentrations of the five TFs around the monitoring area ranged from 0.29 to 5.85 ng/m 3 in outdoor air, 287.4 to 9878.5 μg/kg in indoor dust, 0.0578 to 4.948 μg/kg in vegetables, and 0.447 to 3.00 μg/kg in rice. Notably, tebuconazole and hexaconazole had consistently high contributions over the years. For adults and children, the average daily doses (ADDs) were 1.32 × 10 -5 and 2.69 × 10 -5  mg/kg/day, respectively, in the monitoring area and 4.25 × 10 -6 and 6.42 × 10 -6  mg/kg/day, respectively, in the control area. In the control area, rice and vegetables were the primary media for exposure to TFs in children and adults, collectively accounting for more than 94% of the total TF exposure. Conversely, indoor dust is identified as the main medium of TF exposure in children residing near the pesticide factory, representing approximately 40% of the total exposure. The risks of noncarcinogenic effects on children and adults in the monitoring area were significantly greater than those in the control area, being approximately ten times greater for children, warranting increased attention. The carcinogenic risk to human health is relatively safe., (© 2024. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

Understanding the occurrence and fate of current-use pesticides (CUPs) in coastal and open marine waters is essential for conducting exposure and risk assessments to ensure the protection of marine ecosystems from chemical pollution. While CUPs have been frequently studied in freshwater systems, knowledge of their behavior in marine environments remains fragmentary. This study investigated 28 CUPs across 50 sites along a transect from the Baltic outflow to pristine Arctic waters using ships of opportunity with installed FerryBox system. Overall, 14 CUPs were detected at least at one site at concentrations ranging from sub-ng/L to ng/L. CUP concentrations were higher in the Baltic outflow and decreased along the transect. Atrazine, simazine, tebuconazole, and propiconazole were detected in > 40 % of samples, including remote open sea regions, suggesting their potential for long-range marine transport. This Baltic Sea was identified as a major source of CUPs to connected marine systems. Additional CUPs were detected in the Baltic outflow, encompassing diuron, isoproturon, metazachlor, metolachlor, pyrazon, terbuthylazine, and chlortoluron. Ecotoxicological assessment indicated a moderate risk posed by metolachlor to algae. The use of the described infrastructure holds great promise for advancing our understanding of the occurrence and fate of CUPs in marine environments., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Benzotriazoles (BTR) and bisphenols (BP) are artificial contaminants of emerging concern (CECs) commonly found in everyday products. This study focuses on urban runoff to investigate the occurrence of BTRs and BPs in Iceland, regarded as one of the least polluted places in the world, which made it reasonable to confirm or deny the presence of these micropollutants in its environment. Samples collected in February 2023 (SC1) and August 2024 (SC2) from seven locations along Iceland's Ring Road were evaluated to determine the occurrence of seven BTRs (1H-BTR, 4Me-BTR, 5Me-BTR, 5Cl-BTR, UV-P, UV-326, UV-329) and six BPs (BPF, BPE, BPA, BPZ, BPAP, BPM) in the runoff, using the ultrasound-assisted emulsification-microextraction for analytes isolation and gas chromatography-mass spectrometry for detection (USAEME-GC/MS). All locations showed detectable and varying levels of BTRs and BPs, with 5Cl-BTR (11.6 μg/L) and BPF (56.3 μg/L), both in SC1, demonstrating the highest concentrations, providing valuable insights into their prevalence and distribution. A correlational analysis investigated the connection between these pollutants and various characteristics associated with the locations along the Ring Road. This study contributes to the essential comprehension of these CECs, serving as input for future strategies for monitoring and mitigating their impact., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Benzotriazole ultraviolet absorbers (BUVs), as emerging contaminants of extensive use, especially in plastic sports fields, have aroused increasing concern due to their potential human and environmental impacts. However, BUV exposure from plastic sports field dust is still unknown. This study compared BUVs in plastic sports field dust and indoor dust for the first time. The order of the geometric mean concentrations of the total BUVs (ΣBUVs) in plastic sports field dust was indoor badminton courts (11023 ng g -1 ) > basketball courts (4777 ng g -1 ) > plastic tracks (3779 ng g -1 ) > synthetic turf (1920 ng g -1 ) > tennis courts (689 ng g -1 ). The geometric mean concentrations of ΣBUVs in indoor dust (1150 ng g -1 ) were lower than those in most plastic sports field dust. The dominant BUV was 2-hydroxy-4-(octyloxy)benzophenone (UV-531) in plastic sports field dust, while 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-2H-benzotriazole-2-yl)phenol] (UV-360) was the dominant BUV in indoor dust. Releases from plastic track materials, sneaker soles, and friction between them might be important BUV sources in plastic track dust. The average estimated daily intakes of ΣBUVs from plastic sports field dust for general exercisers were lower than those from indoor dust, but those for exercisers with long time or professional athletes might be higher, potentially posing health risks.

A rapid, simple and highly sensitive stability-indicating reverse-phase high-performance liquid chromatographic technique, coupled with a photodiode array detector, was developed and validated for the estimation of Deferasirox (DFS). The chromatographic separation was achieved using a C-18 (250 × 4.6 mm, 5 μm) stationary phase and a mobile phase composed of 0.1% orthophosphoric acid and acetonitrile at a flow rate of 1 mL/min. The detection was carried out at a wavelength of 245 nm with a constant injection volume of 10 μL throughout the analysis. With an R2 value of 0.9996, the calibration curve was determined to be linear over an appropriate concentration range of 50-500 ng/mL. According to the International Conference on Harmonization (ICH) Q1 (R2) guideline, DFS was evaluated under stress conditions that included hydrolytic (acid, alkali and neutral), oxidative and thermal degradation. The findings demonstrated that significant degradation was observed in acidic degradation conditions, whereas drug substance was found to be stable when exposed to neutral, basic, oxidative and thermal degradation. The developed method was validated as per ICH guidelines. The developed method was employed successfully to estimate the amount of DFS in bulk and pharmaceutical formulation., (© The Author(s) 2023. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

Graphite carbon nitride (g-C 3 N 4 ) is a two-dimensional nano-sheet with electronic properties, which shows unique characteristics with high chemical and thermal stability in its structure. The functionalization of these compounds through covalent bonding is an important step towards significantly improving their properties and capabilities. To achieve this goal, a novel strategy for the covalent functionalization of Fe 3 O 4 @g-C 3 N 4 with thiamine hydrochloride (vitamin B1) via cyanuric chloride (TCT), which is a divalent covalent linker, was presented. The efficiency of Fe 3 O 4 @gC 3 N 4 @Thiamine as a heterogeneous organic catalyst in the synthesis of spirooxindole-pyran derivatives and 2-amino-4H-pyran under solvent-free conditions was evaluated and the yields of high-purity products were presented. In addition, easy recycling and reuse for seven consecutive cycles without significant reduction in catalytic activity are other features of this catalyst. Moreover, the performance of the prepared sorbent in the microextraction technique (herein, magnetic solid phase extraction) was studied. The tebuconazole was selected as the target analyte. The target analyte was extracted and determined by HPLC-UV. Under the optimum condition, the linear range of the method (LDR) was estimated in the range of 0.2-100 μg L -1 (the coefficient of determination of 0.9962 for tebuconazole). The detection limit (LOD) of the method for tebuconazole was calculated to be 0.05 µg L -1 . The limit of quantification (LOQ) of the method was also estimated to be 0.16 µg L -1 . In order to check the precision of the proposed method, the intra-day and inter-day relative standard deviations (RSD%) were calculated, which were in the range of 1.5- 2.8%. The method was used for the successful extraction and determination of tebuconazole in tomato, cucumber, and carrot samples., (© 2024. The Author(s).)

Tebuconazole is one of the most commonly used fungicides in agricultural production, that has the merits of highly effectiveness, broad spectrum and systemic function. Excessive tebuconazole may pose a great threat to human and animal health. Traditional detection techniques for tebuconazole usually have limitations such as expensive equipment, poor antibody stability, and time-consuming procedures. Herein, a sensitive sensor is developed for the rapid detection of tebuconazole based on hydrogel surface-enhanced Raman scattering (SERS) chips. Aggregated Ag nanoparticles (a-AgNPs) with tunable localized surface plasmon resonance (LSPR) wavelength are in-situ synthesized in polyvinyl alcohol (PVA) solution for preparing hydrogel SERS chips. Three hydrogel SERS chips are obtained to match the three commonly used laser wavelengths. On the basis, a match laser wavelength is selected according to the energy levels of tebuconazole and the Fermi level of a-AgNPs to gain a strong chemical enhancement. At the same time, the chip with a corresponding LSPR wavelength to the laser is applied to obtain a strong electromagnetic enhancement. Thus, highly sensitive SERS signal of tebuconazole is obtained. Furthermore, the obtained hydrogel SERS chips have good repeatability, outstanding reproducibility and strong anti-interference ability, and show outstanding reliability in practical applications. As a result, the SERS chips offer a reliable and convenient platform for the quick detection of tebuconazole in foods. The detection limit is as low as 1 ppb, and the recoveries is distributed in the range of 94.66-106.70 %. This work would promote greatly the application of SERS in small molecule detection., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Benzotriazole-type ultraviolet stabilizers (BUVSs) are emerging contaminants whose exposure to wildlife is of concern. In this study, we investigated the contamination status of BUVSs in green turtles (Chelonia mydas) breeding at Ogasawara Islands, Japan, through chemical analysis of 10 BUVSs and 26 congeners of polychlorinated biphenyls (PCBs) in adipose tissue (n = 21) and blood plasma (n = 9). BUVSs were detected significant levels in adipose tissue (19 of 21 turtles), and UV-327 (not detected - 14.8 ng/g-lipid, detection frequency: 76 %), UV-326 (not detected - 24.1 ng/g-lipid, 29 %), and UV-328 (not detected - 5.8 ng/g-lipid, 24 %) were frequently detected. Turtles exhibiting sporadically high concentrations of BUVSs (>10 ng/g-lipid) did not necessarily correspond to individuals with high total PCB concentrations (1.03-70.2 ng/g-lipid). The sporadic occurrence pattern of BUVSs suggested that these contaminants in sea turtles cannot be explained solely by diet but are likely derived from plastic debris., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Dissipative behavior and final residue levels of difenoconazole, prochloraz, propiconazole, and pyraclostrobin in figs were investigated using field trials and laboratory assays. A three-factor, three-level orthogonal test was designed to optimize the pretreatment conditions of the method. A method was established using high-performance liquid chromatography tandem mass spectrometry for the determination of difenoconazole, prochloraz, propiconazole, and pyraclostrobin residues in figs. The limit of quantification for all four targets in figs was 0.002 mg/kg. Difenoconazole, prochloraz, propiconazole, and pyraclostrobin are readily digestible pesticides in figs with half-lives of 6.4, 6.2, 4.8, and 7.9 days, respectively. Residues of difenoconazole, prochloraz, propiconazole, and pyraclostrobin in figs were below the European Union established residue levels of 0.1, 0.03, 0.01, and 0.02 mg/kg, respectively, at day 7 after application. Pyraclostrobin, propiconazole, difenoconazole, and prochloraz were applied twice at doses of 75, 125, 150, and 200 mg a.i./kg at 7-day intervals, and the residues of the four fungicides in figs were acceptable 7 days after the last application. Therefore, the safety interval can be set at 7 days for 70% difenoconazole-prochloraz wettable powder and 40% pyraclostrobin-propiconazole aqueous emulsion according to the protocol., (© 2024 John Wiley & Sons Ltd.)

Pharmaceutical care is important for mental health during the perinatal period, which is often characterized by insomnia. In recent years, prescriptions of melatonin receptor agonists (MRAs) and dual orexin receptor antagonists (DORAs) for insomnia have increased; however, their use during the perinatal period has scarcely been reported. In the present study, we developed a UPLC-MS/MS method for the quantification of ramelteon, its metabolite M-II, suvorexant, and lemborexant in human plasma and breast milk to accumulate information on the safety and transfer of MRAs and DORAs into breast milk. Samples of MRAs (ramelteon and M-II) in plasma and breast milk were prepared using liquid-liquid extraction (LLE) with ethyl acetate. For DORAs (suvorexant and lemborexant), LLE with ethyl acetate was applied to plasma samples. For breast milk samples, significant ion suppression was observed for LLE with ethyl acetate. Solid-phase extraction (SPE) cartridges capable of removing phospholipids improved the matrix effects. Finally, protein precipitation with methanol and an SPE cartridge, InertSep® Phospholipid Remover, were selected for breast milk sample preparation. An ACQUITY UPLC BEH C18 column was used for analyte separation. MRAs and DORAs were eluted using isocratic and gradient elution, respectively, and analyzed using electrospray ionization in the positive mode with multiple reaction monitoring. The range of calibration curve for MRAs and DORAs was 0.1-25 and 0.5-50 ng/ml, respectively. Both the plasma and breast milk samples exhibited good linearity over this range. The method was validated by evaluating its accuracy and precision, matrix effect, recovery, carry-over, stability, and dilution integrity. The validated method was successfully applied to clinical samples donated by breastfeeding women and the milk/plasma (M/P) ratio and relative infant dose (RID) of lemborexant (one case) and suvorexant (two cases) were estimated. The M/P ratio of lemborexant was <1, and the RID was 1.05 %. The M/P ratio of suvorexant was <0.1, and RID was 0.11-0.20 %. This method will be useful for future studies evaluating the safety of these drugs during breastfeeding., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Shuhei Ishikawa reports a relationship with Janssen Pharmaceutical, Otsuka Pharmaceutical, Sumitomo Pharma, EISAI, and MeijiSeika Pharma, Eli Lilly that includes: funding grants and speaking and lecture fees. Ayako Furugen is currently affiliated with the Laboratory of Healthcare Innovation Pharmacy, Faculty of Pharmacy, Keio University. This laboratory is supported by Sato Pharmaceutical Co., Ltd. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Cucumber (Cucumis sativus L.) is the world's most widely consumed salad vegetable, and it is frequently treated with pesticides to prevent pest and disease outbreaks. Pesticide residues in food commodities impede trade and pose a major health risk. Prior to residue estimation, the QuEChERS approach was validated utilising criteria such as limit of detection, limit of quantitation, linearity, accuracy, and precision. The residues of carbendazim, cypermethrin, ethion, profenofos, quinalphos, and triazophos were examined using a Gas Chromatograph equipped with an Electron Capture Detector or a Flame Photometric Detector and a high-performance liquid chromatography coupled to a photo diode array. The initial deposits of carbendazim, cypermethrin, ethion, profenofos, quinalphos, and triazophos at the prescribed dose were 1.235, 0.407, 0.817, 0.960, 0.628, and 0.985 mg/kg, respectively, with a pre-harvest interval of 5.58-11.30 days. According to the consumer risk evaluation data, the Hazard Quotient is less than one, and the Theoretical Maximum Dietary Intake is less than the Maximum Permissible Intake and Maximum Residue Limit, both of which are considered safe for human consumption at the authorised dose., (© 2024. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

For addressing the challenges of strong affinity SERS substrate to organophosphorus pesticides (OPs), herein, a rapid water-assisted layer-by-layer heteronuclear growth method was investigated to grow uniform UiO-66 shell with controllable thickness outside the magnetic core and provide abundant defect sites for OPs adsorption. By further assembling the tailored Au@Ag, a highly sensitive SERS substrate Fe 3 O 4 -COOH@UiO-66/Au@Ag (FCUAA) was synthesized with a SERS enhancement factor of 2.11 × 10 7 . The substrate's suitability for the actual vegetable samples (cowpeas and peppers) was confirmed under both destructive and non-destructive detection conditions, showing a strong SERS response to fenthion and triazophos, with limits of detection of 1.21 × 10 -5 and 2.96 × 10 -3 mg/kg in the vegetables under destructive conditions, and 0.13 and 1.39 ng/cm 2 for non-destructive detection, respectively. The FCUAA substrate had high SERS performance, effective adsorption capability for OPs, and demonstrated good applicability, thus exhibiting great potential for rapid detection of trace OPs residues in the food industry., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier B.V. All rights reserved.)

Rosa roxburghii ( R. roxburghii ) is a unique, edible, medicinal fruit rich in vitamin C found in Southwest China. Triadimefon (TDF) is a triazole fungicide that is widely used to control powdery mildew in R. roxburghii . To assess the safety of TDF in R. roxburghii , an LC-MS/MS method was developed for the simultaneous quantification of TDF and its major metabolite, triadimenol (TDN) in R. roxburghii. Both TDF and TDN showed high correlation coefficients (>0.999) for the solvent- and matrix-matched calibrations. The recovery rates of TDF and TDN in R. roxburghii ranged from 90.18% to 100.42%, with a relative standard deviation ( RSD ) of 1.25%-9.22%. The limit of quantification ( LOQ ) was 0.01 mg·kg -1 . The half-life of TDF in R. roxburghii was between 2.74 and 3.07 days, with terminal residues ranging from <  LOQ to 1.84 mg·kg -1 . Recommended maximum residue limits ( MRL s) and safe pre-harvest intervals ( PHI s) for TDF in R. roxburghii were 0.5 mg·kg -1 and 21 days, respectively. This study provides essential data for TDF's safe and judicious use in R. roxburghii production.

In this work, the electrochemical behavior of 4-phenylurazole (Ph-Ur) was studied and the latter was used as a molecular anchor for the electrochemical bioconjugation of tyrosine (Y). Cyclic voltammetry (CV) and controlled potential coulometry (CPC) allowed the in-situ generation of the PTAD (4-phenyl-3 H-1,2,4-triazole-3,5(4 H)-dione) species from phenylurazole on demand for tyrosine electrolabeling. The chemoselectivity of the reaction was studied with another amino acid (lysine, Lys) and no changes in Lys were observed. To evaluate the performance of tyrosine electrolabeling, coulometric analyses at controlled potentials were performed on solutions of phenylurazole and the phenylurazole-tyrosine mixture in different proportions (2:1, 1:1, and 1:2). The electrolysis of the phenylurazole-tyrosine mixture in the ratio (1:2) produced a charge of 2.07 C, very close to the theoretical value (1.93 C), with high reaction kinetics, a result obtained here for the first time. The products obtained were identified and characterized by liquid chromatography coupled to high-resolution electrospray ionization mass spectrometry (LC-HRMS and LC- HRMS 2 ). Two products were formed from the click reactions, one of which was the majority. Another part of this work was to study the electrochemical degradation of the molecular anchor 4-phenylazole (Ph-Ur). Four stable degradation products of phenylurazole were identified (C 7 H 9 N 2 O, C 6 H 8 N, C 6 H 8 NO, C 14 H 13 N 4 O 2 ) based on chromatographic profiles and mass spectrometry results. The charge generated during the electrolysis of phenylurazole (two-electron process) (2.85 C) is inconsistent with the theoretical or calculated charge (1.93 C), indicating that secondary/parasitic reactions occurred during the electrolysis of the latter. In conclusion, the electrochemically promoted click phenylurazole-tyrosine reactions give rise to click products with high reaction kinetics and yields in the (1:2) phenylurazole-tyrosine ratios, and the presence of side reactions is likely to affect the yield of the click phenylurazole-tyrosine reaction., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

This study conducted the development of an advanced risk assessment algorithm system and safety management strategies using pesticide residue monitoring data from soils. To understand the status of pesticide residues in agricultural soils, monitoring was performed on 116 types of pesticides currently in use across 300 soil sites. The analysis of the monitoring results, alongside the physicochemical properties of the pesticides, led to the selection of soil half-life as a critical component in residue analysis. The use of Toxicity Exposure Ratio (TER) and Risk Quotient (RQ) for environmental risk assessment, based on monitoring data, presents limitations due to its single-component, conservative approach, which does not align with actual field conditions. Therefore, there is a necessity for a risk assessment process applicable in real-world scenarios. In this research, an efficient and accurate risk assessment algorithm system, along with a safety management model, was developed. Using the physicochemical properties of pesticides (such as soil half-life), monitoring results, and toxicity data, cluster analysis and Principal Component Analysis (PCA) validation identified four pesticides: boscalid, difenoconazole, fluquinconazole, and tebuconazole. The k-mean cluster analysis selected three priority management sites where the contribution of these four pesticides to the RQ was between 94-99 %, showing similar results to the RQ calculated for all pesticides. Predictions made with the developed model for the time required for soil half-life based RQ to drop below 1 at these priority sites showed only a 1-9 day difference between the four pesticides of concern and all pesticides, indicating comparable outcomes. The scenario of replacing high-risk pesticides with those of lower risk demonstrated that the RQ could be consistently maintained at about 50 % level. The results of this study suggest that through monitoring, evaluation, and management, effective and accurate environmental safety management of pesticides in soil can be achieved., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Today, the wide use of triazole fungicides due to environmental damage and its side effects has raised global concern. Hence, in this research, poly-vinyl alcohol/polyacrylic-acid/CoFe-PBA@GO electrospun nanofiber was synthesized and applied as effective, degradable, and novel adsorbent at pipette-tip microextraction (PT-μSPE) method for the rapid and concurrent extraction of five of triazole fungicides in fruit and vegetable samples prior to quantitative analysis by high-performance liquid chromatography-ultraviolet. The incorporation of CoFe-PBA@GO with superporous structure and abundant functional groups in a polymer medium improves the extraction efficiency of nanofibers due to hydrogen bonding and π-π interactions formed between analytes and synthesized nano-adsorbent. Various important elements that affect the extraction yield of the target analytes were optimized utilizing a time-variable approach. Under the optimum conditions, dynamic range was attained in the range of 0.3-900.0 ng/mL with correlation coefficients ≥ 0.999. The identification limit of the PT-μSPE-HPLC-UV method ranged from 0.1 to 0.3 ng/mL., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

UV filters and benzotriazole UV stabilizers are considered emerging contaminants in the environment. LC-MS/MS and GC-MS methods, involving a single solid phase extraction protocol, were developed and validated to determine eight UV filters and seven UV stabilizers, respectively in wastewater from a wastewater treatment plant (WWTP) in Lüneburg, Germany. The LC-MS/MS method exhibited extraction recoveries of ≥ 71% at six different fortification levels with limits of detection (LODs) range of 0.02 ng mL -1 - 0.09 ng mL -1 . Extraction recoveries of 47 to 119% at six different fortification levels were obtained for the GC-MS method with LODs range of 0.01 - 0.09 ng mL -1 . Among the UV filters, the highest mean concentration was determined for octocrylene (OCR) in influent (3.49 ng mL -1 ) while the highest mean concentration was measured for 2-hydroxy-4-octyloxybenzophenone (UV 531) in influent (0.44 ng mL -1 ) among the UV stabilizers. Potential risk to aquatic organisms was assessed by the risk quotient approach. Only OCR presented a high risk to aquatic invertebrates whereas 2-ethylhexyl 4-methoxycinnamate (EHMC) and 2-ethylhexyl salicylate (EHS) posed high risks to algae. Benzotriazole UV stabilizers presented negligible risks to aquatic invertebrates and fish. This work reports the detection of rarely studied 4-aminobenzoic acid (PABA) and UV 531 in WWTP influent and effluent. The occurrence and risk assessment of target benzotriazole UV stabilizers in wastewater from a German WWTP was demonstrated for the first time., (© 2024. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

This study aimed to investigate the dissipation pattern, risk assessment, and waiting period of myclobutanil on apple fruit (Malus domestica Borkh.) under temperate conditions in Kashmir, India. The study involved the application of myclobutanil 10 WP at a single recommended dosage (125 g a.i. ha -1 ) and double dosage (250 g a.i. ha -1 ) on Red Velox apple trees, 2 months before harvest. GC equipped with an electron capture detector was used to analyze myclobutanil residues in fruit samples. The study revealed that myclobutanil, at both recommended and double recommended doses, dissipated rapidly and became nondetectable after 55 and 60 days, respectively. The waiting period for myclobutanil application was determined to be 12.41 days for the single dose and 25.58 days for the double dose, respectively. These waiting periods were based on the maximum residue limit of 0.6 ppm as prescribed by the Codex Alimentarius Commission, Food Safety and Standards Authority of India, and European Commission. The study concludes that myclobutanil 10 WP is safe for consumers at both recommended and double recommended doses when applied 2 months before harvest. Risk assessment, considering the average daily apple consumption in India and theoretical maximum residue contributions (TMRCs), indicates negligible health hazards even at double the recommended dosage. The calculated TMRC values at Day 0 were significantly below the maximum permissible intake. For average and maximum myclobutanil residues at single and double doses, the TMRC values were found to be 0.0069 and 0.0070 mg day -1 person -1 and 0.0105 and 0.0106 mg day -1 person -1 , respectively. These results indicate that myclobutanil, when used according to recommended dosages and waiting periods, poses minimal health risks to consumers. The study emphasizes the importance of prudent fungicide use to minimize fungicide residues on fruits, thereby ensuring their safety for consumption., (© 2024 John Wiley & Sons Ltd.)

Although antiretroviral therapy (ART) is highly effective for the treatment of HIV-1 infection to suppress virus in the blood, HIV persists in tissues. HIV persistence in the tissues is due to numerous factors, and one of those factors are antiretroviral (ARV) concentrations. ARV concentrations in tissues must be adequate to suppress HIV at the sites of action. While therapeutic drug monitoring in the plasma is well-known, drug monitoring in the tissues provides local assessments of adequate ARV exposure to prevent localized HIV resistance formation. Towards these efforts, we validated an ultra-high performance liquid chromatography-mass spectrometry (UHPLC-MS/MS) method in human tissues (cervical, rectal, and vaginal tissues) for the simultaneous quantification of five ARVs: bictegravir, cabotegravir, dolutegravir, doravirine, and raltegravir. For this assay, protein precipitation with acetonitrile with stable, isotopically-labeled internal standards followed by supernatant pre-concentration was performed. Analyte separation was accomplished using a multistep UPLC gradient mixture of 0.1 % formic acid in water (A) and acetonitrile (B) with a Waters Cortecs T3 (2.1x100 mm) column. The assay was extensively validated as per the United States Food and Drug Administration Bioanalytical Method Validation Guidance over a clinically observed range (0.05-50 ng/mL) with superb linearity (R2 > 0.99 across all ARVs). The assay run time was 8.5 min. This analytical method achieves appropriate performance of trueness (85.5-107.4 %), repeatability, and precision (CV < 15 %). Our method will be employed for the therapeutic monitoring of guideline-recommended ARVs in human tissues for monitoring therapeutic efficacy in HIV treatment and prevention research efforts., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Sharon A. Riddler reports a relationship with Gilead Sciences Inc that includes: funding grants. Sharon A. Riddler reports a relationship with Merck & Co Inc that includes: funding grants. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Prothioconazole and its metabolite are considered a potential threat to human health and environmental safety. Thus, the development of a sensitive and rapid detection method for prothioconazole is crucial to ensure the safety of agricultural products. In this study, a new hapten of prothioconazole was designed and synthesized, and a selective polyclonal antibody with high affinity against prothioconazole was produced, which was obtained from immunized New Zealand white rabbits. Based on the polyclonal antibody, an indirect competitive enzyme-linked immunosorbent assay (ic-ELISA) and indirect competitive chemiluminescence enzyme immunoassay (ic-CLEIA) were developed for detecting prothioconazole pesticides. Under optimized experimental conditions, the limit of quantification (LOQ) values for ic-CLEIA and ic-ELISA were 1.8 and 10.7 ng mL -1 , respectively. The results demonstrated that the sensitivity (LOQ) achieved by ic-CLEIA was more than five times higher compared to that obtained with ic-ELISA. In addition, the recoveries obtained by adding standard prothioconazole to wheat grain, soybean, and pond water samples were in the range of 81.9 to 104.7% for ic-ELISA and 89.0 to 118.0% for ic-CLEIA.

Substituted diphenylamine antioxidants (SDPAs) and benzotriazole UV stabilizers (BZT-UVs) are industrial additives of emerging environmental concern. However, little is known about their environmental fate and bioaccumulation. This study investigated the concentrations of SDPAs and BZT-UVs in the water, sediment and biota samples in the freshwater ecosystem and adjacent riparian environment using Hamilton Harbour in the Great Lakes of North America as a study site. The bioaccumulation factors and trophodynamics of these contaminants were studied using field-collected samples. Eight target SDPAs and two BZT-UVs (2-(2 H -benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (UV234) and 2-(2 H -benzotriazol-2-yl)-4,6-di- tert -pentylphenol (UV328)) were frequently detected in the sediment, water and biota samples. UV328 showed significantly greater concentrations in water (0.28-2.8 ng L -1 ) and sediment (8.3-48 ng g -1 , dry weight) than other target contaminants, implying greater contamination of UV328 in Hamilton Harbour. SDPAs exhibited trophic dilution in species living in the water, whereas UV234 was biomagnified in the same samples. No clear trophodynamic trend was found for UV328 for water-respiring species. Air-breathing invertebrates had higher concentrations of both SDPAs and BZT-UVs than water-respiring invertebrates, and biomagnification was observed particularly for adult dragonflies. These results suggest that the trophodynamics of SDPAs and BZT-UVs vary depending on whether the food web is terrestrial or aquatic. Future research should investigate the occurrence and partitioning of SDPAs and BZT-UVs in the air-water interface and evaluate the toxicities of these contaminants in air-breathing species.

Quantum mechanics (QM)-driven 1H i terative f unctionalized s pin a nalysis produces HifSA profiles, which encode the complete 1 H spin parameters ("nuclear genotype") of analytes of interest. HifSA profiles enable the establishment of digital reference standards (dRS) that are portable, FAIR (findable - accessible - interoperable - reusable), and fit for the purpose of quantitative 1 H NMR (qHNMR) analysis at any magnetic field. This approach enhances the sustainability of analytical standards. Moreover, the analyte-specific complete chemical shift and J -coupling information in HifSA-based dRS enable computational quantitation of substances in mixtures via QM-total-line-shape fitting (QM-qHNMR). We present the proof of concept for HifSA-based dRS by resolving the highly overlapping NMR resonances in the experimental spectra ("nuclear phenotypes") of the diastereomeric mixture of (2 RS , 4 RS )- and (2 RS , 4 SR )-difenoconazole (DFZ), a widely used antifouling food additive. The underlying 1 H spin parameters are highly conserved in various solvents, are robust against variation in measurement temperature, and work across a wide range of magnetic fields. QM-qHNMR analysis of DFZ samples at 80, 400, 600, and 800 MHz showed high congruence with metrological reference values. Furthermore, this study introduces QM-qHNMR combined with chiral shift reagents for the analysis of all four DFZ stereoisomers: (2 R , 4 R )-, (2 S , 4 S )-, (2 R , 4 S )-, and (2 S , 4 R )-DFZ to perform chiral qHNMR measurements.

The study evaluated Ceremonia 25 EC®, a plant protection product (PPP) containing difenoconazole, in tomato crops, to identify potential risks associated with PPPs, and in addition to this compound, known metabolites from difenoconazole degradation and co-formulants present in the PPP were monitored. An ultra high performance liquid chromatography coupled to quadrupole-Orbitrap mass analyser (UHPLC-Q-Orbitrap-MS) method was validated with a working range of 2 μg/kg (limit of quantification, LOQ) to 200 μg/kg. Difenoconazole degradation followed a biphasic double first-order in parallel (DFOP) kinetic model in laboratory and greenhouse trials, with high accuracy (R 2  > 0.9965). CGA-205374, difenoconazole-alcohol, and hydroxy-difenoconazole metabolites were tentatively identified and semi-quantified in laboratory trials by UHPLC-Q-Orbitrap-MS from day 2 to day 30. No metabolites were found in greenhouse trials. Additionally, 13 volatile co-formulants were tentatively identified by gas chromatography (GC) coupled to Q-Orbitrap-MS, detectable up to the 7th day after PPP application. This study provides a comprehensive understanding of difenoconazole dissipation in tomatoes, identification of metabolites, and detection of co-formulants associated with the applied PPP., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Apple, a major fruit of temperate Himalayas, is sprayed with chemical pesticides around 12 times during the cropping season. Various systemic and contact fungicides are applied for the management of major diseases. In order to manage disease, flusilazole 40 EC is frequently used. However, excessive chemical application has been found to be detrimental for consumer safety. Keeping in view consumer safety, risk assessment, the half-life and waiting period for flusilazole 40 EC were evaluated on the Red Velox variety of apple. The QuEChERS (quick, easy, cheap, effective, rugged and safe) method and high-performance liquid chromatography were adapted for sample processing and analysis, respectively. The recovery percentages of flusilazole at three fortification levels (0.04, 0.09 and 0.50 mg kg -1 ) were 98.85, 99.83 and 98.98%, respectively. Flusilazole at the recommended dose (80 g a.i. ha -1 ) left an initial deposit of 0.733 mg kg -1 , which dissipated by 93.45% in 60 days and was non-detectable beyond this period. Meanwhile flusilazole at double the recommended dose (160 g a.i. ha -1 ) left an initial deposit of 0.913 mg kg -1 , which dissipated by 93.43% in 70 days and was non-detectable beyond this period. Based on the maximum residue limit of 0.3 mg kg -1 as prescribed by the Codex Alimentarius Commission, a waiting period of 28.74 and 46.03 days was recorded for single and double doses, respectively. Moreover, in order to assess the consumer risk, theoretical maximum residue contributions (TMRCs) were derived using flusilazole residues (average and maximum) recorded at various time intervals and compared with the maximum permissible intake, which was found to be 0.42 mg per person per day. Based on the average per capita daily consumption of 6.76 g apple in India, the TMRC values were computed. Although the values of TMRC decreased below maximum permissible intake at the first day after application, indicating minimal consumer health risks, fruits sprayed with a double dose of flusilazole carried the risk even up to the tenth day after flusilazole application. The results of the present study will be valuable for safe and timely use of flusilazole on apple., (© 2024 John Wiley & Sons Ltd.)

Contamination by wastewater has been traditionally assessed by measuring faecal coliforms, such as E. coli and entereococci. However, using micropollutants to track wastewater input is gaining interest. In this study, we identified nine micropollutant indicators that could be used to characterize water quality and wastewater treatment efficiency in pond-based wastewater treatment plants (WWTPs) of varying configuration. Of 232 micropollutants tested, nine micropollutants were detected in treated wastewater at concentrations and frequencies suitable to be considered as indicators for treated wastewater. The nine indicators were then classified as stable (carbamazepine, sucralose, benzotriazole, 4+5-methylbenzotriazole), labile (atorvastatin, naproxen, galaxolide) or intermediate/uncertain (gemfibrozil, tris(chloropropyl)phosphate isomers) based on observed removals in the pond-based WWTPs and correlations between micropollutant and dissolved organic carbon removal. The utility of the selected indicators was evaluated by assessing the wastewater quality in different stages of wastewater treatment in three pond-based WWTPs, as well as selected groundwater bores near one WWTP, where treated wastewater was used to irrigate a nearby golf course. Ratios of labile to stable indicators provided insight into the treatment efficiency of different facultative and maturation ponds and highlighted the seasonal variability in treatment efficiency for some pond-based WWTPs. Additionally, indicator ratios of labile to stable indicators identified potential unintended release of untreated wastewater to groundwater, even with the presence of micropollutants in other groundwater bores related to approved reuse of treated wastewater., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Kathryn Linge, Cynthia Joll reports financial support and equipment, drugs, or supplies were provided by Water Corporation. Kathryn Linge, Cynthia Joll reports financial support was provided by Australian Research Council. Kathryn Linge, Cynthia Joll reports financial support was provided by Water Research Australia., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Metconazole is a novel chiral fungicide with two chiral carbon atoms, but the research on its stereoselective behavior is limited. Therefore, the stereoselective behaviors of metconazole in four fruits, including grape, peach, pear and jujube, were summarized in this study. After determining the absolute configuration of metconazole stereoisomers, a chiral separation method through supercritical fluid chromatography/tandem triple quadrupole mass spectrometry was first developed, which combined an improved QuEChERS method obtained the recoveries of 71.6-113 % with RSD ≤ 19.8 %. The LOD and LOQ were 4.30-95.9 and 10.5-143.2 ng/kg, respectively. Different stereoselective and diastereoselective behaviors were observed in four fruits. Dietary risk assessments of rac-metconazole were performed in populations with different ages and genders. Both acute (RQ a , 0.0124-0.140 %) and chronic (HQ, 0.0234-0.0794 %) intake risks were acceptable. The results of this study would contribute to more complete risk assessments of metconazole and provide data for chiral studies., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Introduction: A specialized service for antifungal blood level determination is not available in Colombia. This service is essential for the proper follow-up of antifungal therapies., Objective: To standardize and validate a simple, sensitive, and specific protocol based on high-performance liquid chromatography with a diode array detector for voriconazole blood level quantification., Materials and Methods: We used an Agilent HPLC™ series-1200 equipment with a UVdiode array detector with an analytical column Eclipse XDB-C18 and pre-column Eclipse- XDB-C18 (Agilent). We used voriconazole as the primary control and posaconazole as an internal control. We performed the validation following the Food and Drug Administration (FDA) recommendations., Results: The best chromatographic conditions were: Column temperature of 25°C, UV variable wavelength detection at 256 nm for voriconazole and 261 nm for posaconazole (internal standard); 50 μl of injection volume, 0,8 ml/min volume flow, 10 minutes of run time, and mobile phase of acetonitrile:water (60:40). Finally, retention times were 3.13 for voriconazole and 5.16 minutes for posaconazole. Quantification range varied from 0.125 μg/ml to 16 μg/ml., Conclusion: The selectivity and chromatographic purity of the obtained signal, the detection limits, and the standardized quantification make this method an excellent tool for the therapeutic monitoring of patients treated with voriconazole.

Rigorous risk assessments for those exposed to pesticides are carried out to satisfy crop protection regulatory requirements. Non-dietary risk assessments involve estimating the amount of residue which can be transferred from plant foliage to the skin or clothes, known as dislodgeable foliar residues (DFRs). DFR data are less available than crop residue data as studies are costly and limited by seasonality. European regulatory authorities are reticent to allow extrapolation of study data to different scenarios as the contributory factors have hitherto been poorly identified. This study is the first to use a new laboratory DFR method to investigate how one such factor, pesticide formulation, may affect DFR on a variety of crops. The study used the active substance difenoconazole as both an emulsifiable concentrate (EC 10%) and a wettable powder (WP 10%) with and without adjuvants (Tween 20 and organophosphate tris(2-ethylhexyl)phosphate TEHP) on tomato, French bean and oilseed rape. A comparable DFR% was retained from the WP and EC formulation on most crops except for tomato, where lower DFR% was retained in the case of WP (39 ± 4.7%) compared to EC (60 ± 1.2%). No significant effect of adjuvant addition was observed for either formulation except when mixing TEHP (0.1% w/v) to the EC 10% on French bean, resulting in 8% DFR reduction compared to the EC formulation alone. This research demonstrates the value of a unique DFR laboratory technique in investigating the importance of the formulation and in-tank adjuvants as factors that affect DFR.

Benzotriazoles (BTRs), benzothiazoles (BTHs), and benzotriazole UV stabilizers (BUVs) have attracted increasing attention due to their ubiquity in the environment, toxicity, and potential ecological risks. However, information on their distributions in the ocean is scarce. In this study, BTRs, BTHs, and BUVs were firstly determined in the surface seawater, sea-surface microlayer (SML), suspended particulate matter (SPM), and sediments of the Yellow Sea (YS) and East China Sea (ECS). The spatial distributions of BTRs, BTHs, and BUVs in the YS and ECS showed offshore decreasing trend in their concentrations, indicating that terrestrial inputs from runoff and rivers had important influences on their distributions. The organic carbon normalized partition coefficients (log K oc ) of target contaminants in surface seawater-SPM (3.06-4.16 L/g) and bottom seawater-sediment (2.55-4.82 L/kg) systems were determined. SPM showed greater sorption capacities for most target contaminants than the sediment. The burial capacities of BTHs, BTRs, and BUVs from SPM to surface sediments were evaluated using their respective log K ow values and their sedimentary fluxes in the YS and ECS were quantified. BTRs, BTHs, and BUVs were enriched in the SML, with the enrichment extents of the suspended particulate phase being obviously lower than those of the dissolved phase. The ecological risks of BTRs, BTHs, and BUVs were evaluated using the risk quotient (RQ) method, which showed no toxic risk to aquatic organisms throughout the water phases, but high risk in nearshore sediments., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The ubiquitous occurrence of benzotriazole ultraviolet stabilizers (BUVSs) in the environment and organisms has warned of their potential ecological and health risks. Studies showed that some BUVSs exerted immune and chronic toxicities to animals by disturbing signaling transduction, yet limited research has investigated the toxic effects on crop plants and the underlying mechanisms of signaling regulation. Herein, a laboratory-controlled hydroponic experiment was conducted on rice to explore the phytotoxicity of BUVSs by integrating conventional biochemical experiments, transcriptomic analysis, competitive sorption assays, and computational studies. The results showed that BUVSs inhibited the growth of rice by 6.30-20.4% by excessively opening the leaf stomas, resulting in increased transpiration. BUVSs interrupted the transduction of abscisic acid (ABA) signal through competitively binding to Ca 2+ -dependent protein kinase (CDPK), weakening the CDPK phosphorylation and further inhibiting the downstream signaling. As structural analogues of ATP, BUVSs acted as potential ABA signaling antagonists, leading to physiological dysfunction in mediating stomatal closure under stresses. This is the first comprehensive study elucidating the effects of BUVSs on the function of key proteins and the associated signaling transduction in plants and providing insightful information for the risk evaluation and control of BUVSs.

An efficient method is presented for simultaneous enantioselective determination of three chiral triazole fungicides (namely paclobutrazol, hexaconazole, and diniconazole) in water samples by DSPE-HPLC-UV. The perfect chiral separation of the enantiomers was achieved on a Chiralpak IH column within 15 min. In order to adsorb and enrich the analytes from water matrices, a cross-linked hydroxypropyl β-cyclodextrin polymer was synthesized. The prepared material exhibited good adsorption capacity, which was assessed by adsorption kinetic and adsorption thermodynamic experiments. One-variable-at-a-time and the response surface methodology were used to optimize the extraction parameters. Under the optimum sample preparation conditions, good linearity (2.0 ~ 800 µg L -1 , R 2  ≥ 0.9978), detection limits (0.6 to 1.0 µg L -1 ), quantitation limits (2.0 to 3.2 µg L -1 ), recoveries (86.7 ~ 105.8%), and the relative standard deviation (intra-day RSD ≤ 3.7%, inter-day RSD ≤ 5.1%) were obtained, satisfying the requirements of pesticides residues determination. These results demonstrated that the proposed method was applicable for routine determination of chiral triazole fungicide residues in water samples., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

The present study describes the dissipation and metabolism of penconazole in horticultural products by a method based on ultra-high performance liquid chromatography-quadrupole-orbitrap (UHPLC-Q-Orbitrap). Targeted and suspected analysis were carried out. Two independent trials were performed under laboratory conditions (on courgette samples), and under greenhouse conditions (on tomatoes) during 43 and 55 days, respectively. In both studies, a pesticide formulation (TOPAS® EW) containing penconazole was used. The results showed that penconazole was relatively short-lived (<30 days) in horticultural products. The proposed method allowed for the tentative identification and semi-quantification of nine metabolites. In addition, the potential toxicity of these metabolites was evaluated, observing that some of them are even more toxic than penconazole, as triazole lactic acid. This research may provide a starting point for understanding the dissipation process of penconazole, the formation pathways of its main metabolites, their concentrations and toxicity to ensure food safety and the environmental protection., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Contamination of cereals with tebuconazole (TEB) can affect the dietary risk assessment. This study investigates, for the first time, how mechanical, thermal, physical-chemical, and biochemical processes affect the TEB level in wheat, rye, and barley. The biochemical process of malting was the most effective for tebuconazole reduction (by 86%) in cereals. Thermal processes were also effective, i.e., boiling (70%) and baking (55%). These processes considerably decreased the concentration of tebuconazole, and Procesing Factors (PFs) were from 0.10 to 0.18 (malting), 0.56 to 0.89 (boiling), and 0.44 to 0.45 (baking), respectively. The concentration of TEB was not reduced after the application of mechanical processing. The risk was estimated in dietary exposure assessment on the basis of the highest reported levels of tebuconazole residues bread. At a high level of rye bread consumption, the potential exposure to tebuconazole reached only 3.5% and 2.7% in children and adults, respectively., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

A new effervescence-assisted switchable deep eutectic solvent-based liquid phase microextraction (EA-SDES-LPME) combined with HPLC-UV was developed for determination of common triazole fungicides in drinking water and beverages, including myclobutanil, flusilazole, hexaconazole and bitertanol. The alternative extraction solvent was prepared with hexafluoroisopropanol and dipropylamine with the merits of time-saving, easy to collect and cost-effectiveness. The SDES can be reversibly switched between hydrophilic and hydrophobic states by pH adjustment. The homogeneous extraction was achieved under the hydrophilic form of SDES, and the bi-phase separation was obtained easily by adjusting pH value to restore the original hydrophobicity. Moreover, the characterization of SDES was investigated by FTIR and 1 H NMR. The main variables affecting extraction efficiency were optimized in detail. Under the optimal conditions, the proposed method shows desirable precision (RSDs less than 18.5%) and acceptable recovery (72.6-95.4%). The lower limits of detection and limits of quantitation were found to be in the range of 1-2 μg L -1 and 5-10 μg L -1 , respectively. The formation mechanism of SDES and the extraction mechanism for target analytes were investigated by density functional theory. The proposed methodology was simplicity, sensitive, time-saving and successfully applied to determine triazole fungicides in drinking water and beverages, making it an alternative technique for the analysis of trace analytes with satisfactory sensitivity., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

A simple way to reduce pesticides in cereal grains is to use washing methods. The challenge of this study was to evaluate the effectiveness of reduction of 3 triazole fungicides (difenoconazole, tebuconazole, tetraconazole) and 3 pyrethroid insecticides (beta-cyfluthrin, cypermethrin, deltamethrin) commonly used in wheat protection. Four different pre-washing methods (hot and cold water washing, twice water, and ultrasound-supported washing) were evaluated. The processing factor (PF) was calculated based on the concentration of pesticides determined by LC-MS/MS in the samples of cereal grains before and after the washing process. PFs were within the range 0.01-0.97. Time, teperature and ultrasound were factors influencing the efficiency of water treatment. The study showed that ultrasound-supported washing eliminated pesticide residues to a greater extent than ordinary washing. This process significantly affected or completely reduced concentrations of triazoles in wheat grains. The highest reduction of residues (99%) was received for tebuconazole and ultrasound washing with heating temperature of 60 °C for a total of 10 min. In all washing processes, pyrethroids were removed with lower efficiency than triazoles. The lowest residue reduction was obtained for cypermethrin and washing under cold water for 5 min (3%; PF = 0.97). Beta-Cyfluthrin showed only a 6-27% reduction regardless of the process (PF: 0.73-0.95). Using static analysis, the relationship between the properties of pesticides and the reduction of their concentration in cereals was clarified and showed a strong correlation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Triazole fungicides (TFs) are extensively used on greenhouse vegetables and are ubiquitously detected in the environment. However, the human health and ecological risks associated with the presence of TFs in the soil are unclear. In this study, ten widely used TFs were measured in 283 soil samples from vegetable greenhouses across Shandong Province, China, and their potential human health and ecological risks were assessed. Among all soil samples, difenoconazole, myclobutanil, triadimenol, and tebuconazole were the top detected TFs, with detection rates of 85.2-100%; these TFs had higher residues, with average concentrations of 5.47-23.8 μg/kg. Although most of the detectable TFs were present in low amounts, 99.3% of the samples were contaminated with 2-10 TFs. Human health risk assessment based on hazard quotient (HQ) and hazard index (HI) values indicated that TFs posed negligible non-cancer risks for both adults and children (HQ range, 5.33 × 10 -10 to 2.38 × 10 -5 ; HI range, 1.95 × 10 -9 to 3.05 × 10 -5 , <1). Ecological risk assessment based on the toxicity exposure ratio (TER) and risk quotient (RQ) values indicated that difenoconazole was a potential risk factor for soil organisms (TER max  = 1 for Eisenia foetida, <5; RQ mean  = 1.19 and RQ max  = 9.04, >1). Moreover, 84 of the 283 sites showed a high risk (RQ site range, 1.09-9.08, >1), and difenoconazole was the primary contributor to the overall risk. Considering their ubiquity and potential hazards, TFs should be continuously assessed and prioritized for pesticide risk management., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Introduction : Posaconazole is a widely used antifungal drug, and its accurate quantification is essential for quality control and assessment of its pharmaceutical products. This study aimed to develop and validate a reverse-phase high-performance liquid chromatography (HPLC) analytical method for quantifying Posaconazole in bulk and dosage form. Methods : The HPLC method was developed and validated based on International Conference on Harmonisation (ICH) guidelines. The developed method was then applied to quantify Posaconazole in a marketed tablet formulation. The method's specificity, linearity, precision, accuracy, robustness, and stability were evaluated. Results : The developed HPLC method showed good linearity over a 2-20 μg/mL concentration range. The percentage recovery of Posaconazole from the bulk and marketed formulations was found to be 99.01% and 99.05%, respectively. The intra-day and inter-day precisions were less than 1%, and the method was stable under different conditions. The HPLC method was successfully applied to quantify Posaconazole in the marketed formulation. Conclusion : The developed and validated HPLC method is reliable and efficient for analyzing Posaconazole in bulk and dosage forms. The method's accuracy, precision, specificity, linearity, robustness, and stability demonstrate its effectiveness. The method can be used for the quality control and assessment of Posaconazole-containing pharmaceutical products., Competing Interests: No competing interests were disclosed., (Copyright: © 2023 Rama A et al.)

The treatment of seeds with pesticides is an extended practice in current agriculture. There is a high risk of exposure in granivorous birds, such as the red-legged partridge (Alectoris rufa), that can consume those seeds remaining on the surface during sowing. Fungicide exposure could in turn affect bird reproductive capacity. To better understand to what extent triazole fungicides are a threat to granivorous birds, we need an easy and reliable method to quantify field exposure. In this study, we tested a novel non-invasive method to detect the presence of triazole fungicide residues in farmland bird faeces. We experimentally exposed captive red-legged partridges to validate the method, and then applied it in a real scenario to assess exposure of wild partridges. We exposed adult partridges to seeds treated with two formulations containing triazole fungicides as active ingredients: Vincit®Minima (flutriafol 2.5%) and Raxil®Plus (prothioconazole 25% and tebuconazole 15%). We collected two types of faeces (caecal and rectal samples) immediately after exposure and 7 days later and quantified the concentrations of the three triazoles and their common metabolite (1,2,4-triazole). The three active ingredients and 1,2,4-triazole were only detected in faeces collected immediately after exposure. Triazole fungicide detection rates in rectal stool were 28.6%, 73.3% and 80% for flutriafol, prothioconazole and tebuconazole, respectively. In caecal samples, detection rates were 40%, 93.3% and 33.3%, respectively. 1,2,4-triazole was detected in 53% of rectal samples. For an applied use of the method in the field, we collected 43 faecal samples from wild red-legged partridges during autumn cereal seed sowing and found detectable levels of tebuconazole in 18.6% of the analysed wild partridges. The results of the experiment were then used to estimate actual exposure levels from this prevalence value found in wild birds. Our study shows that faecal analysis can be a useful tool to assess farmland bird exposure to triazole fungicides, when samples are fresh and the method has been validated for the detection of target molecules., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The need for effective technologies to remediate the insensitive munitions compound 3-nitro-1,2,4-triazol-5-one (NTO) is emerging due to the increasing use by the US Army and environmental concerns about the toxicity and aqueous mobility of NTO. Reductive treatment is essential for the complete degradation of NTO to environmentally safe products. The objective of this study is to investigate the feasibility of applying zero-valent iron (ZVI) in a continuous-flow packed bed reactor as an effective NTO remediation technology. The ZVI-packed columns treated an acidic influent (pH 3.0) or a circumneutral influent (pH 6.0) for 6 months (ca. 11,000 pore volumes, PVs). Both columns effectively reduced NTO to the amine product, 3-amino-1,2,4-triazol-5-one (ATO). The column treating the pH-3.0 influent exhibited prolonged longevity in reducing NTO, treating 11-fold more PVs than the column treating pH-6.0 influent until the breakthrough point (defined as when 85% of NTO was removed). The exhausted columns (defined as when only 10% of NTO was removed) regained the NTO reducing capacity by reactivation using 1 M HCl, fully removing NTO. After the experiment, solid-phase analysis of the packed-bed material showed that ZVI was oxidized to iron (oxyhydr)oxide minerals such as magnetite, lepidocrocite, and goethite during NTO treatment. This is the first report on the reduction of NTO and the concomitant oxidation of ZVI in continuous-flow column experiments. The evidence indicates that treatment in a ZVI-packed bed reactor is an effective approach for the removal of NTO., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Benzotriazoles (BTs) are highly produced chemicals that are commonly used in the manufacture of aircraft de-icing/antifreeze fluids (ADAFs), coolants, etc. BTs have been detected in a variety of water environments, causing health hazards to aquatic species and humans. In this study, 1H-benzotriazole (BTri) and 4-methyl-1H-benzotriazole (4-TTri) were selected to investigate their degradation mechanisms in the aqueous phase initiated by ·OH using a theoretical calculation method. Addition reactions are the main type of reactions of ·OH with BTri and 4-TTri. The total rate constants for the reactions of BTri and 4-TTri with ·OH at 298 K are 8.26 × 10 9  M -1  s -1 and 1.81 × 10 10  M -1  s -1 , respectively. The reaction rate constants increase as the temperature rises, indicating that rising temperatures promote the degradation of BTri and 4-TTri. 7-hydroxy-1H-benzotriazole (1-P1) and 4-hydroxy-benzotriazoles (1-P2) produced via multiple reaction pathways are important transformation products of BTri. After successive reactions with ·OH, 1-P1 and 1-P2 can be successively converted to 4,7-dihydroxy-1H-benzotriazole (1-P7), 4,7-dione-1H-benzotriazole (1-P8), and 1,2,3-triazole-4,5-dicarboxylic acid (1-P9), which is consistent with the product compositions detected in the experiments. The toxicity assessment indicated that the acute toxicity and chronic toxicity of the resulting transformation products are significantly reduced compared to BTri as the degradation process progressed, and ultimately showed no harm to all three aquatic organisms (fish, daphnia, and green algae). Hence, advanced oxidation processes (AOPs) can not only effectively remove BTs from water, but also reduce their toxic effects on aquatic organisms., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)