A tailored dual core-shell magnetic SERS substrate with precise shell-thickness control for trace organophosphorus pesticides residues detection.

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 Fe3O4-COOH@UiO-66/Au@Ag (FCUAA) was synthesized with a SERS enhancement factor of 2.11 × 107. 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/cm2 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.

Standardization and validation of a high-efficiency liquid chromatography with a diode-array detector (HPLC-DAD) for voriconazole blood level determination. / Estandarización y validación de un método de cromatografía líquida de alta eficiencia con detector de arreglo de diodos (HPLC-DAD) para la determinación de niveles sanguíneos de voriconazol

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.

Introducción. Hasta la fecha, Colombia no cuenta con un servicio especializado de medición de niveles séricos de antifúngicos, procedimiento esencial para el adecuado seguimiento del tratamiento de infecciones fúngicas invasoras. Objetivo. Estandarizar y validar un protocolo ­simple, sensible y específico­ basado en la aplicación de cromatografía líquida de alta eficiencia acoplada con un detector de arreglo de diodos para la cuantificación de los niveles séricos de voriconazol. Materiales y métodos. Se usó un equipo HPLC-Agilent™, serie-1200, con un detector UVDAD, una columna analítica Eclipse-XDB-C18 y una pre-columna Eclipse-XDB-C18, ambas de la marca Agilent. Como control primario se utilizó voriconazol y como control interno, posaconazol. La validación se hizo cumpliendo todos los criterios de aceptación recomendados por la Food and Drug Administration (FDA). Resultados. Las mejores condiciones cromatográficas se obtuvieron con los siguientes parámetros: temperatura de la columna de 25 °C, detección UV-VWD de 261 nm, volumen de inyección de 50 µl, flujo de 0,8 ml/minuto y un tiempo de corrido de 10 minutos. La fase móvil usada fue acetonitrilo:agua (60:40) y los tiempos finales de retención fueron de 3,13 para voriconazol y de 5,16 minutos para posaconazol. El rango de cuantificación fue desde 0,125 µg/ml hasta 16 µg/ml. Conclusiones. La selectividad y la pureza de la señal cromatográfica, así como los límites de detección y cuantificación estandarizados hacen de esta metodología una excelente herramienta para el seguimiento terapéutico de pacientes tratados con voriconazol o en profilaxis con este fármaco.

Tracing the dissipation of difenoconazole, its metabolites and co-formulants in tomato: A comprehensive analysis by chromatography coupled to high resolution mass spectrometry in laboratory and greenhouse trials.

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 (R2 > 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.

Use of micropollutant indicator ratios to characterize wastewater treatment plant efficiency and to identify wastewater impact on groundwater.

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.

Quick synthesis of CoFe-PBA@GO with electrochemical method as a novel, sensitive, and degradable nanocomposite applied in nanofibers for triazole extraction before HPLC-UV analysis.

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.

Assessment of flusilazole residues on apples: Detection, quantification and health risk implications.

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.

Stereoselective study on chiral fungicide metconazole in four kinds of fruits: Absolute configuration, SFC-MS/MS enantioseparation, degradation and risk assessment.

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 (RQa, 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.

Dispersive solid phase extraction based on cross-linked hydroxypropyl ß-cyclodextrin polymers for simultaneous enantiomeric determination of three chiral triazole fungicides in water.

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 ß-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, R2 ≥ 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.

Benzotriazole Ultraviolet Stabilizers (BUVSs) as Potential Protein Kinase Antagonists in Rice.

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 Ca2+-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.

Advancing posaconazole quantification analysis with a new reverse-phase HPLC method in its bulk and marketed dosage form.

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.

An effervescence-assisted switchable deep eutectic solvent based liquid-phase microextraction of triazole fungicides in drinking water and beverage.

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 1H 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.

Removal of triazole and pyrethroid pesticides from wheat grain by water treatment and ultrasound-supported processes.

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.

Impact of technological processes on tebuconazole reduction in selected cereal species and the primary cereal product, and dietary exposure assessment.

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.

Dissipation of penconazole formulation in horticultural crops by ultrahigh performance liquid chromatography-high resolution mass spectrometry: From the active substance to metabolites.

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.

[QuEChERS-liquid chromatography-tandem mass spectrometry for determination of 22 triazole pesticide residues in Chinese herbal medicines].

Eight well-known herbals in Zhejiang Province, Zhebawei, are commonly used as traditional Chinese herbal medicines owing to their rich active ingredients. However, the unavoidable use of pesticides during agricultural production has led to pesticide residue problems in these herbs. In this study, a simple, rapid, and accurate method was established to determine 22 triazole pesticide residues in Zhebawei. An improved QuEChERS method was used for sample pretreatment, and Rhizoma Atractylodis Macrocephalae was used as a representative sample. The sample was extracted with acetonitrile to eliminate some polar and nonpolar compounds, pigments, and other impurities, and the purification effects of multiwalled carbon nanotubes (MWCNTs), amino-modified multiwalled carbon nanotubes (MWCNTs-NH2), carboxylated multiwalled carbon nanotubes (MWCNTs-COOH), crosslinked polyvinylpyrrolidone (PVPP), zirconium dioxide (ZrO2), 3-(N,N-diethylamino)-propyltrimethoxysilane (PSA), octadecyl (C18), and graphitized carbon black (GCB) were compared. MWCNTs-COOH and C18 were selected as the purification adsorbents, and their dosages were systematically optimized. The combination of 10 mg of MWCNTs-COOH and 20 mg of C18 was eventually selected as the purification adsorbents. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) was used for analysis, and box graphs were plotted to present the dispersion of each group of recoveries, thus enabling the identification of the data outliers, dispersion distribution, and data symmetry. The established method was systematically verified and showed good linearity over the concentration range of 1-200 µg/L (except for bromuconazole, epoxiconazole, and etaconazole) with correlation coefficients >0.99. The average recoveries of the 22 pesticides at spiked levels of 10, 20, 100, and 200 µg/kg were in the range of 77.0%-115% with relative standard deviations (RSDs) <9.4%. The limits of detection and quantification were 1-2.5 µg/kg and 10-20 µg/kg, respectively. The applicability of the developed method to other herbals was investigated at 100 µg/kg, and the average recoveries of the target pesticides in different matrices ranged from 76.4% to 123% with RSDs <12.2%. Finally, the method established was used to detect triazole pesticide residues in 30 actual Zhebawei samples. The results showed that triazole pesticides were present in Bulbus Fritillariae Thunbergii and Dendranthema Morifolium. Difenoconazole was detected in Bulbus Fritillariae Thunbergii at contents ranging from 41.4 µg/kg to 110 µg/kg, while difenoconazole, myclobutanil, triadimenol and propiconazole were detected in Dendranthema Morifolium at contents ranging from 16.1 µg/kg to 250 µg/kg. The established method can meet the requirements for the accurate quantitative analysis of triazole fungicides in Zhebawei.

Treatment of the insensitive munitions compound, 3-nitro-1,2,4-triazol-5-one (NTO), in flow-through columns packed with zero-valent iron.

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.

The widespread presence of triazole fungicides in greenhouse soils in Shandong Province, China: A systematic study on human health and ecological risk assessments.

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 (TERmax = 1 for Eisenia foetida, <5; RQmean = 1.19 and RQmax = 9.04, >1). Moreover, 84 of the 283 sites showed a high risk (RQsite 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.

A non-invasive method to monitor farmland bird exposure to triazole fungicides.

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.

Mechanistic insight into the degradation of 1H-benzotriazole and 4-methyl-1H-benzotriazole by •OH-based advanced oxidation process and toxicity assessment.

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 × 109 M-1 s-1 and 1.81 × 1010 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.

Prenatal exposure to benzotriazoles and benzothiazoles and child neurodevelopment: A longitudinal study.

Benzotriazoles (BTRs) and benzothiazoles (BTHs) are emerging benzo-heterocyclic compounds that may induce neurotoxicity. However, the effect of prenatal exposure to BTs (BTRs and BTHs) on child neurodevelopment has not been elucidated. We aimed to explore the associations between maternal urinary concentrations of BTs in single or in mixture with child neurodevelopment at the age of two. This study recruited 513 mother-child pairs based on a birth cohort from 2014 to 2015 in Wuhan. Maternal urinary concentrations of eight BTs (four BTRs and four BTHs) in the first, second, and third trimesters were measured. The mental development index (MDI) and psychomotor development index (PDI) of children, as two indexes of neurodevelopment, were assessed at two years old by the Bayley Scales. In the analyses of single BTs, prenatal average tolyltriazole (TTR) exposure level was associated with decreased boys' MDI scores (ß = -2.84, 95 % CI: -5.11, -0.57) and prenatal average 1-H-benzotriazole (1-H-BTR) exposure level was associated with decreased boys' PDI scores (ß = -1.44, 95 % CI: -2.70, -0.17), respectively. Maternal urinary concentrations of benzothiazole (BTH) in the 1st trimester (ß = -1.79, 95 % CI: -2.78, -0.80), 2nd trimester (ß = -1.14, 95 % CI: -2.19, -0.09), and the prenatal average exposure (ß = -2.15, 95 % CI: -3.69, -0.61) were also negatively associated with boys' PDI scores. However, no significantly negative association was observed among girls. In the further mixture analysis, the quantile g-computation model found a significant negative association between prenatal average concentrations of BTs in mixture and boys' PDI scores [ß = -4.80 (95 % CI: -9.08, -0.52)], and BTH weighted the highest in the negative association. As far as we know, this is the first research to estimate the effect of prenatal exposure to BTs on child neurodevelopment. The findings showed that prenatal exposure to BTs was negatively associated with neurodevelopment among boys, suggesting that the associations may be modified by infant sex.