Health risk assessment of triazole fungicides around a pesticide factory in China.

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/m3 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.

Exposure Assessment of Benzotriazole Ultraviolet Absorbers in Plastic Sports Field Dust and Indoor Dust: Are Plastic Sports Fields High Exposure Scenarios?

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.

Fe3O4@gC3N4@Thiamine: a novel heterogeneous catalyst for the synthesis of heterocyclic compounds and microextraction of tebuconazole in food samples.

Graphite carbon nitride (g-C3N4) 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 Fe3O4@g-C3N4 with thiamine hydrochloride (vitamin B1) via cyanuric chloride (TCT), which is a divalent covalent linker, was presented. The efficiency of Fe3O4@gC3N4@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.

Occurrence, spatial distribution, and ecological risk of benzotriazole UV stabilizers (BUVs) in sediments from Bohai sea of China.

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 Σ15BUVs, 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.

Validated UPLC-MS/MS method for quantification of melatonin receptor agonists and dual orexin receptor antagonists in human plasma and breast milk: Application to quantify suvorexant and lemborexant in clinical samples.

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.

Benzotriazoles and bisphenols in wastewater from the food processing industry and the quantitative changes during mechanical/biochemical treatment processes.

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.

Monitoring of current-use pesticides along a Europe-Arctic transect using ships of opportunity.

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.

Dissipation behaviour and dietary risk evaluation of pesticides on cucumber.

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.

Detection of benzotriazole-type ultraviolet stabilizers in sea turtles breeding in the Northwest Pacific Ocean.

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.

Determination and risk assessment of UV filters and benzotriazole UV stabilizers in wastewater from a wastewater treatment plant in Lüneburg, Germany.

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.

Non-target liquid chromatography high-resolution mass spectrometry screening to prioritize unregulated micropollutants that persist through domestic wastewater treatment.

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.

Development and application of an advanced algorithm for environmental risk assessment and safety management of pesticide residues in agricultural soils: Monitoring of currently used pesticide in upland soils.

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.

Lignin-based emulsive liquid-liquid microextraction for detecting triazole fungicides in water, juice, vinegar, and alcoholic beverages via UHPLC-MS/MS.

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.

Dissipation and residue of triadimefon in Rosa roxburghii.

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 (MRLs) and safe pre-harvest intervals (PHIs) 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.

The effect of formulation composition and adjuvant type on difenoconazole dislodgeable foliar residue.

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.

Simultaneous quantification of five antiretrovirals in human tissues using ultra-high performance liquid chromatography-tandem mass spectrometry methods for therapeutic drug monitoring at the sites of action.

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.

Quantitative determination of prothioconazole in wheat grain, soybean, and pond water based on a polyclonal antibody.

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.

Quantum Mechanical Quantitative Nuclear Magnetic Resonance Enables Digital Reference Standards at All Magnetic Fields and Enhances qNMR Sustainability.

Quantum mechanics (QM)-driven 1H iterative functionalized spin analysis produces HifSA profiles, which encode the complete 1H 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 1H 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 (2RS, 4RS)- and (2RS, 4SR)-difenoconazole (DFZ), a widely used antifouling food additive. The underlying 1H 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: (2R, 4R)-, (2S, 4S)-, (2R, 4S)-, and (2S, 4R)-DFZ to perform chiral qHNMR measurements.

Simultaneous determination of four fungicide residues in figs using liquid chromatography tandem mass spectrometry.

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.

Persistence of pesticide residues in weathered avian droppings.

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.