Occupational exposure and risk assessment for agricultural workers of thiamethoxam in vineyards.

Dermal & inhalation exposure was examined and according to these results, risk assessment of agricultural workers to thiamethoxam was performed during pesticide mixing/loading and hand-held sprayer application (11 replicates, each of about 1000 L of spray suspension) in vineyards. For the whole body dosimetry (WBD), clothing (Outer and inner), gauze, and nitrile gloves were analyzed to determine dermal exposure using whole-body dosimetry exposure protocol. The inhalation exposure was measured using a glass fiber filter with an IOM sampler. Analytical method validation of exposure matrices was evaluated including the field recovery and breakthrough test. The dermal exposure amount during mixing/loading was 0.163 mg (0.0004% of the total mixed/loaded active ingredient [a.i.]), whereas there was no inhalation exposure. The gloves (0.154 mg, 94.5%) were the most exposed body parts followed by the chest and stomach (0.009 mg, 5.5%). During application, the dermal and inhalation exposure amounts were 32.3 mg (0.07% of the total applied a.i.) and 10.8 µg (2.4 × 10-6% of the total applied a.i), respectively. The shin (35.1%) had the highest exposure to pesticides, followed by the chest & stomach (15.6%) and pelvis (12.6%). In case of mixing/loading, the amounts of actual dermal exposure (ADE) and actual inhalation exposure (AIE) were 0.0 and 0.0 µg/day, while those of ADE and AIE were 4707.6 and 15.8 µg/day for application. In risk assessment of the two different scenarios, the risk index was much lower than 1 (mixing/loading:0.000, application:0.014), indicating that vineyard workers are at low risk of thiamethoxam exposure. To determine the validity of the risk assessment using WBD method, the urinary metabolite was analyzed. Comparison of biomonitoring data and WBD exposure data show a reliable correlation (r = 0.885, p = 0.0003), suggesting that these are suitable methods to estimate exposure.

4-Coumarate:coenzyme A ligase isoform 3 from Piper nigrum (Pn4CL3) catalyzes the CoA thioester formation of 3,4-methylenedioxycinnamic and piperic acids.

Black pepper, dried green fruit of Piper nigrum L., is a household spice most popular in the world. Piperine, the pungency compound of black pepper, is proposed to partially arise from phenylpropanoid pathway. In the biosynthesis of piperine, 4-coumarate:CoA ligase (4CLs) must play a pivotal role in activating intermediate acids to corresponding CoA thioesters to serve as substrates. Based on transcriptome data, we isolated three P. nigrum 4CL isoforms (Pn4CL1, -2, and -3) from unripe peppercorn. These Pn4CLs were expressed in E. coli for in vitro enzyme assay with putative substrates, namely cinnamic, coumaric, ferulic, piperonylic, 3,4-methylenedioxycinnamic (3,4-MDCA), and piperic acids. Phylogenetic analysis and substrate usage study indicated that Pn4CL1, active towards coumaric and ferulic acids, belongs to class I 4CL for lignin synthesis. Pn4CL2 was a typical cinnamate-specific coumarate:CoA ligase-like (CLL) protein. The Pn4CL3, as class II enzyme, exhibited general 4CL activity towards coumaric and ferulic acids. However, Pn4CL3 was also active towards piperonylic acid, 3,4-MDCA, and piperic acid. Pn4CL3 possessed ∼2.6 times higher catalytic efficiency (kcat/KM) towards 3,4-MDCA and piperic acid than towards coumaric and ferulic acids, suggesting its specific role in piperine biosynthesis. Different substrate preference among the Pn4CL isoforms can be explained by 3-dimensional protein structure modeling, which demonstrated natural variants in amino acid residues of binding pocket to accommodate different substrates. Quantitative PCR analysis of these isoforms indicated that Pn4CL1 transcript level was highest in the roots whereas Pn4CL2 in the fruits and Pn4CL3 in the leaves.

Crystal structure of the indole-3-acetic acid-catabolizing enzyme DAO1 from Arabidopsis thaliana.

Indole-3-acetic acid (IAA), the major form of the plant hormone auxin, regulates almost every aspect of plant growth and development. Therefore, auxin homeostasis is an essential process in plants. Different metabolic routes are involved in auxin homeostasis, but the catabolic pathway has remained elusive until recent studies identified DIOXYGENASE FOR AUXIN OXIDATION (DAO) from rice and Arabidopsis thaliana. DAO, a member of the 2-oxoglutarate/Fe(II)-dependent oxygenase (2ODO) family, constitutes a major enzyme for IAA catabolism. This enzyme catalyzes, with the cosubstrate 2-oxoglutarate, the conversion of IAA into 2-oxoindole-3-acetic acid, a functionally inactive oxidative product of IAA. Here, we report a crystal structure of the unliganded DAO1 from A. thaliana (AtDAO1) and its complex with 2-oxoglutarate. AtDAO1 is structurally homologous with members of the 2ODO family but exhibits unique features in the prime substrate IAA binding site. We provide structural analyses of a putative binding site for IAA, supporting possible structural determinants for the substrate specificity of AtDAO1 toward IAA.

Interactions between cyazofamid and human drug transporters.

We aimed to investigate the intestinal permeability and interaction of cyazofamid with clinically important transporters. The intestinal permeability of cyazofamid was low (0.21 ± 0.02 cm/s), and it is a substrate for P-glycoprotein (P-gp) with a Km value of 83.1 µM, indicated that P-gp in the intestinal lumen could serve as a protective barrier to this fungicide. Cyazofamid was not a substrate for clinically important transporters. However, cyazofamid inhibited organic cation transporter 3 (OCT3) and OAT1, with IC50 values of 1.54 and 17.3 µM, respectively, but could not result in OAT3- and OAT1-mediated cyazofamid-drug interactions because of its low plasma concentration. Cyazofamid poorly interacted with OCT1, OCT2, organic anion transporting polypeptide 1B1 (OATP1B1), OATP1B3, P-gp, breast cancer resistance-related protein, and multidrug resistance-related protein 2. In conclusion, the interactions of cyazofamid with human drug transporters have been evaluated as part of the safety assessment. Given its low intestinal permeability and poor interaction with human drug transporters, cyazofamid might not cause serious toxicity or adverse events.

Epidemiology and Outcome of Powered Mobility Device-Related Injuries in Korea.

BACKGROUND: This study described and analysed the features of powered mobility device (PMD)-related injuries and compared elderly and younger adult injuries. METHODS: Data from Korea Emergency Department-based Injury In-depth Surveillance (EDIIS) database involving eight emergency departments in 2011-2016 were analysed. The inclusion criteria were injuries sustained during the use of PMDs. The variables were compared between adults aged ≥ 65 years and younger adults. Primary and secondary outcomes were severe trauma and poor clinical course accordingly. The logistic regression analysis was used to identify risk factors for study outcomes. RESULTS: A total of 231 adults were enrolled, of whom 150 were ≥ 65 years of age. The total number of PMD-related injuries and the proportion of elderly injured patients increased annually, and most injuries occurred on the roadway and did not involve crash opponents. By multivariate analysis, patients aged ≥ 65 years had a higher injury severity score (adjusted odds ratio [AOR], 2.78; 95% confidence interval [CI], 1.50-5.40) and had a higher incidence of intensive care unit admissions, surgery, and death (AOR, 2.42; 95% CI, 1.16-5.28). CONCLUSION: Given the higher number and severity of injuries sustained among elderly adults ≥ 65 years of age shown in this study, we recommend that safety educations, such as the use of protective equipment and the safe driving on the roadway, are considered for PMD users ≥ 65 years of age.

In Vitro Interaction of AB-FUBINACA with Human Cytochrome P450, UDP-Glucuronosyltransferase Enzymes and Drug Transporters.

AB-FUBINACA, a synthetic indazole carboxamide cannabinoid, has been used worldwide as a new psychoactive substance. Because drug abusers take various drugs concomitantly, it is necessary to explore potential AB-FUBINACA-induced drug-drug interactions caused by modulation of drug-metabolizing enzymes and transporters. In this study, the inhibitory effects of AB-FUBINACA on eight major human cytochrome P450s (CYPs) and six uridine 5'-diphospho-glucuronosyltransferases (UGTs) of human liver microsomes, and on eight clinically important transport activities including organic cation transporters (OCT)1 and OCT2, organic anion transporters (OAT)1 and OAT3, organic anion transporting polypeptide transporters (OATP)1B1 and OATP1B3, P-glycoprotein, and breast cancer resistance protein (BCRP) in transporter-overexpressing cells were investigated. AB-FUBINACA inhibited CYP2B6-mediated bupropion hydroxylation via mixed inhibition with Ki value of 15.0 µM and competitively inhibited CYP2C8-catalyzed amodiaquine N-de-ethylation, CYP2C9-catalyzed diclofenac 4'-hydroxylation, CYP2C19-catalyzed [S]-mephenytoin 4'-hydroxylation, and CYP2D6-catalyzed bufuralol 1'-hydroxylation with Ki values of 19.9, 13.1, 6.3, and 20.8 µM, respectively. AB-FUBINACA inhibited OCT2-mediated MPP+ uptake via mixed inhibition (Ki, 54.2 µM) and competitively inhibited OATP1B1-mediated estrone-3-sulfate uptake (Ki, 94.4 µM). However, AB-FUBINACA did not significantly inhibit CYP1A2, CYP2A6, CYP3A4, UGT1A1, UGT1A3, UGT1A4, UGT1A6, or UGT2B7 enzyme activities at concentrations up to 100 µM. AB-FUBINACA did not significantly inhibit the transport activities of OCT1, OAT1/3, OATP1B3, P-glycoprotein, or BCRP at concentrations up to 250 µM. As the pharmacokinetics of AB-FUBINACA in humans and animals remain unknown, it is necessary to clinically evaluate potential in vivo pharmacokinetic drug-drug interactions induced by AB-FUBINACA-mediated inhibition of CYP2B6, CYP2C8, CYP2C9, CYP2C19, CYP2D6, OCT2, and OATP1B1 activities.

Liquid Chromatography-Tandem Mass Spectrometry for the Simultaneous Analysis of 353 Pesticides in the Edible Insect Tenebrio molitor Larvae (Mealworms).

Tenebrio molitor larvae (mealworm) is an edible insect and is considered a future food. Using liquid chromatography-tandem mass spectrometry (LC-MS/MS), a novel method for simultaneous analysis of 353 target analytes was developed and validated. Various sample preparation steps including "quick, easy, cheap, effective, rugged, and safe" (QuEChERS) extraction conditions, number of acetonitrile-hexane partitions, and dispersive-solid phase extraction (dSPE) sorbents were compared, and the optimal conditions were determined. In the established method, 5 g of homogenized mealworms was extracted with acetonitrile and treated with QuEChERS EN 15662 salts. The crude extract was subjected to three rounds of acetonitrile-hexane partitioning, and the acetonitrile layer was cleaned with C18 dSPE. The final solution was matrix-matched and injected into LC-MS/MS (2 µL). For target analytes, the limits of quantitation (LOQs) were ≤10 µg/kg, and the correlation coefficient (r2) of calibration was >0.990. In recovery tests, more than 90% of the pesticides showed an excellent recovery range (70-120%) with relative standard deviation (RSD) ≤20%. For more than 94% of pesticides, a negligible matrix effect (within ±20%) was observed. The analytical method was successfully applied and used for the detection of three urea pesticides in 4 of 11 mealworm samples.

Liquid Chromatography-Tandem Mass Spectrometry for the Simultaneous Determination of Doxorubicin and its Metabolites Doxorubicinol, Doxorubicinone, Doxorubicinolone, and 7-Deoxydoxorubicinone in Mouse Plasma.

Doxorubicin, an anthracycline antitumor antibiotic, acts as a cancer treatment by interfering with the function of DNA. Herein, liquid chromatography-tandem mass spectrometry was for the first time developed and validated for the simultaneous determination of doxorubicin and its major metabolites doxorubicinol, doxorubicinone, doxorubicinolone, and 7-deoxydoxorubicinone in mouse plasma. The liquid-liquid extraction of a 10 µL mouse plasma sample with chloroform:methanol (4:1, v/v) and use of the selected reaction monitoring mode led to less matrix effect and better sensitivity. The lower limits of quantification levels were 0.5 ng/mL for doxorubicin, 0.1 ng/mL for doxorubicinol, and 0.01 ng/mL for doxorubicinone, doxorubicinolone, and 7-deoxydoxorubicinone. The standard curves were linear over the range of 0.5-200 ng/mL for doxorubicin; 0.1-200 ng/mL for doxorubicinol; and 0.01-50 ng/mL for doxorubicinone, doxorubicinolone, and 7-deoxydoxorubicinone in mouse plasma. The intra and inter-day relative standard deviation and relative errors for doxorubicin and its four metabolites at four quality control concentrations were 0.9-13.6% and -13.0% to 14.9%, respectively. This method was successfully applied to the pharmacokinetic study of doxorubicin and its metabolites after intravenous administration of doxorubicin at a dose of 1.3 mg/kg to female BALB/c nude mice.

Simultaneous determination of 75 abuse drugs including amphetamines, benzodiazepines, cocaine, opioids, piperazines, zolpidem and metabolites in human hair samples using liquid chromatography-tandem mass spectrometry.

A liquid chromatography-tandem mass spectrometric method for the simultaneous determination of 75 abuse drugs and metabolites, including 19 benzodiazepines, 19 amphetamines, two opiates, eight opioids, cocaine, lysergic acid diethylamide, zolpidem, three piperazines and 21 metabolites in human hair samples, was developed and validated. Ten-milligram hair samples were decontaminated, pulverized using a ball mill, extracted with 1 mL of methanol spiked with 28 deuterated internal standards in an ultrasonic bath for 60 min at 50°C, and purified with Q-sep dispersive solid-phase extraction tubes. The purified extracts were evaporated to dryness and the residue was dissolved in 0.1 mL of 10% methanol. The 75 analytes were analyzed on an Acquity HSS T3 column using gradient elution of methanol and 0.1% formic acid and quantified in multiple reaction monitoring mode with positive electrospray ionization. Calibration curves were linear (r ≥ 0.9951) from the lower limit of quantitation (2-200 pg/mg depending on the drug) to 2000 pg/mg. The coefficients of variation and accuracy for intra- and inter-assay analysis at three QC levels were 4.3-12.9% and 89.2-109.1%, respectively. The overall mean recovery ranged from 87.1 to 105.3%. This method was successfully applied to the analysis of 11 forensic hair samples obtained from drug abusers.

A Quantitative Tandem Mass Spectrometry and Scaled-Down QuEChERS Approach for Simultaneous Analysis of Pesticide Multiresidues in Human Urine.

Multiresidual pesticide determination in a biological sample is essential for an immediate decision and response related to various pesticide intoxications. A rapid and simultaneous analytical method for 260 pesticides in human urine was developed and validated using liquid chromatography-tandem mass spectrometry (LC-MS/MS). High speed positive/negative switching electrospray ionization (ESI) mode was used, and scheduled multiple reaction monitoring (MRM) was optimized. Three versions of scaled-down QuEChERS procedures were evaluated, and the procedure using non-buffer reagents (magnesium sulfate and sodium chloride) and excluding cleanup steps was selected for optimum pesticide extraction. The limit of quantitation (LOQ) in this methodology was 10 ng/mL for each target pesticide, and correlation coefficient (r²) values of calibration curves were ≥0.988 (linearity range; 10-250 ng/mL). In accuracy and precision tests, the relative error ranges were -18.4% to 19.5%, with relative standard deviation (RSD) 2.1%-19.9% at an LOQ level (10 ng/mL), and -14.7% to 14.9% (RSD; 0.6%-14.9%) at higher concentrations (50, 150, and 250 ng/mL). Recovery range was 54.2%-113.9% (RSD; 0.3%-20.0%), and the soft matrix effect (range; -20% to 20%) was observed in 75.4% of target pesticides. The established bioanalytical methods are sufficient for application to biomonitoring in agricultural exposures and applicable in the forensic and clinic.

Whole body dosimetry and risk assessment of agricultural operator exposure to the fungicide kresoxim-methyl in apple orchards.

This study examined dermal and inhalation exposure of agricultural operators to kresoxim-methyl during pesticide mixing/loading and speed sprayer application (10 replicates, each of 3000 L of spray suspension) in an apple orchard and performed risk assessment. For the whole body dosimetry (WBD) exposure protocol, outer clothing, inner clothing, gauze, and nitrile gloves were examined to measure dermal exposure. In contrast, an IOM (institute of occupational medicine) sampler with a glass fiber filter was used to measure inhalation exposure. Analytical method accuracy in the exposure matrices was evaluated by a field recovery study. The dermal and inhalation exposure amounts for mixing/loading were 9.7 mg [0.002% of the total mixed/loaded active ingredient (a.i.)] and 1.2 µg (1.7 × 10-6% of the total mixed/loaded a.i.), respectively. The body parts more exposed were the forearms (35.5%), chest & stomach (30.2%), and hands (17.9%). During application, the dermal and inhalation exposure amounts were 66.5 mg (0.009% of the total applied a.i) and 34.8 µg (4.6 × 10-5% of the total applied a.i.), respectively. The shins (18.5%) and chest & stomach (16.0%) were exposed to higher proportion of pesticide, followed by the thighs (15.8%) and back (14.7%). Comparing the exposure pattern as assessed by the WBD method in the present study with the patch method as in our previous study, the ADE (actual dermal exposure) as measured by the WBD method was 25 times less than that measured by the patch method. The daily exposure amounts of ADE and AIE (actual inhalation exposure) for mixing/loading were 711.8 µg/day and 4.3 µg/day, respectively, whereas the amounts of ADE and AIE for application were 1825.8 µg/day and 116.1 µg/day. In risk assessment of the mixing/loading and application scenarios, the AOEL (acceptable operator exposure level) of kresoxim-methyl was used as the reference dose to show that the RI (risk index) was much lower than 1, indicating that agricultural operators are at low risk of exposure to kresoxim-methyl.

Surgical correction of crow's feet deformity with radiofrequency current.

BACKGROUND: There are many published surgical techniques for the correction of crow's feet deformity, but subsequent contour irregularities and early recurrence are often reported. OBJECTIVE: The authors present a radiofrequency (RF) technique to treat crow's feet that can prevent complications while simultaneously maintaining long-term results. METHODS: From April 2010 to February 2012, a total of 52 consecutive patients (3 men and 49 women) underwent surgical correction of crow's feet with an RF current. Following elevation of the skin flap in the temporal area, the lateral portion of the orbicularis oculi muscle was partially elevated and splayed. Then the RF current was applied to the elevated muscle flap until the target temperature of 60°C to 80°C was reached. Clinical outcomes were observed through photographs with patients in a natural smiling position. RESULTS: Mean (SD) patient age was 52.7 (2.2) years (range, 31-73 years). Patients were followed postoperatively during a mean period of 23 months (range, 15-36 months). There were no recurrences of crow's feet during the follow-up period. No major complications were noted. CONCLUSIONS: The main advantage of this surgical technique is preserving continuity of the orbicularis oculi muscle while selectively decreasing muscle tone. Hence, this technique may prevent any contour irregularities. The RF current causes irreversible muscle fibrosis, which in turn provides long-lasting results. While the early results of this series show promising long-term efficacy and a good safety profile, the small number of patients and short-term follow-up period warrant further study.

Probiotic Potential of Bacillus Subtilis Strain I3: Antagonistic Activity Against Chalkbrood Pathogen and Pesticide Degradation for Enhancing Honeybee Health.

To explore the potential of probiotic candidates beneficial for honeybee health through the modulation of the gut microbiome, bee gut microbes were isolated from bumblebee (Bombus terrestris) and honeybee (Apis mellifera) using diverse media and cultural conditions. A total of 77 bee gut bacteria, classified under the phyla Proteobacteria, Firmicutes, and Actinobacteria, were identified. The antagonistic activity of the isolates against Ascosphaera apis, a fungal pathogen responsible for chalkbrood disease in honeybee larvae, was investigated. The highest growth inhibition percentage against A. apis was demonstrated by Bacillus subtilis strain I3 among the bacterial strains. The presence of antimicrobial peptide genes in the I3 strain was detected using PCR amplification of gene fragments encoding surfactin and fengycin utilizing specific primers. The export of antimicrobial peptides by the I3 strain into growth medium was verified using liquid chromatography coupled with mass spectroscopy. Furthermore, the strain's capabilities for degrading pesticides, used for controlling varroa mites, and its spent growth medium antioxidant activity were substantiated. The survival rate of honeybees infected with (A) apis was investigated after feeding larvae with only medium (fructose + glucose + yeast extract + royal jelly), (B) subtilis I3 strain, A. apis with medium and I3 strain + A. apis with medium. Honeybees receiving the I3 strain + A. apis exhibited a 50% reduction in mortality rate due to I3 strain supplementation under experimental conditions, compared to the control group. In silico molecular docking revealed that fengycin hydrolase from I3 strain effectively interacted with tau-fluvalinate, suggesting its potential in bee health and environmental protection. Further studies are needed to confirm the effects of the I3 strain in different populations of honey bees across several regions to account for genetic and environmental variations.

Comparative Biological Half-Life of Penthiopyrad and Tebufenpyrad in Angelica Leaves and Establishment of Pre-Harvest Residue Limits (PHRLs).

To prevent pesticides from exceeding maximum residue limits (MRLs) in crops during export and shipment, it is necessary to manage residue levels during the pre-harvest stages. Therefore, the Republic of Korea establishes pre-harvest residue limits (PHRLs) per crop and pesticide. This study was conducted to set PHRLs for penthiopyrad and tebufenpyrad in angelica leaves, where the exceedance rates of MRLs are expected to be high. The LOQ of the analytical method used was 0.01 mg/kg and it demonstrated good linearity, with a correlation coefficient of 0.999 or higher within the quantitation range of 0.005 to 0.5 mg/kg. The recovery and storage stability accuracy values were in the range of 94.5-111.1%, within the acceptable range (70-120%, RSD ≤ 20%). The matrix effect for both pesticides was in the medium-to-strong range, and it did not significantly impact the quantitative results as a matrix-matched calibration method was employed. Using the validated method, residue concentrations of penthiopyrad 20 (%) EC and tebufenpyrad 10 (%) EC were analyzed. Both pesticides exhibited a decreasing residue trend over time. In Fields 1-3 and their integrated results, the biological half-life was within 2.6-4.0 days for penthiopyrad and 3.0-4.2 days for tebufenpyrad. The minimum value of the regression coefficient in the dissipation curve regression equation was selected as the dissipation constant. The selected dissipation constants for penthiopyrad in Fields 1-3 and their integration were 0.1221, 0.2081, 0.2162, and 0.1960. For tebufenpyrad, the dissipation constants were 0.1451, 0.0960, 0.1725, and 0.1600, respectively. The dissipation constant was used to calculate PHRL per field. Following the principles of the PHRL proposal process, residue levels (%) on PHI dates relative to MRLs were calculated, and fields for proposing PHRLs were selected. For penthiopyrad, since the residue level (%) was less than 20%, the PHRL for Field 3 with the largest dissipation constant was proposed. For tebufenpyrad, as the residue level (%) exceeded 80%, the PHRL proposal could not established. It is deemed necessary to reassess the MRL and 'guidelines for safe use' for tebufenpyrad in angelica leaves.

A New Class of High-Capacity Fe-Based Cation-Disordered Oxide for Li-Ion Batteries: Li-Fe-Ti-Mo Oxide.

Low-cost Fe can be used for forming cation-disordered rocksalt Li-excess (DRX) materials instead of high-cost d0 -species and then the Fe-based DRX can be promising electrode materials because they can theoretically achieve high capacity, resulting from additional oxygen redox reaction and stable cation-disordered structure. However, Fe-based DRX materials suffer from large voltage hysteresis, low electrochemical activity, and poor cyclability, so it is highly challenging to utilize them as practical electrode materials for a cell. Here, novel high-capacity Li-Fe-Ti-Mo electrode materials (LFTMO) with high average discharge voltage and reasonable stability are reported. The effect of Ti/Mo on electrochemical reactions in Fe-based DRX materials (LFTMO) is studied by controlling its composition ratio and using techniques for analyzing the local environment to find the key factors that improve its activity. It is found out that the introduction of appropriate quantity of redox-active Mo4+/5+ to Fe-based DRX materials can help stabilize the oxygen redox reaction via changing a local structure and can suppress a Fe redox reaction, which can cause poor performance. The understandings will help develop high capacity and long cyclability Fe-based DRX electrode materials.

Simultaneous analytical method for 296 pesticide multiresidues in root and rhizome based herbal medicines with GC-MS/MS.

A method for the simultaneous analysis of pesticide multiresidues in three root/rhizome-based herbal medicines (Cnidium officinale, Rehmannia glutinosa, and Paeonia lactiflora) was developed with GC-MS/MS. To determine the concentrations of pesticide residues, 5 g of dried samples were saturated with distilled water, extracted with 10 mL of 0.1% formic acid in acetonitrile/ethyl acetate (7:3, v/v), and then partitioned using magnesium sulfate and sodium chloride. The organic layer was purified with Oasis PRiME HLB plus light, followed by a cleanup with dispersive solid-phase extraction containing alumina. The sample was then injected into GC-MS/MS (2 µL) using a pulsed injection mode at 15 psi and analyzed using multiple reaction monitoring (MRM) modes. The limit of quantitation for the 296 target pesticides was within 0.002-0.05 mg/kg. Among them, 77.7-88.5% showed recoveries between 70% and 120% with relative standard deviations (RSDs) ≤20% at fortified levels of 0.01, and 0.05 mg/kg. The analytical method was successfully applied to real herbal samples obtained from commercial markets, and 10 pesticides were quantitatively determined from these samples.

Potential exposure and risk assessment of agricultural workers to the insecticide chlorantraniliprole in rice paddies.

BACKGROUND: Exposure of agricultural workers in rice paddies to the insecticide chlorantraniliprole and its subsequent potential health risks were investigated during two scenarios (mixing/loading and hand-held spraying). The exposure factors, such as the outer dosimeter, inner dosimeter, gauze, and nitrile gloves, were calculated using whole-body dosimetry to measure dermal exposure. The inhalation exposure was determined using a fiberglass filter which is set with an Institute of Occupational Medicine (IOM) sampler. A recovery test was performed to evaluate the accuracy of the analytical method. RESULTS: The exposure amounts of various matrices were calculated from extraction volume and concentration of the target compound. The dermal exposure to chlorantraniliprole was 0.6 mg [0.001% of the total active ingredient (a.i.)] for mixing and loading, and 28.6 mg (0.066% of the total a.i.) for application. The inhalation exposure to chlorantraniliprole was 7.2 µg (1.3%, 1.2 × 10-5 % of the total applied a.i.) for mixing and loading, and 1.9 µg (0.006%, 4.4 × 10-6 % of the total applied a.i.) for application. The most exposed part of the body was the hand (90.4%) during mixing and loading, whereas the primary sites during application were the thighs (32.8%) and shins (22.6%). For mixing and loading, the amount of actual dermal exposure was 5.5 µg day-1 and that of actual inhalation exposure was 21.9 µg day-1 . By contrast, in the application, the amounts of actual dermal and actual inhalation exposures were 34 178.7 and 5.9 µg day-1 , respectively. CONCLUSIONS: The risk assessment results demonstrated that the risk of chlorantraniliprole exposure in rice paddies was low during application than during mixing and loading. © 2022 Society of Chemical Industry.

Dissipation Kinetics and Risk Assessment of Spirodiclofen and Tebufenpyrad in Aster scaber Thunb.

The dissipation kinetics of spirodiclofen and tebufenpyrad after their application on Aster scaber Thunb were studied for 10 days, including the pre-harvest intervals. Spirodiclofen and tebufenpyrad were used in two greenhouses in Taean-gun, Chungcheongnam province (Field 1) and Gwangyang-si, Jeollanam province (Field 2), Republic of Korea. Samples were taken at 0, 1, 3, 5, 7, and 10 days after pesticide application. The method validations were performed utilizing liquid chromatography (LC)-tandem mass spectrometry (MS/MS). The recoveries of the studied pesticides ranged from 82.0-115.9%. The biological half-lives of spirodiclofen and tebufenpyrad were 4.4 and 3.8 days in Field 1, and 4.5 and 4.2 days in Field 2, respectively. The pre-harvest residue limits (PHRLs; 10 days before harvesting) of Aster scaber were 37.6 mg/kg (Field 1) and 41.2 mg/kg (Field 2) for spirodiclofen, whereas the PHRLs were 7.2 (Field 1) and 3.6 (Field 2) for tebufenpyrad. The hazard quotient for both pesticides at pre-harvest intervals was less than 100% except in the case of spirodiclofen (0 day).

LC-MS/MS Method Minimizing Matrix Effect for the Analysis of Bifenthrin and Butachlor in Chinese Chives and Its Application for Residual Study.

The matrix effect refers to the change in the analytical signal caused by the matrix in which the sample is contained, as well as the impurities that are co-eluted with the target analyte. In crop sample analysis using LC-MS/MS, the matrix effect can affect the quantification results. Chinese chives are likely to exhibit a strong matrix effect when co-extracted with bifenthrin and butachlor due to the presence of phytochemicals and chlorophyll. A novel analytical method was developed to reduce the matrix effects of bifenthrin and butachlor to a negligible level in Chinese chives. The established method had a limit of quantitation of 0.005 mg/kg and correlation coefficients greater than 0.999 within the range of 0.005-0.5 mg/kg. Matrix effects were found to be negligible, with values ranging from -18.8% to 7.2% in four different sources of chives and two leafy vegetables. Compared to conventional analytical methods for the LOQ and matrix effect, the established method demonstrated improved performances. The analytical method was further applied in a residual study in chive fields. The active ingredient of butachlor 5 granule (GR) was not detected after soil admixture application, while that of bifenthrin 1 emulsifiable concentrate (EC) showed a range from 1.002 to 0.087 mg/kg after foliar spraying. The dissipation rate constant (k) of bifenthrin was determined to be 0.115, thus its half-life was calculated to be 6.0 days. From the results, PHI and safety use standards of both pesticides were suggested. The developed analytical method can be applied to accurately determine bifenthrin and butachlor residues in Chinese chives and provides a foundation for further research on the fate and behavior of these pesticides in the environment.

Simple and rapid method for 336 multiresidual pesticide analysis in saliva, determination of their chemical stabilities, and biomonitoring of farmers.

Simultaneous multiresidual pesticide analysis of saliva samples was performed using scaled-down QuEChERS extraction with LC-MS/MS and GC-MS/MS. The optimum extraction procedure using acidified acetonitrile was applicable to 336 pesticides (287 for LC-MS/MS and 49 for GC-MS/MS). To determine pesticide multiresidues in saliva, 100 µL of the sample was extracted with 200 µL of 0.1% formic acid in acetonitrile, and the initial extract was partitioned with 40 mg of MgSO4 and 10 mg of NaCl. The organic supernatants (120 µL) were then mixed with acetonitrile (30 µL) for matrix-matching (4:1, v/v), and the final extract solution was injected into the LC-MS/MS (4 µL) and GC-MS/MS (2 µL) systems. The established analytical method showed a good LOQs between 5 and 25 ng/mL with reliable accuracy/precision values and recovery results (50-140%) for the target pesticides. Under the two different storage conditions, most of the analytes did not undergo chemical changes in the saliva samples, whereas some pesticides were more stable in freeze-thaw processes than those left at room temperature. Biomonitoring of farmers (ten mixers and ten sprayers) was successfully applied using the validated method, and two carbamates (fenobucarb and propamocarb) were determined at trace concentrations (12.5-675.0 ng/mL from 11 positively detected samples).