The enantioselective toxic effect and environmental behavior of chiral pesticides have attracted increasing research attention. In this study, the enantioselective toxicity and residues of hexaconazole (HEX) in earthworms (Eisenia fetida) were investigated. In the present study, significant enantioselective degradation characteristics were observed in artificial soil with the R-enantiomer preferentially degrading (p < 0.05); however, no significant enantioselective bioaccumulation was observed in the earthworms (p > 0.05). The acute toxicity of S-(+)-HEX was higher than that of R-(−)-HEX in earthworms, with 48-h LC₅₀ values of 8.62 and 22.35 μg/cm², respectively. At 25 mg/kg, enantiospecific induction of oxidative stress was observed in earthworms; moreover, S-(+)-HEX had a greater influence on the contents of malonaldehyde, cytochrome P450, and 8-hydroxy-2-deoxyguanosine than R-(−)-HEX. These results were consistent with those of the enrichment analysis of differentially expressed genes. The transcriptome sequencing results showed that S-(+)-HEX had a more significant influence on steroid biosynthesis, arachidonic acid metabolism, and cell cycle processes than R-(−)-HEX, leading to abnormal biological function activities. These results indicate that S-(+)-HEX may pose a higher risk to soil organisms than R-(−)-HEX. This study suggests that the environmental risk of chiral pesticides to nontarget organisms should be assessed at the enantiomeric level.

Triazole fungicides are widely used as broad-spectrum fungicides, non-steroidal antiestrogens and for various industrial applications. Their residues have been frequently detected in multiple environmental and human matrices. The increasingly reported toxicity incidents have led triazole fungicides as emerging contaminants of environmental and public health concern. However, whether triazole fungicides behave as endocrine disruptors by directly mimicking environmental androgens/antiandrogens or exerting potential androgenic disruption indirectly through the inhibition of cytochrome P450 (CYP450) enzyme activity is yet an unresolved question. We herein evaluated five commonly used triazole fungicides including bitertanol, hexaconazole, penconazole, tebuconazole and uniconazole for the androgenic and anti-androgenic activity using two-hybrid recombinant human androgen receptor (AR) yeast bioassay and comparatively evaluated their effects on enzymatic activity of CYP3A4 by P450-Glo™ CYP3A4 bioassay. All five fungicides showed moderate anti-androgenic activity toward human AR with the IC50 ranging from 9.34 μM to 79.85 μM. The anti-androgenic activity remained no significant change after the metabolism mediated by human liver microsomes. These fungicides significantly inhibited the activity of CYP3A4 at the environmental relevant concentrations and the potency ranks as tebuconazole > uniconazole > hexaconazole > penconazole > bitertanol with the corresponding IC50 of 0.81 μM, 0.93 μM, 1.27 μM, 2.22 μM, and 2.74 μM, respectively. We found that their anti-androgenic activity and the inhibition potency toward CYP3A4 inhibition was significantly correlated (R2 between 0.83 and 0.97, p < 0.001). Our results indicated that the risk assessment of triazole pesticides and structurally similar chemicals should fully consider potential androgenic disrupting effects and the influences on the activity of CYP450s.

We tested seven contemporary agrochemicals as potential plant protectants against ozone phytotoxicity. In nine experiments, Bel-W3 tobacco plants were experienced weekly exposures to a) 80 nmol mol−1 of ozone-enriched or ozone-free air in controlled environment chambers, b) an urban air polluted area, and c) an agricultural-remote area. Ozone caused severe leaf injury, reduced chlorophylls' and total carotenoids' content, and negatively affected photosynthesis and stomatal conductance. Penconazole, (35% ± 8) hexaconazole (28% ± 5) and kresoxim-methyl (28% ± 15) showed higher plants’ protection (expressed as percentage; mean ± s.e.) against ozone, although the latter exhibited a high variability. Azoxystrobin (21% ± 15) showed lower protection efficacy and Benomyl (15% ± 9) even lower. Trifloxystrobin (7% ± 11) did not protect the plants at all. Acibenzolar-S-methyl + metalaxyl-M (Bion MX) (−6% ± 17) exhibited the higher variability and contrasting results: in some experiments it showed some protection while in others it intensified the ozone injury by causing phytotoxic symptoms on leaves, even in control plants.

This study was conducted to investigate the pesticide residue concentrations and assess potential human health risks from vegetable consumption in Incheon. A total of 960 samples were collected from the Incheon areas of Korea in 2019. The pesticide residues were analyzed by the multi-residue method of the Korean Food Code for 373 different pesticides using GC–MS/MS, LC–MS/MS, GC-ECD/NPD, and HPLC-UVD. Among the vegetable samples, 869 samples (90.5%) were free from detectable residues, while 91 samples (9.5%) contained residues, and 16 samples (1.7%) had residues exceeding the Korean maximum residue limit (MRLs). A total of 33 different pesticide residues were found, and 11 residues exceeded MRLs. The most frequently detected pesticide residues were chlorfenapyr, fludioxonil, pyridalyl, hexaconazole, and procymidone. Samples exceeding the MRLs were found in aster scaber, coastal hog fennel, lettuce (leaves), mustard green, mustard leaf, perilla leaves, Pimpinella brachycarpa, radish leaves, shepherd’ purse, spinach, and winter-grown cabbage. The potential health risk assessment of pesticides was estimated by calculating the estimated daily intake (EDI) and the acceptable daily intake (ADI). The range of HQs was 0.002–90.621%, which was below 100%. Therefore, the results of this study show that the detected pesticide could not be considered a serious public health problem through the consumption of vegetables.

This study aimed to investigate the concentration of 33 pesticide residues in 60 black tea samples collected from Iran, determine their transfer rate, and assess their health risk during brewing. Pesticide extraction and analysis were performed by using a quick, easy, cheap, effective, rugged, and safe (QuEChERS) method and gas chromatography/tandem mass spectrometry (GC-MS/MS), respectively. The limits of detection (LOD) and the limits of quantification (LOQ) of pesticides were ranged 0.1–7.26 and 0.8–24 μg/kg for dried tea leaves and 0.03–3.1 and 0.09–10 μg/L for the tea infusion, respectively. The levels of pesticide residue in 52 (86.67%) out of 60 tea samples were above the LOD (0.1–7.26 μg/kg). Twenty four (40%) of the samples contained pesticides in a concentration higher than the maximum residue limit (MRL) set by the European Commission (EC). Seven out of 33 validated pesticides were detected in dried tea leaf samples that only four of seven, including buprofezin, chlorpyrifos, hexaconazole, and triflumizole, were transferred into tea infusion, demonstrating that the concentrations of pesticides in infusion were raised during brewing. The risk assessment study for detected pesticides in the tea infusion samples indicated that this beverage consumption was safe for consumers, while the mean residue of some pesticides in positive samples was higher than the MRL; therefore, periodic control of these pesticides should be regularly implemented.

The present study aims to evaluate the comparative effects of methyl parathion and hexaconazole on genotoxicity, oxidative stress, antioxidative defence system and photosynthetic pigments in barley (Hordeum vulgare L. variety karan-16). The seeds were exposed with three different concentrations, i.e. 0.05, 0.1 and 0.5 % for 6 h after three pre-soaking durations 7, 17 and 27 h which represents G₁, S and G₂ phases of the cell cycle, respectively. Ethyl methane sulphonate, a well-known mutagenic agent and double distilled water, was used as positive and negative controls, respectively. The results indicate significant decrease in mitotic index with increasing concentrations of pesticides, and the extent was higher in methyl parathion. Chromosomal aberrations were found more frequent in methyl parathion than hexaconazole as compared to their respective controls. Treatment with the pesticides induced oxidative stress which was evident with higher contents of H₂O₂ and lipid peroxidation, and the increase was more prominent in methyl parathion. Contents of total phenolics were increased; however, soluble protein content showed a reverse trend. Among the enzymatic antioxidants, activities of superoxide dismutase and peroxidase were significantly up-regulated, and more increase was noticed in hexaconazole. Increments in total chlorophyll and carotenoid contents were observed up to 0.1 % but decreased at higher concentration (0.5 %), and the reductions were more prominent in methyl parathion than hexaconazole as compared to their respective controls. Methyl parathion treatment caused more damage in the plant cells of barley as compared to hexaconazole, which may be closely related to higher genotoxicity and oxidative stress.

Hexaconazole is a potential fungicide to be used in the oil palm plantation for controlling the basal stem root (BSR) disease caused by Ganoderma boninense. Therefore, the dissipation rate of hexaconazole in an oil palm agroecosystem under field conditions was studied. Two experimental plots were treated with hexaconazole at the recommended dosage of 4.5 g a.i. palm⁻¹ (active ingredient) and at double the recommended dosage (9.0 g a.i. palm⁻¹), whilst one plot was untreated as control. The residue of hexaconazole was detected in soil samples in the range of 2.74 to 0.78 and 7.13 to 1.66 mg kg⁻¹ at the recommended and double recommended dosage plots, respectively. An initial relatively rapid dissipation rate of hexaconazole residues occurred but reduced with time. The dissipation of hexaconazole in soil was described using first-order kinetics with the value of coefficient regression (r ² > 0.8). The results indicated that hexaconazole has moderate persistence in the soil and the half-life was found to be 69.3 and 86.6 days in the recommended and double recommended dosage plot, respectively. The results obtained highlight that downward movement of hexaconazole was led by preferential flow as shown in image analysis. It can be concluded that varying soil conditions, environmental factors, and pesticide chemical properties of hexaconazole has a significant impact on dissipation of hexaconazole in soil under humid conditions.

Azoxystrobin, buprofezin, dinocap and hexaconazole are widely used in crop protection of mango from flowering to harvest. Residue assessment of these chemicals on mango fruits was done following treatments at the recommended and double doses as per good agricultural practices (GAP). Mango fruit and soil sample preparation was done by QuEChERS, and analysis was done using LC-MS/MS (liquid chromatography mass spectrometry). Using these techniques, the limit of detection (LOD) determined was 1.5 μg kg⁻¹ and limit of quantification (LOQ) was 0.005 mg kg⁻¹ for all analytes. The residue levels on mango initially were 0.265 and 0.55 mg kg⁻¹ for azoxystrobin, 0.63 and 0.974 mg kg⁻¹ for buprofezin, 0.635 and 0.98 mg kg⁻¹ for dinocap and 0.203 and 0.35 mg kg⁻¹ for hexaconazole from standard and double dose treatments, respectively. The dissipation rate of the pesticides on mango fruits was about the same except for azoxystrobin, which dissipated slowly compared with others. The half-life of degradation (DT₅₀) of azoxystrobin was 10.4–12.1 days; buprofezin, 5.8–8.5 days; dinocap, 5.4–6.2 days; and hexaconazole, 4.4–6.1 days. The pre-harvest interval (PHI) based on European Union (EU) MRL (maximum residue limit) requirements were 1 day for azoxystrobin, 15 and 26 days for buprofezin, 27 and 34 days for dinocap, and 19 and 30 days for hexaconazole. The results of this study can be used to produce mango fruits safe for consumption and to meet the regulatory requirements for export of mango fruits from India.

Pollution of drinking water sources with agrochemicals is often a major threat to human and ecosystem health in some river deltas, where agricultural production must meet the requirements of national food security or export aspirations. This study was performed to survey the use of different drinking water sources and their pollution with pesticides in order to inform on potential exposure sources to pesticides in rural areas of the Mekong River delta, Vietnam. The field work comprised both household surveys and monitoring of 15 frequently used pesticide active ingredients in different water sources used for drinking (surface water, groundwater, water at public pumping stations, surface water chemically treated at household level, harvested rainwater, and bottled water). Our research also considered the surrounding land use systems as well as the cropping seasons. Improper pesticide storage and waste disposal as well as inadequate personal protection during pesticide handling and application were widespread amongst the interviewed households, with little overall risk awareness for human and environmental health. The results show that despite the local differences in the amount and frequency of pesticides applied, pesticide pollution was ubiquitous. Isoprothiolane (max. concentration 8.49 μg L⁻¹), fenobucarb (max. 2.32 μg L⁻¹), and fipronil (max. 0.41 μg L⁻¹) were detected in almost all analyzed water samples (98 % of all surface samples contained isoprothiolane, for instance). Other pesticides quantified comprised butachlor, pretilachlor, propiconazole, hexaconazole, difenoconazole, cypermethrin, fenoxapro-p-ethyl, tebuconazole, trifloxystrobin, azoxystrobin, quinalphos, and thiamethoxam. Among the studied water sources, concentrations were highest in canal waters. Pesticide concentrations varied with cropping season but did not diminish through the year. Even in harvested rainwater or purchased bottled water, up to 12 different pesticides were detected at concentrations exceeding the European Commission’s parametric guideline values for individual or total pesticides in drinking water (0.1 and 0.5 μg L⁻¹; respectively). The highest total pesticide concentration quantified in bottled water samples was 1.38 μg L⁻¹. Overall, we failed to identify a clean water source in the Mekong Delta with respect to pesticide pollution. It is therefore urgent to understand further and address drinking water-related health risk issues in the region.