Fragmentation Pattern-Based Screening Strategy Combining Diagnostic Ion and Neutral Loss Uncovered Novel para-Phenylenediamine Quinone Contaminants in the Environment.

Identifying transformed emerging contaminants in complex environmental compartments is a challenging but meaningful task. Substituted para-phenylenediamine quinones (PPD-quinones) are emerging contaminants originating from rubber antioxidants and have been proven to be toxic to the aquatic species, especially salmonids. The emergence of multiple PPD-quinones in various environmental matrices and evidence of their specific hazards underscore the need to understand their environmental occurrences. Here, we introduce a fragmentation pattern-based nontargeted screening strategy combining full MS/All ion fragmentation/neutral loss-ddMS2 scans to identify potential unknown PPD-quinones in different environmental matrices. Using diagnostic fragments of m/z 170.0600, 139.0502, and characteristic neutral losses of 199.0633, 138.0429 Da, six known and three novel PPD-quinones were recognized in air particulates, surface soil, and tire tissue. Their specific structures were confirmed, and their environmental concentration and composition profiles were clarified with self-synthesized standards. N-(1-methylheptyl)-N'-phenyl-1,4-benzenediamine quinone (8PPD-Q) and N,N'-di(1,3-dimethylbutyl)-p-phenylenediamine quinone (66PD-Q) were identified and quantified for the first time, with their median concentrations found to be 0.02-0.21 µg·g-1 in tire tissue, 0.40-2.76 pg·m-3 in air particles, and 0.23-1.02 ng·g-1 in surface soil. This work provides new evidence for the presence of unknown PPD-quinones in the environment, showcasing a potential strategy for screening emerging transformed contaminants in the environment.

Comparative Metabolomics Combined with Physiological Analysis Revealed Cadmium Tolerance Mechanism in Indica Rice (Oryza sativa L.).

Cadmium (Cd) pollution reduces rice production and quality, putting food security and human health at risk. We conducted comparative physiology and metabolomic analyses in two indica rice ('NH199' and 'NH224') to elucidate the Cd-tolerance mechanism. Cd hampered rice growth, induced oxidative stress, and changed the metabolomics profiling of the root. The biochemical and physiological analysis demonstrated that NH224 exhibited a more potent Cd-tolerance ability than NH199. Cd was primarily distributed in root, and NH224 had a lower Cd translocation factor than NH199 by about 24%. The metabolomic analysis revealed 180 and 177 differentially accumulated metabolites between Cd-stressed seedlings and the controls in NH224 and NH199, respectively. In NH224, amino acids biosynthesis, hormone metabolism, lipids-related metabolism, phenylalanine metabolism, and phenylpropanoid biosynthesis pathways were more active and highly associated with antioxidant defense system, biosynthesis of the cell wall and phytochelatins, and maintenance of plasma membrane stability. These findings provide insights into the metabolic profiles of rice following Cd stress and the screening and breeding of Cd-tolerant rice varieties.

Etoxazole stereoselective determination, bioaccumulation, and resulting oxidative stress in Danio rerio (zebrafish).

An environmentally-friendly and fast analytical method for the stereoselective determination of etoxazole was developed and then applied to estimate stereoselective bioaccumulation and elimination in zebrafish using SFC-MS/MS. Optimal enantioseparation conditions were determined using a Chiralpak IG-3 column and CO2/MeOH mobile phase (80/20, v/v), at 3.0 mL/min within 1 min, 30°Me and 18 MPa. A modified QuEChERS method was developed for zebrafish sample pretreatment, and mean recoveries were 88.43-110.12% with relative standard deviations ranging from 0.32 to 5.34%. The enantioselectives of etoxazole enantiomers in zebrafish during uptake and depuration phases were evaluated. Significant enantioselective bioaccumulation was observed, with preferential accumulation of (-)-R-etoxazole compared to its antipode, during uptake at both low and high exposure concentrations. The toxic effects of etoxazole on zebrafish were further explored, and activities of antioxidant enzymes were determined in liver of zebrafish. Significant changes were observed in the SOD and GST activities and in the MDA levels, which indicated the occurrence of oxidative stress in liver of zebrafish. The toxic effects exhibited time- and dose-dependent properties. These results can facilitate the accurate risk evaluation of etoxazole and provide basic knowledge for further study of biotoxicity mechanisms.

Selective extraction of fungicide carbendazim in fruits using ß-cyclodextrin based molecularly imprinted polymers.

Considering the importance of developing a new analytical approach for pesticide residue detection for the sake of ensuring food safety, a ß-cyclodextrin based molecularly imprinted polymer was prepared for selective determination of carbendazim. The polymers consist of a porous and hollow structure demonstrating the selective abundant adsorption sites for carbendazim molecule. The selectivity and adsorption capacity of the imprinted polymers were analyzed with dispersive solid-phase extraction and analyzed with high performance liquid chromatography coupled with ultraviolet. The results of imprinted polymers were higher than non-imprinted polymers with the maximum adsorption capacity of 3.65 mg/g within 30 min of total adsorption time. The reusability of the imprinted polymers was determined to evaluate its effectiveness and stability, which proved that the polymers lost 10% efficiency within seven consecutive recycles. The developed method displayed good linearity over the concentration range of 0.05-2.0 mg/L. The recovery percentage of 81.33-97.23 with relative standard deviations of 1.49-4.66% was obtained from spiked apple, banana, orange, and peach samples with a limit of detection of 0.03 mg/L and a limit of quantification of 0.10 mg/L (signal to noise ratio = 3/10). The overall performance of the proposed method evident that this technique provided a desirable outcome and it can be used as a convenient approach, as it qualifies the analytical standards.

Enantioselective Behavior of Chiral Difenoconazole in Apple and Field Soil.

Difenoconazole is a universal chiral fungicide which is widely used in apples. Recently, it is still employed as racemic mixtures without distinction of the enantiomers, which may lead to an incomplete risk assessment. Here, we analyzed the stereoselective degradation of difenoconazole in apple fruits and open-field soil using an HPLC-UV system. Different trends were established in various apple varieties under identical environmental conditions. No significant differences were found in its enantioselectivity of the degradation processes applied in the field soil of an apple orchard. However, preferential dissipation of (2R,4R)-difenoconazole and (2R,4S)-difenoconazole was observed in Hanfu and Fuji apples, resulting in the enrichment of stereoisomers of (2S,4S)-difenoconazole and (2S,4R)-difenoconazole. Meanwhile, no significant enantioselectivity was detected in Huahong apples. The present study will provide additional information that contributes to the comprehensive evaluation of the risks posed by the application of chiral difenoconazole in agricultural production practices.

Systemic Stereoselectivity Study of Etoxazole: Stereoselective Bioactivity, Acute Toxicity, and Environmental Behavior in Fruits and Soils.

This is the first systemic assessment of the stereoselectivity of etoxazole enantiomers. Etoxazole's stereoselective bioactivity was assessed against target organisms ( Tetranychus urticae eggs and Tetranychus cinnabarinus eggs), and its acute toxicity was assessed toward nontarget aquatic organisms ( Daphnia magna and Danio rerio). Additionally, stereoselective elimination was investigated in three species of fruits (grape and strawberry grown in a greenhouse and apple grown in an open field) and in field soil. The ovicidal activity of (+)-( S)-etoxazole against Tetranychus urticae and Tetranychus cinnabarinus eggs was about 16 and 24 times higher, respectively, than that of (-)-( R)-etoxazole. Inconsistent order of etoxazole isomer toxicity was found toward different aquatic organisms: (+)-( S)-etoxazole showed nearly 8.7 times higher acute toxicity than (-)-( R)-etoxazole toward Daphnia magna, whereas (-)-( R)-etoxazole was ∼4.5 times more toxic to Danio rerio than (+)-( S)-etoxazole. Stereoselective degradation of etoxazole enantiomers showed significant variation in various fruits and field soil. The (+)-( S)-etoxazole was preferentially dissipated in grape and strawberry fruits grown under greenhouse condition, whereas (-)-( R)-etoxazole degraded faster than its antipode in apple fruits and soils under open-field condition. Overall, the stereoselectivity of etoxazole enantiomers should be fully considered in comprehensive environmental health risk in future work.