Ferric chloride assisted QuEChERS method for separate detection of bifenazate and bifenazate-diazene in citrus fruits and its field validation.

Bifenazate is widely recognized as an effective acaricide for citrus production in various regions. Detecting both the parent compound of bifenazate and its metabolite, bifenazate-diazene, simultaneously can be challenging owing to their tendency to undergo chemical interconversion. Current methods developed for detecting bifenazate or bifenazate-diazene residues often involve lengthy incubation periods and may not effectively separate the two compounds. In this study, we developed a convenient and fast method based on a modified QuEChERS method assisted by oxidants to concurrently detect bifenazate and bifenazate-diazene. Based on preliminary analysis, it appears that ferric chloride has the ability to react with a reducing substance present in citrus, which may prevent the reduction of bifenazate-diazene. The method was validated and applied in a field trial. This work reports a novel strategy to establish a balanced 'neutral' condition to create a potential method for efficient determination of bifenazate acaricide residues in fruit matrices.

Dissipation, residue, and dietary risk assessment of dimethachlon in grapes.

Dimethachlon, a dicarboximide fungicide, has gained widespread usage in Asian countries. While considered a low-toxicity fungicide, concerns regarding potential health effects, such as nephrotoxicity, have emerged. To date, neither China nor other countries have established maximum residue limit (MRL) for dimethachlon on grapes, and exposure risk assessment of dimethachlon is lacking. Here, we developed a QuEChERS method coupled with gas chromatography-mass spectrometry (GC-MS) to investigate the dissipation rates and terminal residues of dimethachlon in grapes, along with an assessment of dietary risk to consumers. Our results indicated that the average recoveries of dimethachlon in grapes ranged from 74 to 76%. The limit of quantification (LOQ) was 0.050 mg/kg. After undergoing 112 days of storage at -18 °C, the dissipation rate of dimethachlon in grapes was found to be less than 30%, suggesting a state of stable storage. In the context of good agricultural practice (GAP) guidelines, the half-lives of dimethachlon in grapes were 14.3-18.1 days, which is notably longer compared to the reported values for other crops. The terminal residues of dimethachlon in grapes at 14 and 21 days were found to be < 0.05-0.53 mg/kg and < 0.05-0.29 mg/kg, respectively. Regarding the dietary risk assessment, the calculated risk quotient (RQ) value was significantly below 100%, indicating a negligible chronic risk of dimethachlon in grapes at the recommended dosage. This study provides an important reference for the analysis of dimethachlon and offers valuable empirical data to support the establishment of MRL.

In situ boron-doped cellulose-based biochar for effective removal of neonicotinoids: Adsorption mechanism and safety evaluation.

Biochar materials have been widely employed for adsorption of pollutants, which necessitates further consideration of their efficiency and safety in environmental remediation. In this study, a porous biochar (AC) was prepared through the combination of hydrothermal carbonization and in situ boron doping activation to effectively adsorb neonicotinoids. The adsorption process was shown to be a spontaneous endothermic physical adsorption process, where the predominant interaction forces between the acetamiprid and AC were electrostatic and hydrophobic interactions. The maximum adsorption capacity was 227.8 mg g-1for acetamiprid and the safety of AC was verified by simulating the situation where the aquatic organism (D. magna) was exposed to the combined system (AC & neonicotinoids). Interestingly, AC was observed to reduce the acute toxicity of neonicotinoids owing to the reduced bioavailability of acetamiprid in D. magna and the newly generated expression of cytochrome p450. Thus, it enhanced the metabolism and detoxification response in D. magna, which reducing the biological toxicity of acetamiprid. This study not only demonstrates the potential application of AC from a safety perspective, but also provides insight into the combined toxicity caused by biochar after adsorption of pollutants at the genomic level, which fills the gap in related research.

Hydrophobic-action-driven removal of six organophosphorus pesticides from tea infusion by modified carbonized bacterial cellulose.

The abuse of organophosphorus pesticides (OPPs) in tea planting makes it easy to transfer from tea into its infusion, bringing potential health risks to consumers. Thus, it is essential to adopt reliable techniques to remove OPPs from tea infusion. In this study, three treatment methods were used to modify carbonized bacterial cellulose (CBC) to improve its adsorption performance. Among them, CBC treated by hydrazine hydrate (N-CBC) had the best adsorption effect, whose removal rate for dicrotophos is 13 times that of CBC. The in-depth study of adsorption mechanism proved that hydrophobic interaction dominated the adsorption of OPPs onto N-CBC. The pseudo-second-order kinetic model and Langmuir isotherm model were more suitable to describe the process. Additionally, there were no significant changes in tea infusion quality after N-CBC treatment. This work clarifies that N-CBC benefitted from simple preparation method, excellent adsorption performance and unique adsorption mechanism has potential applications in tea infusion.

In Situ Assembly of Hydrogen-Bonded Organic Framework on Metal-Organic Framework: An Effective Strategy for Constructing Core-Shell Hybrid Photocatalyst.

The hydrogen-bonded organic frameworks (HOFs) have rarely been considered for photocatalytic application, given their weak stability and low activity. One presumably effective strategy to improve the photocatalytic performance of the HOFs is to produce a core-shell composite by fabricating a particular nanostructure using stable HOFs. To this end, the surface-functionalized metal-organic frameworks (MOFs) are used as the host matrix to support the in situ assembly and subsequent multisite growth of the stable HOFs. MOF@HOF eventually obtains core-shell hybrids, i.e., NH2 -UiO-66@DAT-HOF. This newly synthesized core-shell nanostructure exhibits excellent stability and superb photocatalytic performance. For example, in terms of tetracycline degradation, the optimal composite presents an apparent reaction rate constant of 60.7 and 7.6 times higher than its parent materials NH2 -UiO-66 and DAT-HOF. Such a pronounced enhancement in photocatalytic efficiency of the hybrid material is attributed to the broader visible-light utilization range compared to its individual parent material as well as the efficient separation of charge carriers supported by the S-scheme heterojunction. In addition, it is particularly notable that the photocatalytic efficiency of the yielded core-shell nanostructure can remain high after several-cycle applications. This work provides a universal scheme for synthesizing the MOF@HOF core-shell hybrids.

Exploration of emerging environmental pollutants 6PPD and 6PPDQ in honey and fish samples.

N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) and N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone (6PPDQ) can pose a threat to human health through the food chain because of their ubiquitous presence in the environment and the biotoxicity on organisms. In this work, we developed modified QuEChERS methods coupled with high performance liquid chromatography tandem mass spectrometry (HPLC/MS-MS) to explore whether 6PPD and 6PPDQ are present in fish and honey. The proposed methods showed acceptable limits of quantification (0.00043-0.001 mg/kg), linearity (R2 > 0.99), recovery (73.3%-108.3%), matrix effect (70.4%-95.6%) and repeatability (RSD < 8.4%). Accordingly, 6PPD and 6PPDQ have been discovered in snakehead, weever and Spanish mackerel fish, while none of which have been detected in the honey samples. The results of our work contributed to increasing public attention to 6PPD and 6PPDQ in agricultural products and provided important reference for the analysis of them.