Multi-residue monitoring and dietary risk assessment of 17 pesticides and 3 related metabolites in rice and rice flour from markets in China.

Pesticide residues in rice have attracted widespread public attention in recent years. This research aimed to monitor the residues of 17 pesticides and their 3 metabolites in 120 samples of rice and rice flour collected from markets in China using the QuEChERS (Quick, Easy, Cheap, Effective, Rugged, Safe) pretreatment method combined with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The monitoring results showed that isoprothiolane, tricyclazole, fenoxanil, and tebuconazole were detected in the rice samples, with detection frequencies of 33.3%, 17.5%, 8.3%, and 2.5%, and concentrations ranging from 0.02 to 0.1 mg/kg (median = 0.04), 0.01 to 0.17 mg/kg (median = 0.14), 0.04 to 0.06 mg/kg (median = 0.05), and 0.01 to 0.02 mg/kg (median = 0.01), respectively. The residues of these four pesticides were all below their corresponding maximum residue levels (MRLs) set by China. Additionally, isoprothiolane, tricyclazole, fenoxanil, and tebuconazole were detected in rice flour samples, with detection frequencies of 74.2%, 55.0%, 5.0%, and 2.5%, and concentrations ranging from 0.01 to 0.1 mg/kg (median = 0.04), 0.01 to 0.04 mg/kg (median = 0.02), 0.01 to 0.06 mg/kg (median = 0.03), and 0.02 to 0.04 mg/kg (median = 0.03), respectively. Furthermore, the chronic dietary intake risk (HQc), the acute dietary intake risk (HQa), and cumulative dietary risk (HI) for all the detected pesticides were evaluated and found well below 100%, indicating that the dietary intake risks would not pose potential health risks.

Simultaneous determination of residues of multiple pesticides and their metabolites in citrus and orange juice from markets in China: residue levels and dietary risk assessment.

Consumers are becoming more concerned about pesticide residues in food. Since citrus represent a significant portion of the diet, it is appropriate to monitor the pesticide residues in citrus. In this paper, we modified a QuEChERS method combined with HPLC-MS/MS to investigate residue levels of 15 pesticides and 3 metabolites in citrus (whole fruit and pulp) and orange juice from the markets in China. And the dietary exposure risks were evaluated by using the hazard quotient (HQ) and hazard index (HI) methods based on deterministic and probabilistic models. The recoveries of the modified method ranged from 70 to 112% at three spike levels of 0.005-0.5 mg/kg with relative standard deviations of 1.0-18.1%. Pesticide residues were detected in 85.84% of the whole citrus and 40.00% of pulp, with concentrations ranging from 0.005 to 0.47 mg/kg, which did not exceed their maximum residue limits (MRLs) in China. The HQ (0.01-11.41%) and HI (0.07-16.2%) were both less than 100%, demonstrating that chronic, acute, and cumulative dietary risks were acceptable. Notably, the risk for children (1-6 years old, 1.96-16.2%) was higher than that for the general population (0.76-6.25%). The results of our study can provide a valuable reference for regular monitoring to protect public health and ensure pesticide management.

RPS4XL encoded by lnc-Rps4l inhibits hypoxia-induced pyroptosis by binding HSC70 glycosylation site.

Pyroptosis is involved in pulmonary hypertension (PH); however, whether this process is regulated by long non-coding RNAs (lncRNAs) is unclear. Some lncRNAs encode peptides; therefore, whether the regulation of pyroptosis in PH depends on lncRNAs themselves or their encoded peptides needs to be explored. We aimed to characterize the role of the peptide RPS4XL encoded by lnc-Rps4l and its regulatory mechanisms during pyroptosis in PH. Transgenic mice overexpression of lnc-Rps4l was established to rescue the inhibition of hypoxia-induced pyroptosis in pulmonary artery smooth muscle cells (PASMCs). An adeno-associated virus 9 construct with a mutation in the open reading frame of lnc-Rps4l was used to verify that it could inhibit hypoxia-induced PASMCs pyroptosis through its encoded peptide RPS4XL. Glutathione S-transferase (GST) pull-down assays revealed that RPS4XL bound to HSC70, and microscale thermophoresis (MST) was performed to determine the HSC70 domain that interacted with RPS4XL. Through glycosylation site mutation, we confirmed that RPS4XL inhibited hypoxia-induced PASMCs pyroptosis by regulating HSC70 glycosylation. Our results showed that RPS4XL inhibits pyroptosis in a PH mouse model and hypoxic PASMCs by regulating HSC70 glycosylation. These results further clarify the important mechanism of vascular remodeling in PH pathology.

ROS generation and DNA damage contribute to abamectin-induced cytotoxicity in mouse macrophage cells.

The widespread use of abamectin has recently raised safety concerns as abamectin has yielded various toxicities to non-target organisms. However, the underlying mechanisms of abamectin-induced toxicity are still largely unknown. The present study aimed to investigate the abamectin-induced cytotoxicity in mouse macrophage cells (RAW264.7) and its underlying mechanisms. Abamectin treatment caused oxidative stress as characterized by increased intensity of the ROS indicator. Abamectin also led to DNA damage as demonstrated by increased 8-OHdG/dG ratio in cells even at a relatively low dose (NOAEL). Pretreatment with catalase-PEG, a ROS inhibitor, attenuated abamectin-induced DNA damage, indicating that ROS overproduction should be the reason for abamectin-induced DNA damage. The effects of abamectin on ROS elimination and generation were also investigated, and the results showed that abamectin induced concentration-dependent alteration in the expression and activities of CAT, SOD, GPx enzymes and GSH level (ROS elimination), but had limited effects on the expression and activities of NOX, mitochondrial complex I and III (ROS production) in RAW264.7 cells. Therefore, the effects of abamectin on ROS elimination should be the main reason for abamectin-induced oxidative stress in RAW264.7 cells. Abamectin treatment activated MAPK and ATM/ATR signaling pathways as demonstrated by increased phosphorylation of JNK, ATM and ATR. In addition, inhibiting JNK and ATM/ATR signaling pathways partially rescued the decrease in cell viability, indicating that abamectin-induced ROS overproduction and DNA damage might finally lead to cytotoxicity through JNK and ATM/ATR signaling pathways. These findings should be useful for the more comprehensive assessment of the toxic effects of abamectin.

Simultaneous determination of insecticide fipronil and its metabolites in maize and soil by gas chromatography with electron capture detection.

An integrated method for the simultaneous determination of insecticide fipronil and its three metabolites, desulfinyl, sulfide, and sulfone, in maize grain, maize stem, and soil was developed. This three-step method uses liquid-solid extraction with ultrasound or mechanical grinding, followed by liquid-liquid partitioning and florisil solid-phase extraction (SPE) for cleanup. The quantification was conducted by gas chromatography-electron capture detection in triplicate for each sample. The method was validated with five replicates at three fortification concentrations, 0.002, 0.01, and 0.1 mg kg(-1), in each matrix and gave mean recoveries from 83 to 106 % with relative standard deviation ≤ 8.9 %. The limits of quantification (LOQ) were 0.002 mg kg(-1) for the compounds in all matrixes. In the field study in Beijing and Shandong 2012, fipronil-coated maize seeds were planted and the proposed method was applied for checking the possible existence of four compounds in maize and soil samples, but none of them contained residues higher than the LOQs in both application rates. Moreover, the dissipation of fipronil in soil fits first-order kinetics with half-lives 9.90 and 10.34 days in Beijing and Shandong, respectively. Combined with an adequate sample treatment, this technique offers good sensitivity and selectivity in the three complex matrixes. The results could provide guidance for the further research on pesticide distribution and safe use of fipronil as seed coat in cereals.

Determination of clomazone residues in soybean and soil by high performance liquid chromatography with DAD detection.

A simple analysis method to detect clomazone residues in soybean and soil was developed using solid phase extraction coupled with high performance liquid chromatography with diode-array detection. The pesticide residues present in soybean and soil matrices were extracted with methanol-water and extracts purified with Florisil cartridges. The analytes from soybean and soil matrix were eluted with petroleum ether-acetic ether (10 mL, 95:5, v/v) and petroleum ether-acetic ether (2 mL, 95:5, v/v), respectively. The overall recovery of fortified soybean and soil at the levels of 0.01, 0.1 and 0.5 mg/kg ranged from 89.75% to 106.6%, and the coefficients of variation (CV) ranged from 1.68% to 4.93% (n = 3). The limit of quantification (LOQ) is 0.01 mg/kg. This method has been applied to the analysis of clomazone in real samples of soybean and soil. The dissipation of residue over the time in soil coincided with C = 1.189e(-0.0926t ) and the half-lives (T(1/2)) was 7.48 days. The final residue in soybean was lower than 0.01 mg/kg at harvest time. Direct confirmation of the analyte in real samples was achieved by gas chromatography-mass spectrometry.

Determination of fungicide kresoxim-methyl residues in cucumber and soil by capillary gas chromatography with nitrogen-phosphorus detection.

The method of residue analysis of kresoxim-methyl and its dissipation rate in cucumber and soil in a greenhouse were studied. Residues of kresoxim-methyl were extracted from cucumber and soil matrices with acetone, purified by liquid-liquid extraction and Florisil cartridges, and then determined by GC with NP-detector. The limit of detection was estimated to be 9 x 10-12 g, and the minimum determination concentration of kresoxim-methyl in the samples was 0.005 mg kg-1. The average recoveries ranged from 89.4 to 100.2% with a coefficient variation between 2.4 and 8.9%. Dissipation study showed that the half-lives of kresoxim-methyl in cucumber were approximately 6.5 days at both the recommended and double the recommended dosage. Half-lives for both the treatments were approximately 8 days in soil. The present study revealed that the residues in cucumber were below the MRL (0.05 mg kg-1, fixed by EU) after 7 days for both treatments.

Determination of forchlorfenuron residues in watermelon by solid-phase extraction and high-performance liquid chromatography.

A method using solid-phase extraction for cleanup, followed by high-performance liquid chromatography with ultraviolet detection (HPLC/UV), was developed for the determination of forchlorfenuron residues in watermelon. The pesticide is extracted from the sample with acidic acetonitrile, and the extract is loaded onto a primary-secondary amine (PSA) column. The pesticide is eluted with acetone and determined by HPLC/UV. The PSA column was found to provide effective cleanup, removing the greatest number of sample matrix interferences. The acetonitrile extraction followed by the PSA cleanup provided recoveries of >95%, coefficients of variation (precision) of <10%, and sensitivity of 0.005 mg/kg, in agreement with the directives for method validation in residue analysis. The proposed method was successfully used to determine forchlorfenuron residue levels and dissipation rates in watermelon grown in an experimental greenhouse in Beijing, People's Republic of China.