关键词: 超声波提取, 固相萃取, 超高效液相色谱-串联质谱, 皮质类固醇激素, 沉积物

Abstract:

Corticosteroids (CSs) are widely used to treat various inflammatory and immune diseases in humans and animals, such as arthritis and lupus. Thus far, CSs have been frequently detected in diverse pollution sources, such as in the influent and effluent of traditional wastewater treatment plants, livestock farms, and aquaculture. Owing to incomplete removal or limited treatment, CSs can enter the water environment and eventually be adsorbed in the sediment. Due to hydrodynamic effects, CSs can re-enter the surface water through the resuspension of sediments, and pose a hazard to the ecosystem and human health via the enrichment of aquatic organisms and transmission through the food chain. Therefore, trace analysis of CSs in sediments is significant for exploring their prevalence and behavior in multiple environments. However, existing research mainly focuses on the determination of glucocorticoids in water samples, and studies on the systematic quantitative analysis of CSs in environmental solid samples with more complex matrices are scarce. Moreover, majority of previous investigations focused on a limited number of glucocorticoids, making it important to widen the range of target compounds to be studied, including mineralocorticoids.
In this study, the main factors which could influence the accuracy and sensitivity in the determination of 24 target CSs were systematically optimized in the sample pretreatment and instrument analysis. A novel method based on ultrasonic extraction coupled with solid phase extraction (SPE) for sample pretreatment was developed for the simultaneous determination of the 24 CSs in sediments using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The sediment sample was ground to homogenize the particle sizes after freeze-drying. The analytes from 2.0 g of the sample were ultrasonicated and extracted with methanol-acetone (1∶1, v/v). After concentrating and diluting each extract, SPE was performed. The water sample was extracted and purified using hydrophile-lipophile balance (HLB) cartridges, following which the extract was further purified with LC-NH₂ cartridges. The extracts were concentrated using a rotary evaporator, dried under a gentle stream of nitrogen, and re-dissolved in methanol for instrumental analysis. Chromatographic separation was conducted on an Agilent ZORBAX Eclipse Plus C₈ column (100 mm×2.1 mm, 1.8 μm), with a column flow rate of 0.3 mL/min and a gradient of mobile phases A (water with 0.1% acetic acid) and B (acetonitrile). The column temperature was set to 30 ℃ and the injection volume was fixed at 5 μL. Electrospray ionization MS in the dynamic multiple reaction monitoring (DMRM) and selected ion monitoring (SIM) modes were performed in the positive mode for the qualitative and quantitative analysis of the target compounds. Quantitation of the target compounds was carried out using the internal standard method. The effects of different extraction solvents, purification conditions, and MS conditions on the recoveries of the target compounds were investigated. The limits of detection (LODs) (S/N≥3) and limits of quantification (LOQs) (S/N≥10) of all 24 compounds were in the ranges of 0.14-1.25 μg/kg and 0.26-2.26 μg/kg, respectively. The correlation coefficients of linear calibration curves were higher than 0.995 in the range of 1.0-100 μg/L. The recoveries of the 24 CSs at 5, 20, and 50 μg/kg spiked levels ranged from 64.9% to 125.1% with relative standard deviations of 0.4%-12.6% (n=5). The developed method was applied to analyze the CSs in three sediment samples from the rivers of the Pearl River Delta. In all, 11 target compounds were detected in these samples, with contents in the range of 1.25-29.38 μg/kg. The characteristic of this method is efficient, sensitive, reliable, and suitable for the trace determination of varieties of natural and synthesized CSs in environmental sediments.

Key words: ultrasonic extraction, solid phase extraction (SPE), ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), corticosteroids, sediments