关键词: 气相色谱-质谱, 苯胺类化合物, 联苯胺类化合物, 土壤

Abstract:

The complex matrix of soil samples and low extraction efficiency of aniline compounds limit many methods developed for detecting aniline and benzidine compounds in soil. In this study, a rapid and sensitive method based on gas chromatography-mass spectrometry was developed for the simultaneous determination of 14 aniline and benzidine compounds in soil. The collected soil samples were sealed with 5% sodium sulfite solution and refrigerated to inhibit the oxidation of the target compounds for up to 7 d. The extraction efficiencies of accelerated solvent extraction and oscillating dispersion extraction were compared, and the recovery of accelerated solvent extraction was found to be unsuitable. Hence, three-phase oscillating dispersion extraction was adopted. A certain amount of alkaline aqueous solution was added to the test system during extraction to improve the extraction efficiency because aniline and benzidine compounds are weakly alkaline substances. When the pH of the extracted water phase was greater than 12, relatively good recoveries were obtained. Next, a mixed solvent of ethyl acetate-methylene chloride (1∶4, v/v) was added to extract the target compounds via oscillation for 20 min. The solid phase was discarded via centrifugation, and the aqueous and organic phases were transferred to a liquid separation funnel for further separation. Finally, the organic phase was retained. This pretreatment process prevents the co-extraction of acidic compounds or other impurities, thereby enhancing the purification ability of the method. Solid phase extraction (SPE) is generally recommended for soil extraction and purification. A preliminary test showed that compared with other columns, the Florisil SPE column could better retain the target substances and exhibited higher elution efficiency. After purification, the organic phase was concentrated to 1 mL using a nitrogen blower. The analytes were analyzed by gas chromatography-mass spectrometry using a capillary column (DB-35MS, 30 m×0.25 mm×0.25 μm). The temperature program was optimized to separate the target compounds at the baseline. Specifically, the initial oven temperature was set to 60 ℃, held for 2 min, increased to 130 ℃ at a rate of 5 ℃/min, increased to 300 ℃ at a rate of 30 ℃/min, and held for 4 min. The injector and ion source temperatures were 250 and 300 ℃, respectively. Aniline-d₅ and acenaphthene-d₁₀ were used as the internal standards for quantification. The effects of antioxidant addition, extraction solvent type, salting out, and other factors on extraction efficiency were investigated. The results showed that the method performed well under the optimized experimental conditions when actual soils were used as real sample matrices. The accuracy and precision of the proposed method were verified. A total of 14 aniline and benzidine compounds demonstrated good linearities in the range of 0.5-100 mg/L. The method detection limits (MDLs) ranged from 0.02 to 0.07 mg/kg, and the limits of quantification (LOQs) ranged from 0.08 to 0.28 mg/kg. The target compounds were spiked at contents of 1 and 10 mg/kg. The spiked recoveries of the 14 targets in actual soils were 62.9%-101%, and the relative standard deviations (RSDs) of six precision tests were 3.8%-10.3%. The proposed method effectively inhibited the oxidation of aniline and benzidine compounds during extraction, and the target compounds exhibited high recoveries and good stabilities in the presence of three phases. Moreover, the operating procedure was simple and easy to implement. The proposed method was applied to the soil collected from an industrial enterprise in Jiangsu province that was suspected to be contaminated with aniline, and two aniline compounds were detected. The developed method requires a small sample size, and the preservation step is simple and effective. In addition, it can be applied to various types of actual soils. The method meets the requirements of current soil pollution risk control standards for aniline and benzidine compounds in soils.

Key words: gas chromatography-mass spectrometry, aniline compounds, benzidine compounds, soil