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    气相色谱-串联质谱法测定食品接触用纸制品中2种氯丙醇的残留量及其释放规律探讨

    Determination of Residues of 2 Chloropropanols in Food Contact Paper Products by Gas Chromatography-Tandem Mass Spectrometry and Investigation of Their Release Patterns

    • 摘要: 将食品接触用纸制品裁剪成约1 cm2的小块,取10 g样品置于具塞三角烧瓶中,加入200 mL沸水,于80 ℃加热2 h,冷却后,用水定容至250 mL。取5.00 mL上述溶液置于试管中,加入0.05 mL 10 mg·L−1混合内标溶液和1 g氯化钠,溶解后过硅藻土固相萃取小柱,平衡10 min,用18 mL乙酸乙酯洗脱,收集洗脱液,加入4 g无水硫酸钠,静置10 min,过滤。收集过滤液,于45 ℃氮吹至近干,加入2 mL正己烷溶解,快速加入0.04 mL七氟丁酰基咪唑,涡旋30 s,于70 ℃电热鼓风干燥箱中衍生30 min。冷却至室温,加入20%(质量分数)氯化钠溶液2 mL,涡旋1 min,静置分层,取上层溶液,加入0.3 g无水硫酸钠干燥,过0.22 μm尼龙滤膜,采用气相色谱-串联质谱法测定滤液中2种氯丙醇1,3-二氯-2-丙醇(1,3-DCP)、3-氯-1,2-丙二醇(3-MCPD)的含量。2种氯丙醇的衍生物在SH-Rxi-5Sil MS色谱柱上按照柱升温程序分离,采用电子轰击离子源以多反应监测模式检测,同位素内标法定量。结果表明,2种氯丙醇的质量浓度均在0.5~200.0 μg·L−1内与其内标质量浓度的比值和对应的衍生物峰面积与内标衍生物峰面积比值呈线性关系,检出限(3S/N)均为0.25 μg·L−1。按照标准加入法进行回收试验,回收率为80.9%~116%,测定值的相对标准偏差(n=7)为0.58%~0.85%。方法用于分析20批食品接触用纸制品样品,1,3-DCP和3-MCPD均被检出,检出量分别为2.0~16 μg·L−1,2.0~69 μg·L−1;此外,接触食品温度越高、接触食品时间越长,食品接触用纸制品中1,3-DCP和3-MCPD的释放量越高。

       

      Abstract: The food contact paper products were cut into about 1 cm2 of small pieces. The sample (10 g) was taken and placed into a stoppered triangular flask, and 200 mL of boiling water was added. The mixture was heated at 80 ℃ for 2 h. After cooling, the solution was diluted to 250 mL with water. 5.00 mL of the above solution was taken and placed into a test tube, and 0.05 mL of 10 mg · L−1 mixed internal standard solution and 1 g of sodium chloride were added. After dissolution, the solution was passed through a diatomite solid-phase extraction cartridge, equilibrating for 10 min. Then the mixture was eluted with 18 mL of ethyl acetate, and the eluate was collected. 4 g of anhydrous sodium sulfate was added, and the mixture was settled for 10 min. The solution was filtered, and the filtrate was collected. The solution was blown to near dryness with nitrogen at 45 ℃, and the residue was dissolved in 2 mL of n-hexane, and 0.04 mL of heptafluorobutyryl imidazole was quickly added. The mixture was vortexed for 30 s and derivatized in a electric hot blast drying oven at 70 ℃ for 30 min. After cooling to room temperature, 2 mL of 20% (mass fraction) sodium chloride solution was added. The mixture was vortexed for 1 min, allowed to stand for layering, and the upper layer solution was taken. 0.3 g of anhydrous sodium sulfate was added for drying, and the solution was filtered through a 0.22 μm nylon filter membrane. The 2 chloropropanols, including 1,3-dichloro-2-propanol (1,3-DCP) and 3-chloro-1,2-propanediol (3-MCPD) in the filtrate were determined by gas chromatography-tandem mass spectrometry. The derivatives of 1,3-DCP and 3-MCPD were separated on SH-Rxi-5Sil MS chromatographic column by programmed column temperature, ionized by electron impact ion source, detected in multiple reaction monitoring (MRM) mode, and quantified by isotope internal standard method. As shown by the results, linear relationships between the ratios of the corresponding derivative peak area to the internal standard derivative peak area and the ratios of mass concentrations 2 chloropropanols to their internal standards were found in the range of 0.5-200.0 μg · L−1, with the same detection limits (3S/N) of 0.25 μg · L−1. Test for recovery was made by the standard addition method, giving results in the range of 80.9%-116%, with RSDs (n=7) of the determined values in the range of 0.58%-0.85%. This method was applied to analysis of 20 batches of food contact paper product samples, and both 1,3-DCP and 3-MCPD were detected, with the detection amounts in the range of 2.0-16 μg · L−1 and 2.0-69 μg · L−1, respectively. The release amounts of 1,3-DCP and 3-MCPD were higher when food contact paper products were exposed to higher contact temperatures and longer contact time with food.

       

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