Simultaneous Determination of 12 Chloroanisoles in Lake Reservoir Waters by Headspace Solid Phase Microextraction-Gas Chromatography-Mass Spectrometry
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摘要: 氯苯甲醚类化合物（CAs）是地表水中普遍存在的嗅味物质，在世界各地水环境中均可发现CAs的存在，CAs易在食物链中富集和放大，且随着氯原子取代数增加其毒性逐渐增强。水体中CAs属于痕量物质，检测时需要先对其进行富集处理，以往研究大多是对单个物质进行检测。本文建立了采用顶空固相微萃取结合气相色谱-质谱联用技术同时测定湖库水中12种CAs的方法。对顶空固相微萃取过程中的萃取纤维、萃取温度、离子强度、萃取时间及搅拌速率等实验条件进行对比和优化，确认了最佳萃取条件为：萃取温度80℃，离子浓度0.35g/mL，萃取时间40min，搅拌速率1150r/min，样品体积10mL（15mL萃取瓶）。采用气相色谱-质谱选择性离子扫描方式进行定量分析，方法的线性范围为1~50ng/L，检出限为0.045~0.185ng/L，回收率为95.5%~115.1%，相对标准偏差≤ 13.02%。该方法相较于固相萃取及吹扫捕集法的检出限更低，对于样品浓度的变化感应度高，实验仪器的精密度优于其他方法。Abstract:
BACKGROUNDChloroanisoles (CAs) are odorous substances and can easily be found in surface waters. The CAs have been found in water environments worldwide. In the food chain, CAs are easily enriched and amplified. The toxicity increases with the number of chlorine atoms substituted. CAs in waters are trace substances which need to be preconcentrated before determination. Previous studies focused on the detection of individual substances. OBJECTIVESTo establish a method which combines headspace solid phase microextraction and gas chromatography-mass spectrometry together, to simultaneously measure 12 CAs in waters. METHODSThe conditions of extraction fiber, temperature, ionic strength, extraction time and stirring rate were compared and optimized in headspace solid phase microextraction. The optimal extraction conditions were confirmed by the results. Extraction temperature was 80℃, ionic strength was 0.35g/mL, extraction time was 40 minutes, stirring rate was 1150r/min, and sample volume was 10mL (15mL extraction bottle). RESULTSQuantitative analysis was performed by gas chromatography-mass spectrometry with selective ion scanning. The linear ranges of the method were 1-50ng/L, and the recoveries were 95.5%-115.1%. The detection limits were 0.045-0.185ng/L and the relative standard deviation was less than 13.02%. CONCLUSIONSCompared with the solid phase extraction and the purge with trap method, this method has a lower detection limit and higher sensitivity of the sample concentration. Also, the precision of the experimental instrument is relatively better than other methods. -
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表 1 氯苯甲醚的线性关系和方法检出限
Table 1. Linear relationship and detection limits of CAs
目标分析物 保留时间(min) 特征离子 线性范围
(ng/L)相关系数
(R2)方法检出限
(ng/L)3-CA 10.370 142.0 98.9 111.9 1~50 0.9990 0.120 4-CA 10.691 142.0 98.9 111.9 1~50 0.9978 0.125 2-CA 11.051 142.0 127.0 126.9 1~50 0.9991 0.129 2, 6-DCA 13.240 176.0 134.8 177.9 1~50 0.9990 0.074 3, 5-DCA 14.629 176.0 134.8 177.9 1~50 0.9992 0.068 2, 4-DCA 15.682 176.0 134.8 177.9 1~50 0.9991 0.064 2, 3-DCA 16.532 176.0 134.8 177.9 1~50 0.9987 0.057 2, 4, 6-TCA 16.775 210.0 168.8 211.8 1~50 0.9989 0.185 2, 3, 6-TCA 17.907 211.8 211.8 211.8 1~50 0.9997 0.132 2, 3, 4-TCA 21.212 211.8 211.8 211.8 1~50 0.9982 0.106 2, 3, 5, 6-TeCA 21.618 202.8 230.8 245.9 1~50 0.9999 0.086 PCA 26.009 264.6 277.6 281.8 1~50 0.9980 0.045 
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表 2 氯苯甲醚的回收率及相对标准偏差
Table 2. Recoveries and relative standard deviations of CAs
目标分析物 加标浓度
(ng/L)检出浓值
(ng/L)平均回收率
(%)RSD
(%)3-CA 10 10.77 107.7 10.73 50 50.51 101.0 0.46 4-CA 10 11.51 115.1 7.56 50 47.82 95.6 4.13 2-CA 10 9.55 95.5 8.96 50 48.91 97.8 3.26 2, 6-DCA 10 10.09 100.9 13.02 50 49.93 99.9 0.51 3, 5-DCA 10 10.38 103.8 7.90 50 50.77 101.5 1.92 2, 4-DCA 10 10.30 103.0 9.51 50 49.12 98.2 3.04 2, 3-DCA 10 10.24 102.4 9.26 50 49.91 99.8 0.46 2, 4, 6-TCA 10 10.35 103.5 8.27 50 50.08 100.1 0.29 2, 3, 6-TCA 10 10.55 105.5 7.11 50 49.99 100.0 0.46 2, 3, 4-TCA 10 10.37 103.7 1.57 50 56.90 113.8 0.67 2, 3, 5, 6-TeCA 10 9.93 99.3 11.25 50 49.36 98.7 0.25 PCA 10 10.14 101.4 2.57 50 56.17 112.3 1.87
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