Extraction and Detection of Benzo(a)pyrene and Benzo(e)pyrene in Groundwater Using Acetonitrile-(NH4)2SO4-Water System Coupled with Liquid Chromatography
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摘要: 传统的液液萃取技术主要采用与水不相溶的有机溶剂作萃取剂，这种异相萃取的传质速率一般较低，需反复振荡或多次萃取。本文建立了以乙腈-硫酸铵-水的双水相萃取体系高效液相色谱法测定地下水中苯并(a)芘和苯并(e)芘的方法，以密度比水小的乙腈为萃取剂，将其与水样混合(互溶)获得乙腈-水体系，然后加入硫酸铵，溶液澄清、分相后取上层有机相(乙腈)进样分析。考察了萃取剂的选择、双水相的形成条件、离子强度以及pH等对测定结果的影响。两种化合物线性范围为2.00~400.00 ng/mL，相关系数大于0.999。方法检出限为0.012~0.020 ng/mL，平均回收率为94.6%~97.3%，相对标准偏差为1.3%~2.5%。与传统萃取方法相比，该方法具有操作流程简单、快速的特点，可实现对野外环境水样进行原地样品前处理。Abstract: Conventional liquid-liquid extraction (LLE) methods usually use water immiscible organic solvents as the extraction solvents and achieve phase separation through repeated shock or multiple extractions. In this paper, a new method for the determination of benzo(a)pyrene and benzo(e)pyrene in groundwater by High Performance Liquid Chromatography (HPLC) with acetonitrile-(NH4)2SO4-water extraction system is described. In the proposed extraction procedure, a low-density extraction solvent (acetonitrile) was injected into a water sample to form the acetonitrile-water system. A salt (ammonium sulfate) was then injected into the acetonitrile-water solution to separate the system into two phases. The upper organic phase (acetonitrile) was collected and analyzed by HPLC. All the parameters, such as the selection of extraction agent, aqueous two phase formation conditions, ionic strength and pH, are discussed and optimized. The two kinds of compound are linear and in the range of 2.00-400.00 ng/mL, and the correlation coefficient (R2) is greater than 0.999. The detection limits of the method for the compounds ranged from 0.012-0.020 ng/mL and the average recoveries ranged from 94.6%-97.3% with precision of 1.3%-2.5%. Compared with conventional extraction methods, the method has the characteristics of simple operation and rapidity. Pretreatment of environmental water samples can be operated in the field, which is good for the routine analysis of benzo(a)pyrene and benzo(e)pyrene in groundwater.
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表 1 方法精密度和准确度
Table 1. Precision and accuracy tests of the method
化合物 ρB/(ng·mL-1) 平均回收率/% RSD/% 添加
浓度本法分次测定值 苯并(a)芘 20.00 19.21 18.57 18.32 19.46 19.01 94.6 2.6 60.00 56.22 57.37 59.24 58.79 57.71 96.4 2.1 苯并(e)芘 20.00 19.03 18.96 19.21 19.67 19.03 95.9 1.5 60.00 57.35 58.26 59.33 58.22 58.87 97.3 1.3 
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表 2 几种萃取技术测定苯并(a)芘的比较
Table 2. Comparison of extraction techniques for determination of benzo(a)pyrene
萃取方法 萃取剂
用量V/mL萃取时间
t/min浓缩
换相检出限/
(ng·mL-1)回收率/% 富集倍数 LLE-HPLC-FLD 约100 约几十 是 0.002 94~99 约1000倍 SPE-GC-FID 约几十 约几十 是 0.006 92~96 约100倍 ATPE-HPLC-FLD 约几 约几 否 0.012 94~96 近100倍
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[1] 刘淑芹,王鹏.环境中的多环芳烃与致癌性[J].环境保护,1995(9): 42-45. http://www.cnki.com.cn/Article/CJFDTOTAL-HJBU509.018.htm
[2] 李松,饶竹.超高效液相色谱法检测地下水中苯并(a)芘[J].岩矿测试,2010,29(6): 679-682. http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201006010.htm
[3] 欧盟理事会第76/769/EEC号指令[S].
[4] 冯静,王海娇,何超君,张激光.高效液相色谱法测定地下水中苯并(a)芘的不确定度评定[J].岩矿测试,2011,30(5): 617-622. http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201105021.htm
[5] 曹攽,马军,李云木子.荧光-紫外检测器高效液相色谱法检测地下水中16种多环芳烃[J].岩矿测试,2010,29(5): 539-542. http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201005016.htm
[6] 郑海涛,刘菲,刘永刚.固相萃取-气相色谱法测定水中多环芳烃[J].岩矿测试,2004,23(2): 148-152. http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS200402014.htm
[7] 李先国,阎国芳,周晓,虢新运,王岩,刘金燕.固相萃取-高效液相色谱-荧光检测法测定海水中的多环芳烃[J].中国海洋大学学报: 自然科学版,2009,39(5): 1087-1092. http://www.cnki.com.cn/Article/CJFDTOTAL-QDHY200905051.htm
[8] 李竺,陈玲,郜洪文,袁园,赵建夫.SPE-PDA/FLE串联HPLC法测定水样中痕量多环芳烃[J].环境化学,2006,25(4): 503-507.
[9] 马珞,王晓昌,刘俊建.环境样品中多环芳烃的前处理技术研究进展[J].云南化工,2009,36(3): 66-70. http://www.cnki.com.cn/Article/CJFDTOTAL-YNHG200903019.htm
[10] 马春宏,朱红,王良,姜大雨,闫永胜,王庆伟.双水相萃取技术的应用研究进展[J].光谱实验室,2010, 27(5): 1906-1914. http://www.cnki.com.cn/Article/CJFDTOTAL-NCJX201418019.htm
[11] 朱裕穗,杨红国,安彩秀,王磊,刘金巍.双水相萃取-液相色谱法检测人尿中的羟基多环芳烃[J].分析试验室,2012,31(10): 67-71. http://www.cnki.com.cn/Article/CJFDTOTAL-FXSY201210019.htm
[12] 曾云,覃事栋,陈腾,姚康康,王影.乙醇-硫酸铵双水相萃取镉-碘化钾-丁基罗丹明B离子缔合物[J].光谱实验室,2012,29(5): 2963-2966. http://www.cnki.com.cn/Article/CJFDTOTAL-GPSS201205098.htm
[13] 李丽敏,尚庆坤.亲水有机溶剂/无机盐双水相萃取技术在分离提纯生物物质中的应用[J].光谱实验室,2011,28(6): 3073-3078. http://www.cnki.com.cn/Article/CJFDTOTAL-GPSS201106077.htm
[14] 赵新颖,屈锋,董敏,陈凡,罗爱芹,张经华.双水相萃取结合液相色谱法分离蛋白质[J].分析化学,2012,40(1): 38-42. http://www.cnki.com.cn/Article/CJFDTOTAL-FXHX201201007.htm
[15] 朱慧,李克,翟云霞.血清蛋白质组学研究中乙腈沉淀法去除清蛋白的实验研究[J].临床检验杂志,2011(1): 16-18. http://www.cnki.com.cn/Article/CJFDTOTAL-LCJY201101010.htm
[16] 胡洪华,蒋婷,宋海星,胡瀚丹.四种检测法在乙腈沉淀法去除血清蛋白中的比较[J].中国医药导报,2012(23): 85-86. doi: 10.3969/j.issn.1673-7210.2012.23.035
[17] 彭佳黛,冯倩,陈浩春,孙吉康.双水相萃取法分离纯化银针茶α-淀粉酶抑制剂的研究[J].中南林业科技大学学报,2010(9): 198-201. http://www.cnki.com.cn/Article/CJFDTOTAL-ZNLB201009041.htm
[18] 龙文清,黄春芳,刘利民,施踏青,雷良萍.乙醇-硫酸铵双水相萃取荧光法测定痕量α-萘乙酸[J].分析试验室,2007,26(5): 23-26. http://www.cnki.com.cn/Article/CJFDTOTAL-FXSY200705007.htm
[19] 贾风燕,王文文,刘振波,殷军港,刘永明.乙腈-无机盐-水双水相体系萃取-气相色谱法检测鱼肉中拟除虫菊酯[J].化学学报,2012,70(4): 158-491. http://www.cnki.com.cn/Article/CJFDTOTAL-HXXB201204020.htm
[20] 龙文清,黄春芳,陈华龙.丙酮双水相萃取预富集荧光法测定痕量1-萘胺[J].分析试验室,2008,27(12): 19-22. doi: 10.3969/j.issn.1000-0720.2008.12.005
[21] 翟全国,胡满成,刘志宏,夏树屏,高世扬.硫酸铯/乙醇双水相体系的相平衡[J].物理化学学报,2003,19(11): 1089-1092. doi: 10.3866/PKU.WHXB20031122
[22] 刘绍鹏,宗志敏,魏晴,魏贤勇.双水相体系中成相及有机物分配机理的初步研究[J].化工时刊,2010,24(12): 21-24. doi: 10.3969/j.issn.1002-154X.2010.12.006
[23] HJ 478—2009,水质;多环芳烃的测定;液液萃取和固相萃取高效液相色谱法[S].
[24] GB/T 5750.8—2006,生活饮用水标准检验方法;有机物指标[S]
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