有机污染物稳定同位素在线测试技术研究进展

方晶晶; 周爱国; 刘存富; 甘义群; 周建伟; 蔡鹤生; 刘运德; 张彦鹏

有机污染物稳定同位素在线测试技术研究进展

方晶晶^1,2,3,,
周爱国^1,2, ,,
刘存富^1,2,
甘义群^1,2,
周建伟^1,2,
蔡鹤生^1,2,
刘运德^1,2,
张彦鹏^1,2,3

1.
中国地质大学(武汉)环境学院，湖北武汉 430074
2.
中国地质大学(武汉)生物地质与环境地质国家重点实验室，湖北武汉 430074
3.
中国地质大学(武汉)研究生院，湖北武汉 430074

基金项目:

国家自然科学基金项目 41072179

国家自然科学基金项目 41002083

国家自然科学基金项目(41072179, 41002083, 40772156)

国家自然科学基金项目 40772156

详细信息

作者简介:
方晶晶，博士研究生，主要从事环境地质和同位素水文地质的学习与研究。E-mail：fangjingjing0720@163.com

通讯作者:
周爱国，教授，博士生导师，主要从事环境地质和同位素水文地质研究。E-mail：aiguozhou@cug.edu.cn

中图分类号: O656.21;O657.63
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出版历程
- 收稿日期: 2012-03-11
- 录用日期: 2012-08-15
- 发布日期: 2013-03-31

Research Progress on Stable Isotope Online Testing Technology for Organic Contaminants

1.
School of Environmental Studies, China University of Geosciences (Wuhan)，Wuhan 430074，China
2.
State Key Laboratory of Biogeology and Environmental Geology， China University of Geosciences (Wuhan)，Wuhan 430074， China
3.
School of Graduate, China University of Geosciences (Wuhan)，Wuhan 430074，China

摘要

摘要: 为了识别环境中有机污染物的来源和迁移转化，在线的单体稳定同位素分析(CSIA)是必不可少的关键技术，但是在实际应用中还存在问题。本文评价了目前已经开发的6种在线测定单体稳定同位素仪器的发展动态，包括气相色谱-同位素比值质谱计(GC-IRMS)、液相色谱-同位素比值质谱计(LC-IRMS)、直接引进-气相色谱-同位素比值质谱计(DI-GC-IRMS)、气相色谱-四极杆质谱计(GC-qMS)、气相色谱-多接收器电感耦合等离子体质谱计(GC-MC-ICPMS)、气相色谱-光强衰荡光谱仪(GC-CRDS)。提出了在线测试中的5个值得注意的问题：①样品的预富集；②气相色谱(GC)和液相色谱(LC)分离；③多种仪器和多种方法选择使用；④有机化合物稳定同位素标准物质的开发；⑤安全保障。提出了三点建议：一是大力发展直接注入而不经过燃烧的有机污染物同位素测试技术，例如GC-qMS和GC-CRDS技术；二是继续开发研究GC-MC-ICPMS测定有机氯和有机溴同位素技术；三是快速研制有机化合物稳定同位素的国际标准物质。本文认为，在进行单体化合物同位素研究时应作多元素的同位素分析，而其最优的选择是采用直接样品注入而不经过燃烧的测试技术。
- 有机污染物 /
- 单体稳定同位素分析 /
- 单体多元素同位素 /
- 质谱技术
Abstract: Compound-specific isotope analysis (CSIA) online is an indispensable key technique for identifying the sources of organic contaminants in the environment and characterizing their transformation processes, but there are still some problems in practical applications. In this study, firstly, the development of six methods for online determination of compound-specific organic isotope analysis was introduced and reviewed, including Gas Chromatography-Isotope Ratio Mass Spectrometer (GC-IRMS), Liquid Chromatography Coupled-Isotope Ratio Mass Spectrometer (LC-IRMS), Direct Introduction-Gas Chromatography-Isotope Ratio Mass Spectrometer (DI-GC-IRMS), Gas Chromatography-Quadrupole Mass Spectrometer (GC-qMS), Gas Chromatography-Multicollector Inductively Coupled Plasma-Mass Spectrograph (GC-MC-ICPMS) and Gas Chromatography-Cavity Ring-Down Spectroscopy (GC-CRDS). Secondly, five noteworthy problems in online testing were proposed: sample pre-concentration, Gas Chromatography (GC) and Liquid Chromatography (LC) separation, selection of instruments and methods, the development of organic compound stable isotope standard material and safety control. Finally, three suggestions were proposed: 1) to develop vigorously the direct injection technology without combustion, such as GC-qMS and GC-CRDS, 2) to continually develop the determination technology for organic chlorine and organic bromine isotopes and 3) to rapidly develop international stable isotope standards for organic compounds. The new understanding in this study was that when multi-element isotope analysis was applied to study compound-specific isotopes, direct injection technology without combustion was the optimal choice.
- organic contaminants /
- compound-specific isotope analysis (CSIA) /
- compound-specific multielement isotope /
- mass spectrometric technique

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图 1 DI-GC-IRMS系统接收杯排列示意图^[17]

Figure 1. Schematic of the multicollector array on the DI-GC-IRMS^[17]

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图 2 分析氯乙烯(VC)单体氯稳定同位素的GC-IRMS图解^[18]

Figure 2. Schematic of the Gas Chromatography-Isotope Ratio Mass Spectrometry (GC-IRMS) steps used in analyz-ing compound specific chlorine stable isotope of vinyl chloride (VC)^[18]

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图 3 分析有机化合物氯同位素比值的GC-MC-ICPMS装置^[25]

Figure 3. Schematic representation of the GC-MC-ICPMS system used in analyzing organic compound chlorine isotope ratio^[25]

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图 4 分析有机化合物溴同位素比值的GC-MC-ICPMS装置^[29]

Figure 4. Schematic representation of the GC-MC-ICPMS system used in analyzing organic compound bromine isotope ratio^[29]

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图 5 四氯乙烯(PCE)厌氧降解脱氯作用

Figure 5. Anaerobic degration dechlorination of tetrachloroethylene (PCE)

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表 1 有机化合物中常见元素的稳定同位素系统和同位素天然丰度比值

Table 1 Stable isotope systems and natural abundance isotope ratios for typical elements in organic contaminants

元素名称	同位素系统	同位素比值
H	²H/¹H	0.01558
C	¹³C/¹²C	1.123
N	¹⁵N/¹⁴N	0.3663
O	¹⁸O/¹⁶O	0.2005
S	³⁴S/³²S	4.416
Cl	³⁷Cl/³⁵Cl	31.96
Br	⁸¹Br/⁷⁹Br	97.27

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表 2 单体有机污染物稳定同位素比值分析的仪器装置

Table 2 Overview of instrumental setups for compound-specific analyses of stable isotope ratios in organic contaminants

仪器	分离方式	装置系统	分析物	电离作用	质量分析/离子检测	同位素比值
GC-IRMS		燃烧^①	CO₂	EI^②	扇形磁铁/ Faraday杯	¹³C/¹²C
	GC	燃烧/还原^④	N₂			¹⁵N/¹⁴N
	GC×GC^③	热解^⑤	H₂			²H/¹H
		热解	CO			¹⁸O/¹⁶O
LC-IRMS	LC	湿氧化	CO₂	EI	扇形磁铁/ Faraday杯	¹³C/¹²C
GC-IRMS^⑥	GC	—	碎片离子	EI	扇形磁铁/ Faraday杯	³⁷Cl/³⁵Cl
GC-IRMS^⑥	GC	—	碎片离子	EI	扇形磁铁/ Faraday杯	⁸¹Br/⁷⁹Br
GC-qMS	GC	—	分子离子和碎片离子	EI	四极电子倍增器	³⁷Cl/³⁵Cl
GC-MC-ICPMS	GC	ICP^⑦	Cl	ICP	扇形磁铁/ Faraday杯	³⁷Cl/³⁵Cl
		ICP^⑦	Br	ICP	扇形磁铁/ Faraday杯	⁸¹Br/⁷⁹Br
		S	³⁴S/³²S
GC-CRDS^⑧	GC	燃烧	CO₂	—	红外光谱	¹³C/¹²C
注：GC—气相色谱；IRMS—同位素比值质谱；LC—液相色谱；qMS—四极杆质谱；MC-ICPMS—多接收器电感耦合等离子体质谱；CRDS—光腔衰荡光谱^[9]。①—在900~950℃下燃烧；②—电离；③—为分析碳同位素专门报道的应用；④—燃烧后在600~650℃下还原；⑤—在1200~1450℃下热解；⑥—直接引进GC-IRMS，详细情况见正文；⑦—电感耦合等离子体；⑧—由于使用燃烧装置也用GC-C-CRDS表示。

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表 3 几种合成溴代有机化合物⁸¹Br/⁷⁹Br的测试结果^[29]

Table 3 The test results of ⁸¹Br/⁷⁹Br in several synthetic bromine organic compound^[29]

化合物	(⁸¹Br/⁷⁹Br)_Sr校正值
3-溴甲苯(Aldrich，BT)	(9762±1)×10^-4
3-溴甲苯(Riedel，BT)	(9763±2)×10^-4
三溴苯(Aldrich，TBB)	(9768±3)×10^-4
三溴酚(Aldrich，TBP)	(9763±1)×10^-4
二溴乙烷(Aldrich)	(9744±4)×10^-4
2-溴氯苯(Aldrich)	(9759±2)×10^-4

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表 4 稳定同位素标准和常用标准物质

Table 4 The stable isotope standard and standard material used commonly

元素	同位素系统	钢瓶气	国际标准	常用标准物质
H	²H/¹H	H₂	VSMOW	VSMOW1
H	²H/¹H	H₂	VSMOW	VSMOW2
O	¹⁸O/¹⁶O	CO，CO₂	VSMOW	QYTB-1a
O	¹⁸O/¹⁶O	CO，CO₂	VSMOW	QYTB-2a
C	¹³C/¹²C	CO，CO₂	VPDB	NBS22(油)
				IAEA-CH-3(纤维素)
				IAEA-CH-6(蔗糖)
N	¹⁵N/¹⁴N	N₂O，N₂	空气	IAEA-NO-3(硝酸钾)
N	¹⁵N/¹⁴N	N₂O，N₂	空气	EAFE-N-1(硫酸铵)
S	³⁴S/³²S	SO₂	VCDT	IAEA-SO-5(硫酸钡)
S	³⁴S/³²S	SO₂	VCDT	IAEA-SO-6(硫酸钡)
Cl	³⁷Cl/³⁵Cl	CH₃Cl	SMOC	NIST SAM 975(氯化钠)
				ISL-354(氯化钠)
				海水
Br	⁸¹Br/⁷⁹Br	CH₃Br	SMOB	NIST SRM 977(溴化钠)
Br	⁸¹Br/⁷⁹Br	CH₃Br	SMOB	海水

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