饮水中非受控消毒副产物分析方法研究进展

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.综述.

饮水中非受控消毒副产物分析方法研究进展

周颖黎源倩屈卫东

1908年美国率先将氯化消毒剂用于自来水消毒。百年来,饮水消毒成为有效控制介水传染病发生的重要手段…。众所周知,消毒剂与水体中天然有机质、溴或碘等内源性物质及污染物发生反应生成各种消毒副产物(disinfection

by—

products,DBPs)。自1974年从氯化消毒的饮水中发现三氯甲烷后,已发现600~700种DBPs【2J。其中,由世界卫生组织、美国环保局、欧盟及我国给出饮用水水质限量值或指导值的DBPs仅有卤甲烷、卤乙酸、卤乙腈、甲醛、氯化氰、三氯乙醛、三氯酚及氯酸盐和溴酸盐等17种旧J。将有明确限屋值或推荐值的DBPs称为受控DBPs,其他DBPs统称为非受控DBPs,主要有碘代甲烷、卤代硝基甲烷、碘代酸、卤代醛、酮酰胺、卤酰胺、亚硝胺、卤代呋喃酮等【2引。但日益增加的证据显示,某些非受控DBPs比受控DBPs具有更强的毒性或致癌性"…。因而,饮水中非受控DBPs的污染水平、生物学有害效应和暴露评价正成为国际相关研究重点【2’5引。显然,饮水中非受控DBPs的分析方法是开展上述研究的重要基础。一些样品预处理技术和分析方法已被用于鉴定和检测饮水中非受控DBPs【2t8j。因此,笔者旨在对饮水中非受控DBPs分析方法的研究进展加以综述,并对该领域未来研究方向进行探讨。

一、样品预处理

1.液液萃取(1iquid-liquidextraction,u正):LLE是水质分析常用的样品前处理技术。表1[9-111总结了¨.E常见的饮水中非受控DBPs的回收率情况。甲基叔丁基醚(MTBE)是最常用的萃取溶剂。

2.顶空技术(headspacetechniques,HS):Hs广泛用于萃取饮水中挥发性DBPs。传统静态HS,不能浓缩待测组分,故方法灵敏度较低191。动态Hs有吹扫.捕集技术(purge

and

trap,P&T)[93和闭环捕集(closedloopstrippinganalysis,

CLSA)技术¨21等。Cancho等【93比较了LLE和3种Hs富集6种碘代烷烃的效率。结果显示,LLE富集效率最高,接近100%,其次为CLSA(47%一94%),而P&T和静态HS的富集效率分别为5%一70%和36%一56%,且后两者几乎都不

DOI:10.3760/cma.j.issn.0253-9624.2010.10.019

基金项目:国家“十一五”科技支撑计划(2006BAll9802);国家自然科学基金(30771770);复旦大学09年青年基金(EYF201023)

作者单位:200032上海,复旦大学公共卫生学院卫生化学教研室公共卫生安全教育部重点实验室(周颖);四川大学公共卫生学院卫生检验教研室(黎源倩);复旦大学公共卫生学院环境卫生学教研室公共卫生安全教育部重点实验室(屈卫东)

通信作者:屈卫东,Email:wdqu@fudan.edu.cn

表1LI。E预处理饮水中非受控DBPs

化合物秀器裂

鼍黪尹参考文献

碘代甲烷二氯碘甲烷均为MTBE95—109[9]氯溴碘甲烷90—103[9]

二溴碘甲烷102~109『91

氯■碘甲烷66一10l[9]

溴二碘甲烷85~108f91

三碘甲烷100—108

[9]

卤代硝基甲烷三氯硝基甲烷MTBE59—124

[10]

卤乙腈氯溴乙腈MTBE83—143

[10]

卤代酮

l,1.二氯丙酮岍BE

一[10]I,l,l-三氯丙酮~

[10]

l,3.二氯丙酮辨竹鼹

加¨叭

【10]

卤乙酸溴碘乙酸MTBE,pH0.5

NR

[6]

碘乙酸NR

[6]

卤代酸

3 溴-3-碘丙烯酸MTBE,pH0.5

NR

[6]

2一碘-3一甲基丁烯二酸NR

[6]

呋喃酮类

3-氯4(二氯甲基)5一羟MTBE

83基.2(5H)-呋喃酮

正己烷7乙酸乙酯

94

注:NR表示未见报道

富集碘仿。

3.固相萃取(solid

phaseextraction,SPE):SPE是基于液

固分离萃取的样品预处理技术。表2【l埘1列举了饮水中主

要非受控DBPs的SPE情况。

4.固相微萃取(solid

phase

microextraction。SPME):

SPME是在SPE基础上发展的新技术。SPME有液相和顶空2种萃取模式。顶空SPME适用于挥发性化合物的萃取,如碘代甲烷M。、挥发性亚硝胺B刊等。液相SPME可直接萃取水中极性和非极性化合物如MXf28】。Bao等‘驯比较了2种SPME模式萃取水中23种羰基DBPs,结果显示,对低分子量羰基DBPs,液相SPME和顶空SPME有相似的萃取效率(87%一110%);而对低挥发性的二元羧酸,顶空SPME萃取效率较低。水中许多极性DBPs不易被SPME萃取,SPME与衍生化技术结合可改善对极性DBPs的萃取效率m],Ber6nek和Kub6,tovO,¨¨用五氟苄基羟胺盐酸盐(PFBHA)衍

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933

表2

SPE预处理饮水中非受控DBPs

生化水中各种醛类DBPs,然后SPME萃取,方法检出限达到

括气相色谱、液相色谱和毛细管电泳等。表4m5’列举了目彬L级。

前文献报道的饮水中非受控DBPs检测方法的主要内容。

5.样品预处理技术比较:已报道的检测饮水中非受控1.气相色谱(gaschromatography,GC)及其联用技术:DBPs的样品预处理技术比较如表3所示。

GC广泛应用于挥发性和半挥发性非受控DBPs检测(表4)。二、分析方法

对于极性化合物,GC分析前须衍生化。醛和酮类极性DBPs检测饮水中非受控DBPs目前主要是色谱分析方法,包

常用衍生化试剂包括:磺酸甲醇¨3盘】、PFBHAIz9-3¨和

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表3样品预处理技术比较

表4饮水中非受控DBPs检测

化合物

碘代甲烷二氯碘甲烷

GC—ECDGC.EI.MS

10

衍生化反应检测方法

MI)Ls(.s/L)

参考文献

2302

20,lO,10,lO

氯溴碘甲烷

二溴碘甲烷,氯二碘甲烷。溴二碘甲烷,三碘甲烷卤代酮

1,1-二氯丙酮

GC—ECD

GC.EI.MSGC.ECD

…m汐…剐川卅刚№p

[10]

GC—ECDGC.E1.MS

1,1,1-三氯丙酮1,3-二氯丙酮

GC—ECD

GC.EI.MS

GC.ECD

GC.EI.MS

∞∞∞∞加∞

[10]

卤乙腈氯溴乙腈卤代硝基甲烷三氯硝基甲烷

GC,ECDGC.EI.MS

40

GC.ECDGC—EI.MS

∞肿

[10]

l∞

亚硝胺

亚硝基二甲胺

GC.NCD

[19][27][16][18]

57

GC.PCI—MSGC.CI.MS/MS

CE

170000

lO

O.7

[32][33]

丹磺酰氯衍生

HPIC.FD

HPLC—CLD

2903.1

[14][15]

[17][27][16]

HPLC—ESI.MS/MSUPLC.ESI.Ms/MS

亚硝基甲乙胺无

GC.NCDC,C.PCI—MSHPLC.ESI.MS/MS

132O.4

2.4

[15]

[16][14][15][32][”][16]

亚硝基吡咯烷无GC—PCI—MSHPLC.CLD

1.2

30

删C.ESI.MS/MS

CE

2.1

20ooO

870.6

760

亚硝基二乙胺无

GC.NCDC,C..PCI.MSHPLC.CLDHPLC.ESI.Ms/MS

CE

【14][15]

[32]

lO.6160000

DNPH‘∞五11等。电子捕获检测器(electron

capturedetector,

和2.氯-5.氧-3.己烯二酰氯‘371。Taguehi‘弼3用GC.Ms.MS鉴定出含aminoxy结构的两个新型卤代丁醇。Heffner等‘圳用气相色谱.傅立叶变换离子回旋共振质谱仪(Fourier

transformioncyclotron

resonancenlass

ECD)和质谱(ma¥8spectrometry,MS)是Gc分析非受控DBPs常用检测器。ECD检测灵敏度高于MS[10,29],但Ms有定性的优势。采用GC.MS发现r新DBPs,溴碘乙酰胺‘5】

spectrometer,ITTICR—MS)

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续表4饮水中非受控DBPs检测

935

垡坌塑

亚硝基吗啉

堡垒垡垦查

焦塑查鳖

GC—PCI—MSHPLc.CLDHPLC-ESI—MS/MS

CE

竺望坐!!芝生!

90

垄耋塞墼

[16]

O.2

240000

58

亚硝基丙胺

无GC-NCD

GC.PCI.MSHPLC.ESI.MS/MS

1O.2193

1.3

亚硝基丁胺

GC-NCD

GC.pCI.MSHPI£.ESI.MS/MS

3.1O.1125

1.370

亚硝基■苯胺亚硝基毗啶

H眦.ESI.Ms/MS

GC—PCI—MSHPLC.CLDHPLC..ESI..MS/MS

CE

无GC NCD

0.9

210000

[6]

卤乙酸

溴碘乙酸,碘乙酸

甲基化衍生

无无

溴氧乙酸,一溴二氯乙酸,一氯二溴乙酸三溴乙酸卤代酸

3一溴3.碘丙烯酸2一碘-3-甲基J‘烯二酸醛类

脂肪醛(C2-CIO)

PFBOA衍生PFBHA衍生PFBHA衍生

顶空SPME在线PFBHA衍生

DNPH衍生DNPH衍生

二醛类芳香醛

PFBHA衍生

GC.ECDGC.ECDGC-ECDGC.EI.MSGC—E1.MSHPl_c.ESI.MS/MSHPLC.ESI.MS/MS

GC—EI.MSC,C—EI.MS

32

6~20

GC.NCI.MSHPI£一ESI.MS/MSUPLC.MS/MsGC—EI.MS

O.2.0.2

300

[34]

【35]

80

9,80,210,420

磺酸甲醇衍生[13]

甲基化衍生

GC—NCI—MS2020

【6]

[22[30[29[3l

40—4008—200100—4400

400—24000

【3l

[20[2l[3l[31

130一760

6—24

300~2300200—4200

000—43

PFBIn衍生

000

呋喃酮类

3.氯4(二氯甲基)5-羟基-2(5H).呋喃酮

磺酸甲醇衍生BSTFA衍生磺酸丙醇衍生MBTFA衍生

溴代3一氯4(二氯甲基)5.羟基-2(5H).呋喃酮环氧化物l,2.环氧丁烷环氧氟丙烷环氧氯丙烷

水相氨解衍生Gc EI—Ms

50100100

CC.EI—MSCC.EI—MSGC.EI.MSGC—EI.MSGC—El—MS

O.1

[25][28]

30O.08~O.2

7.7

[24]

[36]【24]

磺酸丙醇衍生

0.2一1.0

[26]【26]【26|

注:MDL:方法检出限;PFBOA:五氟苯盐酸羟胺;PFBHA:五氟苄基羟胺盐酸盐;DNPH:2,4-二硝基苯肼;BSTFA:N。O一双(三甲基硅基)三氟乙酰胺;MBTFA:N.甲基双(三氟乙酰胺);C,C.ECD:气相色谱-电子捕获检测;GC.E1.MS:气相色谱 电子轰击质谱;GC—PCI Ms:气相色谱 正化学电

离质谱:GC.NCD:气相色谱.氮化学发光检测器;HPLC—FD:高效液相色谱.荧光检测;HPLC—CLD:高效液相色谱一化学发光检测;HPLC—ESI—MS/

Ms:高效液相色谱.电喷雾串联质谱;UPLC—ESI MS/MS:超高效液相一电喷雾串联质谱;CE:毛细管电泳

从饮水中鉴定出6种新的DBPs。

2.液相色谱(1iquidchromatography,LC)及其联用技术:

包括:离子排阻色谱(i伽.exclusionchromatography,IgC)‘柏1、反相Lc【201和离子色谱㈨1。超高效液相色谱(ultra

liquid

performance

Lc可分析水中分子量大和高极性的DBPs。其分离机制主要chromatography,upkc)是近年发展起来的LC技术,具

936

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制。为防止非受控DBPs的健康危害,一些非受控DBPs会转变成受控DBPs。建立新受控DBPs的分析方法标准是未来的重要研究内容。

参考文献

[1]AkinEW,HoffJC,LippyEC.Waterborneoutbreakcontrol:which

disinfectant?EnvironHe81thPerspect.1982.46:7—12.

有分离度高和分析速度快等特点。UPLC—MS联用技术已被用于快速检测饮水中亚硝基二甲胺‘仃]、碘代DBPs【35’42】。低分辨率的四极杆多级MS具有不同的扫描模式。其母离子扫描模式可用于检测极性卤代DBPs[43…。但低分辨率Ms结构鉴定能力有限。高分辨率的飞行时间质谱(time

mss8

offlisht

spectmmetry,TOF MS)能提供准确的分子量,定性功能

强,可用于DBPs形成机制研究m]。样品基质产生的化学干扰严重影响LC—MS的选择性。高场非对称波形离子迁移质谱(hish

nla88

[2]RichardsonSD.Disinfection

contaminants

in

by,products

andotI-erTrends

in

emerging

drinking

water.TrACAnalytical

field

asymmetric

waveform

ionmobility

spectrometry

Chemistry,2003,22:666-686.

spectrometry,FAIMS)通过在线分离气相离子、去除化学

[3]RichardsonSD,PlewaMJ,WagnerED,etaL

genotoxicity.and

carcinogenicity

in

Occurrence,and

of

regulated

eme晒ng

背景和内源干扰离子可显著提高方法选择性m1。StIltan和GabryeiskiH刊用FAIMS-TOF—MS直接鉴定饮水中痕鼍的未知DBPs,无需样品前处理和色谱分离。此外,电感耦合等离子体质谱(inductively

coupled

disinfectionby—products

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review

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re∞grch.Mutat

Res,2007,636(1-3):178-242.

K,et

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VS.regulatedhaloaceticacids:aretoxic?Environ

Sei

a1.Haloacetonitriles

DBPs

more

nitrogen—containing

plasma-ma88spectrometry,ICP—MS)也

Teehnol,2007,41:645-651.

SD,et

被用于卤代乙酸H1+类DBPs的检测。

3.毛细管电泳(capillaryeleetrophoresis,CE)及其联用技术:CE具有分离效能高,分析速度快和样品消耗鼍低至纳升级等特点,但紫外检测器光程短导致检测灵敏度较低。如以胶束电动cE能在20min内分析水中5种亚硝胺|3“,方法检出限为0.16—0.27ms/L。而激光诱导荧光检测器虽然灵敏度较高,但只适用于有荧光性质的物质。cE与MS联用,可提高检测灵敏度,同时具有结构鉴定功能。Iju等Ⅲ1用CE-MS结合FAIMS,检测饮水中4种硝基胺类DBPs,线性范

[5]PlewaMJ,MuellnerMG,Richardson

synthesis,andmammaliancellhaloacetamides:all

aL

Occurrence,

genotoxicity

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contaminantBissueS.

围在5—1000∥L之间。

4.分析方法比较:表5所述3种饮水中非受控DBPs检测方法的优缺点。

三、总结与展望

饮水中非受控DBPs定性定量检测在世界范围内尚处于起步阶段。未来对于饮水中非受控DBPs的检测研究将围绕提高分析灵敏度、多组分同时分析、新型DBPs发现和鉴定及分析方法标准研制等方面进行:(1)新型富集材料的研制。饮水中非受控DBPs含龟低,样品需先富集。研制新型SPE和SPME富集材料,提高不同极性DBPs物质的富集效率,实现高通量、在线实时富集。(2)研发新的衍生化技术,提高分析方法的灵敏度。(3)各种色谱 质谱技术联用。高分辨率MS如TOF.MS和FTICR.MS,定性功能强大,其与低分辨率四极杆和离子阱多级联用将成为发现和鉴定新DBPs的有力手段。UPLC分析速度快、分离效能高,其与多种MS的多级联用,可显著提高分析方法的灵敏度和多组分同时分析的能力。(4)饮水中非受控DBPs分析方法标准研

[9]Cancho

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(收稿日期:20lO旬l-28)

(本文编辑:李敬文)

饮水中非受控消毒副产物分析方法研究进展

作者:作者单位:

周颖, 黎源倩, 屈卫东

周颖(复旦大学公共卫生学院卫生化学教研室公共卫生安全教育部重点实验室,上海,200032), 黎源倩(四川大学公共卫生学院卫生检验教研室), 屈卫东(复旦大学公共卫生学院环境卫生学教研室公共卫生安全教育部重点实验室)中华预防医学杂志

CHINESE JOURNAL OF PREVENTIVE MEDICINE2010,44(10)1次

刊名:英文刊名:年,卷(期):被引用次数:

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引证文献(1条)

1.刘楠.高志贤.晁福寰 饮用水消毒副产物的卫生监控[期刊论文]-中华预防医学杂志 2010(10)

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