甲基叔丁基醚(MTBE)是目前北美燃料市场最常用的汽油添加剂.由于其化学稳定性强且难于转化,MTBE已成为一种蔓延性的地下水污染物.有氧微生物降解技术被认为是目前对MTBE污染治理最为有效的方法之一,其作用机理是:MTBE在细胞色素酶(CYP-450s)的作用下首先分解成为叔丁醇(TBA),进而完全转化为CO2和H2O.细胞色素酶(CYP-450s)是维管束植物中最为常见的一种酶,我们有理由相信维管束植物细胞能降解MTBE,但试验研究表明超过25种以上的常见植物细胞并不能降解MTBE.TBA是MTBE降解过程中最为稳定的中间产物,植物对其降解的研究目前尚未见报道.本实验用一自行设计的植物反应器来研究柳树(Salix alba)对TBA降解的可能性.长出新根须和嫩叶的柳树枝条在一容积500ml的植物反应器中生长12d(其中TBA溶液450ml)来观察TBA对柳树生长的影响,同时测定柳树对TBA的吸收和降解.TBA及其它可能的降解产物用气相色谱来检测.本实验结果表明在为期12d的时间内,水溶液中15.26%的TBA可以通过柳树的蒸腾作用去除,但是没有检测到任何可能的降解产物,在植物体内也只发现了少量的TBA残留(<1%).同时柳树的根细胞和叶细胞也用来研究对TBA的降解可能性,在为期3d的试验中,柳树的根细胞和叶细胞对TBA的吸收是非常有限的(<10%),也没也没有检测到任何可能的降解产物.本研究结果表明柳树同样也不能降解TBA,也许TBA难被降解就是富含CYP-450s酶的维管束植物不能降解MTBE的原因所在.
Methyl tert-butyl ether (MTBE) is the most commonly used gasoline oxygenate in the North American‘s fuel industry. Its persistence in groundwater is of significant concern, which provides a major stimulus for the investigation and research on the environmental sites contaminated with MTBE. There is evidence that MTBE has become one of the most common contaminants in urban groundwater. Aerobic biodegradation has been viewed as one of the most effective methods for treating MTBE contamination, in which MTBE is broken down to the intermediate tert-butyl alcohol (TBA) through the activities of the enzymes cytochrome P-450 monooxygenase (CYP 450s), and TBA is further metabolized to the final products CO2 and H2O. Enzymes of the CYP 450s are the typical enzyme of vascular paints to play a critical role in the plant metabolism and we therefore have good reasons to believe that paints would be able to metabolize MTBE. Initial studies indicated that more than 24 plants from 15 families were found to be unable to degrade MTBE. Currently there is no data available in the research of phytoremediation of TBA. This paper examined the degradation potential of rert-butyl alcohol (TBA) by willow trees (Salix alba) within a carefully designed bioreactor. Pre-rooted willow trees were kept in an Erlenmeyer flask of 500 mL with 450 mL spiked aqueous solution for 12 days. TBA and other possible intermediates of TBA were measured by GC/FID. Willow tree uptake tests indicated that 15.26% TBA mass in aqueous solution was removed through willow tree activities at 15℃ over a 12-day period of exposure. No any other possible metabolite of TBA was tracked and trace amounts of TBA mass (<1%) were found within the willow tree biomass as insoluble residue during the entire period of tests. Excised willow roots and leaves were also used to investigate the potential of willow trees to degrade TBA within glass vessels with 25 mL spiked solution for 3 days. Results of metabolism tests with excised roots and leaves indicated that significant TBA reduction (>10%) was not observed in any of the tests and any other known metabolite of TBA was not detected. It is to conclude that TBA is also persistent to the attack of plant enzymes of willow trees. The persistency of TBA may be the key to inhibit and/or disrupt the CYP-450s enzymes of willow trees in the processes of the MTBE metabolism.
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柳树对叔丁醇的降解试验
于晓章，StefanTrapp(丹麦技术大学环境与资源研究中心，DK．2800KgsL归gbH丹麦)
【摘要】甲基叔丁基醚(MTBE)是目前北美燃料市场最常用的汽油添加剂。由于其化学稳定性强且难于转化，MTBE
已成为一种蔓延性的地下水污染物。有氧微生物降解技术被认为是目前对MTBE污染冶理最为有效的方法之一，；#作
用机理是：MTBE在细胞色素酶(cYP一450s)的作用F首先分解成为掇丁醇(TBA)，进而完全转化为cn和H，o。细
胞色素酶(cYP_450s)是维管束植物中最为常见的一种酶，我们有理由相信维管束植物细胞能降解M11强，但试验研
究表明超过25种以上的常见植物细胞并不能降解MTBE。TBA是MTBE降解过程中最为稳定的中『日j产物，植物对其
降解的研究目前尚未见报道。本实验用一自行设计的植物反应器来研究柳树【＆f打d脑口)对TBA降解的Ⅱ丁能性。长出
新根须和嫩叶的柳树枝条在一容积500蚰的植物反应器中生长12d(其中113A溶液450向)来观察TBA对柳树生长
的影响，同时测定柳树对TBA的吸收和降解。TBA及其它可能的降解产物用气相色谱来检测。本实验结果表明在为期
12d的时间内．水溶液中1526％的TBA可以通过柳树的燕腾作用去除，但是没有检测到任何可能的降解产物，在植
物体内也只发现了少量的TBA残留(<1％)。同时柳树的根细胞和叶细胞也用来研究对TBA的降解可能性，在为期3d
的试验中，柳树的根细胞和叶细胞对TBA的吸收是非常有限的(<10％)，也没有检测到任何可能的降解产物。本研究
结果表明柳树同样也不能降解1BA，也许TBA难被降解就是富含cⅥ，-450s酶的维管束植物不能降解MTBE的原因所
在。
关键词：降解；甲基叔丁基醚；叔丁J醇：柳树
中图分类号：x173 文献标识码：A 文章编号：1008—8873(2003)01．006．03
Degradanontestsf细-bu聊m∞h0Ibyw订 owtrees，YUⅪao—Zhan毋Stef如Trapp(Environmcnt＆Rcsouces．Tech ical
UniversitvofDenmarkDK一2800K2s．L”曲MDenmark)
AbstractMethyl坨，}butvlecher(MTBE)isthemostcomITlonlyusedgasolineoxygenatcin山eNor由Americ锄’sfuel
indusⅡ*ItspersistenceingroundwaterisofsigII墒cantoncem，whichpfovidesam旬orstimulusfor山einve虬igadon柚d
researchonthenvimnmentalsitescOnta血nated试t|lM7rBE．Thereis videncethatMTBEhasbecomeoneofthemO吼
commonc ntal_11inantsinurban舯undwateLAerobicode舯daⅡonhasbeenviewedasoneofthemoste舨6vem thodsfor
Ⅱtadn2MTBEcon【amina60n，inw11ichMTBEisbrokendowntotlleint锄ediate埘}butyIalcohol(丁BA)throu曲【he
actividesof出en珂rnescytochroⅡ1eP-450monooxygenase(CYP450 )，如dTBAisfurtherm tabonzedtot}le丘nalprodu吣
Co，andH20Enzymesoft|leCYP450sarc山etypicalenzyrrleofvascularpaln也toplayc五吐caliDlein山epl如tInetaboli蛐
andwe山ereforehav200dreasonstobeIieve七hatpaIntswollldbeabletoInet曲olizeMTBEIni廿alstudiesndicatedtha【r∞re
chan24pI卸cs疗Om15fa嘶IicswerefoundtObeunabjet0de譬radeMTBECu仃endyche陀isn0da妇avajlable抽c}le砧search
0fDhv【orcIlledi撕onof’rBA．111is口即erexarllinedthde哪d撕伽poLcn“alof把玎-butylalcob01㈣A)bv“llow吨es(踟拙
口腑口)withinacare矗11lvdesignedbioreac七oL11rc·r00tedwillow廿eesw rek ptinanI狲enmeyernaskof5(10mLwjth450札
s口ikcdaqueouss01udonfor12daysTBAando山erpossibleintenn酣iacesofTBAweremeasuredbyGC，FIDWillow咄
u口taketestsindicatedthat15．26％TBAmassinaqucoussoludonwasremovedt}Ⅱuu2hwillow订eeac6vi6esat15”Covera
12．davDenodofex口osureN aⅡyother口ossiblemetabolneofTBAwastrackcdandhqce姗oun sofTBAmassf<1％)were
fbundwi山in血ewillow廿eebiomasssinsolublere甄duedu订ngmeen廿I℃口criodoftcsts．Exciscdw lIowrootsandleaves
werealsousedtoinvesdgatetIlepotcn6alofwillow慨stodegradeTBA讯thinglassvcssclswim25rnLspikedsolutionfor3
davsResultsof埘Btabolism慨￡switllexcisedroots赳1dleavesirldicatedthat蝣gnifIcantTBArcductioⅡ(>10％)wasⅡot
obser代din柚y0f山etests觚d蚰y0t11erknOwnmet曲oIite0fTBAwasnOtdetectedItistoconclude血atTBAisa王so
De曙istenttot}lcat瞻ckof口lant∞zymesof、V讯owh髓sThep盯sistencyOfTBAmaybemekeycoinhibit卸d，ordismptthe
CYP．450senzvmesofwillowtreesinthe口r00essesOf【hcMTBEmetabOlism
Keywords：degradadon；met}lvl饽，}butylet cr；把盯_butylalcoh01；踟f扛口f幻
MemvlfPr卜butvle廿1er(MTBE)is 山e most
commonlyusedgas01ineoxygena地intheUS(弛get
a1．1999)andisquitep rsis把nttobioticandabiodc
deco唧osinonin窨e eral(Fayolleet 1．2001)．HoweveL
enzvmesofmecytocllr咖∽P．450monooxygenase(CYP
450s)werefoundt0beabIetoworkonthedegradadon
0fMrBEinrIlicr00rgarIisms．humallhvcrsa11d111ice
1ivers(Fay011eeta1．200l，Hongeta1．1999)．0ne
conclusiveresultf如mthestudieswasmat膪，卜butvl
A1cohol(7rBA)is吐屺缸tstableinte珊ediate，a
potendallytoxicproduct(Bradyeta1．1990)．Ag黜fal
de椰anonpa血wayf缸MIBEisshown船F{gI：腓1．Itis
lmown血aten2ymesoftheCYP450sarethetypical
ph懿eImetaboⅡsme zyrneofvascularplants(1(omossa
eta1．1995)．CYP450sarewidespreadandhavemany
fIlncd衄sintheplaIltmetabohsm．We血ercfbrehad譬ood
reasonstoa sumethdt口lantswouIdbe曲letomeaboHze
MTBE．Howeverourprevi sinwsdganonsi dicated
基金项目-勘‘岬cc倒豳咀阳卿0fQIlali廿of恤
(Qu(3一丑∞00啪164X
作者简介i(1966一)，男，劓教授．研究方向为污染的植物修复
B“l：y“i∞zhangob∞nail．㈣．
2002．12．2s’ 003_01．26接受
万方数据
万方数据
万方数据
柳树对叔丁醇的降解试验
作者： 于晓草， Stefan Trapp
作者单位： 丹麦技术大学环境与资源研究中心,DK-2800,Kgs.Lyngby,丹麦
刊名： 生态科学
英文刊名： ECOLOGIC SCIENCE
年，卷(期)： 2003,22(1)
被引用次数： 2次
参考文献(7条)
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期刊] 1990
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organic Chemicals (Volume IV) 1995
5.Komossa D;Langebartels C;Sandermann Jr H Metabolic processes for organic chemicals in plants.
Plant contamination-modeling and simulation of organic chemical processes 1995
6.Hong J Y;Wang Y Y;Bondoc F Y Metabolism of MTBE and other gasoline ethers by human liver
microsomes and heterologously expressed human cytochromes P450:identification of CYP2A6 as a major
catalyst 1999
7.Fayolle F;Vandecasteele J P;Mono F Microbial degradation and fate in the environment of MTBE and
related fuel oxygenates[外文期刊] 2001
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引证文献(2条)
1.朱琳.刘涉江.黄国强.姜斌.李鑫钢 甲基叔丁基醚的降解技术研究进展[期刊论文]-化工进展 2005(10)
2.李荣 超声波降解叔丁醇废水的研究[学位论文]硕士 2005
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