探究微生物推助的类芬顿反应降解四溴联苯醚

·探究微生物推助的类芬顿反应降解四溴联苯醚摘要多溴联苯醚(Polybrominateddiphenylethers，简称PBDEs)几十年来一直被用作阻燃剂，广泛分布于土壤、水体、沉积物中。目前的研究表明，微生物推助的类芬顿反应（Fenton-likeReaction）可以自动产生羟基自由基(HO•)来降解四溴联苯醚（BDE-47）。和传统的（非生物）类芬顿反应比较，微生物推助的类芬顿反应的pH值与自然环境的pH值类似，并且不需要额外添加H2O2或使用UV射线就可以利用还原产生的Fe(II)作为反应物。BDE-47的降解过程是由实验室内纯培养的还原Fe（III）的兼性厌氧细菌，奥奈达希瓦氏菌(ShewancllaoneidensisMR-1)推动的。本研究以乳酸钠为电子供体，水铁矿、针铁矿、柠檬酸铁分别作为电子受体来培养兼性厌氧细菌S.oneidensisMR-1，结果表明，在相同条件下，通过8次厌氧好氧循环过程，在水铁矿、针铁矿、柠檬酸铁中BDE-47分别被降解了83.99%，75.57%，67.74%。通过控制实验条件，证明了驱动BDE-47降解的是羟基自由基(HO•)。微生物推助的类芬顿反应为能够被羟基自由基(HO•)降解的环境污染物提供了一种新的发展途径。关键词：四溴联苯醚；类芬顿反应；奥奈达希瓦氏菌；羟基自由基(HO•)

AbstractThesoilcontaminatedPolybrominateddiphenylethers(PBDEs)isemployedasaflameretardantandiswidespreadedinthesoil,waterandsediment.Inthepresentstudy,amicrobiallydrivenFenton-likereactionwasdesignedtoautocatalyticallygeneratehydroxyl(HO•)radicalsthatdegradePBDEs.Incomparisontoconventional(abiotic)Fenton-likereactions,themicrobiallydrivenFenton-likereactionoperatedatcircumneutralpHanddidnotrequireadditionofexogenousH2O2orUVirradiationtoregenerateFe(II)asFenton-likereagents.ThedegradationprocessofTetrabromodiphenylether(BDE-47)wasmanipulatedundercontrolledlaboratoryconditionsbypureculturesoftheFe(III)-reducingfacultativeanaerobeShewancllaoneidensisMR-1.S.oneidensisMR-1batchcultureswereexposedtoalternatingaerobicandanaerobicconditionsandwereprovidedwithlactate,Fe(III),andBDE-47.Whentheaerobic/anaerobiccyclewassetto3h/24h,83.99%，75.57%，67.74%BDE-47(2ppminitialconcentration)wasdegradedwhenFe(III)wereFerrihydrite,GoethiteandFerriccitraterespectively.Bycontrollingtheexperimentalcondition,ithasbeenprovedthathydroxylradicals(HO•)wasthemajordrivenfactor.ThemicrobiallydrivenFenton-likereactionprovidesthefoundationforthedevelopmentofalternativeinsituremediationtechnologiestodegradeenvironmentalcontaminantssusceptibletoattackbyhydroxylradicals(HO•)generatedbytheFenton-likereaction.KeyWords：Tetrabromodiphenylether;Fenton-likeReaction;Shewancllaoneidensis;hydroxylradicals(HO•)

目录图清单 I表清单 II第一章绪论 11.1研究背景 11.1.1多溴联苯醚的污染来源 11.1.2环境中多溴联苯醚的污染水平 空气和灰尘中的多溴联苯醚 水体和土壤中的多溴联苯醚 生物体中的多溴联苯醚 31.1.3多溴联苯醚的生物毒性 41.1.4多溴联苯醚的降解 光降解法 零价铁法 生物降解法 芬顿法与类芬顿法 61.2S.oneidensisMR-1介导的类芬顿反应降解多溴联苯醚 61.2.1类芬顿法 61.2.2S.oneidensisMR-1介导的类芬顿反应降解多溴联苯醚 71.3论文选题的意义和创新性 81.4研究的内容及思路 8第二章材料与方法 102.1实验材料 102.1.1培养基和化学药品 102.1.2实验主要的仪器 122.2实验方法 132.2.1微生物推助的类芬顿反应降解BDE-47的方法设计 132.2.2亚铁离子和过氧化氢含量分析 亚铁离子含量测定方法 过氧化氢含量测定方法 152.2.3BDE-47含量测定 162.2.4微生物推助的类芬顿反应抑制 17第三章实验结果分析 193.1严格厌氧下S.oneidensisMR-1还原产生的Fe（II） 193.2S.oneidensisMR-1产生的H2O2 203.3微生物推助的类芬顿反应降解BDE-47 213.3.1Fe（II）浓度 213.3.2BDE-47的降解 柠檬酸铁存在时BDE-47的降解 水铁矿存在时BDE-47的降解 针铁矿存在时BDE-47的降解 三种铁矿BDE-47降解情况对比 253.4微生物推助的类芬顿反应抑制 253.4.1微生物推助的类芬顿反应抑制 253.4.2羟基自由基(HO•)的浓度 26第四章实验结果讨论 284.1严格厌氧下S.oneidensisMR-1还原产生的Fe（II） 284.2S.oneidensisMR-1产生的H2O2 284.3微生物推助的类芬顿反应降解BDE-47 294.3.1Fe（II）浓度 294.3.2BDE-47的降解 294.4微生物推助的类芬顿反应抑制 304.4.1微生物推助的类芬顿反应抑制 304.4.2羟基自由基(HO•)的浓度 30第五章结论与展望 315.1实验结论 315.2结论应用 315.3实验不足与展望 32致谢 33参考文献 34

图清单图1MR-1推动类芬顿反应有机物示意图 7图3-1严格厌氧下S.oneidensisMR-1还原产生的Fe（II） 19图3-23h/24h通氧/厌氧循环周期下S.oneidensisMR-1产生的H2O2 20图3-33h/24h通氧/厌氧循环周期下S.oneidensisMR-1产生的Fe（II） 21图3-4柠檬酸铁实验组，对照组，空白组的BDE-47降解情况 23图3-5水铁矿实验组，对照组，空白组的BDE-47降解情况 24图3-6针铁矿实验组，对照组，空白组的BDE-47降解情况 25图3-7三种铁矿BDE-47降解情况对比 25图3-8微生物推助的类芬顿反应的抑制 26图3-9三种铁矿羟基自由基(HO•)的浓度对比 27表清单表2-1基本无机盐培养基成分（1000mL） 10表2-2MineralMix培养基成分（1000mL） 11表2-3VitaminMix培养基成分（1000mL） 11表2-4AminoAcidMix培养基成分（1000mL） 12表2-5实验所用仪器器材 12表2-6BDE-47降解实验实验组，空白组，对照组培养基组成成分表 14表2-7过氧化氢标准溶液制备 16表2-8微生物推助的类芬顿反应抑制试验样品组成 17第一章绪论1.1研究背景多溴联苯醚(Polybrominateddiphenylethers，简称PBDEs)几十年来一直被用作阻燃剂，可在发生火灾时延长逃生时间，从而挽救生命并减少火灾造成的损害。溴通过与气相中的自由基反应起作用可以延缓着火和燃烧的过程ADDINEN.CITE<EndNote><Cite><Author>DeWit</Author><Year>2006</Year><RecNum>35</RecNum><DisplayText><styleface="superscript">[1]</style></DisplayText><record><rec-number>35</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">35</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>DeWit,CynthiaA</author><author>Alaee,Mehran</author><author>Muir,DerekCG</author></authors></contributors><titles><title>LevelsandtrendsofbrominatedflameretardantsintheArctic</title><secondary-title>Chemosphere</secondary-title></titles><periodical><full-title>Chemosphere</full-title></periodical><pages>209-233</pages><volume>64</volume><number>2</number><dates><year>2006</year></dates><isbn>0045-6535</isbn><urls></urls></record></Cite></EndNote>[\o"DeWit,2006#35"1]。同样，PBDEs由于其良好的的阻燃性也在很多产品中被使用，例如房屋内的装潢、电器、厨房用具，纺织布料；汽车和飞机上的电子产品，塑料制品等等。由于PBDEs在生活中被广泛使用，人们接触到该物质的几率非常大。相对分子质量大、熔点高、蒸气压低、水溶性低及Kow值高的化学特性使PBDEs具有亲脂性和生物易累积性的特点。这些特点使其能在高营养级生物体内的脂肪和蛋白质中聚集，并通过食物链放大，从而对整个生态环境和生物链造成影响ADDINEN.CITE<EndNote><Cite><Author>任金亮</Author><Year>2006</Year><RecNum>36</RecNum><DisplayText><styleface="superscript">[2]</style></DisplayText><record><rec-number>36</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">36</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>任金亮</author><author>王平</author></authors></contributors><titles><title>多溴联苯醚环境行为的特征与研究进展</title><secondary-title>化工進展</secondary-title></titles><periodical><full-title>化工進展</full-title></periodical><pages>1152-1157</pages><volume>25</volume><number>10</number><dates><year>2006</year></dates><isbn>1000-6613</isbn><urls></urls></record></Cite></EndNote>[\o"任金亮,2006#36"2]。PBDEs的化学式为C12H(0-9)Br(10-1)O,根据溴原子数量不同而分为10个同系组，共209种同系物。但市场上主要生产和使用的有三种同系物：五溴联苯醚（BDE-99），八溴联苯醚（BDE-197）和十溴联苯醚（BDE-209）ADDINEN.CITE<EndNote><Cite><Author>Hites</Author><Year>2004</Year><RecNum>37</RecNum><DisplayText><styleface="superscript">[3]</style></DisplayText><record><rec-number>37</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">37</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Hites,RonaldA</author></authors></contributors><titles><title>Polybrominateddiphenylethersintheenvironmentandinpeople:ameta-analysisofconcentrations</title><secondary-title>Environmentalscience&technology</secondary-title></titles><periodical><full-title>EnvironSciTechnol</full-title><abbr-1>Environmentalscience&technology</abbr-1></periodical><pages>945-956</pages><volume>38</volume><number>4</number><dates><year>2004</year></dates><isbn>0013-936X</isbn><urls></urls></record></Cite></EndNote>[\o"Hites,2004#37"3]。尽管世界上使用最多的PBDEs污染物是BDE-209，但四溴联苯醚（BDE-47）和BDE-99在生物圈中的含量是最高的。且有研究表明，溶于有机溶剂中的BDE-209在紫外线或日光的照射下会迅速脱溴降解为低溴代联苯醚ADDINEN.CITE<EndNote><Cite><Author>Söderström</Author><Year>2004</Year><RecNum>38</RecNum><DisplayText><styleface="superscript">[4]</style></DisplayText><record><rec-number>38</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">38</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Söderström,Gunilla</author><author>Sellström,Ulla</author><author>deWit,CynthiaA</author><author>Tysklind,Mats</author></authors></contributors><titles><title>Photolyticdebrominationofdecabromodiphenylether(BDE209)</title><secondary-title>Environmentalscience&technology</secondary-title></titles><periodical><full-title>EnvironSciTechnol</full-title><abbr-1>Environmentalscience&technology</abbr-1></periodical><pages>127-132</pages><volume>38</volume><number>1</number><dates><year>2004</year></dates><isbn>0013-936X</isbn><urls></urls></record></Cite></EndNote>[\o"Söderström,2004#38"4]，从而对环境造成更大的威胁。1.1.1多溴联苯醚的污染来源PBDEs可从各种产品，例如聚氨酯，计算机，电视等中挥发进入到环境。作为添加剂，它们可以从电子产品和家具中释放出来，存在于房屋和办公室的空气和灰尘中。由于工业化国家收集回收的大约50-80％的废弃物最终进入中国，印度，巴基斯坦，越南，菲律宾等劳动力成本较低，环境法规不太严格的国家ADDINEN.CITE<EndNote><Cite><Author>Schwarzer</Author><Year>2005</Year><RecNum>48</RecNum><DisplayText><styleface="superscript">[5]</style></DisplayText><record><rec-number>48</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">48</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Schwarzer,Stefan</author><author>DeBono,Andréa</author><author>Giuliani,Gregory</author><author>Kluser,Stéphane</author><author>Peduzzi,Pascal</author></authors></contributors><titles><title>E-waste,thehiddensideofITequipment'smanufacturinganduse</title></titles><dates><year>2005</year></dates><urls></urls></record></Cite></EndNote>[\o"Schwarzer,2005#48"5]。电子产品回收处理过程中导致的PBDEs无限制的排放使这些发展中国家成为世界PBDEs库最主要的来源ADDINEN.CITEADDINEN.CITE.DATA[\o"Bi,2007#49"6,\o"Wong,2007#50"7]。与其他半挥发性有机化合物（SVOCs）类似，PBDEs在大气中以气态和颗粒态同时存在，这是影响其流动性和大气循环途径的关键因素ADDINEN.CITE<EndNote><Cite><Author>Bennett</Author><Year>2001</Year><RecNum>51</RecNum><DisplayText><styleface="superscript">[8]</style></DisplayText><record><rec-number>51</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">51</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Bennett,DeborahH</author><author>Scheringer,Martin</author><author>McKone,ThomasE</author><author>Hungerbühler,Konrad</author></authors></contributors><titles><title>Predictinglong-rangetransport:asystematicevaluationoftwomultimediatransportmodels</title><secondary-title>Environmentalscience&technology</secondary-title></titles><periodical><full-title>EnvironSciTechnol</full-title><abbr-1>Environmentalscience&technology</abbr-1></periodical><pages>1181-1189</pages><volume>35</volume><number>6</number><dates><year>2001</year></dates><isbn>0013-936X</isbn><urls></urls></record></Cite></EndNote>[\o"Bennett,2001#51"8]。因为细颗粒不容易从大气悬浮物中被扫除，所以PBDEs足够稳定，存留时间长，在环境中可长时间被运输ADDINEN.CITE<EndNote><Cite><Author>HERZKE</Author><Year>2003</Year><RecNum>52</RecNum><DisplayText><styleface="superscript">[9]</style></DisplayText><record><rec-number>52</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">52</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>HERZKE,Dorte</author><author>BERGER,Urs</author><author>NYGARD,Torgeir</author><author>VETTER,Walter</author></authors></contributors><titles><title>Organochlorines,organobrominesandtheirmetabolitesineggsofNorwegianbirdsofprey</title><secondary-title>Organohalogencompounds</secondary-title></titles><periodical><full-title>Organohalogencompounds</full-title></periodical><pages>466-469</pages><volume>61</volume><dates><year>2003</year></dates><isbn>1026-4892</isbn><urls></urls></record></Cite></EndNote>[\o"HERZKE,2003#52"9]。大气传输和沉积已被确定为农村和偏远地区存在PBDEs的原因ADDINEN.CITE<EndNote><Cite><Author>TerSchure</Author><Year>2004</Year><RecNum>53</RecNum><DisplayText><styleface="superscript">[10]</style></DisplayText><record><rec-number>53</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">53</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>TerSchure,ArnoutFH</author><author>Larsson,Per</author><author>Agrell,Cecilia</author><author>Boon,JanP</author></authors></contributors><titles><title>AtmospherictransportofpolybrominateddiphenylethersandpolychlorinatedbiphenylstotheBalticSea</title><secondary-title>Environmentalscience&technology</secondary-title></titles><periodical><full-title>EnvironSciTechnol</full-title><abbr-1>Environmentalscience&technology</abbr-1></periodical><pages>1282-1287</pages><volume>38</volume><number>5</number><dates><year>2004</year></dates><isbn>0013-936X</isbn><urls></urls></record></Cite></EndNote>[\o"TerSchure,2004#53"10]。偏远地区，如极地地区存在高浓度的PBDEs化合物表明，由于远距离大气迁移，沉积和再挥发，PBDEs现在可能已经在世界范围内分布，这一过程被称为“蝗虫效应”ADDINEN.CITEADDINEN.CITE.DATA[\o"Hale,2008#55"11-14]。除此之外，河流湖泊也向环境中提供了PBDEs的来源。由于PBDEs具有良好的挥发性，从产品中挥发释放出来的PBDEs溶解于水中及污水的直接排放都可向水源提供PBDEs污染物。水溶性和辛醇-水分配系数是预测水相行为的重要物理化学因素。根据Tomy等人的研究ADDINEN.CITE<EndNote><Cite><Author>Tomy</Author><Year>2001</Year><RecNum>66</RecNum><DisplayText><styleface="superscript">[15]</style></DisplayText><record><rec-number>66</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">66</key></foreign-keys><ref-typename="ConferenceProceedings">10</ref-type><contributors><authors><author>Tomy,G</author><author>Tittlemier,S</author><author>Braekevelt,E</author><author>Halldorson,T</author><author>Stern,G</author></authors></contributors><titles><title>Thephysico-chemicalpropertiesofsomebrominatedflameretardants</title><secondary-title>FirstInternationalWorkshoponBrominatedFlamesRetardants,Stockholm,Sweden</secondary-title></titles><dates><year>2001</year></dates><urls></urls></record></Cite></EndNote>[\o"Tomy,2001#66"15]，PBDEs的水溶解度通常随着溴含量的增加而降低，LogKow值通常随着溴含量的增加而增加。尽管关于PBDEs在水性介质中的行为的信息很少，但低溴代同系物，如BDE-47和BDE-99，比较高溴化的同类物在水中溶解度更高，流动性更好。土壤环境,包括表层土壤、水底的沉积物,因其具有较强的吸附能力是环境中PBDEs的主要储存介质，对PBDEs在全球的移动和分布起到缓冲和减缓作用ADDINEN.CITE<EndNote><Cite><Author>Leung</Author><Year>2007</Year><RecNum>62</RecNum><DisplayText><styleface="superscript">[16]</style></DisplayText><record><rec-number>62</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">62</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Leung,AnnaOW</author><author>Luksemburg,WilliamJ</author><author>Wong,AnthonyS</author><author>Wong,MingH</author></authors></contributors><titles><title>Spatialdistributionofpolybrominateddiphenylethersandpolychlorinateddibenzo-p-dioxinsanddibenzofuransinsoilandcombustedresidueatGuiyu,anelectronicwasterecyclingsiteinsoutheastChina</title><secondary-title>Environmentalscience&technology</secondary-title></titles><periodical><full-title>EnvironSciTechnol</full-title><abbr-1>Environmentalscience&technology</abbr-1></periodical><pages>2730-2737</pages><volume>41</volume><number>8</number><dates><year>2007</year></dates><isbn>0013-936X</isbn><urls></urls></record></Cite></EndNote>[\o"Leung,2007#62"16]。含PBDEs的电子垃圾在大量堆放电子垃圾的区域，遭到长期露天堆放带来的日晒雨淋,使电子废弃物中添加的PBDEs挥发和沉降进入周围的大气和土壤,造成间接污染。因为对电子垃圾主要采用集中处理的方式,在电子垃圾处置地区有相对较高的土壤PBDEs含量。在河流沉积物中,由于沉积物有巨大的吸附能力，PBDEs同系物种类较多，且以三溴联苯醚（BDE-28）、BDE-47、BDE-99、六溴联苯醚（BDE-153）、七溴联苯醚(BDE-183)和BDE-209为主ADDINEN.CITE<EndNote><Cite><Author>陈泽秋</Author><Year>2018</Year><RecNum>64</RecNum><DisplayText><styleface="superscript">[17]</style></DisplayText><record><rec-number>64</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">64</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>陈泽秋</author><author>陈家长</author><author>孟顺龙</author></authors></contributors><titles><title>多溴联苯醚在环境中的污染现状与毒理效应研究进展</title><secondary-title>中国农学通报</secondary-title></titles><periodical><full-title>中国农学通报</full-title></periodical><pages>91-98</pages><volume>34</volume><number>31</number><dates><year>2018</year></dates><urls></urls></record></Cite></EndNote>[\o"陈泽秋,2018#64"17]。1.1.2环境中多溴联苯醚的污染水平空气和灰尘中的多溴联苯醚室外的PBDEs浓度根据国家和地区的不同有很大的差距，以下列举了一些典型地区与国家的PBDEs浓度。Jaward等人通过研究欧洲25个城区和46个乡村地区发现，总共八种PBDEs同系物的浓度在0.5~250pg/m3ADDINEN.CITE<EndNote><Cite><Author>Jaward</Author><Year>2004</Year><RecNum>39</RecNum><DisplayText><styleface="superscript">[18]</style></DisplayText><record><rec-number>39</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">39</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Jaward,FodayM</author><author>Farrar,NickJ</author><author>Harner,Tom</author><author>Sweetman,AndrewJ</author><author>Jones,KevinC</author></authors></contributors><titles><title>PassiveairsamplingofPCBs,PBDEs,andorganochlorinepesticidesacrossEurope</title><secondary-title>Environmentalscience&technology</secondary-title></titles><periodical><full-title>EnvironSciTechnol</full-title><abbr-1>Environmentalscience&technology</abbr-1></periodical><pages>34-41</pages><volume>38</volume><number>1</number><dates><year>2004</year></dates><isbn>0013-936X</isbn><urls></urls></record></Cite></EndNote>[\o"Jaward,2004#39"18]，其中英国由于其对火灾的严格管制及PBDEs生产量较大，成为了欧洲地区PBDEs排放最多的地区ADDINEN.CITE<EndNote><Cite><Author>Prevedouros</Author><Year>2004</Year><RecNum>40</RecNum><DisplayText><styleface="superscript">[19]</style></DisplayText><record><rec-number>40</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">40</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Prevedouros,K</author><author>Jones,KC</author><author>Sweetman,AJ</author></authors></contributors><titles><title>European-scalemodelingofconcentrationsanddistributionofpolybrominateddiphenylethersinthepentabromodiphenyletherproduct</title><secondary-title>Environmentalscience&technology</secondary-title></titles><periodical><full-title>EnvironSciTechnol</full-title><abbr-1>Environmentalscience&technology</abbr-1></periodical><pages>5993-6001</pages><volume>38</volume><number>22</number><dates><year>2004</year></dates><isbn>0013-936X</isbn><urls></urls></record></Cite></EndNote>[\o"Prevedouros,2004#40"19]。北美地区的PBDEs的浓度在5~100pg/m3ADDINEN.CITE<EndNote><Cite><Author>Hoh</Author><Year>2005</Year><RecNum>41</RecNum><DisplayText><styleface="superscript">[20]</style></DisplayText><record><rec-number>41</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">41</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Hoh,Eunha</author><author>Hites,RonaldA</author></authors></contributors><titles><title>Brominatedflameretardantsintheatmosphereoftheeast-centralUnitedStates</title><secondary-title>Environmentalscience&technology</secondary-title></titles><periodical><full-title>EnvironSciTechnol</full-title><abbr-1>Environmentalscience&technology</abbr-1></periodical><pages>7794-7802</pages><volume>39</volume><number>20</number><dates><year>2005</year></dates><isbn>0013-936X</isbn><urls></urls></record></Cite></EndNote>[\o"Hoh,2005#41"20]。中国的PBDEs浓度非常高，据检测，广州的PBDEs浓度为1943pg/m3ADDINEN.CITE<EndNote><Cite><Author>Chen</Author><Year>2006</Year><RecNum>42</RecNum><DisplayText><styleface="superscript">[21]</style></DisplayText><record><rec-number>42</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">42</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Chen,Lai-Guo</author><author>Mai,Bi-Xian</author><author>Bi,Xin-Hui</author><author>Chen,She-Jun</author><author>Wang,Xin-Ming</author><author>Ran,Yong</author><author>Luo,Xiao-Jun</author><author>Sheng,Guo-Ying</author><author>Fu,Jia-Mo</author><author>Zeng,EddyY</author></authors></contributors><titles><title>Concentrationlevels,compositionalprofiles,andgas-particlepartitioningofpolybrominateddiphenylethersintheatmosphereofanurbancityinSouthChina</title><secondary-title>Environmentalscience&technology</secondary-title></titles><periodical><full-title>EnvironSciTechnol</full-title><abbr-1>Environmentalscience&technology</abbr-1></periodical><pages>1190-1196</pages><volume>40</volume><number>4</number><dates><year>2006</year></dates><isbn>0013-936X</isbn><urls></urls></record></Cite></EndNote>[\o"Chen,2006#42"21]，珠三角地区的十五种PBDEs浓度为1450pg/m3ADDINEN.CITE<EndNote><Cite><Author>Zhang</Author><Year>2009</Year><RecNum>43</RecNum><DisplayText><styleface="superscript">[22]</style></DisplayText><record><rec-number>43</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">43</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhang,Xianming</author><author>Diamond,MiriamL</author><author>Ibarra,Catalina</author><author>Harrad,Stuart</author></authors></contributors><titles><title>Multimediamodelingofpolybrominateddiphenyletheremissionsandfateindoors</title><secondary-title>Environmentalscience&technology</secondary-title></titles><periodical><full-title>EnvironSciTechnol</full-title><abbr-1>Environmentalscience&technology</abbr-1></periodical><pages>2845-2850</pages><volume>43</volume><number>8</number><dates><year>2009</year></dates><isbn>0013-936X</isbn><urls></urls></record></Cite></EndNote>[\o"Zhang,2009#43"22]。澳大利亚地区的PBDEs，浓度非常低，只有1.7~6.8pg/m3ADDINEN.CITE<EndNote><Cite><Author>Toms</Author><Year>2009</Year><RecNum>44</RecNum><DisplayText><styleface="superscript">[23]</style></DisplayText><record><rec-number>44</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">44</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Toms,Leisa-MareeL</author><author>Bartkow,MichaelE</author><author>Symons,Robert</author><author>Paepke,Olaf</author><author>Mueller,JochenF</author></authors></contributors><titles><title>Assessmentofpolybrominateddiphenylethers(PBDEs)insamplescollectedfromindoorenvironmentsinSouthEastQueensland,Australia</title><secondary-title>Chemosphere</secondary-title></titles><periodical><full-title>Chemosphere</full-title></periodical><pages>173-178</pages><volume>76</volume><number>2</number><dates><year>2009</year></dates><isbn>0045-6535</isbn><urls></urls></record></Cite></EndNote>[\o"Toms,2009#44"23]。相比于室外，室内由于用到较多的含有PBDEs的物品导致PBDEs的浓度更高，大约是室外浓度的50倍ADDINEN.CITE<EndNote><Cite><Author>Wilford</Author><Year>2004</Year><RecNum>47</RecNum><DisplayText><styleface="superscript">[24]</style></DisplayText><record><rec-number>47</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">47</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Wilford,BryonyH</author><author>Harner,Tom</author><author>Zhu,Jiping</author><author>Shoeib,Mahiba</author><author>Jones,KevinC</author></authors></contributors><titles><title>PassivesamplingsurveyofpolybrominateddiphenyletherflameretardantsinindoorandoutdoorairinOttawa,Canada:implicationsforsourcesandexposure</title><secondary-title>Environmentalscience&technology</secondary-title></titles><periodical><full-title>EnvironSciTechnol</full-title><abbr-1>Environmentalscience&technology</abbr-1></periodical><pages>5312-5318</pages><volume>38</volume><number>20</number><dates><year>2004</year></dates><isbn>0013-936X</isbn><urls></urls></record></Cite></EndNote>[\o"Wilford,2004#47"24]。此外，室内光源的存在，较小的空间和较弱的空气循环不可避免地导致较高的气体浓度。且室内PBDEs分子颗粒相比室外更容易吸附在细颗粒表面，而室内较弱的空气循环会增加细颗粒的沉积ADDINEN.CITEADDINEN.CITE.DATA[\o"Zhang,2009#43"22,\o"Mandalakis,2009#45"25,\o"Wei,2009#46"26]。水体和土壤中的多溴联苯醚部分国家水体中PBDEs的含量可在文献中找到。1977年及1987~1988年在日本全国范围内的河流，河口，海水样本中没有找到BDE-153、BDE-197，BDE-209。在北美，安大略湖1999年地表水的PBDEs水平为4~13pg/LADDINEN.CITE<EndNote><Cite><Author>Luckey</Author><Year>2002</Year><RecNum>60</RecNum><DisplayText><styleface="superscript">[27]</style></DisplayText><record><rec-number>60</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">60</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Luckey,F</author><author>Fowler,B</author><author>Litten,S</author></authors></contributors><titles><title>EstablishingbaselinelevelsofpolybrominateddiphenylethersinLakeOntariosurfacewaters</title><secondary-title>Unpublishedmanuscriptdated</secondary-title></titles><periodical><full-title>Unpublishedmanuscriptdated</full-title></periodical><volume>3</volume><number>01</number><dates><year>2002</year></dates><urls></urls></record></Cite></EndNote>[\o"Luckey,2002#60"27]。其中，BDE-47和BDE-99被认为占PBDEs总量的90％以上。据报道，1999年欧洲荷兰沿海水域的BDE-47，BDE-99和BDE-153浓度分别约为1,0.5和0.1pg/L。这些水域中的BDE-209含量范围为0.1~4pg/LADDINEN.CITE<EndNote><Cite><Author>Booij</Author><Year>2002</Year><RecNum>61</RecNum><DisplayText><styleface="superscript">[28]</style></DisplayText><record><rec-number>61</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">61</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Booij,Kees</author><author>Zegers,BartN</author><author>Boon,JanP</author></authors></contributors><titles><title>Levelsofsomepolybrominateddiphenylether(PBDE)flameretardantsalongtheDutchcoastasderivedfromtheiraccumulationinSPMDsandbluemussels(Mytilusedulis)</title><secondary-title>Chemosphere</secondary-title></titles><periodical><full-title>Chemosphere</full-title></periodical><pages>683-688</pages><volume>46</volume><number>5</number><dates><year>2002</year></dates><isbn>0045-6535</isbn><urls></urls></record></Cite></EndNote>[\o"Booij,2002#61"28]。部分国家土壤中PBDEs的含量在文献中也有提及。在中国，陈社军等人研究发现,南海北部湾海域和珠江三角洲是目前世界上已报道的沉积物中PBDEs含量最高的区域之一，在该区域表层沉积物样品中,PBDEs含量达到了12.7~7361.0ng/gADDINEN.CITE<EndNote><Cite><Author>陈社军</Author><Year>2005</Year><RecNum>63</RecNum><DisplayText><styleface="superscript">[29]</style></DisplayText><record><rec-number>63</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">63</key></foreign-keys><ref-typename="Thesis">32</ref-type><contributors><authors><author>陈社军</author><author>麦碧娴</author><author>曾永平</author><author>罗孝俊</author><author>余梅</author><author>盛国英</author><author>傅家谟</author></authors></contributors><titles><title>珠江三角洲及南海北部海域表层沉积物中多溴联苯醚的分布特征</title></titles><dates><year>2005</year></dates><urls></urls></record></Cite></EndNote>[\o"陈社军,2005#63"29]。20世纪80年代在大阪地区收集的河流沉积物中PBDEs的总含量，包括BDE-47，六溴联苯醚和BDE-209的范围为33~410ng/gADDINEN.CITE<EndNote><Cite><Author>Watanabe</Author><Year>1987</Year><RecNum>65</RecNum><DisplayText><styleface="superscript">[30]</style></DisplayText><record><rec-number>65</rec-number><foreign-keys><keyapp="EN"db-id="0w9wz5t9q0trxhe0aafptdpv0w0zzsswtraw">65</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Watanabe,Isao</author><author>Kashimoto,Takashi</author><author>Tatsukawa,Ryo</author></authors></contributors><titles><title>Polybrominatedbiphenylethersinmarinefish,shellfishandriverandmarinesedimentsinJapan</title><secondary-title>Chemosphere</secondary-title></titles><periodical><full-title>Chemosphere</full-title></periodical><pages>2389-2396</pages><volume>16</volume><number>10-12</number><dates><year>1987</year></dates><isbn>0045-65