探究微生物推助的類芬頓反應(yīng)降解四溴聯(lián)苯醚

·探究微生物推助的類芬頓反應(yīng)降解四溴聯(lián)苯醚摘要多溴聯(lián)苯醚(Polybrominateddiphenylethers，簡稱PBDEs)幾十年來一直被用作阻燃劑，廣泛分布于土壤、水體、沉積物中。目前的研究表明，微生物推助的類芬頓反應(yīng)（Fenton-likeReaction）可以自動(dòng)產(chǎn)生羥基自由基(HO?)來降解四溴聯(lián)苯醚（BDE-47）。和傳統(tǒng)的（非生物）類芬頓反應(yīng)比較，微生物推助的類芬頓反應(yīng)的pH值與自然環(huán)境的pH值類似，并且不需要額外添加H2O2或使用UV射線就可以利用還原產(chǎn)生的Fe(II)作為反應(yīng)物。BDE-47的降解過程是由實(shí)驗(yàn)室內(nèi)純培養(yǎng)的還原Fe（III）的兼性厭氧細(xì)菌，奧奈達(dá)希瓦氏菌(ShewancllaoneidensisMR-1)推動(dòng)的。本研究以乳酸鈉為電子供體，水鐵礦、針鐵礦、檸檬酸鐵分別作為電子受體來培養(yǎng)兼性厭氧細(xì)菌S.oneidensisMR-1，結(jié)果表明，在相同條件下，通過8次厭氧好氧循環(huán)過程，在水鐵礦、針鐵礦、檸檬酸鐵中BDE-47分別被降解了83.99%，75.57%，67.74%。通過控制實(shí)驗(yàn)條件，證明了驅(qū)動(dòng)BDE-47降解的是羥基自由基(HO?)。微生物推助的類芬頓反應(yīng)為能夠被羥基自由基(HO?)降解的環(huán)境污染物提供了一種新的發(fā)展途徑。關(guān)鍵詞：四溴聯(lián)苯醚；類芬頓反應(yīng)；奧奈達(dá)希瓦氏菌；羥基自由基(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?)

目錄圖清單 I表清單 II第一章緒論 11.1研究背景 11.1.1多溴聯(lián)苯醚的污染來源 11.1.2環(huán)境中多溴聯(lián)苯醚的污染水平 空氣和灰塵中的多溴聯(lián)苯醚 水體和土壤中的多溴聯(lián)苯醚 生物體中的多溴聯(lián)苯醚 31.1.3多溴聯(lián)苯醚的生物毒性 41.1.4多溴聯(lián)苯醚的降解 光降解法 零價(jià)鐵法 生物降解法 芬頓法與類芬頓法 61.2S.oneidensisMR-1介導(dǎo)的類芬頓反應(yīng)降解多溴聯(lián)苯醚 61.2.1類芬頓法 61.2.2S.oneidensisMR-1介導(dǎo)的類芬頓反應(yīng)降解多溴聯(lián)苯醚 71.3論文選題的意義和創(chuàng)新性 81.4研究的內(nèi)容及思路 8第二章材料與方法 102.1實(shí)驗(yàn)材料 102.1.1培養(yǎng)基和化學(xué)藥品 102.1.2實(shí)驗(yàn)主要的儀器 122.2實(shí)驗(yàn)方法 132.2.1微生物推助的類芬頓反應(yīng)降解BDE-47的方法設(shè)計(jì) 132.2.2亞鐵離子和過氧化氫含量分析 亞鐵離子含量測(cè)定方法 過氧化氫含量測(cè)定方法 152.2.3BDE-47含量測(cè)定 162.2.4微生物推助的類芬頓反應(yīng)抑制 17第三章實(shí)驗(yàn)結(jié)果分析 193.1嚴(yán)格厭氧下S.oneidensisMR-1還原產(chǎn)生的Fe（II） 193.2S.oneidensisMR-1產(chǎn)生的H2O2 203.3微生物推助的類芬頓反應(yīng)降解BDE-47 213.3.1Fe（II）濃度 213.3.2BDE-47的降解 檸檬酸鐵存在時(shí)BDE-47的降解 水鐵礦存在時(shí)BDE-47的降解 針鐵礦存在時(shí)BDE-47的降解 三種鐵礦BDE-47降解情況對(duì)比 253.4微生物推助的類芬頓反應(yīng)抑制 253.4.1微生物推助的類芬頓反應(yīng)抑制 253.4.2羥基自由基(HO?)的濃度 26第四章實(shí)驗(yàn)結(jié)果討論 284.1嚴(yán)格厭氧下S.oneidensisMR-1還原產(chǎn)生的Fe（II） 284.2S.oneidensisMR-1產(chǎn)生的H2O2 284.3微生物推助的類芬頓反應(yīng)降解BDE-47 294.3.1Fe（II）濃度 294.3.2BDE-47的降解 294.4微生物推助的類芬頓反應(yīng)抑制 304.4.1微生物推助的類芬頓反應(yīng)抑制 304.4.2羥基自由基(HO?)的濃度 30第五章結(jié)論與展望 315.1實(shí)驗(yàn)結(jié)論 315.2結(jié)論應(yīng)用 315.3實(shí)驗(yàn)不足與展望 32致謝 33參考文獻(xiàn) 34

圖清單圖1MR-1推動(dòng)類芬頓反應(yīng)有機(jī)物示意圖 7圖3-1嚴(yán)格厭氧下S.oneidensisMR-1還原產(chǎn)生的Fe（II） 19圖3-23h/24h通氧/厭氧循環(huán)周期下S.oneidensisMR-1產(chǎn)生的H2O2 20圖3-33h/24h通氧/厭氧循環(huán)周期下S.oneidensisMR-1產(chǎn)生的Fe（II） 21圖3-4檸檬酸鐵實(shí)驗(yàn)組，對(duì)照組，空白組的BDE-47降解情況 23圖3-5水鐵礦實(shí)驗(yàn)組，對(duì)照組，空白組的BDE-47降解情況 24圖3-6針鐵礦實(shí)驗(yàn)組，對(duì)照組，空白組的BDE-47降解情況 25圖3-7三種鐵礦BDE-47降解情況對(duì)比 25圖3-8微生物推助的類芬頓反應(yīng)的抑制 26圖3-9三種鐵礦羥基自由基(HO?)的濃度對(duì)比 27表清單表2-1基本無機(jī)鹽培養(yǎng)基成分（1000mL） 10表2-2MineralMix培養(yǎng)基成分（1000mL） 11表2-3VitaminMix培養(yǎng)基成分（1000mL） 11表2-4AminoAcidMix培養(yǎng)基成分（1000mL） 12表2-5實(shí)驗(yàn)所用儀器器材 12表2-6BDE-47降解實(shí)驗(yàn)實(shí)驗(yàn)組，空白組，對(duì)照組培養(yǎng)基組成成分表 14表2-7過氧化氫標(biāo)準(zhǔn)溶液制備 16表2-8微生物推助的類芬頓反應(yīng)抑制試驗(yàn)樣品組成 17第一章緒論1.1研究背景多溴聯(lián)苯醚(Polybrominateddiphenylethers，簡稱PBDEs)幾十年來一直被用作阻燃劑，可在發(fā)生火災(zāi)時(shí)延長逃生時(shí)間，從而挽救生命并減少火災(zāi)造成的損害。溴通過與氣相中的自由基反應(yīng)起作用可以延緩著火和燃燒的過程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]。同樣，PBDEs由于其良好的的阻燃性也在很多產(chǎn)品中被使用，例如房屋內(nèi)的裝潢、電器、廚房用具，紡織布料；汽車和飛機(jī)上的電子產(chǎn)品，塑料制品等等。由于PBDEs在生活中被廣泛使用，人們接觸到該物質(zhì)的幾率非常大。相對(duì)分子質(zhì)量大、熔點(diǎn)高、蒸氣壓低、水溶性低及Kow值高的化學(xué)特性使PBDEs具有親脂性和生物易累積性的特點(diǎn)。這些特點(diǎn)使其能在高營養(yǎng)級(jí)生物體內(nèi)的脂肪和蛋白質(zhì)中聚集，并通過食物鏈放大，從而對(duì)整個(gè)生態(tài)環(huán)境和生物鏈造成影響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>多溴聯(lián)苯醚環(huán)境行為的特征與研究進(jìn)展</title><secondary-title>化工進(jìn)展</secondary-title></titles><periodical><full-title>化工進(jìn)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的化學(xué)式為C12H(0-9)Br(10-1)O,根據(jù)溴原子數(shù)量不同而分為10個(gè)同系組，共209種同系物。但市場(chǎng)上主要生產(chǎn)和使用的有三種同系物：五溴聯(lián)苯醚（BDE-99），八溴聯(lián)苯醚（BDE-197）和十溴聯(lián)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]。盡管世界上使用最多的PBDEs污染物是BDE-209，但四溴聯(lián)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，溶于有機(jī)溶劑中的BDE-209在紫外線或日光的照射下會(huì)迅速脫溴降解為低溴代聯(lián)苯醚ADDINEN.CITE<EndNote><Cite><Author>S?derstr?m</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>S?derstr?m,Gunilla</author><author>Sellstr?m,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"S?derstr?m,2004#38"4]，從而對(duì)環(huán)境造成更大的威脅。1.1.1多溴聯(lián)苯醚的污染來源PBDEs可從各種產(chǎn)品，例如聚氨酯，計(jì)算機(jī)，電視等中揮發(fā)進(jìn)入到環(huán)境。作為添加劑，它們可以從電子產(chǎn)品和家具中釋放出來，存在于房屋和辦公室的空氣和灰塵中。由于工業(yè)化國家收集回收的大約50-80％的廢棄物最終進(jìn)入中國，印度，巴基斯坦，越南，菲律賓等勞動(dòng)力成本較低，環(huán)境法規(guī)不太嚴(yán)格的國家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]。電子產(chǎn)品回收處理過程中導(dǎo)致的PBDEs無限制的排放使這些發(fā)展中國家成為世界PBDEs庫最主要的來源ADDINEN.CITEADDINEN.CITE.DATA[\o"Bi,2007#49"6,\o"Wong,2007#50"7]。與其他半揮發(fā)性有機(jī)化合物（SVOCs）類似，PBDEs在大氣中以氣態(tài)和顆粒態(tài)同時(shí)存在，這是影響其流動(dòng)性和大氣循環(huán)途徑的關(guān)鍵因素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?yàn)榧?xì)顆粒不容易從大氣懸浮物中被掃除，所以PBDEs足夠穩(wěn)定，存留時(shí)間長，在環(huán)境中可長時(shí)間被運(yùn)輸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]。大氣傳輸和沉積已被確定為農(nóng)村和偏遠(yuǎn)地區(qū)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]。偏遠(yuǎn)地區(qū)，如極地地區(qū)存在高濃度的PBDEs化合物表明，由于遠(yuǎn)距離大氣遷移，沉積和再揮發(fā)，PBDEs現(xiàn)在可能已經(jīng)在世界范圍內(nèi)分布，這一過程被稱為“蝗蟲效應(yīng)”ADDINEN.CITEADDINEN.CITE.DATA[\o"Hale,2008#55"11-14]。除此之外，河流湖泊也向環(huán)境中提供了PBDEs的來源。由于PBDEs具有良好的揮發(fā)性，從產(chǎn)品中揮發(fā)釋放出來的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-水分配系數(shù)是預(yù)測(cè)水相行為的重要物理化學(xué)因素。根據(jù)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的水溶解度通常隨著溴含量的增加而降低，LogKow值通常隨著溴含量的增加而增加。盡管關(guān)于PBDEs在水性介質(zhì)中的行為的信息很少，但低溴代同系物，如BDE-47和BDE-99，比較高溴化的同類物在水中溶解度更高，流動(dòng)性更好。土壤環(huán)境,包括表層土壤、水底的沉積物,因其具有較強(qiáng)的吸附能力是環(huán)境中PBDEs的主要儲(chǔ)存介質(zhì)，對(duì)PBDEs在全球的移動(dòng)和分布起到緩沖和減緩作用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的電子垃圾在大量堆放電子垃圾的區(qū)域，遭到長期露天堆放帶來的日曬雨淋,使電子廢棄物中添加的PBDEs揮發(fā)和沉降進(jìn)入周圍的大氣和土壤,造成間接污染。因?yàn)閷?duì)電子垃圾主要采用集中處理的方式,在電子垃圾處置地區(qū)有相對(duì)較高的土壤PBDEs含量。在河流沉積物中,由于沉積物有巨大的吸附能力，PBDEs同系物種類較多，且以三溴聯(lián)苯醚（BDE-28）、BDE-47、BDE-99、六溴聯(lián)苯醚（BDE-153）、七溴聯(lián)苯醚(BDE-183)和BDE-209為主ADDINEN.CITE<EndNote><Cite><Author>陳澤秋</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>陳澤秋</author><author>陳家長</author><author>孟順龍</author></authors></contributors><titles><title>多溴聯(lián)苯醚在環(huán)境中的污染現(xiàn)狀與毒理效應(yīng)研究進(jìn)展</title><secondary-title>中國農(nóng)學(xué)通報(bào)</secondary-title></titles><periodical><full-title>中國農(nóng)學(xué)通報(bào)</full-title></periodical><pages>91-98</pages><volume>34</volume><number>31</number><dates><year>2018</year></dates><urls></urls></record></Cite></EndNote>[\o"陳澤秋,2018#64"17]。1.1.2環(huán)境中多溴聯(lián)苯醚的污染水平空氣和灰塵中的多溴聯(lián)苯醚室外的PBDEs濃度根據(jù)國家和地區(qū)的不同有很大的差距，以下列舉了一些典型地區(qū)與國家的PBDEs濃度。Jaward等人通過研究歐洲25個(gè)城區(qū)和46個(gè)鄉(xiāng)村地區(qū)發(fā)現(xiàn)，總共八種PBDEs同系物的濃度在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]，其中英國由于其對(duì)火災(zāi)的嚴(yán)格管制及PBDEs生產(chǎn)量較大，成為了歐洲地區(qū)PBDEs排放最多的地區(qū)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]。北美地區(qū)的PBDEs的濃度在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]。中國的PBDEs濃度非常高，據(jù)檢測(cè)，廣州的PBDEs濃度為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]，珠三角地區(qū)的十五種PBDEs濃度為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]。澳大利亞地區(qū)的PBDEs，濃度非常低，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，室內(nèi)由于用到較多的含有PBDEs的物品導(dǎo)致PBDEs的濃度更高，大約是室外濃度的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，室內(nèi)光源的存在，較小的空間和較弱的空氣循環(huán)不可避免地導(dǎo)致較高的氣體濃度。且室內(nèi)PBDEs分子顆粒相比室外更容易吸附在細(xì)顆粒表面，而室內(nèi)較弱的空氣循環(huán)會(huì)增加細(xì)顆粒的沉積ADDINEN.CITEADDINEN.CITE.DATA[\o"Zhang,2009#43"22,\o"Mandalakis,2009#45"25,\o"Wei,2009#46"26]。水體和土壤中的多溴聯(lián)苯醚部分國家水體中PBDEs的含量可在文獻(xiàn)中找到。1977年及1987~1988年在日本全國范圍內(nèi)的河流，河口，海水樣本中沒有找到BDE-153、BDE-197，BDE-209。在北美，安大略湖1999年地表水的PBDEs水平為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被認(rèn)為占PBDEs總量的90％以上。據(jù)報(bào)道，1999年歐洲荷蘭沿海水域的BDE-47，BDE-99和BDE-153濃度分別約為1,0.5和0.1pg/L。這些水域中的BDE-209含量范圍為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]。部分國家土壤中PBDEs的含量在文獻(xiàn)中也有提及。在中國，陳社軍等人研究發(fā)現(xiàn),南海北部灣海域和珠江三角洲是目前世界上已報(bào)道的沉積物中PBDEs含量最高的區(qū)域之一，在該區(qū)域表層沉積物樣品中,PBDEs含量達(dá)到了12.7~7361.0ng/gADDINEN.CITE<EndNote><Cite><Author>陳社軍</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>陳社軍</author><author>麥碧嫻</author><author>曾永平</author><author>羅孝俊</author><author>余梅</author><author>盛國英</author><author>傅家謨</author></authors></contributors><titles><title>珠江三角洲及南海北部海域表層沉積物中多溴聯(lián)苯醚的分布特征</title></titles><dates><year>2005</year></dates><urls></urls></record></Cite></EndNote>[\o"陳社軍,2005#63"29]。20世紀(jì)80年代在大阪地區(qū)收集的河流沉積物中PBDEs的總含量，包括BDE-47，六溴聯(lián)苯醚和BDE-209的范圍為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