周思琪,李佳琦,杜爾登*,李 淼,劉 翔
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UV/Cl工藝對三氯生的去除與降解機(jī)理研究
周思琪1,李佳琦1,杜爾登1*,李 淼2,劉 翔2
(1.常州大學(xué)環(huán)境與安全工程學(xué)院,江蘇 常州 213164;2.清華大學(xué)環(huán)境學(xué)院,北京 100084)
對UV/Cl高級氧化工藝降解水中廣譜抗菌劑三氯生(TCS)進(jìn)行研究,對比單一UV、單一Cl和UV/Cl工藝對TCS的去除效果.考察UV光強(qiáng)、余氯初始濃度、溶液pH值和氨氮濃度等因素對反應(yīng)的影響,探究TCS在UV/Cl工藝中的降解機(jī)理,評估其生態(tài)風(fēng)險.結(jié)果表明,與單一UV、單一Cl相比,TCS在UV/Cl工藝中降解效果較好,反應(yīng)符合準(zhǔn)一級反應(yīng)動力學(xué),降解速率常數(shù)隨UV光強(qiáng)、余氯初始濃度增大而增大,隨NH4+-N濃度的增加而減小.基于HRMS Q-TOF解析出17種中間產(chǎn)物,提出了降解反應(yīng)路徑.發(fā)光細(xì)菌毒性分析和ECOSAR預(yù)測均表明,TCS在UV/Cl工藝中產(chǎn)生毒性較高的中間產(chǎn)物,隨著反應(yīng)的進(jìn)行,產(chǎn)生了毒性較低的中間產(chǎn)物,生態(tài)環(huán)境風(fēng)險得以減少.
三氯生(TCS);UV/Cl;高級氧化工藝;影響因素;降解機(jī)理;毒性評價
藥品和個人護(hù)理用品(PPCPs)包括各種藥用化合物,以及日常個人護(hù)理用品,如化妝品、殺菌劑、洗護(hù)用品、芳香劑等,涵蓋范圍廣泛[1-2].
三氯生(TCS)是一種典型的PPCPs類新興污染物,作為廣譜抗菌劑,廣泛應(yīng)用于生活用品中.TCS全球每年產(chǎn)量約1500t,其中96%以上使用后排入污水系統(tǒng)并最終進(jìn)入環(huán)境[3].研究表明, 在河流、湖泊、海洋、沉積物、土壤、甚至哺乳動物體內(nèi)檢測出TCS[4].TCS對淡水水生物種(綠藻、水蚤、魚類)具有很高的毒性,會引起細(xì)菌耐藥性、內(nèi)分泌紊亂,甚至增加致癌物的形成[5].因此,TCS對水生生物和人體健康的影響不容忽視.
UV/Cl工藝?yán)米贤饩€照射氯產(chǎn)生羥基自由基(·OH)和氯自由基(·Cl)[6-9],兩者結(jié)合,能夠有效去除有機(jī)污染物.UV/Cl工藝對典型PPCPs類污染物,如布洛芬、卡馬西平、莠去津等都有良好的去除效果[10-11].作為一種新型的高級氧化工藝,UV/Cl工藝在水處理方面具有潛在的應(yīng)用前景.
本研究采用UV/Cl高級氧化工藝降解TCS,考察不同因素(UV光強(qiáng)、余氯初始濃度、溶液pH值、氨氮濃度)對TCS降解效果的影響,解析反應(yīng)過程中的降解中間產(chǎn)物,評價TCS及其中間產(chǎn)物的生態(tài)風(fēng)險,以期為水中TCS的去除和風(fēng)險評價提供理論依據(jù),為水質(zhì)安全提供技術(shù)保障.
TCS(色譜純)購自于阿拉丁(上海),實驗所配制儲備液濃度4mg/L. NaClO(有效氯含量6%~14%)購自于阿拉丁(上海),使用DPD分光光度法測定游離余氯濃度,儲備液游離余氯濃度為621mg/L.甲醇(HPLC級)購自于Sigma公司(美國).其他藥劑(NH4)2SO4、NaOH、HCI、Na2HPO4·12H2O、KH2PO4、Na2SO3購自上海國藥集團(tuán),均為分析純.實驗用水均采用超純水(電導(dǎo)率18.3MΩ·cm).
本實驗的UV光反應(yīng)裝置采用波長254nm的UV汞燈(上海飛利浦),溶液配制在40mL表面皿中,通過磁力攪拌器(HJ-6,江蘇金怡)確保反應(yīng)均勻.調(diào)節(jié)燈管與反應(yīng)液表面的距離來改變UV強(qiáng)度.通過紫外輻射計(UV-B,北師大光電儀器廠)確定光強(qiáng).
取20mL濃度為4mg/L的TCS溶液,使用0.2mol/L磷酸鹽緩沖液、氫氧化鈉和稀鹽酸調(diào)節(jié)溶液pH值.然后投加1~5mg/L的NaClO溶液于TCS溶液中,打開UV汞燈,開始降解反應(yīng).在不同反應(yīng)時間取樣,立即投加過量Na2SO3溶液(5g/L)終止反應(yīng),用HPLC-MS/MS(Thermo TSQ quantum Access Max)測定剩余TCS濃度.考察單一UV、單一Cl和UV/Cl工藝對TCS的去除效果的影響,探究不同因素(UV光強(qiáng)、余氯初始濃度、溶液pH值、氨氮濃度)對UV/Cl工藝降解TCS的影響.所有反應(yīng)均進(jìn)行3次平行實驗,取平均值.
使用HPLC-MS/MS測定剩余TCS濃度,色譜條件:Thermo Accucore C18色譜柱(3mm×50mm,2.6 μm); 采用梯度洗脫程序,流動相為水和甲醇,流速0.6mL/min;柱溫25℃.質(zhì)譜條件:SRM掃描,負(fù)離子模式,TCS子母離子對/為286.8/35.3,轟擊電壓43V.
根據(jù)美國EPA 1694標(biāo)準(zhǔn)方法[12],對TCS反應(yīng)液進(jìn)行固相萃取預(yù)處理.
使用HRMS Bruker Impact II Q-TOF質(zhì)譜儀(Bruker Daltonics Inc, USA)鑒別降解中間產(chǎn)物,色譜條件為:Waters HSS T3C18色譜柱(2.1mm×50mm, 1.7μm);流動相為甲醇和水;質(zhì)譜條件:負(fù)離子模式, CID碎片模式,碰撞能量值(CE%)20%~50%.
選用費(fèi)氏弧菌()作為指示細(xì)菌進(jìn)行急性毒性實驗,考察UV/Cl工藝過程中TCS及其中間產(chǎn)物的毒性變化.采用生物毒性分析儀(ATD- P1,北京金達(dá)清創(chuàng))測定發(fā)光細(xì)菌的發(fā)光強(qiáng)度,利用相對抑制率評估急性毒性,每個樣品測定3組平行數(shù)據(jù),前后設(shè)置2組空白對照.由式(1)計算發(fā)光細(xì)菌發(fā)光強(qiáng)度的相對抑制率():
式中:L為樣品發(fā)光強(qiáng)度;0為陰性對照發(fā)光強(qiáng)度.
在光強(qiáng)1000 μW/cm2,TCS初始濃度4mg/L,余氯初始濃度2mg/L,溶液pH值為7.0條件下,分別考察單一UV、單一Cl和UV/Cl工藝對TCS降解的影響,并用準(zhǔn)一級反應(yīng)動力學(xué)方程擬合實驗數(shù)據(jù).結(jié)果見圖1和表1.
圖1 單一UV、單一Cl、UV/Cl對TCS降解的影響 Fig.1 Effect of single UV photolysis, single chlorination, the UV/Chlorine process on TCS degradation
表1 不同工況下TCS的準(zhǔn)一級反應(yīng)動力學(xué)模型參數(shù) Table 1 Parameters of pseudo-first-order kinetics at different conditions of TCS degradation
由圖1和表1可知,反應(yīng)300s, TCS在單一UV和單一Cl條件下分別去除67.5%和77.3%.而在UV/Cl工藝中去除率達(dá)100%.與單一UV,單一Cl相比,UV/Cl工藝明顯提高TCS的去除率.由式(2)、(3)得, TCS的3種降解反應(yīng)均符合準(zhǔn)一級反應(yīng),反應(yīng)速率常數(shù)分別為0.0032,0.0045和0.0082s-1,反應(yīng)相關(guān)系數(shù)2為0.9822,0.9925和0.9770.由此可知,TCS在UV/Cl工藝中的去除效果最好.
式中:[TCS]表示時刻反應(yīng)體系中TCS濃度, mg/L;[TCS]0表示TCS初始濃度,mg/L;為準(zhǔn)一級表觀動力學(xué)速率常數(shù),s-1.
ClO
-
+H
2
O?HClO+OH
-
(4)
由式(4)、(5)可知,NaClO在水溶液中以HClO和ClO-2種形式存在.經(jīng)UV照射,HClO/CIO-可以生成·OH和·Cl兩種自由基,其中·OH是非選擇性氧化劑,能夠與有機(jī)基團(tuán)反應(yīng), ·Cl是強(qiáng)氧化劑,對親電官能團(tuán)具有較高的反應(yīng)活性[6,13-14].兩者結(jié)合加速了對TCS的氧化降解.
考察TCS初始濃度4mg/L,余氯初始濃度2mg/L,溶液pH值為7.0的條件下,不同光強(qiáng)對TCS反應(yīng)的影響,結(jié)果見圖2和表2.
圖2 UV光強(qiáng)對UV/Cl工藝降解TCS的影響 Fig.2 Effect of UV intensity on TCS degradation by the UV/chlorine process
圖2和表2表明,光強(qiáng)對氯氧化TCS的影響效果顯著.隨著光強(qiáng)的增強(qiáng),反應(yīng)速率常數(shù)逐漸增加.當(dāng)光強(qiáng)從0增加到2000μW/cm2時,反應(yīng)速率常數(shù)由0.0042s-1升高為0.0115s-1.半衰期也由105.5s下降到34.4s.主要因為光強(qiáng)影響自由基的生成,光強(qiáng)增大,產(chǎn)生的自由基增多.在余氯初始濃度一定的條件下,單位時間內(nèi)光強(qiáng)越大,與TCS反應(yīng)的自由基越多.從而加快TCS的降解反應(yīng)速率.此外,反應(yīng)速率常數(shù)和光強(qiáng)具有明顯的線性相關(guān)性(圖3).李青松等[15]使用紫外/過硫酸鈉(UV/SPS)降解TCS具有相似的結(jié)論.
表2 不同UV光強(qiáng)下TCS的準(zhǔn)一級反應(yīng)動力學(xué)模型參數(shù) Table 2 Parameters of pseudo-first-order kinetics of TCS degradation at different UV intensities
圖3 UV光強(qiáng)對反應(yīng)速率常數(shù)的影響 Fig.3 Influence of different UV intensities on the
改變余氯初始濃度,考察其對TCS降解的影響,其他條件:TCS初始濃度4mg/L,光強(qiáng)500 μW/cm2,溶液pH值為7.0.結(jié)果見圖4和表3.
從圖4和表3可知,余氯初始濃度增加,TCS反應(yīng)加快,反應(yīng)速率常數(shù)逐漸增大.當(dāng)溶液中余氯濃度從1mg/L增加至5mg/L,反應(yīng)速率由0.0059s-1增加為0.0138s-1.半衰期也由105.2s減小到21.1s.擬合余氯初始濃度和反應(yīng)速率常數(shù),相關(guān)系數(shù)為0.9812,線性關(guān)系良好(圖5).
圖4 余氯濃度對UV/Cl工藝降解TCS反應(yīng)的影響 Fig.4 Effect of free chlorine residual on TCS degradation by the UV/chlorine process
表3 不同余氯濃度下準(zhǔn)一級反應(yīng)動力學(xué)模型參數(shù) Table 3 Parameters of pseudo-first-order kinetics of TCS degradation at various initial residual chlorine dose
TCS初始濃度一定時,余氯初始濃度增加即生成的HClO數(shù)量增加,促使產(chǎn)生更多的·OH和·Cl,從而加速TCS的氧化反應(yīng)速率[16].
圖5 余氯初始濃度對反應(yīng)速率常數(shù)的影響 Fig.5 Influence of various initial residual chlorine dose on the
在光強(qiáng)500μW/cm2,TCS初始濃度4mg/L,余氯初始濃度2mg/L條件下,用氫氧化鈉和鹽酸調(diào)節(jié)pH值,考察不同溶液pH值對反應(yīng)的影響.結(jié)果見圖6和表4.
圖6 pH值對UV/Cl工藝降解TCS反應(yīng)的影響 Fig.6 Effect of pH value on TCS degradation by the UV/chlorine process
表4 不同pH值下TCS的準(zhǔn)一級反應(yīng)動力學(xué)模型參數(shù) Table 4 Parameters of pseudo-first-order kineticsof TCS degradation at different pH values
由圖6和表4可知, UV/Cl工藝中,TCS在不同溶液pH值內(nèi)均有去除效果,且在堿性條件中的去除效果優(yōu)于酸性條件.當(dāng)溶液pH值從5.0增加到9.0時,反應(yīng)速率常數(shù)由0.0017s-1升高到0.0055s-1.隨著溶液pH值增大,TCS去除率明顯升高,在溶液pH值為9.0時去除效果最好.
在酚類親電取代反應(yīng)中,反應(yīng)速率與芳香烴的形態(tài)有關(guān).離子態(tài)物質(zhì)的親電性較強(qiáng),與自由基的反應(yīng)速率是分子態(tài)的104~105倍[17]. TCS的pKa為8.1,當(dāng)溶液呈堿性時,TCS以離子態(tài)的形式存在,而TCS在酸性溶液中大部分以分子態(tài)的形式存在,故堿性溶液中TCS的降解速率高于酸性溶液中[18].
考察光強(qiáng)500μW/cm2,TCS初始濃度4mg/L,余氯初始濃度2mg/L,溶液pH值為7.0時,氨氮濃度對反應(yīng)的影響.結(jié)果見圖7和表5.
由圖7和表5可知,隨著氨根離子濃度的增加, TCS在UV/Cl工藝中的降解速率逐漸降低.當(dāng)氨根離子濃度從0升高到4mg/L,反應(yīng)速率常數(shù)從0.0044s-1減少至0.0016s-1.900s內(nèi)TCS的去除率從98.7%下降至71.7%.氨氮濃度和反應(yīng)速率常數(shù)成明顯負(fù)相關(guān)(圖8),說明溶液中氨根離子對TCS的去除有明顯抑制作用.溶液中的氨根離子先與NaClO溶液反應(yīng),降低HClO/CIO-的濃度,從而減少·OH和·Cl的生成量,因此TCS在UV/Cl工藝中的反應(yīng)速率降低[19].
圖7 氨氮濃度對UV/Cl工藝降解TCS反應(yīng)的影響 Fig.7 Effect of ammonia concentration on TCS degradation by the UV/chlorine process
表5 不同氨氮濃度下TCS的準(zhǔn)一級反應(yīng)動力學(xué)模型參數(shù) Table 5 Parameters of pseudo-first-order kinetics of TCS degradation at different ammonia concentrations
圖8 氨氮濃度對反應(yīng)速率常數(shù)的影響 Fig.8 Influence of ammonia concentrations on the
表6 TCS及降解中間產(chǎn)物質(zhì)譜參數(shù) Table 6 Mass spectrum parameters of TCS and its intermediates
續(xù)表6
序號化合物保留時間(min)分子式[M-H]-結(jié)構(gòu)式 理論質(zhì)荷比(m/z)實際質(zhì)荷比(m/z)?(10-6ppm) 9Pr254-b12.3C12H8Cl2O2252.9829252.98310.8 10Pr236-a6.6C12H9ClO3235.0167235.01690.9 11Pr236-b12.3C12H9ClO3235.0167235.01680.4 12Pr250-a14.4C12H7ClO4248.9960248.99600.0 13Pr250-b16C12H7ClO4248.9960248.99610.4 14Pr1249.1C6H4O3123.0088123.0087-0.8 15Pr144-a12.3C6H5ClO2142.9905142.99060.7 16Pr144-b13.2C6H5ClO2142.9905142.99060.7 17Pr162-a0.9C6H4Cl2O160.9566160.95670.6 18Pr162-b1.3C6H4Cl2O160.9566160.9564-1.2
圖9 TCS、氯代TCS、羥基化TCS的色譜圖、二級質(zhì)譜 Fig.9 Chromatogram and MS2spectrums of TCS ,TCS-Cl and TCS-OH
圖10 TCS在UV/Cl工藝中的可能反應(yīng)路徑 Fig.10 Proposed reaction pathway of TCS by the UV/chlorine process
使用HRMS Q-TOF進(jìn)行檢測,解析出17種降解中間產(chǎn)物.結(jié)果見表6和圖9.從圖9a、圖9b可以看出,TCS出峰時間為12.3min,分子離子的質(zhì)荷比/為286.9442,有2個主要碎片離子,/分別為214.9907和141.9832.
在反應(yīng)過程中,TCS主要發(fā)生氯代反應(yīng)和羥基加成反應(yīng).TCS苯環(huán)上的氫原子與·Cl進(jìn)行親核取代反應(yīng),生成氯代化合物.一氯代產(chǎn)物具有2個同分異構(gòu)體,保留時間分別為8.3min(TCS-Cl-a)和11.6min (TCS-Cl-b)(圖9c、圖9d、圖9e).此外,·Cl進(jìn)一步取代苯環(huán)上的H產(chǎn)生二氯代產(chǎn)物(TCS-2Cl).這與Fiss 等[20]鑒定的TCS氯代產(chǎn)物相同,說明氯代產(chǎn)物是TCS進(jìn)行氯氧化反應(yīng)的主要產(chǎn)物.
在UV照射、自由氯的聯(lián)合作用下,·OH誘導(dǎo)TCS進(jìn)行羥基加成反應(yīng),生成羥基化產(chǎn)物TCS-OH (圖9f、圖9g).繼而發(fā)生氯取代反應(yīng),生成Pr338-a和Pr338-b(表6).同樣,TCS-Cl也可能發(fā)生羥基加成反應(yīng)生成Pr338-a和Pr338-b.隨后,TCS及氯代產(chǎn)物發(fā)生脫氯氫化、脫氯羥基化、羥基加成、脫氫等[17]反應(yīng),生成具有同分異構(gòu)體的Pr254-a、Pr254-b、Pr236-a、Pr236-b、Pr250-a和Pr250-b.在·OH的親核作用下Pr250醚鍵斷裂,羥基化生成單個苯環(huán)的小分子羥基化產(chǎn)物.Pr338等含氯化合物也可能發(fā)生脫氯,醚基斷裂,羥基化等反應(yīng)生成單環(huán)產(chǎn)物Pr144-a、Pr144-b、Pr162-a、Pr162-b和Pr124.這些中間產(chǎn)物與已有報道的降解TCS反應(yīng)中間產(chǎn)物相同,表明TCS在不同工藝中降解具有相似的降解路徑[21-23].基于以上分析,提出TCS降解反應(yīng)機(jī)制,見圖10.
在光強(qiáng)500μW/cm2,TCS初始濃度4mg/L,余氯初始濃度2mg/L,溶液pH值為7.0的典型條件下,進(jìn)行降解反應(yīng).利用費(fèi)氏弧菌的發(fā)光強(qiáng)度指示溶液中TCS及其中間產(chǎn)物的毒性,毒性大小用發(fā)光抑制率(%)表示,見圖11.反應(yīng)前,TCS溶液對發(fā)光細(xì)菌的相對抑制率高達(dá)99%.反應(yīng)300s時,TCS去除率為83.2%,但相對抑制率僅下降13.5%.當(dāng)反應(yīng)進(jìn)行到480s時,TCS幾乎完全降解,去除率為93.6%.此時TCS反應(yīng)液平均抑制率降低為49.7%.延長反應(yīng)時間至1200s,抑制率逐漸降低,最終抑制率降為36.8%.反應(yīng)前期,TCS反應(yīng)液的相對抑制率沒有隨TCS的去除同步下降.但反應(yīng)持續(xù)到中后期,TCS完全去除,反應(yīng)液的相對抑制率逐步降低,表明反應(yīng)后期產(chǎn)生的中間產(chǎn)物毒性明顯低于TCS.
圖11 TCS在UV/Cl工藝中對發(fā)光細(xì)菌的發(fā)光抑制率 Fig.11 Inhibition rate of TCS degradation by the UV/chlorine processon luminescent bacteria
使用ECOSAR軟件(美國EPA),預(yù)測TCS及其中間產(chǎn)物對魚類、水蚤、綠藻的急性毒性[24-25],結(jié)果見表7.TCS的LC50(魚96h)值為0.97mg/L,前期產(chǎn)物TCS-Cl、TCS-2Cl及Pr338的LC50(魚96h)值分別為0.29, 0.08, 0.81mg/L.與TCS相比,反應(yīng)前期產(chǎn)物對水生生物具有較高的急性毒性.然而其余中間產(chǎn)物的LC50(魚96h)值均高于TCS.可認(rèn)為反應(yīng)持續(xù)到中后期時,產(chǎn)生的中間產(chǎn)物對水生生物急性毒性明顯降低.發(fā)光細(xì)菌急性毒性實驗也驗證了這一結(jié)論.TCS在UV/Cl工藝中產(chǎn)生毒性風(fēng)險較高的中間產(chǎn)物,隨著反應(yīng)的進(jìn)行,產(chǎn)生了毒性較低的中間產(chǎn)物,生態(tài)環(huán)境風(fēng)險得以減少.
表7 利用ECOSAR預(yù)測TCS及其中間產(chǎn)物的急性毒性 Table 7 Estimated acute toxicity of TCS and its intermediates by ECOSAR software
3.1 與單一UV、單一Cl相比,反應(yīng)300s, TCS在UV/Cl工藝中去除率達(dá)100%,TCS在UV/Cl工藝中降解效果較好.
3.2 TCS降解速率常數(shù)隨UV光強(qiáng)和余氯初始濃度增加而增加,隨氨氮濃度的增大而減小.堿性條件明顯促進(jìn)TCS的降解反應(yīng).
3.3 使用HRMS Q-TOF解析出17種中間產(chǎn)物, UV/Cl工藝降解TCS主要涉及氯代、羥基加成、脫氯氫化、脫氯羥基化、醚鍵裂解和脫氫等反應(yīng).
3.4 TCS在降解過程中產(chǎn)生TCS-Cl和TCS-2Cl等毒性較高的中間產(chǎn)物.與TCS相比,TCS-2Cl的急性毒性高于TCS一個數(shù)量級.隨著反應(yīng)進(jìn)行,產(chǎn)生了毒性較低的中間產(chǎn)物,反應(yīng)時間1200s后,毒性抑制率降為36.8%, 生態(tài)環(huán)境風(fēng)險得以減少.
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Removal and degradation mechanism of triclosan by the UV/chlorine process.
ZHOU Si-qi1, LI Jia-qi1, DU Er-deng1*, LI Miao2, LIU Xiang2
(1.School of Environmental & Safety Engineering, Changzhou University, Changzhou 213164, China;2.School of Environmental, Tsinghua University, Beijing 100084, China)., 2019,39(3):1000~1008
Degradation of triclosan(TCS), a kind ofbroad-spectrum antimicrobial agent, was studied in water by the UV/chlorine advanced oxidation process. The removal of TCS by single UV, single chlorination and the UV/chlorine process was compared. The effect of different factors on the UV/chlorine process was investigated, including UV intensity, initial residual chlorine, pH value and ammonia concentration. The degradation mechanism and the ecological risk were further discussed. The results indicated that TCS had higher removal by the UV/chlorine process compared with single UV and single chlorination. The reaction fitted pseudo-first-order kinetics. The degradation rate increased with the increase of UV intensity and initial residual chlorine, while decreased with the increase of ammonia concentration. Seventeen intermediates were identified byHRMS Q-TOF, and the possible degradation pathway was also proposed. Both luminescent bacteria experiment and ECOSAR prediction showed that intermediates with high toxicity were produced on TCS degradation by the UV/chlorine process. With the process of reaction, intermediates generated with lower toxicity, and the ecological environment risk was reduced.
triclosan (TCS);UV/chlorine;advanced oxidation process;influencing factors;degradation mechanism;toxicity evaluation
X522
A
1000-6923(2019)03-1000-09
周思琪(1996-),女,江蘇徐州人,常州大學(xué)碩士研究生,主要從事飲用水水質(zhì)安全保障技術(shù).發(fā)表論文1篇.
2018-08-06
江蘇省研究生實踐創(chuàng)新計劃項目(SJCX18-0960);國家水體污染控制與治理科技重大專項(2017ZX07202-002)
* 責(zé)任作者, 副教授, duerdeng@cczu.edu.cn