曹徐齊,隋 倩*,呂樹(shù)光,趙文濤,郭 盈,邱兆富,顧小鋼,余 剛

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曹徐齊1,2,隋 倩1,2*,呂樹(shù)光1,趙文濤3,郭 盈1,邱兆富1,顧小鋼1,余 剛2

(1.華東理工大學(xué)資源與環(huán)境工程學(xué)院,國(guó)家環(huán)境保護(hù)化工過(guò)程環(huán)境風(fēng)險(xiǎn)評(píng)價(jià)與控制重點(diǎn)實(shí)驗(yàn)室,上海 200237；2.清華大學(xué)環(huán)境學(xué)院,新興有機(jī)污染物控制北京市重點(diǎn)實(shí)驗(yàn)室,北京 100084；3.同濟(jì)大學(xué)環(huán)境科學(xué)與工程學(xué)院,上海 200092)

采用固相萃取–高效液相色譜/串聯(lián)質(zhì)譜法,分析上海市某生活垃圾填埋場(chǎng)滲濾液中7種典型藥物和個(gè)人護(hù)理品(PPCPs)的濃度水平,并考察該填埋場(chǎng)的滲濾液處理工藝對(duì)目標(biāo)PPCPs的處理效果.結(jié)果表明,所建立的分析方法具備較好的回收率(89%~173%)、相對(duì)標(biāo)準(zhǔn)偏差(<20%)和方法檢出限(0.025~1.0μg/L),能滿足實(shí)際環(huán)境樣品的分析需要.應(yīng)用該方法檢測(cè)到滲濾液中目標(biāo)PPCPs的含量在低于檢出限(90%,總?cè)コ士蛇_(dá)到97%以上,出水PPCPs濃度范圍為

藥物和個(gè)人護(hù)理品；填埋場(chǎng)；滲濾液；膜生物反應(yīng)器；反滲透

研究表明,在地表水[1–3]、地下水[4–5]、飲用水[2,6]等水體環(huán)境中存在著痕量的藥物和個(gè)人護(hù)理品(PPCPs),可能會(huì)對(duì)微生物和水生動(dòng)植物的生長(zhǎng)和繁殖造成不利影響[7–8].環(huán)境中PPCPs的主要來(lái)源包括污水處理廠出水、醫(yī)藥工業(yè)和醫(yī)院廢水排放、垃圾填埋和禽畜養(yǎng)殖等[9–10].目前關(guān)于污染源的研究主要集中于污水處理廠,而有關(guān)填埋場(chǎng)滲濾液中PPCPs的研究還較為有限,滲濾液處理過(guò)程中PPCPs的去除情況更是鮮有報(bào)道.

由于缺乏有效的回收管理機(jī)制,垃圾填埋場(chǎng)成為大部分過(guò)期或失效的PPCPs的最終歸宿.通過(guò)廢物中的游離水、有機(jī)物分解產(chǎn)生的水、雨水以及地表和地下徑流等的淋濾,這些PPCPs同其他污染物被浸出,形成成分復(fù)雜、濃度極高的垃圾滲濾液.已有研究分別報(bào)道了日本[11]、美國(guó)[12]、德國(guó)[13]的垃圾填埋場(chǎng)滲濾液中存在高濃度(μg/L~mg/L量級(jí))的咖啡因、避蚊胺、布洛芬、雙氯芬酸、異丙安替比林等PPCPs.這些含高濃度PPCPs的滲濾液可能通過(guò)土壤下滲入周圍地下水[13–15],經(jīng)過(guò)地下水和地表水的自然交換過(guò)程,影響填埋場(chǎng)周邊的環(huán)境.與國(guó)外研究相比,目前國(guó)內(nèi)有關(guān)滲濾液中PPCPs的研究還十分有限.Peng等在廣州市郊一座已封場(chǎng)和一座仍在填的填埋場(chǎng)的滲濾液中分別檢出了高濃度的布洛芬(77.0~202μg/L)、水楊酸(5.3~150μg/L)和氯貝酸(10.4~158μg/L)等PPCPs.Wu等[16]在上海市兩座垃圾中轉(zhuǎn)站和一座填埋場(chǎng)的滲濾液中檢測(cè)到了磺胺類、喹諾酮類、四環(huán)素類、大環(huán)內(nèi)酯類以及氯霉素類等各類抗生素,其中紅霉素的濃度最高,可達(dá)39.8μg/L.

傳統(tǒng)的填埋場(chǎng)滲濾液處理工藝可分為生物處理技術(shù),如膜生物反應(yīng)器(MBR)、升流式厭氧污泥床(USAB)等,以及物化處理技術(shù),如納濾(NF)、反滲透(RO)等[17–18].而關(guān)于這些處理工藝對(duì)滲濾液中PPCPs的去除效率的研究還鮮少報(bào)道.根據(jù)《生活垃圾填埋污染控制標(biāo)準(zhǔn)》[19],處理后達(dá)到排放標(biāo)準(zhǔn)限值的滲濾液可直接排放;對(duì)于無(wú)法達(dá)到排放標(biāo)準(zhǔn)的滲濾液,應(yīng)送往城市污水處理廠進(jìn)行處理.由于目前尚無(wú)PPCPs的排放標(biāo)準(zhǔn),如果PPCPs未能被有效削減,則高濃度的PPCPs或者隨著滲濾液直接排放進(jìn)入受納水體,對(duì)該水體環(huán)境的生態(tài)安全造成威脅;或者進(jìn)入城市污水處理廠,可能對(duì)受納污水處理廠產(chǎn)生一定沖擊[20],影響污水廠對(duì)PPCPs的處理效果.因此,考察實(shí)際滲濾液處理工藝對(duì)滲濾液中PPCPs的去除情況具有重要的意義.

本文選擇上海市某典型生活填埋場(chǎng)作為研究對(duì)象,采用固相萃取–高效液相色譜/串聯(lián)質(zhì)譜(SPE–HPLC–MS/MS)的分析方法,分析了7種典型PPCPs(卡馬西平、美托洛爾、甲氧芐啶、吉非羅齊、雙氯芬酸、氯霉素、苯扎貝特)在填埋場(chǎng)滲濾液原液以及MBR工藝出水和碟管式反滲透(DTRO)工藝出水中的濃度,揭示了各工藝單元對(duì)滲濾液中PPCPs的處理效果.

1 材料與方法

1.1 試劑與標(biāo)準(zhǔn)品

表1 待測(cè)PPCPs的藥劑學(xué)類別、物質(zhì)結(jié)構(gòu)、保留時(shí)間及質(zhì)譜參數(shù) Table 1 Therapeutic classes, chemical structures, retention time and mass spectrometric parameters of selected PPCPs

PPCPs標(biāo)準(zhǔn)品(表1):卡馬西平(CBZ)、美托洛爾(MTP)、甲氧芐啶(TP)、吉非羅平(GF)、雙氯芬酸(DF)、氯霉素(CP)、苯扎貝特(BF)分別購(gòu)自Sigma–Aldrich公司(德國(guó))和Dr. Ehrenstorfer公司(德國(guó)).

內(nèi)標(biāo)(IS):阿特拉津–5D(Atrazine–5D)、2–甲–4–氯丙酸–3D(Mecoprop–3D)、吉非羅齊–6D(GF–6D)和氯霉素–5D(CP–5D)分別購(gòu)自Witega公司(德國(guó))、Dr. Ehrenstorfer公司和CDN公司(加拿大).

其他試劑:甲醇、甲酸為色譜純,其余藥品或試劑均為分析純.

1.2 水樣采集

本研究所采集的填埋場(chǎng)滲濾液來(lái)自于上海市浦東新區(qū)某生活垃圾處理場(chǎng)的新建填埋庫(kù)區(qū).該庫(kù)區(qū)占地約20hm2,總庫(kù)容約403萬(wàn)m3,目前仍然在填.設(shè)計(jì)垃圾處理規(guī)模約為900t/d,設(shè)計(jì)滲濾液處理規(guī)模為400t/d.滲濾液的基本性質(zhì)如表2所示.該填埋場(chǎng)采用工藝對(duì)滲濾液進(jìn)行處理.其中MBR工藝為分置式膜生物反應(yīng)器,總體積約為3800m3,設(shè)計(jì)水力停留時(shí)間(HRT)為9d,污泥濃度(MLSS)為15000mg/L,超濾膜材質(zhì)為聚偏氟乙烯(PVDF);DTRO工藝凈水回收率可達(dá)75%,平均每周清洗一次.MBR/DTRO工藝的具體流程如圖1所示,工藝基本參數(shù)如表3所示.處理后的滲濾液清液可達(dá)到三級(jí)排放標(biāo)準(zhǔn),最終排入市政污水處理廠.

分別于2015年5月和10月對(duì)該填埋場(chǎng)滲濾液原液(水樣S0)、MBR工藝出水(水樣M0)和DTRO工藝出水(水樣D0)進(jìn)行水樣采集和分析,采樣點(diǎn)位置如圖1所示.每次采樣時(shí),每個(gè)采樣點(diǎn)共采集水樣2份,均為瞬時(shí)樣.樣品置于棕色玻璃瓶中,采集后迅速運(yùn)至實(shí)驗(yàn)室4℃保存.

表2 填埋場(chǎng)滲濾液及各工藝出水的基本性質(zhì) Table 2 Basic characteristics of the leachates and effluents from the investigated landfill site

1.3 樣品處理和分析

考慮到S0和M0水樣的COD較高,直接進(jìn)行前處理可能會(huì)影響固相萃取柱對(duì)水樣中待測(cè)物質(zhì)的分離效果,因此,前處理前,先將S0和M0水樣分別稀釋50倍和10倍.

用47mm的玻璃纖維濾紙(GF/F,Whatman)過(guò)濾水樣,取100mL過(guò)濾后的水樣,加入400的內(nèi)標(biāo)混合液200μL,調(diào)節(jié)pH=7.0.固相萃取時(shí),用5mL甲醇、3′5mL高純水依次通過(guò)SPE小柱(Oasis HLB,6cc/500mg,Waters)進(jìn)行活化和平衡,而后將含有內(nèi)標(biāo)的過(guò)濾液以5~10mL/min的流速通過(guò)SPE小柱.接著將5mL甲醇/水混合液(醇/水=1:19)通過(guò)SPE小柱,以清洗小柱,并繼續(xù)抽真空30min,除去水份.再以1mL/min的流速用甲醇洗脫小柱,洗脫液收集于10mL具塞玻璃刻度離心管中.最后以高純氮吹掃洗脫液(水浴溫度35℃)至剛好吹干,加入0.4mL甲醇/水混合液(醇/水=1:4),置于渦旋振蕩器混合均勻,移入進(jìn)樣瓶,待色譜分析.

采用高效液相色譜(HPLC,Ultimate 3000, Dionex,USA)–串聯(lián)質(zhì)譜(ESI–MS/MS,API3200, AB Sciex,USA)對(duì)樣品進(jìn)行定量測(cè)定,色譜柱型號(hào)為Xbridge C18(3.5μm′3.0mm′150mm, Waters, USA).采用梯度洗脫,離子源為正(ESI+)、負(fù)(ESI–)兩種模式,通過(guò)多反應(yīng)監(jiān)測(cè)(MRM)模式對(duì)待測(cè)物進(jìn)行定量分析.具體方法見(jiàn)Chen等[21].

1.4 方法回收率及質(zhì)量控制

為保證實(shí)驗(yàn)準(zhǔn)確性,考察實(shí)驗(yàn)方法的回收率情況.同時(shí)進(jìn)行加標(biāo)和不加標(biāo)兩種樣品的分析,即每種水樣各取100mL,設(shè)置對(duì)照組,其中一組定量加入200μL濃度均為400μg/L的PPCPs混標(biāo)溶液和內(nèi)標(biāo)溶液,另一組只加入相同體積和濃度的內(nèi)標(biāo)溶液,然后按照1.3所述的方法對(duì)樣品進(jìn)行前處理和儀器分析,采用內(nèi)標(biāo)法定量.對(duì)比不同組樣品測(cè)得濃度的差值與已知加標(biāo)濃度,可得到不同水樣中各PPCPs的相對(duì)回收率(RR).

采樣時(shí),將500mL高純水置于棕色玻璃采樣瓶中,攜帶至取樣現(xiàn)場(chǎng),采樣時(shí)暴露于采樣環(huán)境中,采樣結(jié)束后,與實(shí)際水樣一同運(yùn)送至實(shí)驗(yàn)室處理,測(cè)定其中目標(biāo)PPCPs的濃度,該樣品作為現(xiàn)場(chǎng)空白,用于考察采樣過(guò)程中目標(biāo)化合物的污染情況.實(shí)驗(yàn)室分析前,再準(zhǔn)備一個(gè)同待測(cè)水樣等量的高純水樣品和一個(gè)以高純水為介質(zhì)的加標(biāo)樣品,測(cè)定其中目標(biāo)PPCPs的濃度,分別作為程序空白和加標(biāo)樣品,以監(jiān)測(cè)該批樣品各PPCPs在前處理過(guò)程中的受污染情況和回收率情況.此外,所有水樣均進(jìn)行平行雙樣測(cè)定,計(jì)算所得結(jié)果的相對(duì)標(biāo)準(zhǔn)偏差(RSD),以保證實(shí)驗(yàn)測(cè)定的精密性.

2 結(jié)果與討論

2.1 方法性能評(píng)價(jià)

各PPCPs標(biāo)準(zhǔn)曲線的濃度范圍為5~ 500μg/L,根據(jù)目標(biāo)化合物與對(duì)應(yīng)內(nèi)標(biāo)峰面積的比值建立標(biāo)準(zhǔn)曲線,各物質(zhì)線性相關(guān)性>0.99.

表4 目標(biāo)PPCPs在滲濾液及MBR和DTRO工藝出水中的相對(duì)回收率(RR)、儀器定量限(IQL)和方法檢出限(LOQ) Table 4 Relative recovery (RR), instrumental quantification limit (IQL), limit of quantification (LOQ) of target PPCPs in the leachates and effluents of MBR and DTRO processes

為考察方法的重現(xiàn)性,回收率實(shí)驗(yàn)中,每種介質(zhì)均做4組平行樣;實(shí)驗(yàn)結(jié)果表明,2種水樣在加標(biāo)和未加標(biāo)時(shí),各PPCPs的RSD均<20%,符合環(huán)境樣品分析方法的一般要求.最終得目標(biāo)PPCPs在各水樣中的RR如表4所示.對(duì)于基質(zhì)成分較為復(fù)雜的滲濾液和MBR出水,CBZ、GF、DF、CP和BF在其稀釋液中具有89%~128%的RR,說(shuō)明該分析方法對(duì)其具有一定的可靠性.與此同時(shí),MTP和TP具有相對(duì)較高的RR(133%~173%),這可能是由于復(fù)雜基質(zhì)對(duì)其內(nèi)標(biāo)物質(zhì)的抑制效果較強(qiáng),對(duì)其相對(duì)回收率產(chǎn)生了一定的影響.

以目標(biāo)化合物色譜峰信噪比(S/N)為10:1的對(duì)應(yīng)濃度作為儀器定量限(IQL).方法定量限(LOQ)的計(jì)算公式如式(1)所示:

式中:RR為目標(biāo)化合物在對(duì)應(yīng)介質(zhì)中的相對(duì)回收率;為樣品的稀釋倍數(shù)(DTRO出水的稀釋倍數(shù)為1倍);為樣品的濃縮倍數(shù).得到檢測(cè)方法的IQL和LOQ見(jiàn)表4.結(jié)果表明,目標(biāo)PPCPs在滲濾液原液中的LOQ范圍為0.11~1.0/L,在MBR工藝出水中的LOQ范圍為0.025~0.20μg/L,在DTRO出水中的LOQ范圍為0.003~0.042μg/L.此外,現(xiàn)場(chǎng)空白和程序空白實(shí)驗(yàn)結(jié)果表明,空白實(shí)驗(yàn)組中全部目標(biāo)PPCPs的值均

2.2 滲濾液原液的PPCPs濃度

滲濾液原液中PPCPs的檢出濃度如圖2所示.其中TP和CP兩種物質(zhì)在2次采樣中均未被檢出,BF只在5月份采集的滲濾液樣品中被檢出,而其余四種物質(zhì),即CBZ、MTP、GF和DF,在兩次采集樣品中均被檢出.其中,DF的濃度最高,兩次采樣的濃度均超過(guò)20μg/L;MTP其次,濃度約為9μg/L;而CBZ和GF的濃度在1~3μg/L的范圍.可以看出,滲濾液中目標(biāo)PPCPs的濃度遠(yuǎn)高于污水廠進(jìn)水等其他污染源中PPCPs的存在水平[1–3,22],因此,滲濾液作為PPCPs的潛在污染源,不容忽視.

對(duì)比2次采樣結(jié)果,各檢出物質(zhì)的濃度水平基本保持一致.這可能是由于采樣季節(jié)分別處于春季和秋季,溫度和降水等氣候條件較為相似,而這些條件對(duì)于滲濾液的性質(zhì)具有重要意義[23];同時(shí),目標(biāo)化合物多為長(zhǎng)期服用藥物,用藥量較為固定,也可能是兩次采樣結(jié)果較為相近的原因.

表5 目標(biāo)PPCPs在其他國(guó)家或地區(qū)填埋場(chǎng)滲濾液中的最高濃度與本研究的比較 Table 5 Comparison of the maximum concentrations of target PPCPs in landfill leachates between other countries/regions and this study

注:

同其他研究滲濾液中PPCPs的文獻(xiàn)相比(表5),本研究中大多數(shù)目標(biāo)化合物(CBZ、TP、GF、DF、CP)的最高濃度均相似于或低于其他文獻(xiàn)報(bào)道.例如TP和CP在本研究中均未被檢出,而在一項(xiàng)關(guān)于美國(guó)19處填埋場(chǎng)滲濾液里有機(jī)污染物存在情況的調(diào)查中檢測(cè)到了濃度為0.37μg/L的TP[24];在美國(guó)西部一座填埋場(chǎng)的滲濾液中也檢測(cè)出了0.064μg/L的TP[25];而在上海兩座垃圾中轉(zhuǎn)站和一座填埋場(chǎng)的滲濾液中檢出CP的濃度范圍為0.010~0.88μg/L[16].本研究中GF的濃度同美國(guó)五座填埋場(chǎng)[25]和廣州郊區(qū)兩座填埋場(chǎng)[15]滲濾液的最高檢出濃度均處于2~3μg/L的水平,DF的濃度也與廣州郊區(qū)填埋場(chǎng)[15]滲濾液中的濃度相似(20~30μg/L).值得注意的是,本研究分析了滲濾液中BF的濃度,兩次采樣結(jié)果分別為0.7μg/L和

2.3 PPCPs在滲濾液處理工藝中的去除率

滲濾液原液檢出的5種物質(zhì),在MBR工藝出水中也均被檢出;而在DTRO出水中,DF、BF和MTP在至少一次采集樣品中被檢出,其他PPCPs濃度均低于LOQ.對(duì)未檢出物質(zhì),以LOQ/2的值作為其檢出濃度,根據(jù)式(2)分別計(jì)算MBR工藝和DTRO工藝對(duì)目標(biāo)PPCPs的去除率R.所得各處理工藝的去除率結(jié)果如表6所示:

式中:in為目標(biāo)PPCPs的進(jìn)水濃度(滲濾液原液濃度和MBR出水濃度分別作為MBR工藝和DTRO工藝的進(jìn)水濃度),μg/L;ef為目標(biāo)PPCPs的出水濃度(MBR出水濃度和DTRO出水濃度分別作為MBR工藝和DTRO工藝的出水濃度),μg/L.

表6 MBR工藝和DTRO工藝對(duì)滲濾液中PPCPs的去除率以及MBR/DTRO工藝的總?cè)コ?Table 6 Removal efficiencies of target PPCPs by the MBR and DTRO processes and the total removal efficiencies by the MBR/DTRO treatment

注:–表示工藝出水濃度低于檢出限.

DTRO工藝對(duì)CBZ、MTP、GF和DF的去除率在82%~99%的范圍內(nèi),均較為理想.這與其他文獻(xiàn)報(bào)道的污水處理廠RO工藝對(duì)PPCPs的去除率大多在99%左右的結(jié)果基本一致[33–36].

MBR/DTRO工藝對(duì)滲濾液中PPCPs的總?cè)コ?97%.最終排入污水處理廠的出水中,各PPCPs的濃度范圍為

3 結(jié)論

3.1 采用固相萃取–高效液相色譜/串聯(lián)質(zhì)譜法,檢測(cè)填埋場(chǎng)滲濾液原液、MBR處理工藝出水以及DTRO處理工藝出水中的卡馬西平、美托洛爾、甲氧芐啶、吉非羅齊等7種PPCPs,分析方法具備可靠的回收率(89%~173%),相對(duì)標(biāo)準(zhǔn)偏差(<20%)和方法檢出限(0.025~1.0μg/L),能滿足實(shí)際環(huán)境樣品的分析需要.

3.2 在7種待測(cè)PPCPs中,卡馬西平、美托洛爾、吉非羅齊、雙氯芬酸和苯扎貝特在滲濾液原液中被檢出,其中雙氯芬酸濃度最大(23μg/L);美托洛爾次之,濃度在9μg/L左右;其余物質(zhì)的濃度水平在1~3μg/L之間.兩次采樣得到的滲濾液PPCPs濃度水平基本一致.與國(guó)內(nèi)外相關(guān)文獻(xiàn)報(bào)道相比,本研究的滲濾液PPCPs檢出濃度相似于或略低于其它文獻(xiàn)報(bào)道.

3.3 滲濾液MBR工藝對(duì)待測(cè)PPCPs的去除率范圍為21%~98%,優(yōu)于MBR工藝去除生活污水中PPCPs的結(jié)果.DTRO工藝對(duì)PPCPs的去除率可達(dá)90%以上.該MBR/DTRO工藝對(duì)滲濾液中PPCPs的總?cè)コ?97%,出水中PPCPs的濃度范圍為

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* 責(zé)任作者, 副教授, suiqian@ecust.edu.cn

Occurrence and removal of pharmaceuticals and personal care products in leachates from a landfill site of municipal solid waste

CAO Xu-qi1,2, SUI Qian1,2*, LU Shu-guang1, ZHAO Wen-tao3, GUO Ying1, QIU Zhao-fu1, GU Xiao-gang1, YU Gang2

(1.State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, School of Resource and Environmental Engineering, East China University of Science and Technology, Shanghai 200237, China；2.Beijing Key Laboratory for Emerging Organic Contaminants Control, School of Environment, Tsinghua University, Beijing 100084, China；3.College of Environmental Science and Engineering, Tongji University, Shanghai 200092, China)., 2016,36(7)：2027~2034

The concentrations of 7selected pharmaceuticals and personal care products (PPCPs) in the leachate samples from a landfill site of municipal solid waste in Shanghai were determined by solid phase extraction and high liquid chromatography-electrospray tandem mass spectrometry. Besides, the removal efficiencies of the leachate treatment processes for the target PPCPs were investigated. The developed analytical method showed acceptable recoveries (89%~173%), relative standard deviation (<20%) and limits of quantification (0.025~1.0μg/L), meeting the requirement for detecting environmental samples. The results showed that the target PPCPs ranged from below limit of quantification (90%, respectively, and the total removal efficiencies were above 97%. The concentrations of target PPCPs in the final effluent were from

pharmaceuticals and personal care products；landfill；leachate；membrane bioreactor；reverse osmosis

X703

A

1000-6923(2016)07-2027-08

曹徐齊(1990–),男,浙江湖州人,華東理工大學(xué)碩士研究生,主要從事水環(huán)境中藥物和個(gè)人護(hù)理品的調(diào)查與去除機(jī)理的研究.

2015-12-23

國(guó)家自然科學(xué)基金(51208199,51408425,21577033);中央高?；究蒲袠I(yè)務(wù)費(fèi)專項(xiàng)資金(22A201514057);高等學(xué)校博士學(xué)科點(diǎn)專項(xiàng)科研基金(20130072120033);新興有機(jī)污染物控制北京市重點(diǎn)實(shí)驗(yàn)室開(kāi)放基金