個(gè)人護(hù)理用品(PCPs)的生態(tài)毒性和處理工藝效果研究進(jìn)展

孫洪芹，江文靜，郭艷敏，杜陽(yáng)，呂錫武，孫麗偉*

1.東南大學(xué)能源與環(huán)境學(xué)院，南京210096

2.東南大學(xué)無(wú)錫分校無(wú)錫太湖水環(huán)境工程研究中心，無(wú)錫214000

個(gè)人護(hù)理用品(PCPs)的生態(tài)毒性和處理工藝效果研究進(jìn)展

孫洪芹1,2，江文靜1，郭艷敏1，杜陽(yáng)1，呂錫武1,2，孫麗偉1,2*

1.東南大學(xué)能源與環(huán)境學(xué)院，南京210096

2.東南大學(xué)無(wú)錫分校無(wú)錫太湖水環(huán)境工程研究中心，無(wú)錫214000

個(gè)人護(hù)理用品的大量使用導(dǎo)致其生產(chǎn)量和排放量也日漸增加,會(huì)不可避免地進(jìn)入環(huán)境,對(duì)生態(tài)環(huán)境和人體健康產(chǎn)生影響。本文歸納整理了個(gè)人護(hù)理用品的分類(lèi),總結(jié)了其中代表化合物對(duì)水生生物的生態(tài)毒性研究現(xiàn)狀,分析比較了主要廢水處理工藝技術(shù)對(duì)個(gè)人護(hù)理用品的去除效果,為今后對(duì)這類(lèi)物質(zhì)的生態(tài)毒性和處理工藝研究提供參考。

個(gè)人護(hù)理用品；分類(lèi)；毒性效應(yīng)；處理效果

個(gè)人護(hù)理用品(personal care products,PCPs)屬于高產(chǎn)量化學(xué)物質(zhì)(HPVCs),在生產(chǎn)制造和使用過(guò)程中,個(gè)人護(hù)理用品成分不可避免的排放到環(huán)境中。部分PCPs具有持久性和生物蓄積的潛能[1]。由于PCPs對(duì)環(huán)境生物和人體具有危害性,而成為當(dāng)前國(guó)際上關(guān)注的對(duì)象[2-4]。美國(guó)環(huán)保署(EPA)將藥物和個(gè)人護(hù)理用品歸納為一類(lèi)新興污染物加以管理,統(tǒng)稱(chēng)為藥品和個(gè)人護(hù)理品(pharmaceuticals and personal care products,PPCPs)。當(dāng)前環(huán)境科學(xué)領(lǐng)域?qū)PCPs類(lèi)物質(zhì)的高度關(guān)注,一方面是因?yàn)橐呀?jīng)發(fā)現(xiàn)這類(lèi)物質(zhì)中許多都具有環(huán)境內(nèi)分泌干擾效應(yīng)等一系列不同性質(zhì)的環(huán)境危害,另一方面由于其持續(xù)性排放量大,而傳統(tǒng)的污水處理工藝對(duì)其去除效果有限,導(dǎo)致納污水體中的污染物濃度雖然較低但變化幅度較小,可以通過(guò)長(zhǎng)期暴露引起生物體的慢性中毒,形成所謂“偽持久性(pseudo persistent)”現(xiàn)象[5]。當(dāng)前針對(duì)PPCPs的環(huán)境行為研究已經(jīng)開(kāi)展了大量工作,也已經(jīng)積累了大量生態(tài)毒性的數(shù)據(jù),但是對(duì)其中個(gè)人護(hù)理用品的研究仍然較少。由于這類(lèi)物質(zhì)結(jié)構(gòu)多樣,在生物體內(nèi)存在諸多靶點(diǎn),毒理學(xué)作用機(jī)制是十分復(fù)雜,傳統(tǒng)污水處理工藝不能有效的去除,因此是未來(lái)受關(guān)注的重點(diǎn)污染物。

1 PCPs的主要分類(lèi) (The main classification of PCPs)

美國(guó)環(huán)保署(EPA)并沒(méi)有對(duì)PCPs進(jìn)行明確分類(lèi),只是將其作為一類(lèi)污染物同藥物聯(lián)合定義。Pedrouzo等[6]將個(gè)人護(hù)理用品分為6大類(lèi):有機(jī)紫外線(xiàn)濾過(guò)劑、抗菌劑、防腐劑、麝香香水、殺蟲(chóng)劑和硅氧烷。由于目前沒(méi)有標(biāo)準(zhǔn)的分類(lèi)方法,本文按照PCPs的用途,借鑒Pedrouzo等[6]的分類(lèi)方法結(jié)合Pal等[7]提到的包括蚊蟲(chóng)驅(qū)逐劑,抗菌劑和抗真菌劑,表面活性劑,芳香劑和防曬油等,分別對(duì)有機(jī)紫外線(xiàn)濾過(guò)劑,蚊蟲(chóng)驅(qū)逐劑,抗菌劑和抗真菌劑,表面活性劑,芳香劑,防腐劑和硅氧烷進(jìn)行介紹。

1.1 有機(jī)紫外線(xiàn)濾過(guò)劑

紫外線(xiàn)濾過(guò)劑是一類(lèi)用來(lái)保護(hù)人體皮膚和頭發(fā)免受紫外線(xiàn)傷害的物質(zhì)[8],常應(yīng)用于洗發(fā)液,防曬霜和護(hù)唇膏等各類(lèi)個(gè)人護(hù)理用品中,有機(jī)紫外線(xiàn)濾過(guò)劑通過(guò)吸收紫外線(xiàn)而發(fā)揮作用,常用的化合物種類(lèi)有[6]:(1)苯甲酮(BP-1,BP-3,BP-4)；(2)2-苯基苯丙咪唑-5-磺酸(PBSA)；(3)4-羥喹(HBP)；(4)2-羥基-4-甲氧基二苯甲酮(HMB)；(5)異戊基甲氧基肉桂酸酯(IAMC),這類(lèi)物質(zhì)作為日常護(hù)理用品,源源不斷地被排放進(jìn)入環(huán)境中,加之具有內(nèi)分泌干擾活性和發(fā)育毒性的潛在危害[9],因而其安全性受到國(guó)內(nèi)外研究者的廣泛關(guān)注。

1.2 蚊蟲(chóng)驅(qū)逐劑

蚊蟲(chóng)驅(qū)逐劑是我國(guó)夏季常用個(gè)人護(hù)理用品中未達(dá)到驅(qū)蚊效果最多使用的添加成分,其中最常用的化學(xué)物質(zhì)是避蚊胺[10-12]。避蚊胺又稱(chēng)驅(qū)蚊胺,即間甲基-N,N-二乙基苯甲酰胺,簡(jiǎn)稱(chēng)DEET。目前,由于驅(qū)蚊產(chǎn)品的商業(yè)化,避蚊胺已經(jīng)在包括地表水,地下水等的水源中被檢測(cè)到[13-15]。

1.3 抗菌劑和抗真菌劑

抗菌劑和抗真菌劑是用來(lái)抑制或阻止微生物生長(zhǎng)的化學(xué)品,不同于消毒劑,其主要作用于活體組織表面用以抑制微生物增長(zhǎng)?？咕鷦┖涂拐婢鷦┑闹饕繕?biāo)污染物是三氯生(2,4,4'-三氯-2'-羥基二苯醚)和三氯卡班[16-18]。三氯生已被報(bào)道存在于國(guó)內(nèi)外不同水體中。

1.4 表面活性劑

表面活性劑是一類(lèi)加入很少劑量就可以很好的降低表面張力的化學(xué)品,廣泛應(yīng)用在洗面奶、肥皂、洗滌劑中。烷基酚聚氧乙烯醚類(lèi)化合物是一種廣泛應(yīng)用的非離子表面活性劑,有研究證明烷基酚的碳鏈越長(zhǎng),其毒性越高[19]。全世界表面活性劑的產(chǎn)量和使用量很大,因而在多數(shù)水體中都檢測(cè)出表面活性劑[7]。

1.5 芳香劑

芳香劑是一種合成的用來(lái)替代天然麝香的化合物,又稱(chēng)為合成麝香,廣泛應(yīng)用于香皂、香水、牙膏、沐浴乳等日常用品中,按其化學(xué)結(jié)構(gòu)分為硝基,多環(huán)和大環(huán)的麝香化合物。考慮到對(duì)人類(lèi)和環(huán)境的毒性,歐盟決定限制硝基麝香化合物在消費(fèi)品中的應(yīng)用[20-21]。當(dāng)前應(yīng)用最廣泛的是多環(huán)麝香化合物(PCM)[22-24],主要污染物是佳樂(lè)麝香和吐納麝香[25]。

1.6 防腐劑

化妝品中防腐劑的使用是為了抑制微生物的生長(zhǎng),延長(zhǎng)化妝品的使用期限。這類(lèi)物質(zhì)由于是中性所以結(jié)構(gòu)很穩(wěn)定,沒(méi)有可察覺(jué)的氣味或味道,并且不會(huì)導(dǎo)致褪色和變硬[6]。大多數(shù)的防腐劑對(duì)人體有一定程度的毒害作用,常用的防腐劑有:(1)對(duì)羥基苯甲酸酯類(lèi)；(2)苯氧基乙醇；(3)4-氯-3-甲苯酚；(4)三氯生及三氯卡班等。

1.7 硅氧烷

硅氧烷作為一類(lèi)新興的PCPs,常被用于止汗藥,護(hù)膚品和防曬霜,護(hù)發(fā)素等個(gè)人護(hù)理用品中[6]。硅氧烷是由交替的硅氧鍵形成支架通過(guò)硅原子與有機(jī)側(cè)鏈上相連。這些組分經(jīng)常在化妝品中被用來(lái)起軟化,保濕作用。最近有報(bào)道顯示環(huán)硅氧烷有一定的直接或間接地毒性效應(yīng),更重要的是大量的硅氧烷已經(jīng)通過(guò)生活廢水進(jìn)入水生環(huán)境[26-27]。硅氧烷包括:八甲基環(huán)四硅氧烷(D4),十甲基環(huán)戊硅氧烷(D5)以及各類(lèi)甲基、乙基硅氧烷。D5是PCPs最常用的硅氧烷。

2 PCPs對(duì)水生生物的生態(tài)毒性研究現(xiàn)狀(The research status about ecotoxicity of PCPs on aquatic organism)

隨著檢測(cè)技術(shù)的進(jìn)步和提高,水中PCPs污染物的檢出也越來(lái)越多。表1中列舉了已經(jīng)被報(bào)道的一些PCPs污染物在水環(huán)境中的檢出現(xiàn)狀。

PCPs受到關(guān)注不僅是由于其越來(lái)越頻繁地在水環(huán)境,同時(shí)在人體血液和母乳中(表2)被檢測(cè)到,更多是因?yàn)樗鼈儗?duì)包括人類(lèi)在內(nèi)的生態(tài)系統(tǒng)中的生物具有一定的危害和內(nèi)分泌干擾性能。由于受美國(guó)優(yōu)先污染物的引導(dǎo),PCPs的研究發(fā)展緩慢,關(guān)于其對(duì)水生生物生態(tài)毒性的研究也有限。

2.1 有機(jī)紫外線(xiàn)濾過(guò)劑中二苯甲酮類(lèi)物質(zhì)對(duì)水生生物的生態(tài)毒性研究現(xiàn)狀

當(dāng)前關(guān)于二苯甲酮類(lèi)物質(zhì)對(duì)水生生物的生態(tài)毒性研究較少。有學(xué)者研究了14種二苯甲酮類(lèi)有機(jī)紫外線(xiàn)濾過(guò)劑對(duì)日本三角渦蟲(chóng)(Dugesia japonica)的急性毒性[41],結(jié)果表明:這14種二苯甲酮類(lèi)物質(zhì)的48 h半致死濃度范圍和96 h半致死濃度范圍分別在0.9～ 145mg·L-1和0.5～77mg·L-1之間且這14種二苯甲酮類(lèi)物質(zhì)的半致死濃度值排序依次為:氧苯酮(oxybenzone)＞美克西酮(mexenone)＞5-氯-2-羥基二苯甲酮(5-chloro-2-hydroxybenzophenone)＞2,4-二羥基二苯甲酮(2,4-dihydroxybenzophenone)＞2-羥基二苯甲酮(2-hydroxybenzophenone)＞二苯酮-8(dioxybenzone)＞二苯基甲酮(benzophenone)＞2,2’,4,4’-四羥基二苯甲酮(2,2′,4,4′-tetrahydroxybenzophenone)＞4-羥基二苯甲酮(4-hydroxybenzophenone)＞3-羥基二苯甲酮(3-hydroxybenzophenone)＞4,4’-二羥基二苯甲酮(4,4′-dihydroxybenzophenone)＞2,2’-二羥基-4,4’-二甲氧基二苯甲酮(2,2′-dihydroxy-4,4′-dimethoxybenzophenone)＞2,3,4-三羥基二苯甲酮(2,3,4-trihydroxybenzophenone)＞磺異苯酮(sulisobenzone)。

表1 幾種PCPs成分在水環(huán)境中的檢測(cè)現(xiàn)狀Table 1 The detection of several PCPs components in aquatic environment

表2 幾種PCPs成分在人體環(huán)境中的檢測(cè)現(xiàn)狀Table 2 The detection of several PCPs components in human bodies

此外,關(guān)于二苯甲酮對(duì)斑點(diǎn)叉尾鮰魚(yú)卵巢細(xì)胞(CCO)的生長(zhǎng)影響結(jié)果表明當(dāng)二苯甲酮以1～10μg·mL-1的濃度直接作用于CCO細(xì)胞時(shí),CCO細(xì)胞均受到抑制,且隨著二苯甲酮濃度的增加抑制作用也增大[42]；而當(dāng)1μg·mL-1的二苯甲酮間接作用于CCO細(xì)胞時(shí),其代謝產(chǎn)物對(duì)CCO呈現(xiàn)明顯的促進(jìn)作用。

2.2 抗菌劑和防腐劑中成分三氯生對(duì)水生生物的生態(tài)毒性研究現(xiàn)狀

三氯生廣泛用作洗滌劑,殺菌劑和防腐劑中。作為護(hù)膚和化妝用品中常用的一種抗菌劑,對(duì)三氯生的研究開(kāi)展的也最為廣泛。有研究顯示,排放到水環(huán)境中的三氯生會(huì)對(duì)水環(huán)境中的水生生物造成潛在危害[43]。三氯生對(duì)羊角月牙藻、魚(yú)腥藻和舟型藻等海洋藻類(lèi)均會(huì)產(chǎn)生抑制作用,且抑制作用隨著三氯生濃度的增加而增大[44]。有學(xué)者研究三氯生對(duì)小球藻[45]和羊角月牙藻[46]的96 h急性毒性,結(jié)果表明三氯生對(duì)小球藻和羊角月牙藻的96 h半抑制效應(yīng)濃度分別為0.065mg·L-1和0.112mg·L-1,毒性結(jié)果均判定為高毒。

三氯生對(duì)其他水生生物的研究結(jié)果顯示三氯生對(duì)暴露于其中的蝌蚪產(chǎn)生明顯的抑制作用,三氯生的暴露濃度越高,蝌蚪的刺激反應(yīng)和存活率越低,導(dǎo)致其體重下降,游動(dòng)行為減少[47]。三氯生對(duì)生命早期階段的日本雄性青鳉魚(yú)的肝臟卵黃原蛋白細(xì)胞的合成會(huì)產(chǎn)生潛在誘導(dǎo)作用,三氯生的代謝產(chǎn)物雖然會(huì)對(duì)雄性青鳉魚(yú)產(chǎn)生弱雌激素作用但是并沒(méi)有對(duì)其繁殖和后代產(chǎn)生不利影響[48]。

2.3 表面活性劑對(duì)水生生物的生態(tài)毒性研究現(xiàn)狀

壬基酚十氧乙烯醚對(duì)斜生柵藻生長(zhǎng)的影響研究[49]表明壬基酚十氧乙烯醚在低濃度(0.05mg·L-1)時(shí)對(duì)斜生柵藻的生長(zhǎng)表現(xiàn)為一定的促進(jìn)作用,但當(dāng)質(zhì)量濃度升高(大于0.75mg·L-1)時(shí),斜生柵藻開(kāi)始表現(xiàn)出生長(zhǎng)抑制效應(yīng),且隨著壬基酚十氧乙烯醚處理質(zhì)量濃度的增加抑制程度上升。同時(shí),對(duì)脂肪醇聚氧乙烯醚對(duì)鹽藻的毒性研究[50]結(jié)果表明高濃度的脂肪醇聚氧乙烯醚(2.0mg·L-1和4.0mg·L-1)對(duì)鹽藻生長(zhǎng)具有一定的抑制作用,同時(shí)高濃度組處理的鹽藻的可溶性蛋白含量顯著低于對(duì)照組和低濃度組。

此外,對(duì)壬基酚聚氧乙烯醚對(duì)多刺裸腹溞的毒性研究結(jié)果顯示壬基酚聚氧乙烯醚對(duì)多刺裸腹溞的存活、生長(zhǎng)和繁殖均有一定的毒害作用,且24 h和48 h半致死濃度分別為3.37mg·L-1和2.11mg·L-1,毒性結(jié)果均判定為高毒[51]。

2.4 芳香劑中合成麝香對(duì)水生生物的生態(tài)毒性研究現(xiàn)狀

3種多環(huán)麝香對(duì)美麗猛水蚤(Nitocra spinipes)的亞慢性研究結(jié)果表明試驗(yàn)設(shè)置的吐納麝香濃度對(duì)幼蟲(chóng)時(shí)期的美麗猛水蚤不產(chǎn)生影響[52]。佳樂(lè)麝香對(duì)青少年時(shí)期的美麗猛水蚤的最低影響濃度為0.02mg·L-1,比對(duì)成年美麗猛水蚤的最低影響濃度(1.9mg·L-1)低近100倍；而當(dāng)薩利麝香的濃度為0.3mg·L-1時(shí),實(shí)驗(yàn)結(jié)束時(shí)暴露于其中的所有美麗猛水蚤均死亡。

Breitholtz等[53]研究了多環(huán)麝香化合物對(duì)青鳉魚(yú)(Medaka larvae)的雌激素受體、卵黃蛋白原細(xì)胞、孕烷X受體和細(xì)胞色素P450 3A基因在青鳉魚(yú)整個(gè)生命時(shí)期的表達(dá),結(jié)果表明多環(huán)麝香化合物對(duì)出生24 h的青鳉魚(yú)均表現(xiàn)為高毒,它們的96 h半致死濃度排序依次為佳樂(lè)麝香(0.95mg·L-1)＞吐納麝香(1.0mg·L-1)＞薩利麝香(2.0mg·L-1)；同時(shí)研究表明佳樂(lè)麝香和吐納麝香均會(huì)影響肝臟色素細(xì)胞和卵黃蛋白原細(xì)胞在雄性青鳉魚(yú)整個(gè)生命時(shí)期的基因表達(dá)和調(diào)節(jié)水平。

3 PCPs的去除研究現(xiàn)狀(The elimination status of PCPs)

PCPs在水環(huán)境中的濃度雖然很低,但是由于其使用基數(shù)大,其污染已經(jīng)分布全球各個(gè)國(guó)家。盡管當(dāng)前采用的污水處理工藝對(duì)水中污染物的去除效率越來(lái)越高,但由于缺乏對(duì)PCPs的管理限制及專(zhuān)門(mén)的處理設(shè)施,PCPs的去除效果仍具有很大的不確定性。Temes等[54]通過(guò)以FeCl3為混凝劑、活性炭吸附以及臭氧氧化進(jìn)行對(duì)比,結(jié)果發(fā)現(xiàn):臭氧氧化和活性炭吸附對(duì)水中的新型污染物具有良好的去除效率。當(dāng)前的許多研究表明[62-64,68-70]:高級(jí)氧化法和膜處理法尤其是高級(jí)氧化與其他工藝聯(lián)用對(duì)新型污染物質(zhì)具有良好的去除效果,活性污泥法和膜吸收工藝對(duì)這類(lèi)污染物也有一定的的去除效果。表3是幾種主流廢水處理工藝對(duì)PCPs成分去除的比較。

3.1 活性污泥法

活性污泥法處理PCPs污染物存在著一定的局限性,有些微量污染物無(wú)法被完全去除,甚至?xí)谰玫某练e在污泥沉淀中[55]。Kanda等[56]考察了6種不同處理工藝(包括氧化溝、活性污泥、濕地、濾床等)的污水處理廠(chǎng)對(duì)PCPs物質(zhì)的處理效果,發(fā)現(xiàn)活性污泥工藝對(duì)三氯生、佳樂(lè)麝香、吐納麝香均具有良好的去除效果:三氯生在出水中去除率最高可達(dá)95.6%；對(duì)佳樂(lè)麝香和吐納麝香的去除效率均在70%～83%和73%～96%范圍內(nèi)。Ying和Kookana[57]在對(duì)澳大利亞的19種污水處理廠(chǎng)的調(diào)查研究中發(fā)現(xiàn)三氯生在好氧硝化污泥中能被生物降解,而在厭氧消化污泥中三氯生基本不被降解,且在整個(gè)工藝周期內(nèi),三氯生一直存在但對(duì)污泥活性沒(méi)有影響；在選出的活性污泥處理工藝中,三氯生的去除率在72%到93%之間。Plassche和Balk[58]以及Carballa等[59]研究發(fā)現(xiàn)厭氧活性污泥對(duì)合成麝香物質(zhì)的去除率有一個(gè)很大的變動(dòng)去除率范圍在40%～95%之間。

3.2 混凝和絮凝法

有研究表明加入混凝劑對(duì)污水進(jìn)行前處理可以提高污染物質(zhì)的去除率[60],但是對(duì)PCPs物質(zhì)的去除均達(dá)不到良好的效果[61]。Suarez等[60]在對(duì)醫(yī)院廢水前處理的研究中發(fā)現(xiàn)絮凝沉淀法對(duì)吐納麝香的去除率在69.1%～97.7%之間,對(duì)佳樂(lè)麝香的去除率在69.3%～89.1%之間,對(duì)薩利麝香的去除率在60.9%～94.5%之間,較高的去除率可能與這些麝香化合物強(qiáng)烈的親脂特性促進(jìn)了它們與固體脂質(zhì)物質(zhì)的相互作用有關(guān)。Westerhoff等[62]考察了硫酸鋁混凝沉淀對(duì)飲用水水源中個(gè)人護(hù)理品的去除效果,在pH為6.8,Al3+投加量為6.3mg·L-1時(shí),避蚊胺的去除率僅為25%～50%。Carballa等[59]研究發(fā)現(xiàn),絮凝法對(duì)合成麝香的去除率最高。

3.3 高級(jí)氧化法

與其他水處理方法相比,高級(jí)氧化法具有反應(yīng)快、處理效果好的等特點(diǎn)[63],高級(jí)氧化法也常被用來(lái)處理新型污染物。馬軍等[64]研究了H2O2投加量與二苯甲酮的去除關(guān)系,研究發(fā)現(xiàn),單獨(dú)投加臭氧對(duì)二苯甲酮的去除率就很高,H2O2投加量的增加對(duì)二苯甲酮的去除影響不大。Westerhoff等[62]研究發(fā)現(xiàn)氯氣的存在可以很好地降低水中三氯生的濃度,但是氯氣氧化受pH和所氧化物質(zhì)結(jié)構(gòu)影響；同時(shí),加入臭氧進(jìn)行前處理可以提高避蚊胺的去除效率。

3.4 吸附法

劉光明和尹大強(qiáng)[65]通過(guò)吸附樹(shù)脂對(duì)壬基酚聚氧乙烯醚進(jìn)行吸附研究,結(jié)果證實(shí)所采用的吸附樹(shù)脂均對(duì)壬基酚聚氧乙烯醚具有良好的吸附效果,且溫度對(duì)吸附效果的影響較大,溫度升高,吸附量增加。Reungoat等[66]研究了運(yùn)用生物活性炭濾池去除水中新型污染物的處理效果,活性炭濾池對(duì)PCPs的去除效率在90%以上。張青梅等[67]研究表明,后交聯(lián)反應(yīng)能顯著改善氯甲基化聚苯乙烯交聯(lián)微球?qū)PnEO的吸附性能。但是吸附劑的成本一般較高,吸附飽和后,吸附劑處理不當(dāng)也會(huì)引起環(huán)境的二次污染。

3.5 膜處理技術(shù)

膜處理技術(shù)主要包括超濾(UF)、納濾(NF)和反滲透技術(shù)(RO)[68],Yoon等[69]在研究中發(fā)現(xiàn),膜技術(shù)對(duì)PCPs物質(zhì)具有良好的處理效果,且納濾處理效果要高于超濾處理效果,這可能與膜的孔徑和化學(xué)物的結(jié)構(gòu)有關(guān)。同時(shí),研究結(jié)果表明:尺寸截留和疏水性吸附是膜處理技術(shù)的主要作用機(jī)制。Ozaki等[70]利用低壓聚酰胺反滲透膜工藝對(duì)對(duì)藥物及個(gè)人護(hù)理品和內(nèi)分泌干擾物進(jìn)行去除效果研究,結(jié)果表明:溶液pH對(duì)不離解溶質(zhì)的去除不產(chǎn)生影響；不同pH時(shí),溶質(zhì)的離解度成為影響聚酰胺RO膜去除效率的主要因素。雖然膜技術(shù)對(duì)PCPs污染物具有良好的去除效果。但是,高濃度廢水的處置是該工藝必須面臨的問(wèn)題。

表3 幾種主流廢水處理工藝對(duì)PCPs成分去除的比較Table 3 The comparison of removal effeciency by several main wastewater treatment process

4 結(jié)語(yǔ)(Conclusion)

PCPs的研究起步較晚,有些P CPs的化學(xué)物質(zhì)甚至沒(méi)有被報(bào)道研究過(guò),這將是未來(lái)對(duì)新型污染物進(jìn)行研究的重要課題,也是為研究新型污染物的去除必須要做的準(zhǔn)備,需要各國(guó)學(xué)者的共同努力。同時(shí),PCPs的組成成分復(fù)雜,通常一種個(gè)人護(hù)理用品中含有兩種或以上的污染組分,其在環(huán)境中的危害性也存在各組分之間的協(xié)同,相加和拮抗等不同的方式的相互作用,故對(duì)個(gè)人護(hù)理用品這一大類(lèi)物質(zhì)的研究需要更加嚴(yán)謹(jǐn)對(duì)待。作為研究者為更好地去除水環(huán)境中的PCPs物質(zhì),必須全面了解其毒性特性,了解其作用機(jī)制及生物降解性。而作為管理者,應(yīng)對(duì)在環(huán)境容納量之內(nèi)的相應(yīng)的PCPs物質(zhì)進(jìn)行嚴(yán)格管理,并要求PCPs化學(xué)品進(jìn)入污水系統(tǒng)之前進(jìn)行前處理,減少其污染排放量,達(dá)到減輕環(huán)境負(fù)擔(dān)的目的。

[1]Brausch J M,Rand G M.A review of personal care products in the aquatic environment:Environmental concentrations and toxicity[J].Chemosphere,2011,82(11):1518-1532

[2]Smital T,Luckenbach T,Sauerborn R,et al.Emerging contaminants—pesticides,PPCPs,microbial degradation products and natural substances as inhibitors of multixenobiotic defense in aquatic organisms[J].Mutation Research/Fundamental and Molecular Mechanisms of Mutagenesis,2004,552(1):101-117

[3]Bound J P,Voulvoulis N.Pharmaceuticals in the aquatic environment--A comparison of risk assessment strategies [J].Chemosphere,2004,56(11):1143–1155

[4]Ternes T A,Kreckel P,Mueller J.Behavior and occurrence of estrogens in municipal sewage treatment plants--II.Aerobic batch experiments with activated sludge[J]. The Science of the Total Environment,1999,225(1-2): 91–99

[5]Peck A M.Analytical methods for the determination of persistent ingredients of personal care products in environmental matrices[J].Analytical and Bioanalytical Chemistry,2006,386(4):907-939

[6]Pedrouzo M,Borrull F,Marcé R M,et al.Analytical methods for personal-care products in environmental waters[J].TrAC Trends in Analytical Chemistry,2011,30 (5):749-760

[7]Pal A,He Y,Jekel M,et al.Emerging contaminants of public health significance as water quality indicator compounds in the urban water cycle[J].Environment International,2014,71:46-62

[8]Manová E,von Goetz N,Hungerbuehler K.Aggregate consumer exposure to UV filter ethylhexyl methoxycinnamate via personal care products[J].Environment International,2015,74:249-257

[9]Balmer M E,Buser H R,Müller M D,et al.Occurrence of some organic UV filters in wastewater,in surface waters,and in fish from Swiss lakes[J].Environmental Science&Technology,2005,39(4):953-962

[10]毛海舫,李瓊,俞根發(fā),等.驅(qū)蚊酯的合成及應(yīng)用研究[J].香料香精化妝品,2005,6:3-4. Mao H F,Li Q,Yu G F,et al.Study on the synthesis and application of insectifugeester[J].Flavour Fragrance Cosmetics,2005,6:3-4(in Chinese)

[11]林翔云.全天然驅(qū)蚊液和驅(qū)蚊油及其應(yīng)用研究[J].中華衛(wèi)生殺蟲(chóng)藥械,2012,4:358-360 Lin X Y.Application of natural mosquito-repelling liquid and oil[J].Chinese Journal of Hygienic Insecticides and Equipments,2012,4:358-360(in Chinese)

[12]Cunningham V L,Buzby M,Hutchinson T,et al.Effects of human pharmaceuticals on aquatic life:Next steps[J]. Environmental Science&Technology,2006,40(11): 3456-3462

[13]Sandstrom M W,Kolpin D W,Thurman E M,et al. Widespread detection of N,N‐diethyl‐m‐toluamide in US Streams:Comparison with concentrations of pesticides,personal care products,and other organic wastewater compounds[J].Environmental Toxicology and Chemistry,2005,24(5):1029-1034

[14]Kolpin D W,Skopec M,Meyer M T,et al.Urban contribution of pharmaceuticals and other organic wastewater contaminants to streams during differing flow conditions [J].Science of the Total Environment,2004,328(1):119-130

[15]Langford K H,Thomas K V.Inputs of chemicals from recreational activities into the Norwegian coastal zone[J]. Journal of Environmental Monitoring,2008,10(7):894-898

[16]Benotti M J,Trenholm R A,Vanderford B J,et al.Pharmaceuticals and endocrine disrupting compounds in US drinking water[J].Environmental Science&Technology, 2008,43(3):597-603

[17]Kasprzyk-Hordern B,Dinsdale R M,Guwy A J.The occurrence of pharmaceuticals,personal care products,endocrine disruptors and illicit drugs in surface water in South Wales,UK[J].Water Research,2008,42(13): 3498-3518

[18]Cha J,Cupples A M.Detection of the antimicrobials triclocarban and triclosan in agricultural soils following land application of municipal biosolids[J].Water Research, 2009,43(9):2522-2530

[19]李秀環(huán),李華,陳澄宇,等.不同種類(lèi)農(nóng)藥表面活性劑對(duì)大型溞的急性毒性[J].應(yīng)用生態(tài)學(xué)報(bào),2013,24(8): 2319-2324 LiX H,Li H,Chen C Y,et al.Acute toxicity of different type pesticide surfactants toDaphnia magna[J].Chinese Journal of Applied Ecology,2013,24(8):2319-2324(in Chinese)

[20]Rimkus G G,Wolf M.Nitro musk fragrances in biota from freshwater and marine environment[J].Chemosphere,1995,30(4):641-651

[21]Hawkins D R,Elsom L F,Kirkpatrick D,et al.Dermal absorption and disposition of musk ambrette,musk ketone and musk xylene in human subjects[J].Toxicology Letters,2002,131(3):147-151

[22]Ricking M,Schwarzbauer J,Hellou J,et al.Polycyclic aromatic musk compounds in sewage treatment plant effluents of Canada and Sweden––first results[J].Marine Pollution Bulletin,2003,46(4):410-417

[23]Fromme H,Otto T,Pilz K.Polycyclic musk fragrances in different environmental compartments in Berlin(Germany)[J].Water Research,2001,35(1):121-128

[24]曾祥英,桂紅艷,陳多宏,等.環(huán)境中合成麝香污染現(xiàn)狀研究[J].環(huán)境監(jiān)測(cè)管理與技術(shù),2007,19(2):10-14 Zeng X Y,Gui H Y,Chen D H,et al.Advance in study on synthetic musk in environment[J].The Administration and Technique of Environment Monitoring,2007,19(2): 10-14(in Chinese)

[25]Eschke H D.Synthetic Musks in Different Water Matrices.In:The Handbook of Environmental Chemistry.[M]. Series Anthropogenic Compounds,2004,3X:17-28

[26]Biesterbos J W H,Beckmann G,van Wel L,et al.Aggregate dermal exposure to cyclic siloxanes in personal care products:Implications for risk assessment[J].Environment International,2015,74:231-239

[27]徐琳,史亞利,蔡亞岐.天津地區(qū)甲基硅氧烷的污染水平及分布特征研究[C].中國(guó)化學(xué)會(huì)第28屆學(xué)術(shù)年會(huì)第2分會(huì)場(chǎng)摘要集,2012

[28]Wu J L,Lam N P,Martens D,et al.Triclosan determination in water related to wastewater treatment[J].Talanta, 2007,72(5):1650-1654

[29]Sabaliunas D,Webb S F,Hauk A,et al.Environmental fate of triclosan in the River Aire Basin,UK[J].Water Research,2003,37(13):3145-3154

[30]Fu M,Li Z,Gao H.Distribution characteristics of nonylphenol in Jiaozhou Bay of Qingdao and its adjacent rivers [J].Chemosphere,2007,69(7):1009-1016

[31]李卓娜,周群芳,劉稷燕,等.多環(huán)麝香(PCMs)的環(huán)境行為及毒性效應(yīng)[J].化學(xué)進(jìn)展,2012,24(4):606-615 Li Z N,Zhou Q Y,Liu J Y,et al.Environmental behavior and toxicological effects of polycyclic musks[J].Pregress in Chemistry,2012,24(4):606-615(in Chinese)

[32]Calafat A M,Wong L Y,Ye X,et al.Concentrations of the sunscreen agent benzophenone-3 in residents of the United States:National Health and Nutrition Examination Survey 2003–2004[J].Environmental Health Perspectives,2008,116(7):893-897

[33]Ye X,Kuklenyik Z,Needham L L,et al.Automated online column-switching HPLC-MS/MS method with peak focusing for the determination of nine environmental phenols in urine[J].Analytical Chemistry,2005,77(16): 5407-5413

[34]Ye X,Kuklenyik Z,Needham L L,et al.Quantification of urinary conjugates of bisphenol A,2,5-dichlorophenol, and 2-hydroxy-4-methoxybenzophenone in humans by online solid phase extraction–high performance liquid chromatography–tandem mass spectrometry[J].Analytical and Bioanalytical Chemistry,2005,383(4):638-644

[35]Wolff M S,Teitelbaum S L,Windham G,et al.Pilot study of urinary biomarkers of phytoestrogens,phthalates,and phenols in girls[J].Environmental Health Perspectives, 2007:116-121

[36]Allmyr M,Adolfsson-Erici M,McLachlan M S,et al.Triclosan in plasma and milk from Swedish nursing mothers and their exposure via personal care products[J].Science of the Total Environment,2006,372(1):87-93

[37]Adolfsson-Erici M,Pettersson M,Parkkonen J,et al.Triclosan,a commonly used bactericide found in human milk and in the aquatic environment in Sweden[J]. Chemosphere,2002,46(9):1485-1489

[38]Darbre P D,Aljarrah A,Miller W R,et al.Concentrations of parabens in human breast tumours[J].Journal of Applied Toxicology,2004,24(1):5-13

[39]Rimkus G G,Wolf M.Polycyclic musk fragrances in human adipose tissue and human milk[J].Chemosphere, 1996,33(10):2033-2043

[40]Müller S,Schmid P,Schlatter C.Occurrence of nitro and non-nitro benzenoid musk compounds in human adiposetissue[J].Chemosphere,1996,33(1):17-28

[41]Li M H.Acute toxicity of benzophenone-type UV filters and paraben preservatives to freshwater planarian,Dugesia japonica[J].Toxicological&Environmental Chemistry,2012,94(3):566-573

[42]王宇飛,鄔紅娟,文琛,等.二苯甲酮對(duì)斑點(diǎn)叉尾鲴魚(yú)卵巢細(xì)胞生長(zhǎng)的影響[J].環(huán)境科學(xué)與技術(shù),2009,32(5): 14-16 Wang Y F,Wu H J,Wen S,et al.Optimum conditions of improved MTT assay for estimating in vitro acute cytotoxicity in different fish cells[J].Environmental Science &Technology,2009,32(5):14-16(in Chinese)

[43]徐海麗,林毅,孫倩,等.三氯生的生態(tài)效應(yīng)及其在環(huán)境中的遷移轉(zhuǎn)化[J].生態(tài)毒理學(xué)報(bào),2012,7(3):225-233 Xu H L,Lin Y,Sun Q,et al.Ecological effects of triclosan and its transport and transformation[J].Asian Journal of Ecotoxicology,2012,7(3):225-233(in Chinese)

[44]Orvos D R,Versteeg D J,Inauen J,et al.Aquatic toxicityof triclosan[J].Environmental Toxicology and Chemistry,2002,21(7):1338-1349

[45]伍筱琳,劉仁沿,李紅霞,等.三氯生對(duì)小球藻的生長(zhǎng)效應(yīng)研究[J].海洋通報(bào),2009,28(3):117-120 Wu X L,Liu R Y,Li H X,et al.Effects of triclosan on the growth ofChlorella spp[J].Marine Science Bulletin, 2009,28(3):117-120(in Chinese)

[46]李義剛,劉濱揚(yáng),彭穎,等.三氯生對(duì)羊角月牙藻生長(zhǎng)及其抗氧化系統(tǒng)的影響[J].生態(tài)毒理學(xué)報(bào),2013,8(3): 357-365 Li Y G,Liu B Y,Peng Y,et al.Toxic effects of triclosan on growth and antioxidase activity ofSeleaastrum capricoruutum[J].Asian Journal of Ecotoxicology,2013,8(3): 357-365(in Chinese)

[47]Fraker S L,Smith G R.Direct and interactive effects of ecologically relevant concentrations of organic wastewater contaminants onRana pipienstadpoles[J].Environmental Toxicology,2004,19(3):250-256

[48]Ishibashi H,Matsumura N,Hirano M,et al.Effects of triclosan on the early life stages and reproduction of medaka Oryzias latipesand induction of hepatic vitellogenin[J]. Aquatic Toxicology,2004,67(2):167-179

[49]朱術(shù)超,劉濱揚(yáng),陳本亮,等.3種藥物及個(gè)人護(hù)理品對(duì)斜生柵藻生長(zhǎng)及光系統(tǒng)II的影響[J].中山大學(xué)學(xué)報(bào):自然科學(xué)版,2014,53(1):121-126 Zhu S C,Liu B Y,Chen B L,et al.Effects of three pharmaceuticals and personal care products on growth and photosystem II inSceuedesmus obliquus[J].Acta Scienlarum Naturalium Univerisitatis Sunyatseni,2014,53(1): 121-126(in Chinese)

[50]耿慶華,姜莉,張侃,等.表面活性劑脂肪醇聚氧乙烯醚對(duì)鹽藻的毒性研究[J].沈陽(yáng)師范大學(xué)學(xué)報(bào):自然科學(xué)版,2014,32(3):435-440 Geng Q H,Jiang L,Zhang K,et al.Toxic effects of surfactants fatty alcohol ethoxylates onDunaliella[J].Journal of Shenyang Normal University(Natural Science Edition),2014,32(3):435-440(in Chinese)

[51]胡雪雷,周靜韻,段舜山.壬基酚與壬基酚聚氧乙烯醚對(duì)多刺裸腹溞的復(fù)合毒性效應(yīng)[J].生態(tài)環(huán)境學(xué)報(bào), 2011,11:25 Hu X L,Zhou J Y,Duan S S.Synergistic toxic effects of nonylphenol and nonylphenol ethoxylate onMoina macroocopa[J].Ecology and Environmental Sciences,2011, 11:25(in Chinese)

[52]Breitholtz M,Wollenberger L,Dinan L.Effects of four synthetic musks on the life cycle of the harpacticoid copepodNitocra spinipes[J].Aquatic Toxicology,2003,63(2): 103-118

[53]Yamauchi R,Ishibashi H,Hirano M,et al.Effects of synthetic polycyclic musks on estrogen receptor,vitellogenin, pregnane X receptor,and cytochrome P450 3A gene expression in the livers of male medaka(Oryzias latipes)[J]. Aquatic Toxicology,2008,90(4):261-268

[54]Ternes T A,Meisenheimer M,McDowell D,et al.Removal of pharmaceuticals during drinking water treatment [J].Environmental Science&Technology,2002,36(17): 3855-3863

[55]趙琦,何小娟,李旭東,等.藥物和個(gè)人護(hù)理用品(PPCPs)處理方法研究進(jìn)展[J].凈水技術(shù),2010(4):5-10 Zhao Q,He X J,Li X D,et al.Research progress on treatment processes of pharmaceuticals and personal care products(PPCPs)[J].Water Purification Technology, 2010(4):5-10(in Chinese)

[56]Kanda R,Griffin P,James H A,et al.Pharmaceutical and personal care products in sewage treatment works[J]. Journal of Environmental Monitoring,2003,5(5):823-830

[57]Ying G G,Kookana R S.Triclosan in wastewaters and biosolids from Australian wastewater treatment plants[J]. Environment International,2007,33(2):199-205

[58]Plassche E J,van de Balk F.Environmental risk assessment of the polycyclic musks AHTN and HHCB according to the EU-TGD[R].National Institute of Public Health and the Environment(RIVM),1997

[59]Carballa M,Omil F,Ternes T,et al.Fate of pharmaceutical and personal care products(PPCPs)during anaerobic digestion of sewage sludge[J].Water Research,2007,41(10):2139-2150

[60]Suarez S,Lema J M,Omil F.Pre-treatment of hospital wastewater by coagulation– flocculation and flotation [J].Bioresource Technology,2009,100(7):2138-2146

[61]Ternes T.The occurrence of micopollutants in the aquatic environment:A new challenge for water management[J]. Water Science&Technology,2007,55(12):327-332

[62]Westerhoff P,Yoon Y,Snyder S,et al.Fate of endocrinedisruptor,pharmaceutical,and personalcare product chemicals during simulated drinking watertreatment processes[J].Environmental Science& Technology, 2005,39(17):6649-6663

[63]Nakada N,Shinohara H,Murata A,et al.Removal of selected pharmaceuticals and personal care products (PPCPs)and endocrine-disrupting chemicals(EDCs)during sand filtration and ozonation at a municipal sewage treatment plant[J].Water Research,2007,41(19):4373-4382

[64]馬軍,高金勝.于穎慧,等.O3/H2O2系統(tǒng)對(duì)水中二苯甲酮的去除效能及其機(jī)理探討[J].黑龍江大學(xué)自然科學(xué)學(xué)報(bào),2003,20(1):86-91 Ma J,Gao J S,Yu Y H,et al.Study on the efficiency and mechanism of degradation of benzo phenone in water by O3/H2O2system[J].Journal of Natural Science of Heilongjiang Univerisity,2003,20(1):86-91(in Chinese)

[65]劉光明,尹大強(qiáng).大孔吸附樹(shù)脂對(duì)烷基酚聚氧乙烯醚的吸附行為[J].生態(tài)環(huán)境,2008,17(5):1769-1773. Liu G M,Yin D Q.Sorption behavior of macroporous resin for alkylphenol ethoxylates[J].Ecology and Environment,2008,17(5):1769-1773(in Chinese)

[66]Reungoat J,Escher B I,Macova M,et al.Biofiltration of wastewater treatment plant effluent:Effective removal of pharmaceuticals and personal care products and reduction of toxicity[J].Water Research,2011,45(9):2751-2762

[67]張青梅,季必燕,劉鳳玲,等.樹(shù)脂吸附法去除水中的壬基酚聚氧乙烯醚[J].環(huán)境化學(xué),2008,27(4):458-462 Zhang Q M,Ji B Y,Liu F L,et al.AD sorption of nonylphinol polyethoxylates[J].Environmental Chemistry, 2008,27(4):458-462(in Chinese)

[68]唐玉霖,高乃云,龐維海,等.藥物和個(gè)人護(hù)理用品在水環(huán)境中的現(xiàn)狀與去除研究[J].給水排水,2008,34(5): 116-121 Tang Y L,Gao N Y,Pang W H,et al.Research on status and removal of pharmaceuticals and personal care products in aquatic environment[J].Water&Wastewater Engineering,2008,34(5):116-121(in Chinese)

[69]Yoon Y,Westerhoff P,Snyder S A,et al.Removal of endocrine disrupting compounds and pharmaceuticals by nanofiltration and ultrafiltration membranes[J].Desalination,2007,202(1):16-23

[70]Ozaki H,Ikejima N,Shimizu Y,et al.Rejection of pharmaceuticals and personal care products(PPCPs)and endocrine disrupting chemicals(EDCs)by low pressure reverse osmosis membranes[J].Water Science and Technology,2008,58(1):73

Progress in Ecotoxicity and Removal Treatment of Personal Care Products

Sun Hongqin1,2,Jiang Wenjing1,Guo Yanmin1,Du Yang1,Lu Xiwu1,2,Sun Liwei1,2,*
1.Department of Energy and Environment,Southeast University,Nanjing 210096,China
2.Taihu Lake Water Environment Engineering Research Center(Wuxi),Southeast University,Wuxi 214000,China

8 January 2016 accepted 4 March 2016

The increasing consume of personal care products(PCPs)has resulted in the increasing of the production and the afterwards discharging.Some components have harmful effects on ecosystem and human health.In this paper,the classification,the research status of ecological effects on aquatic ecosystem of typical components in PCPs was summarized.Furthermore,the removing efficiencies by different treatment processes are also compared. The reference significance for the research about the ecological effects and treatment is expected.

personal care products;classification;toxic ecological effect;treatment efficiency

2016-01-08 錄用日期:2016-03-04

1673-5897(2016)1-094-09

X171.5

A

10.7524/AJE.1673-5897.20160108002

孫洪芹,江文靜,郭艷敏,等.個(gè)人護(hù)理用品(PCPs)的生態(tài)毒性和處理工藝效果研究進(jìn)展[J].生態(tài)毒理學(xué)報(bào),2016,11(1):94-102

Sun H Q,Jiang W J,Guo Y M,et al.Progress in ecotoxicity and removal treatment of personal care products[J].Asian Journal of Ecotoxicology,2016, 11(1):94-102(in Chinese)

國(guó)家水體污染控制與治理科技重大專(zhuān)項(xiàng)(2012ZX07101-005)

孫洪芹(1990-),女,碩士研究生,研究方向?yàn)樗廴究刂萍盎瘜W(xué)品效應(yīng)評(píng)價(jià),E-mail:sunhongqin123456@163.com

),E-mail:liwei-sun@seu.edu.cn

簡(jiǎn)介:孫麗偉(1964-)，女，博士，副教授，碩士生導(dǎo)師，研究方向?yàn)榄h(huán)境污染物的生態(tài)效應(yīng)評(píng)價(jià)、環(huán)境微生物檢測(cè)新方法的開(kāi)發(fā)及生活廢水的生態(tài)學(xué)凈化方法等。