水體中微界面對PhACs環(huán)境行為影響的研究進展

但孝香, 劉建超, 陸光華

(1. 河海大學淺水湖泊綜合治理與資源開發(fā)教育部重點實驗室，江蘇 南京 210098；2. 河海大學環(huán)境學院，江蘇 南京 210098)

藥物活性化合物(pharmaceuticals, PhACs)作為一種新型環(huán)境污染物，主要包括抗生素、抗菌藥、消炎止痛藥、抗抑郁藥、激素等。我國每年有超過200萬t 4 000多種PhACs被用于農(nóng)業(yè)、水產(chǎn)養(yǎng)殖業(yè)、畜牧業(yè)和人類健康維護等方面[1]。大部分PhACs使用后并未完全代謝，而是以母體及其代謝產(chǎn)物的形式排出體外，而后直接排入水環(huán)境或者進入市政污水處理廠或者農(nóng)業(yè)污水處理設施[1-5]。然而傳統(tǒng)的污水處理工藝對大部分藥物并不能完全去除，隨同污水處理廠尾水進入水環(huán)境。因此污水處理廠尾水被認為是PhACs進入自然水體環(huán)境的主要來源[2-3]。除此之外，養(yǎng)殖廢水、制藥廢水、過期藥品處理不當也是天然水體PhACs的主要來源[4]。為了準確評估環(huán)境中PhACs可能產(chǎn)生的生態(tài)風險，須建立準確高效的PhACs檢測方法。表1對比了不同國家對PhACs的前處理和檢測方法。從表1看出，目前PhACs的分析檢測手段主要依賴于高效液相色譜-質(zhì)譜聯(lián)用(HPLC-MS)和氣相色譜-質(zhì)譜聯(lián)用技術(shù)(GC-MS)。

表1 國內(nèi)外PhACs的前處理和檢測方法

注：LOQ:定量限; LOD:檢測限; ASE:加速溶劑萃取; SPE:固相萃取; PLE:加壓流體萃取。

對于極性強、不易揮發(fā)的物質(zhì)(如雙氯芬酸、大環(huán)內(nèi)酯類抗生素、阿司匹林等)一般采用HPLC-MS檢測。

表2 國內(nèi)外不同環(huán)境介質(zhì)中檢測到的PhACs種類及濃度

注：ND表示未檢出。

近年來，PhACs先后在污水、地表水、地下水、甚至自來水中都有檢出。表2對比了國內(nèi)外不同環(huán)境介質(zhì)中檢測到的PhACs種類及濃度。十幾個國家的地表水中累計檢測出80多種PhACs，濃度最高達到μg/L水平[13-14]。對我國河流、湖泊水體中158種藥物及個人護理品進行的調(diào)查研究結(jié)果表明，檢出頻率較高的前10種污染物都是抗生素類PhACs[15]?？傮w而言，磺胺類檢出率高，濃度達到1 390 ng/L；而氟喹諾酮類、大環(huán)內(nèi)酯類、四環(huán)素類和β內(nèi)酰胺類抗生素在中國地表水中最高質(zhì)量濃度分別達到了6 800 ng/L[16]、3 700 ng/L[17]、1 000 ng/L[18]和4 500 ng/L[19]。目前PhACs監(jiān)測方法標準沒有統(tǒng)一，瞬時采樣不能反映真實的連續(xù)情況，PhACs污染水平在各類水體中呈現(xiàn)出較大的空間和時間上的差異性。雖然 PhACs 的半衰期不長，但由于頻繁地使用并進入水環(huán)境，導致其形成“假持續(xù)”現(xiàn)象。此外PhACs是針對生物疾病而設計，具有特殊的藥理、生理功能，短期內(nèi)并不一定會凸顯其危害性，但這些污染物往往以復雜的混合物形式存在，易產(chǎn)生協(xié)同作用，長期暴露可能對非靶生物的新陳代謝產(chǎn)生明顯影響，從而影響非靶生物體正常的生理生化功能，對生態(tài)系統(tǒng)安全和人類健康構(gòu)成潛在威脅。我國對PhACs類污染物的排放沒有制定相應的法規(guī)，目前歐盟也只對雌二醇、炔雌醇和雙氯芬酸制定了相應的排放閾值(分別為0.4 ng/L、0.035 ng/L和100 ng/L)。

近年來，我國對水環(huán)境中PhACs的殘留、環(huán)境行為和歸宿進行了初步研究。但水環(huán)境中 PhACs 并不是單獨存在的，它們在水體中的環(huán)境行為不僅與其他有機污染物直接相關(guān)，還受到水體納米顆粒物、膠體、懸浮顆粒物等環(huán)境介質(zhì)的影響與控制。這些不同性質(zhì)和不同尺寸的顆粒物構(gòu)成的水/顆粒物微界面體系是污染物進行物理、化學和生物轉(zhuǎn)化的重要載體和場所，決定著污染物的環(huán)境行為與生態(tài)效應?，F(xiàn)有研究顯示，目前大部分PhACs的分析都集中在液相中，缺少沉積物、懸浮物，尤其是膠體等固相中的濃度分析。本文分別從水環(huán)境界面污染特征、影響因素、環(huán)境風險及PhACs管理方法4個方面對現(xiàn)有研究進行了總結(jié)，討論了現(xiàn)有研究存在的問題，并對今后的研究進行了展望。

1 PhACs在微界面結(jié)合特性及賦存狀態(tài)

水體微界面是水環(huán)境中普遍存在的實體，如自然水體中的懸浮顆粒物(suspended particulate matter, SPM)、腐殖質(zhì)、礦物微粒、細菌、病毒、無機和有機膠體，人工生態(tài)系統(tǒng)的濾料、吸附劑、活性污泥等。這些具有一定粒度的顆粒物對河流中碳和營養(yǎng)物的遷移扮演著重要的角色[26]。微界面的活性反應基團與周圍水溶液可以發(fā)生幾乎所有的物理、化學反應，如絡合、氧化等。除此之外，天然水體中顆粒物間的聚集、絮凝、溶膠，人工設施中活性污泥的生物氧化、膜與纖維過濾、濾料層等也都涉及微界面反應過程。目前，PhACs在水體中的分布研究主要集中在水/懸浮顆粒物、水/沉積物等二維構(gòu)相中，忽略了納米顆粒物、膠體等典型環(huán)境微界面的存在，不能反映水體PhACs污染的真實風險水平[27]。

1.1 沉積物對PhACs的吸附

沉積物是非常復雜的體系，包括金屬氧化物、黏土礦物和有機質(zhì)等，對環(huán)境中的PhACs、無機陽離子和重金屬都具有很強的吸附能力，因此是很多PhACs的最終歸宿[28]。國內(nèi)外不同地區(qū)的水體沉積物中都有不同濃度PhACs的檢出，其質(zhì)量比一般在幾十μg/kg左右[29]。不同沉積物組分對PhACs的吸附機理不同，如鐵鋁硅氧化物類沉積物與水接觸后形成大量的表面羥基，易與抗生素類PhACs中羧基、氨基和酮基官能團發(fā)生相互作用，從而被氧化物吸附。黏土類沉積物與PhACs相互作用的主要機制是離子交換作用和氫鍵作用等[30]。而類固醇類PhACs吸附特性受沉積物粒徑的顯著影響，低質(zhì)量濃度(1 ng/L)固醇類PhACs優(yōu)先吸附于黏土類沉積物中，直徑介于0.87 ～1.43 μm，高質(zhì)量濃度(500 μg/L)PhACs主要吸附于泥沙類沉積物，直徑介于8.1 ～17.7 μm。此外，沉積物與陽離子吸附強度明顯高于陰離子，且陰離子吸附大都是可逆的，而中性離子的吸附則忽略不計[31]。

1.2 SPM對PhACs的吸附

SPM指顆粒直徑在0.45 μm以上，以懸浮態(tài)存在于水體中的顆粒物，含有較高比例的微生物和藻類等活性有機組分[32]。SPM在國內(nèi)外河流平均質(zhì)量濃度范圍為29.8 ～100 mg/L[33-34]，其在水體中廣泛存在，并對水體PhACs的吸附起著重要作用[35]。世界各大水體中都有SPM吸附PhACs的研究報告，總體結(jié)果顯示SPM吸附PhACs水平低于水體溶解水平，質(zhì)量比范圍為6.4～149 ng/g[35-37]。SPM的微觀形狀不規(guī)則，各個單體可以聚集成絮狀、鏈狀、分枝狀等，其表面凹凸不平且具有孔隙結(jié)構(gòu)，使SPM能夠充分地與PhACs接觸，并且能夠大量吸附PhACs，進而影響PhACs的環(huán)境歸趨[38]。同時，SPM對PhACs吸附與PhACs辛醇-水分配系數(shù)Kow密切相關(guān)，隨Kow值增加，PhACs疏水性增強，因而在SPM上吸附量增加[37]。

1.3 膠體對PhACs的吸附

天然水體中膠體物質(zhì)通常是粒徑介于1 nm～1 μm 的無機和有機非均相顆?；旌衔铮溲趸F、鋁硅酸鹽、表面活性劑等；此外，工程納米材料、微塑料等納米顆粒物不斷進入水環(huán)境，使膠體微界面表面效應更加復雜[39]。膠體的物質(zhì)組成決定了其具有體積小、比表面大、表面點位密集、吸附位點多、成分復雜等特點，可通過共價鍵合、靜電吸附、表面絡合等作用對N/P循環(huán)、絡合沉降及污染物的分布、轉(zhuǎn)化等環(huán)境行為產(chǎn)生重要影響[40-41]。

膠體是水環(huán)境中多種污染物重要的“匯”，其對PhACs的貢獻率可達30%～40%[3, 42]，而對激素類PhACs的貢獻率達到60%以上，遠高于SPM對激素類PhACs 30%的吸附貢獻率；而且膠體與PhACs的標準化吸附系數(shù)Kcoc比沉積物要高1～2個數(shù)量級[43]。我國不同水體膠體對PhACs的吸附結(jié)果顯示，長江下游水體膠體中PhACs的總質(zhì)量濃度范圍為2 419～5 065 ng/L[44]，珠江流域抗生素類PhACs在膠體中平均質(zhì)量濃度范圍分別為23.2～108 ng/L[45]。而內(nèi)陸湖泊白洋淀中抗生素類PhACs在膠體中平均質(zhì)量比1 381 ng/g(干重)[46]，與上述自然水體相比，污水處理廠尾水膠體中PhACs質(zhì)量濃度較低，為0.03～147.5 ng/L[47]，占比在36%以下[42]。相較于市政污水，自然水體是多種PhACs的重要歸宿[48]。

2 環(huán)境因素對微界面作用的影響

2.1 離子強度

2.2 溶解有機物

溶解有機物(dissolved organic matter, DOM)是指水中能通過0.45 μm濾膜的有機物組分，主要成分為腐殖質(zhì)，是以醌和多元酚為芳香核心的多聚物，其芳香核心主要有羧基、羰基、多肽等，并通過—O—、=CH-等鍵相連，其在水體中普遍存在[55]。河流及湖泊自然水體中含有大量的DOM，其含量約占總有機物的25%[56]，而城市污水中DOM含量更高，約占到總有機物的40%[57]。膠體態(tài)顆粒物中有機質(zhì)含量達49%～71%，膠體分子量越小，有機質(zhì)C/N值增加，有機質(zhì)活性越高[58]。在土壤中，PhACs的吸附分配系數(shù)與DOM的濃度呈正相關(guān)關(guān)系，高濃度DOM能促進有機物的吸附，減弱其在土壤中的遷移能力[59]。而在水體膠體中，增加DOM可以減緩膠體中卡巴呋喃、雄烯二酮和睪酮的光解速率，增加它們在環(huán)境中的持久性[60-61]。此外，DOM還具有一定的光化學活性，不僅可以在吸收光子后將能量傳遞給PhACs[62]，還可以在光的照射下產(chǎn)生·OH等活性中間體，然后活性中間體與PhACs發(fā)生反應，影響PhACs環(huán)境行為[63]。

2.3 表面活性劑

表面活性劑是一大類有機化合物，具有很強的表面活性，能使液體的表面張力顯著下降，作為乳化劑、洗滌劑、滲透劑、分散劑、表面改性劑等數(shù)十種功能產(chǎn)品而應用于日常生活和工農(nóng)業(yè)生產(chǎn)領(lǐng)域。表面活性劑進入環(huán)境介質(zhì)后，通過降低沉積物/水之間的界面張力，增加疏水性有機物(hydrophobic organic contaminants, HOCs)在水相中的溶解度，同時促進HOCs從沉積物上的解吸并再次吸附在表面活性劑的單體上，進而影響HOCs的生物可利用性[64]。非離子表面活性劑能夠吸附在水體膠體表面，產(chǎn)生位阻效應；而陰離子表面活性劑可提高膠體的Zeta電位絕對值，使膠體靜電效應和位阻效應同時增強[65]。對于疏水性PhACs來說，表面活性劑能降低其界面張力，增加PhACs的水溶解度和生物有效性，從而影響其在水環(huán)境中的遷移轉(zhuǎn)化過程及環(huán)境行為[66-67]。

2.4 水動力作用

水動力作用是影響PhACs在水體微界面分配的重要因素。流速、水流紊動強度、水力停留時間(hydraulic retention time, HRT)等水動力因素會通過改變水體微界面運動狀態(tài)及水體理化性質(zhì)對PhACs的遷移轉(zhuǎn)化過程產(chǎn)生影響[68]。研究發(fā)現(xiàn)，當HRT為45.9 h時，雌醇(E1)、雌二醇(E2)、炔雌醇(E3)的降解速率分別為46.2%、44.6%、0.0%，當水力停留時間為137.5 h時，其降解速率分別為84.3%、59.2%、40.0%。當HRT增大時，水體中膠體濃度增加，膠體對PhACs吸附量變大，從而抑制PhACs降解速率[69]。此外，流速的增大會減小邊界層厚度，增大水體溶解氧含量、氧化還原電位等參數(shù)，使PhACs在水體里的擴散由分子擴散轉(zhuǎn)為紊動擴散，從而增強PhACs在水/SPM界面的交換量，對PhACs在水/SPM兩相間的分配產(chǎn)生影響[30]。

3 PhACs微界面結(jié)合體風險評價

根據(jù)當前水體污染水平及實驗室生態(tài)風險評估數(shù)據(jù)，雖然PhACs引起水生生物急性毒性風險概率較低，但慢性毒性風險不容忽視，將威脅生態(tài)環(huán)境及人體健康[1]。尤其是PhACs長期暴露對高等水生生物的慢性毒性風險有待深入研究[70]。PhACs長期暴露可以干擾生物體內(nèi)分泌物的合成、代謝、結(jié)合等過程，影響其生長、發(fā)育等行為，還可能引起水生生物免疫功能抑制和癌癥等病變的發(fā)生[71-72]。PhACs在水生生物代謝、抗氧化、神經(jīng)、生殖等系統(tǒng)產(chǎn)生毒害作用已經(jīng)被證實，但大多集中于實驗室模擬水體PhACs暴露研究，而對天然水體中膠體等微界面存在對此類PhACs生態(tài)風險評價的研究鮮有報道[73]。

大部分PhACs具有潛在的基因毒性，這意味著它們可以直接破壞DNA或者產(chǎn)生活性物質(zhì)(如親電基團或自由基)破壞DNA。實驗表明，黑頭呆魚(Pimephalespromelas)分別在黃體酮(P4)-粉粒顆粒物(1.36 m2/g)、P4-黏粒顆粒物(19.9 m2/g)水生體系中暴露7 d后，黃體酮(P4)-粉粒顆粒物體系顯著降低了黑頭呆魚卵黃蛋白原和雄激素受體的基因表達[74]。Duong等[73]的研究同樣表明而雌激素(E1、E2、BPA)-SPM體系對雄性青鳉魚具有同樣的誘導效應，可顯著增加雄性青鳉魚的卵黃蛋白原水平。從環(huán)境介質(zhì)粒徑來看，粒徑越小，介質(zhì)對激素類PhACs吸附能力越強[26]，從而加強PhACs在水生生物體內(nèi)的累積和內(nèi)分泌干擾效應[73]，且尺寸效應在高等水生生物魚體內(nèi)表現(xiàn)得更為明顯[75]。水體中碳納米管、富勒烯等納米級微界面能夠改變水生生物(如：搖蚊幼蟲)對PhACs的吸收途徑，通過體外吸附和體內(nèi)解吸過程增加PhACs在生物體內(nèi)的生物累積風險[76-77]。同時，膠體微界面的存在還能增強菲、芘等污染物在大型蚤體內(nèi)的被動擴散過程，從而增加其細胞毒性[78]。因此，需開展和運用多種可靠的模型進行環(huán)境暴露預測，加強PhACs對人體暴露和生物累積的研究，建立基于人體健康和生態(tài)環(huán)境安全的PhACs風險評價基準[79-80]。

4 PhACs管理方法

針對當前PhACs管理過程中存在的問題，需要加強環(huán)境管理和控制技術(shù)開發(fā)，結(jié)合我國PhACs生產(chǎn)和使用特點，開展生態(tài)環(huán)境中PhACs的分布和遷移轉(zhuǎn)化規(guī)律研究，識別高風險PhACs母體及其降解產(chǎn)物，判斷其引起健康風險的主要途徑，進而開發(fā)新型的控制技術(shù)。對于醫(yī)院的藥物管理，應做到以下幾點：①加強基層醫(yī)院藥庫管理，②建立藥物網(wǎng)絡管理平臺，③提升藥物管理人員素質(zhì)[81]。對于養(yǎng)殖業(yè)獸藥管理，則應做到：①廣泛宣傳畜禽健康養(yǎng)殖知識和藥物殘留對人類健康的危害，②加強獸藥生產(chǎn)經(jīng)營管理，③加強飼料生產(chǎn)管理，④加強獸藥殘留監(jiān)控[82]。另外，要積極開展科普宣傳，提高全民對此類污染物的認知，減少不必要的藥物使用，科學處置廢棄藥品和生活護理品，同時加強對過期PhACs的收集處理，降低PhACs進入環(huán)境的可能性。

5 展 望

a. 我國對水環(huán)境中PhACs污染特征的監(jiān)測數(shù)據(jù)積累較少，并且缺乏統(tǒng)一的監(jiān)測和檢測標準，數(shù)據(jù)可比性差，有必要進一步推進PhACs相關(guān)監(jiān)測和檢測標準體系建設，為此類污染物的監(jiān)測和控制提供基礎(chǔ)技術(shù)和規(guī)范依據(jù)。

b. 目前大部分有關(guān)PhACs污染研究只涉及水溶液，缺乏一個整體性的環(huán)境監(jiān)測分析體系。應將PhACs在水環(huán)境中沉積物、懸浮物和膠體中的含量分析納入在內(nèi)，更加準確地了解PhACs的去向和環(huán)境影響。

c. 大部分PhACs呈現(xiàn)低濃度下的慢性作用，多種污染物及介質(zhì)共存的復合毒性作用更是不可忽視，因此基于PhACs低濃度、復合污染的特征，研究PhACs及其代謝產(chǎn)物的毒性效應和作用機制，是正確認識其健康風險和修訂水質(zhì)標準的基礎(chǔ)。

d. PhACs在不同水環(huán)境中的污染特征和人口數(shù)量、生活水平、用藥習慣、畜牧養(yǎng)殖密集程度等因素息息相關(guān)，并存在較大差異。這些因素一定程度上決定了PhACs區(qū)域污染水平，因此必須有針對性地加強重要流域水環(huán)境中持續(xù)性PhACs的監(jiān)測研究，并通過建立信息網(wǎng)絡實現(xiàn)主要污染物的動態(tài)監(jiān)測和風險預警，更加直觀地反應水體中PhACs的污染狀況。

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