中國典型城市水環境中鄰苯二甲酸酯類污染水平與生態風險評價

張璐璐，劉靜玲，何建宗，李華

1. 河北科技大學環境科學與工程學院，石家莊 050018 2. 北京師范大學環境學院 水環境模擬國家重點實驗室，北京 100875 3. 香港公開大學科技學院，香港

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中國典型城市水環境中鄰苯二甲酸酯類污染水平與生態風險評價

張璐璐1,2,3,*，劉靜玲2，何建宗3，李華1

1. 河北科技大學環境科學與工程學院，石家莊 050018 2. 北京師范大學環境學院 水環境模擬國家重點實驗室，北京 100875 3. 香港公開大學科技學院，香港

鄰苯二甲酸酯類(PAEs)作為一類重要的環境激素類化學物質，被廣泛應用于塑料的增塑劑中。隨著工業的發展，中國PAEs的需求量迅速增加，PAEs已成為中國城市水環境的重要風險因子，因此需要對其進行生態風險評價。本研究首先針對我國典型城市水環境中PAEs的污染現狀進行文獻綜述，總結歸納得到我國典型城市水環境中PAEs的污染分布特征；其次運用熵值法計算了我國典型水環境中PAEs對于藻類、水蚤和魚類種群的生態風險，并依據生態風險等級劃分標準將PAEs生態風險劃分為4個水平。文獻綜述結果表明我國城市水環境中的PAEs濃度多數都高于8.00 μg·L-1，超過了我國地表水環境質量標準(PRC-NS 2002)和飲用水質量標準(PRC-NS 2006)中的規定限值，且在大城市或PAEs工業區周圍的污染水平要顯著高于其他區域。將我國與國外典型城市水環境中PAEs的污染水平進行比較，結果表明我國水環境中的PAEs污染水平明顯高于其他國家。此外，我國城市水環境中PAEs的污染不僅出現在地表水環境中，而且在廣東東莞等地的地下水環境中也出現了PAEs污染，PAEs濃度范圍為0.0～6.7 μg·L-1。生態風險評價的結果表明，鄰苯二甲酸二丁酯(DBP)、鄰苯二甲酸二異辛酯(DEHP)和鄰苯二甲酸丁芐酯(BBP)是我國城市水環境中最主要的風險因子。PAEs污染分布特征和生態風險評價的結果表明我國城市水環境中的PAEs生態風險值總體處于10 ≤ 風險熵(RQ) <100到RQ ≥ 100水平，尤其是在大城市或者PAEs工業密集區域，因此，亟需對我國城市水環境中PAEs的生態風險進行早期預警和風險管理。

鄰苯二甲酸酯類(PAEs)；城市水環境；污染分布特征；生態風險評價

鄰苯二甲酸酯類，又稱酞酸酯，縮寫PAEs，是鄰苯二甲酸形成的酯的統稱。PAEs一般為無色液體，具有低揮發性、難溶于水和易溶于有機溶液等特點[1]。它是一類重要的環境激素類物質，主要用于塑料的增塑劑，也廣泛應用于日常生活用品中，例如玩具、食品包裝材料、醫用血袋和膠管、乙烯地板、壁紙、清潔劑、潤滑油和個人護理用品等[2]。因此，PAEs作為普遍存在的污染物廣泛存在于水體、土壤和大氣環境中[3-4]。例如，根據美國有毒物質釋放數據庫(Toxics Release Inventory (TRI) database)計算，2012年美國PAEs的釋放量為1 492 674 kg，其中釋放到大氣環境中的PAEs有1 354 968 kg，釋放到水環境中的PAEs有237 kg[5]。

由于PAEs可能具有致癌性、致畸性和致突變性[6-9]，美國和其他很多國家把PAEs列為優先控制污染物[10-11]。雖然在某些區域和國家已經采取了很多控制措施來限制和降低PAEs的生產與使用[12]，但在亞洲PAEs的生產、使用并未得到有效控制。隨著工業的發展，我國PAEs的用量迅速增加，在2010年我國PAEs用量高達1.36×106t[13]；在2010—2015期間，我國年均PAEs的用量增幅約為7.7%[14]；此外，我國還是PAEs最大的進口國。由于PAEs在環境中具有難降解、生物富集和內分泌干擾效應，因此PAEs已成為我國城市水環境的重要風險因子。

對PAEs有效的環境管理取決于準確評價其生態風險水平，因此越來越多的研究對環境中PAEs的潛在生態風險進行評價[15-16]。PAEs對于水生生物的有害影響一般會隨著烷基鏈長度的增加而加大，但由于酯類較低的水溶性特點，該趨勢會在烷基鏈長度達到生物機體耐受量限值時發生改變[17]。根據大量的研究結果，烷基鏈大于6個的PAEs在溶解限值時，對于很多水生生物的急性和慢性毒性測試結果表明無毒[18]。因此，本研究主要關注低分子量的PAEs，如鄰苯二甲酸二甲酯(DMP)、鄰苯二甲酸二乙酯(DEP)、鄰苯二甲酸二丁酯(DBP)、鄰苯二甲酸丁芐酯(BBP)、鄰苯二甲酸二己酯(DHP)和鄰苯二甲酸二異辛酯(DEHP)。雖然我國的環境科學工作者已經意識到PAEs在水環境中的生態風險，但多數研究僅集中于單一水環境中PAEs的污染現狀與生態風險評價，對我國典型城市水環境中PAEs的生態風險管理存在不確定性。因此，本研究首先對我國典型城市水環境中PAEs的污染現狀的文獻進行綜述，總結歸納得到我國典型城市水環境中PAEs的污染分布特征；其次運用熵值法計算了我國典型水環境中PAEs對于藻類、水蚤和魚類種群的生態風險，對于我國城市水環境安全具有重要的現實意義。

1 材料與方法 (Materials and methods)

1.1 數據收集方法

為了準確掌握我國典型城市水環境中PAEs的污染分布特征，本研究首先運用文獻綜述法對中國知網、萬方、Elsevier、Springer、Google Scholar和PubMed數據庫中關于我國典型城市水環境中PAEs的污染現狀的文章和碩、博士論文等進行文獻綜述，由于通過PAEs、污染現狀和分布特征等關鍵詞收索到的文獻數量較多，因此本研究主要分析有關我國典型城市水環境中PAEs污染分布特征的文章。有關PAEs對目標生物的毒理數據主要從USEPA的ECOTOXicology數據庫[5]和相關文獻中獲得[19]。

1.2 環境介質中PAEs的分析方法

PAEs的分析步驟主要可以分為：樣品前處理、萃取、清洗、分離和檢測。萃取和清洗是PAEs分析中最具挑戰和關鍵的步驟，直接關系到整個分析方法能否確定檢出限。萃取方法可以分為溶劑萃取或液-液萃取[20]和固相微萃取(SPME)[21]；對于分離和檢測步驟，研究主要關注分析技術如液相色譜-質譜(LC-MS)[22]，氣相色譜-質譜(GC-MS)[23]以及其他技術[24-25]。Cai等[26]開發了一種新分析方法來檢測水體中PAEs濃度，主要包括固相萃取、用乙腈定量解吸和高效液相色譜(HPLC)的分析方法。雖然不同研究中采用的分析方法會影響到PAEs數據的結果，但由于本研究旨在掌握我國城市典型水環境中PAEs的整體污染水平，因此分析方法的差異不會影響到本文的結論。

1.3 PAEs生態風險評價方法

PAEs的生態風險評價方法依據歐盟技術指導性文件[27]和先前的研究[15]，主要采用熵值法來評價水體中PAEs的潛在生態風險[28-29]。在本研究中，風險熵(RQ)被用來評估目標生物的生態風險，它主要是根據環境中PAEs的測量濃度(MEC)與預測的無效應濃度(PNEC)之間的比值。PNEC的估算是根據毒理學的相關濃度(LC50或EC50)與安全系數(f)的比值。因此，魚類、水蚤和藻類對DMP、DEP、DnBP和BBP的LC50或EC50被應用于生態風險值的計算。PAEs的風險熵計算公式為：

根據相關的文獻，我們把生態風險分為下面4個水平[30]：

當RQ < 1.00時，表示無顯著風險；當1.00 ≤ RQ < 10.0時，表示存在較小的潛在負效應；當10.0 ≤ RQ < 100時，表示存在顯著的潛在負效應；當RQ ≥ 100時，表示存在預期的潛在負效應。

2 研究結果(Results)

2.1 我國PAEs的生產和消費

表1列出了我國大陸地區2000—2010年PAEs的供應和需求量，在2000—2010期間PAEs的表觀消費量顯著增加，其中2010年比2000年的產量增加了183.54%，表觀消費量增加了79.18%。表2列出了我國PAEs的主要生產企業及其產量，其中齊魯增塑劑有限公司作為內地最大的PAEs制造商，其年產量高達40.00×104t，主要生產鄰苯二甲酸二辛酯(DOP)、DBP、鄰苯二甲酸二異壬酯(DiNP)和鄰苯二甲酸二異癸酯(DiDP)；PAEs生產企業集中分布在山東、廣東、浙江和江蘇省。

2.2 水環境中的PAEs污染水平

根據我國典型水環境中PAEs的污染分布特征，除廣州(城市湖泊)、北京(城市湖泊)和長江江蘇段外，我國典型河流和湖泊水體中PAEs濃度多數均高于8.00 μg·L-1，而根據我國地表水環境質量標準[32]和飲用水環境質量標準[33]，DEHP的濃度限值為8.00 μg·L-1或DBP的濃度限值為3.00 μg·L-1和DEHP的濃度限值為8.00 μg·L-1、DBP的濃度限值為3.00 μg·L-1或DEP的濃度限值為3.00 μg·L-1。因此，我國水環境中PAEs的潛在生態風險不容忽視[34-35]。將我國典型水環境中PAEs的污染水平與其他國家相比，結果表明整體上我國水環境中的PAEs污染水平較高，但在尼日利亞西南部的Ogun河PAEs的污染水平較高，達到395.00～4 775.00 μg·L-1，它的最大值要高于我國地表水環境質量標準的597倍(表3)。

表1 我國大陸地區2000—2010年PAEs的供應和需求量(104t)

隨著城市PAEs消費量的日益增加，導致城市水環境中PAEs污染水平顯著高于農村地區。這主要是因為城市水環境會接收大量未經有效處理的工業廢水，如德國柏林市污水處理廠所排放的廢水中PAEs濃度較高(高達182.00 μg·L-1)。此外，PAEs的污染不僅發生在地表水水環境中，也會污染地下水環境，如廣東省東莞市地下水的PAEs濃度范圍為0.00～6.70 μg·L-1。盡管如此，PAEs在地表水環境中(河流、湖泊和水庫)的污染水平要顯著高于地下水環境[36]。

表2 2006年我國PAEs的主要生產企業及其產量[31]

表3 我國與其他國家水環境中PAEs的污染水平

表4 生態風險評價中魚類、水蚤和藻類的急性毒性數據(LC50或EC50)

表5 我國典型水環境中DMP、DEP、DBP、BBP、DHP和DEHP對魚類種群的RQ以及總生態風險(μg·L-1)

2.3 我國典型水環境中的PAEs的生態風險評價

在我國PAEs對水環境造成的生態風險仍處于未知狀態。PAEs對水生生態系統的影響主要取決于PAEs的輸入量和其毒性參數。本研究中PAEs的生態風險評價方法以歐盟技術指導性文件為基礎[27]，該文件要求至少同時考慮魚類、水蚤和藻類的LC50或EC50。PAEs的毒性數據主要來源于Staples的綜述“Aquatic Toxicity of Eighteen Phthalate Esters”[28]。RQ值是根據最大無影響效應濃度(NOEC)、最低的LC50或EC50以及安全系數(1 000)進行計算[27]。表4列出了RQ計算過程中3個種群對PAEs的LC50、EC50和NOEC。表5～7列出了我國典型城市水環境中典型PAEs對魚類、水蚤和藻類的RQ值，3個種群的RQ值呈現明顯差異。在我們計算的6種PAEs中，DBP、DEHP和BBP為最主要的風險物質。DMP對Lepomis macrochirus的RQ變化范圍為0.00～2.78，對Daphnia magna的RQ變化范圍為0.00～25.10，對Selenastrum capricornutum的RQ變化范圍為0.00～0.66。相比而言，DEP、DBP、BBP和DEHP在長江-江蘇段、松花江-吉林段對Lepomis macrochirus種群、在北京-朝陽公園湖泊對Selenastrum capricornutum種群的RQ達到預期的潛在負效應水平，即RQ > 100。一般來說，藻類對于PAEs極其敏感，而Daphnia magna的RQs相對較小。除了DMP、DEP和DHP以外，多數PAEs的RQs變化范圍都在10.0～100.00，這表明我國水環境中的PAEs存在顯著的潛在負效應，研究發現DMP、DEP和DHP主要通過生長限制對魚類、水蚤和藻類產生生態風險[15, 28]。

為了計算PAEs在我國水環境中的聯合效應，本研究將各個點位中各種PAEs的RQ進行加和計算，得到PAEs的總生態風險。結果表明，在長江三角洲-徐州段魚類、水蚤和藻類種群的總生態風險處于無顯著風險水平，即RQ < 1.00，魚類種群總的風險值變化范圍為0.16 (長江三角洲-徐州段)～1 407.00 (長江-江蘇段)，水蚤種群總生態風險變化范圍為0.04 (長江三角洲-徐州段)～333.00 (長江-江蘇段)，藻類種群總生態風險變化范圍為0.31 (長江三角洲-徐州段)～2 634.00 (長江-江蘇段)。總生態風險的結果表明在長江-江蘇段PAEs對魚類、水蚤和藻類種群均存在顯著的潛在負效應，即RQ > 100。

對于城市湖泊來說，除北京什剎海外，頤和園和官廳水庫中PAEs的生態風險處于無顯著風險或較小的潛在負效應水平，大部分城市湖泊的PAEs生態風險處于存在顯著的潛在負效應或預期的潛在負效應水平。對于城市河流來說，除長江-武漢段豐水期外，大部分河流的PAEs生態風險處于存在顯著的潛在負效應或預期的潛在負效應水平。對于其他水環境來說，如北京污水處理廠進水的PAEs生態風險處于存在預期的潛在負效應水平，而其他水環境多數處于存在較小的潛在負效應或顯著的潛在負效應水平。因此，需要對我國城市水環境中PAEs的生態風險進行研究，可以通過長期或短期的毒理學數據，表征PAEs混合物在水環境中的綜合效應，建立水環境中可靠的PAEs生態風險評價方法。

此外，大量研究結果表明PAEs可以在生物體內產生生物富集效應[70-72]。Cheng等[71]檢測了香港市場上20多種魚類體內PAEs濃度，結果表明在淡水魚類體內ΣPAEs濃度范圍為1.66～3.14 μg·g-1(濕重)，在海洋魚類體內ΣPAEs濃度范圍為1.57～7.10 μg·g-1(濕重)；其中在淡水魚類和海洋魚類中，DEHP和DBP均為主要的PAEs風險物質。Mo等[73]檢測了珠江三角洲9個種植園中11種蔬菜的PAEs濃度，結果表明ΣPAEs濃度范圍為0.07～11.20 μg·g-1(干重)，PAEs濃度均值為3.20 μg·g-1(干重)，其中Brassica parachinensis體內PAEs濃度最高，這些結果表明PAEs可以通過胃腸消化系統在生物體內富集，而PAEs的生物富集系數變化范圍為0.0001～0.61。

表6 我國典型水環境中DMP、DEP、DBP、BBP、DHP和DEHP對水蚤種群的RQ以及總生態風險(μg·L-1)

表7 我國典型水環境中DMP、DEP、DBP、BBP、DHP和DEHP對藻類種群的RQ以及總生態風險(μg·L-1)

我國作為全球范圍內最大的PAEs生產國和消費國，PAEs應用廣泛，它已經嚴重威脅到我國水環境生態安全。總體而言，我國PAEs的主要來源為塑料業和增塑劑相關的產業。由于我國對PAEs和以PAEs為原料產品的需求日益增加，因此我國未來PAEs的污染水平將日益嚴峻。PAEs的生態風險評價主要是基于準確檢測環境介質中PAEs的濃度和相關的毒理學參數。需要通過PAEs在水環境中長期的生物暴露研究才能確定自然條件下PAEs對水環境造成的生態影響。目前，亟需掌握我國不同環境介質中PAEs的來源、污染分布特征、毒性參數和生態風險水平，尤其是在高度城市化的地區和PAEs工業密集區域。

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The Occurrence and Ecological Risk Assessment of Phthalate Esters (PAEs) in Urban Aquatic Environments of China

Zhang Lulu1,2,3,*, Liu Jingling2, Ho Kinchung3, Li Hua1

1. School of Environmental Science and Technology, Hebei University of Science and Technology, Shijiazhuang 050018, China 2. State Key Joint Laboratory of Environmental Simulation and Pollution Control, School of Environment, Beijing Normal University, Beijing 100875, China 3. School of Science and Technology, The Open University of Hong Kong, HKSAR, China

Received 14 July 2015 accepted 15 October 2015

Phthalate esters (PAEs) are endocrine disruptors and have been used as plasticizing agents in cellulosics and elastomers. The demand for PAEs has grown rapidly, especially in China. It will lead to much more environmental PAE contamination. PAEs are listed as the chemical that poses significant ecological risk. This paper reviews the literature concerning the pollution status of PAEs, summarizes the main characteristics of PAEs in typical aquatic environment in China, assesses the ecological risk of PAEs to alage, daphnia, and fish by risk quotient (RQ) approach which is based on the predicted no effect concentration (PNEC) and PAE concentrations in aquatic environments. The results showed that PAEs concentrations in most of river and lake waters were higher than 8.00 μg·L-1, which are higher than the concentrations of PAEs in the Environmental Quality Standards for Surface Water (PRC-NS 2002) (DEHP, 8.00 μg·L-1and DBP, 3.00 μg·L-1) and Standards for Drinking Water Quality (PRCNS 2006) (DEHP, 8.00 μg·L-1, DBP, 3.00 μg·L-1and DEP, 3.00 μg·L-1), respectively. With the increasing consumption of PAEs in metropolitan areas, the concentrations of PAEs detected in urban water bodies were obviously higher than those in other areas of China. Compared with other countries, the PAE concentrations in the waters of China are higher than global PAE levels. Furthermore, PAE pollution of water bodies was found not only in surface waters but also in underground waters; for instance, PAE concentrations in the range of 0.00-6.70 μg·L-1were detected in underground waters in Dongguan, Guangdong Province, China. The results of RQs showed that significant (10 ≤ RQ < 100) or very significant (RQ ≥ 100) potential adverse effects for algae, daphnia, and fish in aquatic environments near PAE-based industrial and urban areas, and DBP, DEHP and BBP contributed the most. Thus, the ecological risk of PAEs in Chinese aquatic environments should be considered, especially in areas where commercial plastics are produced.

phthalate esters (PAEs); urban aquatic environment; pollution level; ecological risk; China

10.7524/AJE.1673-5897.20150714001

國家重點基礎研究發展計劃(2015CB458900)；河北科技大學博士啟動基金(1181200)

張璐璐(1985-)，女，博士，浙江浦江人，講師，研究方向為污染生態學，E-mail: zhanglulu19850703@163.com

2015-07-14 錄用日期：2015-10-15

1673-5897(2016)2-421-15

X171.5

A

簡介：張璐璐(1985-)，女，工學博士，講師，主要研究方向為污染生態學及生態毒理學。

張璐璐, 劉靜玲, 何建宗, 等. 中國典型城市水環境中鄰苯二甲酸酯類污染水平與生態風險評價[J]. 生態毒理學報，2016, 11(2): 421-435

Zhang L L, Liu J L, He K C, et al.The occurrence and ecological risk assessment of phthalate esters (PAEs) in urban aquatic environments of China [J]. Asian Journal of Ecotoxicology, 2016, 11(2): 421-435 (in Chinese)