2020, Vol. 41
2. 中国环境科学研究院环境污染控制工程技术研究中心, 北京 100012;
3. 中国环境科学研究院环境基准与风险评估国家重点实验室, 北京 100012
, YANG Yong-zhe1 , WANG Hai-yan2,3
, DONG Wei-yang2,3 , YAN Guo-kai2,3 , CHANG Yang2,3 , LI Ze-wen2,3 , ZHAO Yuan-zhe1,2,3 , LING Yu2,3
2. Research Center for Environmental Pollution Control Engineering Technology, Chinese Research Academy of Environmental Sciences, Beijing 100012, China;
3. State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China
邻苯二甲酸酯(phthalate esters, PAEs)又名酞酸酯, 是一类重要的有机化合物, 被广泛用于塑料工业, 作为聚氯乙烯(PVC)材料的粘合剂和增塑剂, 以提高其柔韧性和加工能力[1~4], 还被应用于其他非增塑剂行业, 包括化妆品、驱虫剂、推进剂、装饰性油墨和润滑油制造等行业[5, 6].由于其广泛应用, PAEs在空气、水、沉积物、土壤和食物中被广泛检测出[7~10].曾报道PAEs对人体的生殖和发育有潜在危害, 可导致内分泌紊乱和生殖机能失常等[11~13].因此, PAEs被公认为全球性的环境有机污染物, 已引起世界各国的重视.美国环保署(environmental protection agency, USEPA)将6种PAEs[邻苯二甲酸二甲酯(dimethyl phthalate, DMP)、邻苯二甲酸二乙酯(diethyl phthalate, DEP)、邻苯二甲酸二丁酯(di-n-butyl phthalate, DBP)、邻苯二甲酸丁基苄酯(butyl-benzyl phthalate, BBP)、邻苯二甲酸(2-乙基己基)酯(di-2-ethylhexyl phthalate, DEHP)和邻苯二甲酸二正辛酯(di-n-octyl phthalate, DnOP)]列为优先控制污染物[14].
由于PAEs的高疏水性, 水体中的PAEs易与底部沉积物结合并且沉积物对其具有高吸收率和低运输潜力[15].沉积物作为污染物的长期储层, 与水体进行物质和能量交换, 其中的PAEs对水生生物构成潜在的威胁[16].国内外学者对沉积物中的PAEs分布特征及生态风险评价做了大量研究, Chen等[17]发现了中国台湾高雄港沉积物中∑6PAEs含量范围为400.0~34 800.0 ng ·g-1, DEHP占比达92%；Li等[18]研究了中国九龙江沉积物中∑6PAEs的空间分布, 发现DIBP和DEHP具有高风险, 而DBP和DINP具有中等风险；Gao等[19]的研究发现, 太湖沉积物中∑6PAEs含量范围为5 150.0~20 900.0 ng ·g-1, 沉积物中的DEP对水生态系统具有较高的风险；董雷等[20]的研究发现，丰水期长江武汉段沉积物中PAEs主要来源于塑料、重化工工业和生活垃圾；Zhang等[21]的研究发现，长江口及临江地区沉积物中∑6PAEs含量范围为480.0~29 940.0 ng ·g-1, DEHP和DBP含量超过环境风险水平(environmental risk levels, ERL)值, 对海洋环境存在潜在危害；Zhang等[22]的研究发现，渤海沉积物中∑16PAEs含量高于黄海, 并运用风险熵(risk quotient, RQ)评价发现DBP和DiBP在沉积物中达到高风险水平；Liu等[23]的研究发现，在高度城市化和工业化的珠江三角洲地区河流沉积物中∑16PAEs含量较高.Srivastava等[24]通过高效液相色谱法对印度Gomti河沉积物中5种PAEs进行定量和定性分析, 确定了DMP、DEP、DBP、DEHP和DOP的含量(10.5、4.6、10.4、31.6和5.2 ng ·g-1)；Adeogun等[25]研究了尼日利亚(Epe和Lagos)两个澙湖沉积物中3种PAEs含量高于水中, 且DEP和DEHP是含量最高的；Arfaeinia等[26]的研究发现波斯湾北部工业区和农业区沉积物PAEs污染水平显著高于城市区和自然区, 主要来源为工业和农业活动.
松花江是我国第三大水系, 为黑龙江、吉林和内蒙古提供饮用水和农业灌溉用水等, 同时松花江流域因其丰富的煤炭资源、石油、电力、森林等非金属资源, 沿岸分布了许多重工业城市如哈尔滨、吉林及佳木斯市等.近年来由于流域社会经济的快速发展, 河流沉积物中部分污染物含量较高, 部分河流水生生态系统遭到破坏, 水体自净能力受到损伤, 区域内分布的煤化工、塑料制品和农业等成为PAEs潜在的污染来源[27, 28].目前有关松花江流域沉积物PAEs空间分布特征的研究主要集中在松花江部分河段.陆继龙等[29]的研究发现, 第二松花江沉积物PAEs中DBP(7 632.4 ng ·g-1)和DEHP(6 367.6 ng ·g-1)含量均已超过了美国华盛顿州的警戒标准(均为610.0 ng ·g-1), 从上游至下游沉积物中5种PAEs呈现先增加后减少的趋势.崔志丹等[30]报道第二松花江上游松花湖沉积物中∑6PAEs含量范围为33.7~2 062.3 ng ·g-1, 生态风险较低, 只有部分点位存在低度生态风险.杨艳艳[31]研究了松花江(嫩江、第二松花江和松花江主段)2016年丰水期∑6PAEs含量范围为819.4~24 035.4 ng ·g-1, DBP和DEHP的含量较高, DBP和DEHP对生态环境潜在风险较高.但尚未发现对松花江干支流、上下游和不同区域沉积物中PAEs含量分布特征、风险评价和来源分析的综合报道.
本研究主要研究了松花江干支流、上下游和不同区域沉积物中PAEs含量分布特征, 并采用主成分分析法, 探讨其主要来源；采用商值法和环境风险水平(ERL)法, 开展污染水平分析和风险评估, 以期为松花江水生态恢复保护及风险管控提供科学依据.
1 材料与方法 1.1 样品采集本研究于2017年3月(枯水期)在松花江流域布置19个采样点, 其中嫩江4个采样点(N1~N4), 第二松花江(“二松”)3个采样点(D1~D3), 松花江主段(“松主段”)10个采样点(S1~S10), 黑龙江2个采样点(H1和H2)；其中N1~N3、D1、S1~S3、S9和S10为农业自然区域点位, N4、D2和D3、S4~S8为城市工业区域点位(图 1和表 1).使用抓斗采样器(ZGCSC-5, 上海梓桂仪器有限公司)采集沉积物样品, 每个点位随机采集3份沉积物平行样.采集的样品用锡箔纸包好, 置于不锈钢盒中, -20℃冰箱保存, 备用.
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图 1 松花江流域采样点分布示意 Fig. 1 Sampling sites in the Songhua River |
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表 1 松花江流域采样点信息 Table 1 Information of sampling sites |
1.2 仪器与试剂
Agilent 7890A-5975C气相色谱-质谱联用仪(美国Agilent公司)；FreeZone®冷冻干燥机(美国Labconco公司)；Visiprep DL SPE固相萃取装置(美国Supelco公司)；ASE-350加速溶剂萃取仪(美国Thermo Fisher公司)；SE812氮吹浓缩仪(北京帅恩科技有限公司).
∑6PAEs混合标准溶液(美国o2si公司), 包括DMP、DEP、DBP、BBP、DEHP和DnOP；EPA525.2内标混标(含苊-d10、菲-d10和-d12)和2种替代物混标(HJ805-2016对三联苯-d14和2-氟联苯, HJ 950-2018)标准品购于美国o2si公司；正己烷、丙酮和甲醇均为农残级(美国MREDA和德国MERCK)；无水硫酸钠(优级纯, 天津津科)、硅藻土(20目~100目, 国药集团)和石英砂(20目~100目, 国药集团).
1.3 样品预处理与分析沉积物样品经真空冷冻干燥(Free Zone®冷冻干燥机, 美国Labconco公司)、研磨和过0.15 mm筛后, 取5 g样品(精确到0.000 1 g), 加2 g硅藻土作分散剂, 采用加速溶剂萃取仪(ASE-350加速溶剂萃取仪, 美国Thermo Fisher公司)进行萃取, 以正己烷和丙酮1 :1为萃取溶剂, 萃取仪载气压力为0.8 MPa, 加热温度为100℃, 萃取池压力为8.3~13.8 MPa, 预加热平衡5 min, 静态萃取5 min, 溶剂淋洗体积为60%池体积, 氮气吹扫时间为60 s, 静态萃取2次, 将萃取液氮吹浓缩至2 mL进行铜粉脱硫, 然后采用Aglient硅胶小柱串联PSA小柱(N-丙基乙二胺固相萃取柱)对萃取液进一步净化, 先在串联好的小柱上加入2 g无水硫酸钠脱水, 然后加入20 mL正己烷进行柱子的活化, 活化后进行上样, 上样完成后用丙酮和正己烷混合溶剂(体积比为1 :1)洗脱3次, 将收集到的洗脱液氮吹浓缩至1 mL, 用于GC-MS分析.
采用TOC-VCPH型总有机碳分析仪, 配有SSM-5000A固体样品进样装置(Shimadzu公司, 日本)测定沉积物样品中总有机碳(TOC)含量.
1.4 仪器分析条件气相色谱参考条件：DB-5MS 122-5562UI毛细管柱(60 m×0.25 mm×0.25 μm)；载气为高纯氦气(纯度>99.999%)；流速1.0mL ·min-1, 恒流模式；进样口温度(280℃)；进样量(1.0 μL)；分流方式(不分流)；色谱柱升温程序：60℃保留2 min, 以10℃ ·min-1升温到200℃, 保持2 min, 再以5℃ ·min-1升温到300℃, 保持15 min.
质谱参考条件：离子源温度[230℃电子轰击源(EI)]；离子化能量(70 eV)；四级杆温度(150℃)；接口温度(280℃)；扫描质量范围(45~450 u)；扫描模式(Scan定性, Sim定量).
1.5 质量保证与质量控制本研究采用方法空白、空白加标、样品平行样和内标法定量进行质量控制和质量保证, 为避免分析过程产生的污染, 每一批处理10个样品, 溶剂空白和方法空白各1个, 空白加标和基质加标各1个(检测仪器的重现性和稳定性).每一个样品均添加替代标准物测方法回收率, 回收率介于63.6% ~114.4%；目标化合物的平行样标准偏差范围为0.3% ~16.4%, 所有样品上机测试3次, 最终结果取3次平行平均值.方法空白样品仅检出含量较低的DEHP, 在最后结果中扣除.空白加标回收率为73.2% ~117.1%, 基质加标回收率76.5% ~119.0%, 检出限为0.1(BBP)~3.1(DBP) ng ·g-1, 定量限为2.6~9.1 ng ·g-1.
1.6 数据分析使用SPSS Statistics 23软件对所得数据进行统计学分析, 多独立样本非参数检验(中位数检验, Kruskal-Wallis, Jonckheere-Terpstra)和T检验分析数据之间的差异性, Pearson相关性用于分析PAEs含量与TOC含量之间的相关性, 主成分分析用来估计沉积物中PAEs的可能来源.此外, 用ArcMap 10.2(GIS)软件绘制松花江流域采样点位.
1.7 生态风险评价目前有关PAEs生态风险影响评价研究较少, 尚未建立起统一的标准.为此, 以ERL值评价沉积物PAEs的生态风险.此外, 还采用商值法半定量表征PAEs的生态风险, 通过从US EPA数据库(http://cfpub.epa.gov/ecotox/)获得5种PAEs对相对敏感生物的毒性数据, 计算得到这5种PAES(DBP、DEHP、DEP、BBP和DMP)相对应的预测无影响含量值(PNEC), 并根据风险按熵公式计算出风险熵[32]：
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式中, EC为环境暴露含量值(ng ·g-1)；PNEC为计算得到的预期无影响含量值(ng ·g-1).
HQ值被分为4个级别以评估生态风险, 等级为[33]：当HQ < 0.1, 无生态风险；0.1≤HQ < 1, 低生态风险水平；1≤HQ < 10, 中等生态风险水平；HQ≥10, 高生态风险.
2 结果与讨论 2.1 松花江表层沉积物PAEs含量分布2017年3月松花江流域19个采样点位表层沉积物中6种PAEs均有检出, 其∑6PAEs含量范围(以干重计, 下同)为6 832.5~36 298.9 ng ·g-1, 平均值为18 388.6 ng ·g-1. DEHP检出含量最高, 范围为4 808.4~18 909.5 ng ·g-1, 平均值为10 636.9 ng ·g-1(表 2).
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表 2 松花江表层沉积物样品中∑6PAEs Table 2 Concentrations of ∑6PAEs in the sediments of the Songhua River |
干流点位∑6PAEs含量范围为6 832.5~36 298.9 ng ·g-1, 平均值为18 616.9 ng ·g-1, 支流点位∑6PAEs含量范围为10 367.6~26 593.3 ng ·g-1, 平均值为18 264.1 ng ·g-1.支流点位∑6PAEs平均含量比干流点位略低, 但差异不显著(P>0.05), 与杨艳艳[31]研究9月样点不一致, 这可能由于9月支流多接纳农田退水, 但3月冬季农业退水较少, 支流沉积物中PAEs含量相对较低, 而干流PAEs来源较广, 故而导致干支流差异变小.支流点位各PAEs单体含量与干流点位差异不大(表 2).黑龙江H1和H2点位∑6PAEs含量分别为19 207.3 ng ·g-1和16 648.4 ng ·g-1, 平均值为17 927.9 ng ·g-1.
不同江段干支流∑6PAEs平均含量既存在一定相似性, 又呈现某些差异性.嫩江支流∑6PAEs平均含量(19 802.3 ng ·g-1)与嫩江干流(19 515.6 ng ·g-1)接近, 松主段支流(18 497.8 ng ·g-1)与松主段干流(17 237.2 ng ·g-1)相比差异不大, 与整个流域干支流含量分布一致.二松支流∑6PAEs平均含量(15 907.6 ng ·g-1)显著低于二松干流(20 959.2 ng ·g-1), 这主要是因为二松干流点位位于吉林和长春等重工业城市的下游, 而支流点位多位于工业较分散的区域或是城市上游, 受经济社会和工业影响较小.嫩江(19 659.0 ng ·g-1)、松主段(18 119.6 ng ·g-1)、黑龙江(17 927.9 ng ·g-1)和二松(17 591.5 ng ·g-1)这4个江段∑6PAEs平均含量相差不大, 且经多独立样本非参数检验表明, 各江段∑6PAEs含量分布无显著性差异(P>0.05), 这可能与松花江流域各江段均有农业退水、工业废水和生活污水等汇入有关, 导致各江段∑6PAEs含量差异较小.
松花江上、中、下游点位∑6PAEs含量范围分别为14 323.7~24 619.3、10 367.6~20 660.5和6 832.5~36 298.9 ng ·g-1, 平均值分别为18 772.9、15 784.6和20 454.7 ng ·g-1.从上游到下游干支流∑6PAEs平均含量呈现先降后升的趋势.下游点位含量最高, 可能是由于松花江下游流域流经了工业城市佳木斯、鹤岗和七台河市等, 下游西林(S9)点位紧临于以煤化工、煤炭采选和造纸等为主要产业的佳木斯市下游, ∑6PAEs含量最高达到36298.9 ng ·g-1, 流经煤炭丰富的鹤岗市的梧桐河向松主段汇入也会贡献一定的PAEs, 且松花江下游流经我国著名的商品粮基地“三江平原”, 大量农业退水直接排入致使下游沉积物中PAEs累积；倭肯河中游(S6)和桔源林场(S7)点位分别位于七台河市和伊春市周边, PAEs含量升高可能与城市工业废水与生活污水的排放有关.从上游到中游∑6PAEs含量下降可能是因为上游嫩江和第二松花江沿岸曾聚集大量以冶金、化工、造纸、化纤、石油开采等工业为主的齐齐哈尔市、大庆市、松原市、长春市和吉林市等大中型城市, 工业排污影响较大, 但中游城市工业聚集密度不如上游, 故∑6PAEs含量相对于上游偏低.最小值出现在松花江干流佳木斯上(S8)点位, 该点位远离城市, 自然环境好, 受重工业及人类活动影响较小.
从农业自然区域和城市工业区域来看, 农业自然区域∑6PAEs平均含量(18 677.5 ng ·g-1)与城市工业区域∑6PAEs平均含量(18 063.7 ng ·g-1)相近, 经T检验(P>0.05)表明两种区域类型的∑6PAEs平均含量无显著性差异, 而Wang等[34]的研究发现江苏省河流沉积物中工业∑PAEs含量显著高于农业点位.这可能与松花江流域产业结构有关, 东北是我国重要的商品粮基地, 农业自然区域高PAEs值与蔬菜温室、塑料薄膜、农药和化肥的大量使用密切相关[35].同时松花江流域是老工业基地, 沿岸的城市生活污水以及工业废水的汇入使得沉积物中∑6PAEs含量升高.从组成情况来看, 在城市工业区域和农村自然区域DEHP含量平均值贡献率分别为68.0%和55.5%, DBP含量平均值贡献率分别为31.2%和43.7%, DBP和DEHP是2种主要的PAEs污染物, 两者含量平均值贡献率高达98%以上, 这与Arfaeinia等[26]对波斯湾农业和工业等区域河流沉积物的研究一致.
沉积物中∑6PAEs污染以DBP和DEHP为主, 这与Gao等[19]和陆继龙等[29]的研究结果一致(表 3).松花江流域沉积物中DBP含量略高于珠江三角洲和巢湖, 并明显高于其他河流(表 3)；DEHP含量低于珠江三角洲和高雄港1~2倍, 高于其他河流；但DMP、DEP和BBP含量低于其他河流；松花江流域∑6PAEs含量处于中等水平, 表明松花江流域水生生态系统面临一定的PAEs风险.
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表 3 国内外河流、湖泊沉积物中PAEs污染水平比较1)/ng ·g-1 Table 3 Comparison of ∑6PAEs in sediments of the Songhua River with other waterbodies in China and abroad/ng ·g-1 |
多数研究表明, 河流沉积物中的TOC含量是影响有机物吸附的主要因素之一[40, 41], 因此松花江流域表层沉积物中的PAEs含量水平可能与TOC相关联.本研究采样点沉积物中TOC含量为0.0% ~2.7%(平均值为0.9%), PAEs与TOC相关性如图 2所示, 在P=0.05的置信水平上, PAEs与TOC相关性不显著.表明松花江流域17个点位∑6PAEs平均含量不受沉积物中TOC含量影响, 可能与运输、混合、沉淀机制和源组成等因素有关[42, 43].
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图 2 PAEs含量与TOC的相关性 Fig. 2 Relationship between the concentrations of PAEs and TOC |
松花江沉积物∑6PAEs中各PAE单体相对占比为：DEHP(57.80%)>DBP(41.35%)>DEP(0.28%)>BBP(0.25%)>DMP(0.20)>DnOP(0.07%).N1、N2、N3、S7和S9点位DBP占比范围为50.3% ~67.5%, 其余点位除D3点位外DEHP占比范围为56.0% ~87.3%(图 3), 可以看出松花江干支流沉积物中PAEs主要组分为DEHP和DBP.国内许多研究表明河流沉积物中PAEs以DEHP和DBP为主要组分, 如长江武汉段、太湖和黄河[44~47], 这可能是因为PAEs是亲脂性的有机污染物, 其辛醇-水分配系数较高, 水溶性低, 进入水体的PAEs易于在沉积物中富集, 尤其对于吸附能力强和水中溶解度相对较小的DBP和DEHP, 另一方面也可能是因为DBP和DEHP属于最为普遍的PAEs[48~50], 而DMP对光敏感[51], 并且在硝酸盐和强氧化剂的影响下容易分解[52, 53], 这些特征可能影响DMP的分布.
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图 3 松花江表层沉积物PAEs在各点位组成特征分布 Fig. 3 ∑6PAEs composition characteristics in sediments of the Songhua River |
采用主成分分析法分析松花江表层沉积物中PAEs的来源结果如图 4所示, 沉积物样品提出两个主成分, 每个主成分(PC)的特征值均大于1, 方差贡献率分别为57.71%和84.27%, 在第一主成分(PC1)中, DMP(0.9)、BBP(0.8)、DEP(0.8)、DnOP(0.8)和DBP(0.7)呈现很高的正载荷, 说明他们来源相似, 而DEP和DBP广泛存在于个人护理产品的添加剂中[54, 55], DMP和DBP也是生活垃圾中的主要PAEs类污染物[56, 57], BBP和DnOP则主要用于合成皮革、墨水、密封剂和粘合剂[58].第二主要成分(PC2)中DEHP(0.6)载荷最高, DEHP主要用于聚合物工业生产中的增塑剂, 以提高柔韧性、可加工性和一般处理性能[59, 60], 同时DEHP主要应用于农业, 是白色和黑色塑料薄膜中主要成分[61, 62], 据调查2017年黑吉两省塑料薄膜的农业消费量约为20.2万t, 覆盖面积达到37.7万hm2[63].由此可见, PC1可能主要来源于化妆品、个人护理品和人类日常用品, 而PC2则来源于含有增塑剂的工业产品以及农业生产活动中.总而言之, 松花江表层沉积物中PAEs主要来源于人类日常生活用品、农业生产以及含有增塑剂的工业生产, 这与陆继龙等[29]的研究结果一致.
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图 4 PAEs单体主成分分析因子载荷值 Fig. 4 Factor loadings of PAEs congeners by principal component analysis |
本研究参考van Wezel等[64]确定的两种PAEs的ERL值(DBP和DEHP的ERL值分别为700 ng ·g-1和1 000 ng ·g-1), 当相对污染系数(RCF=CPAEs/ERL, CPAEs为PAEs环境暴露含量)结果小于1, PAEs不存在内分泌干扰和生态毒性风险；结果大于1, PAEs存在内分泌干扰和生态毒性风险.至于其他单体PAEs, 国家海洋局推荐使用美国华盛顿颁布的沉积物质量警戒线[65], 各组分均为610 ng ·g-1.松花江所有点位表层沉积物中的DBP和DEHP均超过了美国华盛顿州颁布的质量警戒水平且RCF值均大于1, 表明DBP和DEHP对研究区域生态环境存在内分泌干扰和生态毒性风险, 这与国内部分河流一致[66~68], 其余4种PAEs均未超过美国华盛顿沉积物质量警戒线, 表明DMP、DEP、BBP和DnOP这4种PAEs生态风险较小.
采用商值法进一步评价了松花江沉积物中5种PAEs对水生生物的风险(表 4), 5种PAEs的HQ值排序如下：DBP>DEHP>DEP>BBP>DMP.其中DMP和BBP在各江段的HQ值均小于0.1, 表明DMP和BBP对各江段水生生物均无生态风险.DEP在各江段的HQ值均大于0.1而小于1, 表明DEP对各江段水生生物生态风险处于低水平.DBP和DEHP在各江段的HQ值均大于10, 表明DBP和DEHP对各江段水生生物具有高生态风险.支流沉积物中DEP和DEHP对水生生物的风险比干流稍高, 而干流沉积物中DBP对水生生物的风险比支流高.
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表 4 PAEs的HQ分布 Table 4 HQ values of PAEs |
3 结论
(1) 松花江干支流表层沉积物中∑6PAEs范围为6 832.5~36 298.9 ng ·g-1, 平均值为18 388.6 ng ·g-1, 与国内外其他河流相比, 含量水平处于中等.干流点位∑6PAEs平均含量与支流点位差异不显著；从上游到下游干支流∑6PAEs含量呈现先降后升的趋势；各江段∑6PAEs平均含量相差不大, 无显著性差异；农业自然区域∑6PAEs平均含量与城市工业区域接近, 区域差异对松花江流域∑6PAEs平均含量无显著性影响.松花江流域沉积物中∑6PAEs含量不受TOC影响.
(2) 松花江沉积物∑6PAEs中各PAEs单体相对占比为：DEHP>DBP>DEP>BBP>DMP>DnOP, 表明松花江干支流沉积物中PAEs主要组分为DEHP和DBP, 其中DEHP是最主要的污染物, 其单体贡献率为57.80%.
(3) 松花江表层沉积物中PAEs主要来源于人类日常生活用品, 农业生产以及含有增塑剂的工业生产, 这与研究区域内产业布局一致.
(4) 松花江表层沉积物中DMP和BBP对水生生物无生态风险, DEP处于低生态风险水平, 而DEHP和DBP对水生生物具有高生态风险.
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