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邻苯二甲酸酯(phthalate esters,PAEs)是一类应用广泛的塑料化合物,具有低挥发性、疏水性及溶于大多有机溶剂的特点[1],与各类日用产品(包括建筑材料、汽车产品、食品包装、个人护理产品等)之间以范德华力和氢键相结合,属于非紧密结合[2],作为增塑剂使用主要用于增强材料的柔韧性、可塑性、延展性和耐用性等[3 − 4],可在制造、销售、使用及废弃处理等环节被释放到环境介质中[5]. 据不完全统计,2010年我国已成为全球塑料制造和消费的最大国家之一,对PAEs增塑剂的需求量突破100万 t[6];2014年,增塑剂全球生产和消费量达840万 t,其中PAEs类占比70%左右[7 − 8];全球对PAEs的需求量持续扩张,预计增速可达年均1.3%左右[6,9];目前,我国年均PAEs增塑剂产量和消费量占全国总量的90%左右,占全球总量的20%[8,10],其中邻苯二甲酸(2-乙基己基)酯(bis-(2-ethylhexyl) phthalate,DEHP)是用量最高的单体之一[11 − 12]. 有研究表明,PAEs在环境介质中广泛存在,土壤[13 − 14]、地下水[15]、河流沉积物[16]等中均有检出. DEHP作为一种典型的PAEs类化合物,95%被用作聚氯乙烯(polyvinyl chloride,PVC)中的增塑剂,PVC曾是世界上产量最大的通用塑料,应用非常广泛,从室内装修、家用产品到医疗耗材等涉及到日常生活的方方面面,从而提高人体接触DEHP的机率[17 − 18];此外,DEHP是油墨溶剂的一种成分,在化妆品和杀虫剂中作为非活性化合物使用[17]. 有学者指出,DEHP因其高性能和低成本已成为我国目前使用最广泛、生产量最大的增塑剂之一,DEHP生产量占PAEs产量约80%左右[19 − 20]. Naohide等[21]也指出增塑剂广泛应用于PVC成型与加工中,DEHP使用最广泛,通过评估日本房屋灰尘得出DEHP的中位含量为2.1 mg·g−1,占检测到的PAEs和非PAEs增塑剂总含量的85%. DEHP已被许多国家的不同权威机构列为优先控制的有毒污染物[22]. 长期暴露在DEHP环境下对人体、动物和植物均具有危害性. 已有的动物实验和人体健康风险评估研究发现,DEHP可导致实验动物或接触人类出现生殖器官突变、胚胎突变、幼体发育异常、肝脏功能异常、免疫系统功能异常、干扰内分泌调节剂等病变问题[23 − 26]. 植物体内富集是长期暴露在PAEs残留环境下最直接的影响,其中DEHP在烟叶[27]、桃果[28]、水稻[29]等植物组织中均有检出. 由于DEHP在环境介质中的高检出率[30 − 31],致使其环境危害不容小觑.
近年来,由于土壤环境中PAEs污染突出使得它们成为土壤污染关注的热点. 国内外已开展的PAEs土壤污染研究多集中于农业土壤[32],鲜有关注其他类型的土壤,亦如塑料增塑剂的末端处置去处之一非正规生活垃圾填埋场. 郑仲等[33]指出,塑料是生活垃圾主要组分之一,PAEs在不同组分(塑料、布类、金属等)中均有检出,其中DEHP检出率最高. DEHP作为最常见的PAEs类单体化合物,通常被作为土壤及沉积物中PAEs污染的标志物[34],并经研究证实DEHP可作为化学指标预测土壤中PAEs的发生和归宿[35]. 当被废弃进入填埋场后,一部分可被填埋物/土壤吸附滞留,另一部分则经物理、化学等反应后,被释放伴随渗滤液在环境介质中迁移、扩散,威胁填埋区及周边环境安全[36].
土壤是人类生存和发展过程中重要的环境资源,而非正规生活垃圾填埋场作为历史遗留环境问题,主要分布在城乡结合部、环境敏感区、主要交通干线沿线及河流和水利枢纽管理范围内,占用大量土地资源[37]. 截至2017年,非正规生活垃圾填埋场在册登记数量约2.7×104 个[38],2018—2019年,长江经济带11个省市因生活垃圾填埋场环境污染被督办案件数807 个,占同期督办案件总数的24.82%[39]. 2021年,浙江省住房和城乡建设厅发布《生活垃圾填埋场现状调查指南》,围绕实现全省原生垃圾“零填埋”的前提,开展非正规生活垃圾填埋场综合整治,明确将PAEs中DEHP列为生活垃圾特征污染物,需监测土壤中DEHP赋存水平.
环境风险评价分为生态风险评价和人体健康风险评价. 生态风险评价多基于熵值法,健康风险评估多采用美国环保局提出的EPA模型[40]. 古文等[41]基于熵值法得出化工园区土壤和沉积物中PAEs呈现中、高程度风险的结论. 李婷[42]利用熵值法和USEPA模型计算,指出研究区DEHP对水生生物影响最大,为高风险,且非致癌风险水平较高. 陶红等[43]通过USEPA模型评估银川市城区不同功能区灰尘中PAEs人体健康风险,研究表明各功能区地表灰尘中的主要PAEs单体为DEHP,其次为邻苯二甲酸二丁酯(dibutyl phthalate,DnBP),二者贡献率占比97.07%,且有2个样点的DEHP致癌风险超过EPA推荐的致癌水平,应引起一定的重视.
本研究选择浙江省某非正规生活垃圾填埋场作为研究对象,从两个维度聚焦非正规生活垃圾填埋场原状土壤不同层深中DEHP污染问题:(1)监测不同土层原状土壤中DEHP赋存水平,对标环境质量标准进行评估分析,以期为后续填埋场原址土地合理开发利用提供科学指导;(2)基于生态风险和人体健康风险两个层面,关注填埋场土壤DEHP环境风险,旨在作为后续原址土壤环境风险分级及科学管理的参考依据.
新型污染物邻苯二甲酸(2-乙基己基)酯在非正规生活垃圾填埋场原状土壤中赋存水平及环境风险评估
The pollution level and environmental risk assessment of new pollutant DEHP (bis (2-ethylhexyl) phthalate) on undisturbed soil of informal landfill
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摘要: 邻苯二甲酸(2-乙基己基)酯(DEHP)是一种环境新型有机污染物,作为最常见的增塑剂被广泛应用于生产生活中. 本研究选择某非正规生活垃圾填埋场不同土层的原状土壤作为研究对象,采集土壤样品共168 份,分析其DEHP赋存水平,比对现有环境质量标准,初步判断其环境风险,并采用熵值法和USEPA模型评估DEHP产生的生态风险及人体健康风险. 结果表明,送检样品中只有1 份土壤样品超出GB36600-2018中第一类用地筛选值, 67 份样品超出美国土壤控制标准. 使用熵值法模拟研究区原状土壤中,DEHP含量对敏感受体藻类、甲壳类及鱼类的生态风险,统计结果表明整体以中、高生态风险为主. 通过USEPA模型计算得出,研究区送检土壤样品中DEHP的非致癌风险均可接受,致癌风险成人不可接受率高达10.7%,儿童高达17.1%,且上层土壤致癌风险普遍高于中下层. 因此,非正规生活垃圾填埋场原状土层中DEHP环境风险明显需予以重视.
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关键词:
- 邻苯二甲酸(2-乙基己基)酯 /
- 非正规生活垃圾填埋场 /
- 熵值法 /
- USEPA模型.
Abstract: DEHP (bis-(2-ethylhexyl) phthalate) is a commonly used plasticizer in daily life and manufacturing, and it is an increasing organic contaminant in the environment. The research object in this study was undisturbed soil from informal landfill sites at varying depths. To examine the amounts of DEHP occurrence, 168 soil samples with varying landfill ages and layer depths were gathered. The dangers to human health and the environment posed by DEHP were evaluated using the USEPA model and the entropy technique. According to the results, 67 of the submitted samples surpassed US soil control criteria, and one soil sample exceeded the first category land screening value in GB36600-2018. In the undisturbed soil layer of the research region, the ecological risk of DEHP was mostly medium to high when fish, crustaceans, and algae were chosen as sensitive receptors. Through the USEPA model calculation, the non-carcinogenic risk of DEHP was determined to be acceptable; the unacceptable risk of cancer in adults was as high as 10.7%, and in children, it was as high as 17.1%. Additionally, compared to the middle and bottom soil layers, the top soil layer often had a greater cancer risk. It is important to consider the environmental effects of DEHP on the undisturbed soil layer of informal landfill sites.-
Key words:
- bis-(2-ethylhexyl) phthalate /
- informal landfill /
- entropy method /
- USEPA model.
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表 1 健康风险暴露评估模型参数
Table 1. Health risk exposure assessment model parameters
参数
Parameter单位
Unit参数值
Value参考文献
Reference成人
Adult儿童
Child摄入率IRS mg·d−1 100 200 [45] 土壤黏附因子AF mg·cm−1 0.07 0.2 [45] 皮肤接触表面积SA cm2·d−1 57000 28000 [45] 暴露持续时间ED a 24 6 [45] 人体体重BW kg 70 15 [45] 暴露频率EF d·a−1 350 350 [45] 体积转换因子CF L·cm−3 0.000001 0.000001 [45] 颗粒物排放因子PET m3·kg−1 1.36×109 1.36×109 [45] 呼吸速率Ij m3·d−1 13.5 13.5 [40] 平均暴露时间AT d 致癌/非致癌 25550 /365×ED[45] 非致癌物经某种途径摄入的日均
推荐剂量RfDmg·kg−1·d−1 0.02 [40] 皮肤吸收因子ABS — 0.1 [45] 致癌率CFS mg·kg−1·d−1 0.014 [40] 表 2 原状土不同层深中DEHP含量
Table 2. DEHP content in different depths of undisturbed soil
地块信息
Plot
information原状土送样层深度/m
Depth of sample layer
for undisturbed soil样品数量/份
Sample
quantityDEHP含量/( mg·kg−1) 标准差
Standard deviation变异系数
Variable coefficient最小值
Minimum最大值
Maximum平均值
Average中位
Median一期 上(0—1) 28 0.4 57.4 7.4 4.8 10.8 150% 中(1—2) 28 0.4 22.8 5.1 3.2 4.7 90% 下(2—3) 28 0.1 41.4 5.4 3.6 7.7 140% 二期 上(0—1) 28 0.4 39.6 6.2 3.7 7.6 120% 中(1—2) 28 0.5 16.8 4.5 3.1 3.9 90% 下(2—3) 28 0.3 16.9 3.7 2.9 3.3 90% 表 3 不同土层原状土中DEHP在不同暴露途径下ADD摄入量
Table 3. ADD intake of DEHP in undisturbed soils of different soil layers under different exposure pathways
类型
Type土层
Soil layer暴露途径
Route of
exposureADD/(mg·kg−1·d−1) 一期 二期 最大值
Maximum最小值
Minimum平均值
Average最大值
Maximum最小值
Minimum平均值
Average成人非致癌 上 经口摄入 7.86×10−5 5.48×10−7 1.01×10−5 5.42×10−5 5.48×10−7 8.44×10−6 皮肤接触 3.14×10−4 2.19×10−6 4.03×10−5 2.16×10−4 2.19×10−6 3.37×10−5 呼吸摄入 5.46×10−4 3.81×10−6 7.03×10−5 3.77×10−4 3.81×10−6 5.86×10−5 中 经口摄入 3.12×10−5 5.48×10−7 7.02×10−6 2.30×10−5 6.85×10−7 6.15×10−6 皮肤接触 1.25×10−4 2.19×10−6 2.80×10−5 9.18×10−5 2.73×10−7 2.46×10−5 呼吸摄入 2.17×10−4 3.81×10−6 4.87×10−5 1.60×10−4 4.76×10−6 4.28×10−5 成人非致癌 下 经口摄入 5.67×10−5 1.37×10−7 7.37×10−6 2.32×10-5 0 4.89×10−6 皮肤接触 2.26×10−4 5.47×10−7 2.94×10−5 9.24×10-5 0 1.95×10−5 呼吸摄入 3.94×10−4 9.52×10−7 5.12×10−5 1.61×10−4 0 3.40×10−5 成人致癌 上 经口摄入 2.70×10−5 1.88×10−7 3.47×10−6 1.86×10−5 1.88×10−7 2.89×10−6 皮肤接触 1.08×10−4 7.50×10−7 1.38×10−5 7.4×10−5 7.50×10−7 1.15×10−5 呼吸摄入 1.87×10−4 1.31×10−6 2.41×10−5 1.29×10−4 1.31×10−6 2.01×10−5 中 经口摄入 1.07×10−5 1.88×10−7 2.41×10−6 7.89×10−6 2.35×10−7 2.11×10−6 皮肤接触 4.27×10−5 7.50×10−7 9.60×10−6 3.15×10−5 9.37×10−7 8.42×10−6 呼吸摄入 7.44×10−5 1.31×10−6 1.67×10−5 5.48×10−5 1.63×10−6 1.47×10−5 下 经口摄入 1.94×10−5 4.70×10−8 2.53×10−6 7.94×10−6 0 1.68×10−6 皮肤接触 7.76×10−5 1.87×10−7 1.01×10−5 3.17×10−5 0 6.69×10−6 呼吸摄入 1.35×10−4 3.26×10−7 1.76×10−5 5.52×10−5 0 1.17×10−5 儿童非致癌 上 经口摄入 7.34×10−4 5.11×10−6 9.44×10−5 5.06×10−4 5.11×10−6 7.88×10−5 皮肤接触 2.05×10−3 1.43×10−5 2.64×10−4 1.42×10−3 1.43×10−5 2.21×10−4 呼吸摄入 5.46×10−4 3.81×10−6 7.03×10−5 3.77×10−4 3.81×10−6 5.86×10−5 中 经口摄入 2.92×10−4 5.11×10−6 6.55×10−5 2.15×10−4 6.39×10−6 5.74×10−5 皮肤接触 8.16×10−4 1.43×10−5 1.83×10−4 6.01×10−4 1.79×10−5 1.61×10−4 呼吸摄入 2.17×10−4 3.81×10−6 4.87×10−5 1.60×10−4 4.76×10−6 4.28×10−5 下 经口摄入 5.29×10−4 1.28×10−6 6.88×10−5 2.16×10−4 0 4.57×10−5 皮肤接触 1.48×10−3 3.58×10−6 1.93×10−4 6.05×10−4 0 1.28×10−4 呼吸摄入 3.94×10−4 9.52×10−7 5.12×10−5 1.61×10−4 0 3.40×10−5 儿童致癌 上 经口摄入 6.29×10−5 4.38×10−7 8.09×10−6 4.34×10-5 4.38×10−7 6.75×10−6 皮肤接触 1.76×10−4 1.23×10−6 2.27×10−5 1.22×10−4 1.23×10−6 1.89×10−5 呼吸摄入 4.68×10−5 3.26×10−7 6.02×10−6 3.23×10−5 3.26×10−7 5.03×10−6 中 经口摄入 2.50×10−5 4.38×10−7 5.61×10−6 1.84×10−5 5.48×10−7 4.92×10−6 皮肤接触 7.00×10−5 1.23×10−6 1.57×10−5 5.16×10−5 1.53×10−6 1.38×10−5 呼吸摄入 1.86×10−5 3.26×10−7 4.18×10−6 1.37×10−5 4.08×10−7 3.67×10−6 下 经口摄入 4.54×10−5 1.10×10−7 5.90×10−6 1.85×10−5 0 3.91×10−6 皮肤接触 1.27×10−4 3.07×10−7 1.65×10−5 5.19×10−5 0 1.10×10−5 呼吸摄入 3.38×10−5 8.16×10−8 4.39×10−6 1.38×10−5 0 2.91×10−6 -
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