进口再生塑料颗粒中特征污染物的筛选及污染特征研究

白月娇; 林晔; 岳波; 孟棒棒; 张颖; 王超

doi:10.12153/j.issn.1674-991X.20230591

进口再生塑料颗粒中特征污染物的筛选及污染特征研究

doi: 10.12153/j.issn.1674-991X.20230591

白月娇^{1, 2,},
林晔²,
岳波^1, ,,
孟棒棒¹,
张颖^{1, 2},
王超^{1, 2}

1.
中国环境科学研究院固体废物污染控制技术研究所
2.
沈阳建筑大学市政与环境工程学院

基金项目: 国家重点研发计划项目(2019YFC1904802)

详细信息

作者简介:
白月娇(1998—)，女，硕士研究生，主要从事固体废物污染防治研究，1419963055@qq.com

通讯作者:
岳波(1980—)，男，研究员，博士，主要从事固体废物污染防治研究，yuebo@craes.org.cn

中图分类号: X705
计量
- 文章访问数: 95
- HTML全文浏览量: 34
- PDF下载量: 30
- 被引次数: 0
出版历程
- 收稿日期: 2023-08-12
- 录用日期: 2023-12-21
- 修回日期: 2023-09-15

Study on screening of characteristic pollutants and pollution characteristics in imported regenerated plastic particles

BAI Yuejiao^{1, 2
,},
LIN Ye²,
YUE Bo^{1
, ,},
MENG Bangbang¹,
ZHANG Ying^{1, 2},
WANG Chao^{1, 2}

1.
Research Institute of Solid Waste Management, Chinese Research Academy of Environmental Sciences
2.
School of Municipal and Environmental Engineering, Shenyang Jianzhu University

摘要

摘要:
为了掌握进口再生塑料颗粒中污染物的污染特性，选取5种不同类型的进口再生塑料颗粒，基于来源及再生利用过程分析其可能含有的污染物类型，筛选出重金属、双酚类化合物〔包括四溴双酚A（BPA）与四溴双酚S（BPS）〕和挥发性有机物(VOCs)3种特征污染物进行污染特征分析。结果发现，5种再生塑料颗粒中检测出6种重金属，包括Cr、Mn、Pb、Cd、Cu、Hg，其中Cr、Mn、Pb的浓度相对较高；5种再生塑料颗粒中BPS的检出率达100%，BPA的检出率为20%~100%，且BPS浓度大于BPA，这可能与实际生产中使用BPS等代替BPA有关；5种再生塑料颗粒中检测出的VOCs中，除二氯甲烷外均为苯的同系物。研究结果可为塑料颗粒后续的再生利用提供基础数据支持，并有助于相关部门进一步规范进口再生塑料颗粒的管控。
- 再生塑料颗粒 /
- 特征污染物 /
- 重金属 /
- 双酚类化合物 /
- 挥发性有机物
Abstract:
In order to understand the pollution characteristics of pollutants in imported recycled plastic particles, five different types of imported recycled plastic particles were selected. Based on the source and recycling process, the possible types of pollutants were identified. Three characteristic pollutants, namely heavy metals, bisphenol compounds (including tetrabromobisphenol A (BPA) and tetrabromobisphenol S (BPS)), and volatile organic compounds (VOCs), were screened out and their pollution characteristics were analyzed. The results showed that six heavy metals, Cr, Mn, Pb, Cd, Cu, and Hg, were detected in the five types of recycled plastic particles, with relatively high concentrations of Cr, Mn, and Pb. The detection rate of BPS reached 100%, and the detection rate of BPA was between 20% and 100%. The mass concentration of BPS in the five recycled plastic particles was greater than that of BPA, which may be related to the use of BPS or other substitutes for BPA in actual production. Most of the detected VOCs, except for dichloromethane, were homologues of benzene. The results could provide basic data support for subsequent recycling work and help relevant departments further regulate the control of imported recycled plastic particles.
- recycled plastic particles /
- characteristic pollutants /
- heavy metal /
- bisphenol compounds /
- volatile organic compounds

HTML全文

图 1 再生塑料颗粒中不同重金属浓度

Figure 1. Diagram of different heavy metal content in recycled plastic particles

下载: 全尺寸图片幻灯片

图 2 5种再生塑料颗粒中BPA、BPS平均浓度

Figure 2. Average content diagram of BPA and BPS in 5 kinds of recycled plastic particles

下载: 全尺寸图片幻灯片

图 3 5种再生塑料颗粒中VOCs平均浓度

Figure 3. Average content diagram of VOCs in 5 kinds of recycled plastic particles

下载: 全尺寸图片幻灯片

图 4 5种再生塑料颗粒中VOCs综合毒性占比

Figure 4. Toxicity ratio diagram of VOCs in 5 kinds of recycled plastic particles

下载: 全尺寸图片幻灯片

表 1 进口再生塑料颗粒基本情况

Table 1. Basic information of imported recycled plastic particles

类型	英文学名	中文学名	推荐用途	使用特性	外观颜色
PE	polyethylene	聚乙烯	管材、发泡、注塑、包装膜、方便袋等	通用塑料	黑、灰、米白、乳白
PP	polypropylene	聚丙烯	卡板、挡泥板、保险杠、拉丝、丙纶纱、编制包装、桌椅、吹瓶等	通用塑料	黑、灰、绿、白、灰、浅灰
PS	polystyrene	聚苯乙烯	发泡、管道、护栏等	通用塑料	黑、绿、浅绿、浅红、浅茶、白
PET	polyethylene-terephthalate	聚对苯二甲酸乙二醇酯	填充物、化纤、纺丝、纤维、吸塑等	工程塑料	白、蓝、绿、透明
ABS	acrylonitrile-butadiene- styrene copolymers	丙烯腈-丁二烯-苯乙烯共聚合物	游戏机外壳、空调、冰箱	通用塑料	黑、灰、白

下载: 导出CSV

表 2 高效液相色谱测定条件

Table 2. Determination conditions of high-performance liquid chromatography

色谱柱	柱长/mm	内径/mm	粒度/μm	柱温	流动相体积比	流速/(mL/min)	可变波长扫描紫外检测器/nm
C18	250	4.6	5	室温	甲醇∶水为60∶40	1	224

下载: 导出CSV

表 3 再生塑料颗粒中BPA和BPS检出率

Table 3. Detection rate of BPA and BPS in recycled plastic particles %　

化合物	PE	PP	PS	PET	ABS
BPA	70	80	75	20	100
BPS	100	100	100	100	100

下载: 导出CSV

表 4 VOCs毒性指标LD₅₀

Table 4. Toxicity index LD₅₀ of VOCs

序号	CAS编号	中文名	英文名	分子式	LD₅₀/（mg/kg）
1	75-09-2	二氯甲烷	methylene dichloride	CH₂Cl₂	2 080
2	108-88-3	甲苯	toluene	C₇H₈	7 530
3	100-41-4	乙基苯	ethylbenzene	C₈H₁₀	3 500
4	106-42-3	对二甲苯	p-xylene	C₈H₁₀	5 000
5	100-42-5	苯乙烯	styrene	C₈H₈	1 000
6	95-47-6	邻二甲苯	o-xylene	C₈H₁₀	6 125
7	622-96-8	对甲乙苯	4-ethyltoluene	C₉H₁₂	4 850
8	95-63-6	1,2,4-三甲基苯	1,2,4-trimethylbenzene	C₉H₁₂	1 760
9	103-65-1	正丙苯	n-propylbenzene	C₉H₁₂	6 040
10	620-14-4	间甲乙苯	3-ethyltoluene	C₉H₁₂
11	611-14-3	邻甲乙苯	2-ethyltoluene	C₉H₁₂	5 000
12	526-73-8	联三甲苯	1,2,3-trimethylbenzene	C₉H₁₂	5 000
13	141-93-5	1,3-二乙基苯	diethylbenzene	C₁₀H₁₄	1 200
14	105-05-5	1,4-二乙基苯	p-diethylbenzene	C₁₀H₁₄	1 200
注：LD₅₀指在一定时间内经口或经皮给予受试样品后，受试动物发生死亡概率是50%的剂量。

下载: 导出CSV

参考文献(44)

[1]	RAGAERT K, DELVA L, van GEEM K. Mechanical and chemical recycling of solid plastic waste[J]. Waste Management,2017,69:24-58. doi: 10.1016/j.wasman.2017.07.044
[2]	张书敏, 江龙发, 周丽萍, 等. 再生塑料颗粒固体废物的典型特征及其识别技术[J]. 中国口岸科学技术,2021(9):70-76. ZHANG S M, JIANG L F, ZHOU L P, et al. Typical characteristics and identification technology of recycled plastic particles solid waste[J]. China Port Science and Technology,2021(9):70-76.
[3]	李干杰. 全面禁止洋垃圾入境维护国家生态环境安全和人民群众身体健康[N]. 人民日报, 2017-07-28(11).
[4]	杨艳艳, 李世平, 谢丹平, 等. 废塑料再生利用二噁英污染特征及暴露风险[J]. 中国环境科学,2023,43(9):4926-4933. YANG Y Y, LI S P, XIE D P, et al. Pollution characteristics and exposure risk of PCDD/Fs from plastic waste recycling industry[J]. China Environmental Science,2023,43(9):4926-4933.
[5]	郭慧鑫, 朱燕, 金海林, 等. 废旧塑料资源化过程中污染物释放特性研究[J]. 环境科学与技术,2021,44(增刊1):270-275. GUO H X, ZHU Y, JIN H L, et al. Study on release characteristics of pollutants in waste plastics recycling process[J]. Environmental Science & Technology,2021,44(Suppl 1):270-275.
[6]	ALAM O, WANG S J, LU W T. Heavy metals dispersion during thermal treatment of plastic bags and its recovery[J]. Journal of Environmental Management,2018,212:367-374. doi: 10.1016/j.jenvman.2018.02.034
[7]	王成, 李哲, 魏健, 等. 水中微塑料来源、生态毒理效应及处理技术研究进展[J]. 环境工程技术学报,2023,13(5):1883-1892. WANG C, LI Z, WEI J, et al. Research progress on sources, ecotoxicological effect and treatment technology of microplastics in water[J]. Journal of Environmental Engineering Technology,2023,13(5):1883-1892.
[8]	PIVNENKO K, ERIKSEN M K, MARTÍN-FERNÁNDEZ J A, et al. Recycling of plastic waste: presence of phthalates in plastics from households and industry[J]. Waste Management,2016,54:44-52. doi: 10.1016/j.wasman.2016.05.014
[9]	韩余. 我国快餐食品包装物中典型有害物污染特征及健康风险[D]. 北京: 中央民族大学, 2020.
[10]	刘忠瑞, 孙立文, 李洋洋, 等. 塑料食品包装材料中双酚A的迁移量检测[J]. 食品安全质量检测学报,2018,9(10):2350-2355. LIU Z R, SUN L W, LI Y Y, et al. Determination of migration quantity of bisphenol A from plastic packaging materials of food[J]. Journal of Food Safety & Quality,2018,9(10):2350-2355.
[11]	CHEN D, KANNAN K, TAN H L, et al. Bisphenol analogues other than BPA: environmental occurrence, human exposure, and toxicity: a review[J]. Environmental Science & Technology,2016,50(11):5438-5453.
[12]	张子金, 林煜棋, 张煜娴, 等. 南京毒性挥发性有机化合物夏冬季源解析及健康风险评估[J]. 环境科学,2021,42(12):5673-5686. ZHANG Z J, LIN Y Q, ZHANG Y X, et al. Source analysis and health risk assessment of toxic volatile organic compounds in Nanjing in summer and winter[J]. Environmental Science,2021,42(12):5673-5686.
[13]	张梦茹, 徐桂芹, 黄国忠, 等. 再生塑料颗粒中可挥发苯系物暴露特征及健康风险评价[J]. 环境化学,2023,42(9):2935-2945. ZHANG M R, XU G Q, HUANG G Z, et al. Exposure characteristics and health risk assessment of volatile benzene homologues in recycled plastic pellets[J]. Environmental Chemistry,2023,42(9):2935-2945.
[14]	王涛, 马明, 邵敏, 等. 高效液相色谱法同时测定塑料食品接触材料中双酚S、双酚A和4, 4'-二氯二苯砜的迁移量[J]. 理化检验-化学分册,2017,53(12):1398-1402. WANG T, MA M, SHAO M, et al. Simultaneous determination of migration of bisphenol S, bisphenol A and 4, 4'-dichlorodiphenyl sulfone in plastic food contact materials by HPLC[J]. Physical Testing and Chemical Analysis Part B (Chemical Analysis),2017,53(12):1398-1402.
[15]	孙福春, 肇子春, 刘孟春, 等. VOC气体检测仪在进口废塑料检验中的应用[J]. 再生资源与循环经济,2011,4(7):43-44. doi: 10.3969/j.issn.1674-0912.2011.07.016 SUN F C, ZHAO Z C, LIU M C, et al. Application of VOC gas detector in the inspection of import waste plastics[J]. Recyclable Resources and Circular Economy,2011,4(7):43-44. doi: 10.3969/j.issn.1674-0912.2011.07.016
[16]	LITHNER D, LARSSON Å, DAVE G. Environmental and health hazard ranking and assessment of plastic polymers based on chemical composition[J]. Science of the Total Environment,2011,409(18):3309-3324. doi: 10.1016/j.scitotenv.2011.04.038
[17]	RAMANAYAKA S, VITHANAGE M, ZHANG H, et al. Role of soil organic matter on the retention and mobility of common plastic additives, Di(2-ethylhexyl) phthalate, bisphenol A and benzophenone, in soil[J]. Environmental Research,2023,236:116725. doi: 10.1016/j.envres.2023.116725
[18]	TANG Z W, HUANG Q F, CHENG J L, et al. Polybrominated diphenyl ethers in soils, sediments, and human hair in a plastic waste recycling area: a neglected heavily polluted area[J]. Environmental Science & Technology,2014,48(3):1508-1516.
[19]	DIMITRAKAKIS E, JANZ A, BILITEWSKI B, et al. Determination of heavy metals and halogens in plastics from electric and electronic waste[J]. Waste Management,2009,29(10):2700-2706. doi: 10.1016/j.wasman.2009.05.020
[20]	NAKASHIMA E, ISOBE A, KAKO S, et al. Quantification of toxic metals derived from macroplastic litter on ookushi beach, Japan[J]. Environmental Science & Technology,2012,46(18):10099-10105.
[21]	ALAM O, BILLAH M, DING Y J. Characteristics of plastic bags and their potential environmental hazards[J]. Resources, Conservation and Recycling,2018,132:121-129. doi: 10.1016/j.resconrec.2018.01.037
[22]	张杰聪, 温云铎, 吴晓丹, 等. 儿童玩具中重金属污染及健康风险评价[J]. 生态毒理学报,2022,17(4):345-353. ZHANG J C, WEN Y D, WU X D, et al. Contamination and health risk assessment of heavy metals in toys[J]. Asian Journal of Ecotoxicology,2022,17(4):345-353.
[23]	向静雅, 王倩, 邵明帅, 等. 深圳海滩塑料垃圾及其重金属污染分析[J]. 中国环境科学,2020,40(7):3097-3105. XIANG J Y, WANG Q, SHAO M S, et al. Assessment of beach plastic waste and its heavy metal pollution in Shenzhen[J]. China Environmental Science,2020,40(7):3097-3105.
[24]	丁世环. 液相色谱-质谱联用法在奶瓶双酚类化合物含量测定中的应用研究[J]. 云南化工,2018,45(8):95-97. DING S H. Application of liquid Chromatography-Mass Spectrometry in the determination of bisphenol compounds in milk bottles[J]. Yunnan Chemical Technology,2018,45(8):95-97.
[25]	ROCHESTER J R. Bisphenol A and human health: a review of the literature[J]. Reproductive Toxicology,2013,42:132-155. doi: 10.1016/j.reprotox.2013.08.008
[26]	杨岳, 关成立, 陈珊媛. 挥发性有机污染物VOCs处理技术研究进展[J]. 广州化工,2020,48(7):27-29. YANG Y, GUAN C L, CHEN S Y. Research progress on treatment technology of volatile organic compounds[J]. Guangzhou Chemical Industry,2020,48(7):27-29.
[27]	谢利, 于江, 任鹏刚, 等. 顶空/气相色谱-质谱法分析方便面印刷包装材料中挥发性有机物[J]. 分析化学,2011,39(9):1368-1372. XIE L, YU J, REN P G, et al. Analysis of volatile organic compounds in printing and plastic packaging materials of instant noodles by headspace gas chromatography-mass spectrometry[J]. Chinese Journal of Analytical Chemistry,2011,39(9):1368-1372.
[28]	张可冬, 余晓志, 李慧勇, 等. 食品包装用聚苯乙烯树脂中苯乙烯和乙苯单体的测定方法[J]. 分析仪器,2011(5):30-33. ZHANG K D, YU X Z, LI H Y, et al. Determination of styrene and ethylbenzene monomers in food packaging polystyrene[J]. Analytical Instrumentation,2011(5):30-33.
[29]	王芳, 刘曙, 沈康俊, 等. 食品接触材料及制品非有意添加物风险评估与监管[J]. 中国塑料,2019,33(4):89-95. WANG F, LIU S, SHEN K J, et al. Risk assessment and supervision of non-intentionally added substances in food contact materials and articles[J]. China Plastics,2019,33(4):89-95.
[30]	AL-QUTOB M, ASAFRA A, NASHASHIBI T, et al. Determination of different trace heavy metals in children's plastic toys imported to the west bank/Palestine by ICP/MS-environmental and health aspects[J]. Journal of Environmental Protection,2014,5(12):1104-1110. doi: 10.4236/jep.2014.512108
[31]	毛少华, 顾卫华, 白建峰, 等. ICP-OES法测定废家电外壳HIPS中4种重金属[J]. 塑料,2019,48(3):123-126. MAO S H, GU W H, BAI J F, et al. Determination of four heavy metals from HIPS of waste appliances by ICP-OES[J]. Plastics,2019,48(3):123-126.
[32]	向文平, 罗思. 不同批次再生聚乙烯塑料中重金属的含量状况探究[J]. 再生资源与循环经济,2018,11(10):36-39. doi: 10.3969/j.issn.1674-0912.2018.10.011 XIANG W P, LUO S. Investigation on heavy metal content in different batches of recycled polyethylene plastics[J]. Recycling Research,2018,11(10):36-39. doi: 10.3969/j.issn.1674-0912.2018.10.011
[33]	汪仕韬, 周敏, 殷晶晶, 等. 电感耦合等离子体质谱法同时测定食品包装用聚对苯二甲酸乙二醇酯材料中9种重金属[J]. 分析科学学报,2020,36(3):453-456. WANG S T, ZHOU M, YIN J J, et al. Determination of nine kinds of heavy metals in polyethylene terephthalate materials for food packaging by ICP-MS[J]. Journal of Analytical Science,2020,36(3):453-456.
[34]	邱月, 李根容, 龙梅, 等. 超高效合相色谱法快速检测塑料食品接触材料中13种紫外吸收剂[J]. 色谱,2019,37(9):990-995. doi: 10.3724/SP.J.1123.2019.03026 QIU Y, LI G R, LONG M, et al. Rapid determination of 13 ultraviolet absorbents in plastic food contact materials by ultra-performance convergence chromatography[J]. Chinese Journal of Chromatography,2019,37(9):990-995. doi: 10.3724/SP.J.1123.2019.03026
[35]	沈梦楠, 高士祥. 多溴联苯醚与四溴双酚A的生物代谢研究进展[J]. 环境工程技术学报,2015,5(5):418-423. SHEN M N, GAO S X. Biological metabolic transformation of polybrominated diphenyl ethers and tetrabromobisphenol A[J]. Journal of Environmental Engineering Technology,2015,5(5):418-423.
[36]	高永刚, 张艳艳, 高建国, 等. 衍生化气相色谱-质谱法测定玩具和食品接触材料中双酚A[J]. 色谱,2012,30(10):1017-1020. GAO Y G, ZHANG Y Y, GAO J G, et al. Determination of bisphenol A from toys and food contact materials by derivatization and gas chromatography-mass spectrometry[J]. Chinese Journal of Chromatography,2012,30(10):1017-1020.
[37]	国家卫生健康委员会. 生活饮用水卫生标准: GB 5749—2022[S]. 北京: 中国标准出版社, 2022.
[38]	蒋小良, 曾铭, 郝雨, 等. 食品包装材料中双酚A在食品模拟物中迁移规律的研究[J]. 分析测试技术与仪器,2013,19(3):133-137. JIANG X L, ZENG M, HAO Y, et al. Study on migration rule of bisphenol A in food packing materials in food simulants[J]. Analysis and Testing Technology and Instruments,2013,19(3):133-137.
[39]	王学臣, 聂赛赛, 王帅, 等. 拉链排咪、塑料制品和印刷行业VOCs排放特征比对分析[J]. 环境监测管理与技术,2020,32(6):65-67. WANG X C, NIE S S, WANG S, et al. Comparison of VOCs emission characteristics in zipper, plastics and printing industry[J]. The Administration and Technique of Environmental Monitoring,2020,32(6):65-67.
[40]	LINSSEN J P H, JANSSENS J L G M, ROOZEN J P, et al. Combined gas chromatography and sniffing port analysis of volatile compounds of mineral water packed in polyethylene laminated packages[J]. Food Chemistry,1993,46(4):367-371. doi: 10.1016/0308-8146(93)90006-2
[41]	周良春, 张晓飞, 马俊辉, 等. 顶空气相色谱法测定食品接触用聚苯乙烯塑料中11种挥发性有机物[J]. 分析仪器,2018(6):27-33. ZHOU L C, ZHANG X F, MA J H, et al. Determination of 11 VOCs in polystyrene plastics used as food contact material by headspace gas chromatography with FID[J]. Analytical Instrumentation,2018(6):27-33.
[42]	CHYTIRI S, GOULAS A E, BADEKA A, et al. Volatile and non-volatile radiolysis products in irradiated multilayer coextruded food-packaging films containing a buried layer of recycled low-density polyethylene[J]. Food Additives and Contaminants,2005,22(12):1264-1273. doi: 10.1080/02652030500241645
[43]	王瑞文, 张春林, 丁航, 等. 电子制造业塑料件生产过程的挥发性有机物排放特征分析[J]. 环境科学学报,2019,39(1):4-12. WANG R W, ZHANG C L, DING H, et al. Emission characteristics of volatile organic compounds (VOCs) from the production processes of plastic parts in electronic manufacturing industry[J]. Acta Scientiae Circumstantiae,2019,39(1):4-12.
[44]	魏亚楠, 宋薇, 朱烁, 等. 挥发性有机毒性污染物综合生物毒性评价研究[J]. 煤炭与化工,2018,41(8):151-155. WEI Y N, SONG W, ZHU S, et al. Research on the comprehensive biological toxicity evaluation of volatile organic toxic pollutants[J]. Coal and Chemical Industry,2018,41(8):151-155. ⊗