生态环境学报 ›› 2023, Vol. 32 ›› Issue (12): 2128-2140.DOI: 10.16258/j.cnki.1674-5906.2023.12.005
刘宁1(
), 孔宇1, 任春廷1, 潘超1, 李晓娜1,2,*(), 王震宇1,2
收稿日期:2023-06-11
出版日期:2023-12-18
发布日期:2024-02-05
通讯作者:
*李晓娜。E-mail: xiaonali@jiangnan.edu.cn作者简介:刘宁（1995年生），女，博士研究生，主要从事新污染物的环境健康研究。E-mail: liuningchn@126.com
基金资助:
LIU Ning1(), KONG Yu1, REN Chunting1, PAN Chao1, LI Xiaona1,2,*(), WANG Zhenyu1,2
Received:2023-06-11
Online:2023-12-18
Published:2024-02-05
摘要：
随着印刷业的快速发展，碳粉的产量不断增加，致使废碳粉排放量升高。目前，国际上对废碳粉的处置以直接填埋为主，在环境中持续累积且具有暴露风险。废碳粉中含有微纳米塑料、纳米氧化物、纳米炭等多种新污染物，存在潜在生态环境和人体健康风险。如何科学处置废碳粉，实现其资源化利用是管控废碳粉中新污染物环境健康风险的关键。该综述首先探讨了多种典型颗粒新污染物的单独和复合生态效应以及其与环境中土壤、水体等介质的相互作用，提出废碳粉可能具备生物毒性和生态风险。废碳粉可通过呼吸、接触及食物链传递等途径造成人体暴露，可能会对人体呼吸系统、肾脏、肝脏、肠道代谢、神经发育、心脏代谢、血管、生殖等产生毒性，其毒性具有尺寸、剂量和暴露时间依赖性。依据废碳粉的成分组成和性能分析归纳总结了其可能的回收和高值化利用技术，并对未来废碳粉的环境地球化学过程、环境健康和资源化利用等方面研究进行了展望，包括：1）发展环境中废碳粉的分离提取与检测定量技术，明确废碳粉的环境赋存量和赋存形态；2）结合实验室和中宇宙模拟与机器学习来探究环境相关浓度下废碳粉的生态和人体健康效应，并实现其风险评估；3）加强废碳粉回收和资源化利用的技术的创新，发展碳粉全生命周期的安全性评估体系，建立健全规范废碳粉处置的相关环境管理政策法规。该文旨在为有效控制废碳粉中新污染物的环境健康风险提供理论依据，为促进废碳粉资源高效利用与印刷业绿色发展奠定技术基础。
中图分类号:
刘宁, 孔宇, 任春廷, 潘超, 李晓娜, 王震宇. 废碳粉中新污染物的环境健康风险与资源化利用[J]. 生态环境学报, 2023, 32(12): 2128-2140.
LIU Ning, KONG Yu, REN Chunting, PAN Chao, LI Xiaona, WANG Zhenyu. Environmental Health Risks and Resource Utilization of Emerging Contaminants in Toner Waste[J]. Ecology and Environment, 2023, 32(12): 2128-2140.
图1 碳粉的使用与废碳粉的产生示意图 PEPs指打印机释放颗粒物；VOCs指挥发性有机化合物；PM指颗粒材料
Figure 1 Schematic diagram of toner use and waste toner formation
图2 废碳粉的生物地球化学过程与健康风险
Figure 2 Biogeochemical processes and environmental health risks of waste toner
| 新污染物 | 生物 | 处理 (尺寸; 浓度; 时间) | 研究结果 | 文献 | ||
|---|---|---|---|---|---|---|
| PS MNPs | 小麦 Triticum aestivum L. | 0.1, 5 μm; 水培: 0‒200 mg∙L−1; 6 d 土培: 0‒100 mg∙kg−1; 10 d | (1) 水培条件下, 200 mg∙L−1的PSMPs抑制了小麦的生长 (2) 土培条件下, 10 mg∙kg−1的PSMPs对小麦的生长抑制最强 | 廖苑辰, | ||
| 洋葱 Allium cepa L. | 50 nm; 0, 10, 100, 1000 mg∙L−1; 72 h | (1) PSNPs (10－1000 mg∙L−1) 诱导洋葱根部产生细胞毒性、遗传毒性和氧化损伤 (2) 毒性随暴露浓度增大而增大 | Giorgetti et al., | |||
| 水稻 Oryza sativa L. | 50 nm; 0, 100, 1000 mg∙L−1; 96 h | PSNPs被根部吸收并转移到芽上, 影响根细胞超微结构、萌发过程、幼苗生长和根系有丝分裂活性, 诱导细胞遗传学畸变 | Spanò et al., | |||
| 蚕豆 Vicia faba L. | 0.1, 5 μm; 0, 10, 50, 100 mg∙L−1; 48 h | (1) 100 nm PS MPs暴露所产生的氧化损伤和遗产毒性比5 μm多 (2) 100 nm PSMPs可以进入蚕豆根，可能会通过阻塞细胞连接或细胞壁孔、破坏营养物质运输等来产生毒性 | Jiang et al., | |||
| 胡萝卜 Daucus carota L. | 0.1‒5 μm; 0, 10, 20 mg∙L−1; 7 d | (1) 粒径≤0.1 μm的PSMPs可以进入胡萝卜根部 (2) 20 mg∙L−1的PSMPs可导致胡萝卜生长下降并影响其品质 | Dong et al., | |||
| 土壤线虫 Caenorhabditis elegans | (1) 100 nm; 0‒1000 mg∙kg−1; 96 h (2) 50, 200 nm; 0, 17.3, 86.8 mg∙L−1; 24 h (3) 0.1, 0.5, 1, 2, 5 μm; 0, 1 mg∙L−1; 48 h | (1) PSNPs (≥1 mg∙kg−1) 暴露降低了线虫的卵形成和孵化率 (2) PS MNPs会影响线虫的能量代谢、运动、寿命和生殖功能 | Lei et al., | |||
| 水蚤 Daphnia magna | (1) 71 nm; 0, 1 mg∙L−1; 96 h (2) 0.7, 3 μm; 0, 2, 6 mg∙L−1; 6 d | (1) PSNPs诱导了水蚤新生儿的氧化应激, 免疫防御和糖代谢紊乱 (2) PSMPs削弱了捕食者诱导的水蚤防御 | Liu et al., | |||
| 海参 Apostichopus japonicus | 0.1, 20 μm; 0, 100 mg∙kg−1; 60 d | 100 nm和20 μm的PSMNPs对海参的生长性能、消化、免疫系统、细菌病原抗性均有不利影响 | Liu et al., | |||
| 斑马鱼 Danio rerio | 44 nm; 0, 1, 10, 100 μg∙L−1; 30 d | 环境相关质量浓度 (1‒100 μg∙L−1) 的PS-NPs会导致斑马鱼免疫反应功能障碍以及其肠道中微生物组组成和功能的改变 | Teng et al., | |||
| 青鳉鱼 Oryzias melastigma | 2, 200 μm; 0, 0.3, 3 mg∙kg−1; 28 d | PSMPs (3 mg∙kg−1) 显著影响了青鳉鱼的肠道微生态特征 (结构和功能)和宿主代谢特征 | Feng et al., | |||
| 海洋微藻 Heterosigma akashiwo | 1 μm; 0, 1, 2, 5, 10, 30, 75 mg∙L−1; 96 h | 高质量浓度 (≥5 mg∙L−1) 的PSMPs可以抑制藻类细胞的生长, 造成细胞膜损伤、细胞质和细胞器外排和破坏 | Wang et al., | |||
| 原生动物 Ochromonas gloeopar | 0.07, 3 μm; 0, 0.4, 0.8, 1.6, 2 mg∙L−1; 11 d | PSMPs (≥0.4 mg∙L−1, 3 μm) 对原生动物具有显著的生长抑制和藻类清除率降低作用 | Kong et al., | |||
| 原生动物 Uronema marinum | 0.5, 1.07, 2.14, 5 μm; (0, 2, 4, 6, 8, 10)×105 items∙mL−1; 96 h | PSMPs (1×106 items∙mL−1, 0.5‒5 μm) 抑制了原生动物U. marinuma 的丰度、体积和生物量, 影响了海洋食物网 | Zhang et al., | |||
| 嗜碱盐单胞菌 Halomonas alkaliphile | NH2-PS: 50, 1000 nm; PS: 55 nm; 0, 20, 40, 80, 160, 320 mg∙L−1; 2 h | (1) PS MNPs在高质量浓度 (80 mg∙L−1) 下均抑制嗜碱盐单胞菌的生长, 影响了海洋的氮循环 (2) 带正电荷的纳米塑料对细菌的氧化应激高于带负电荷的纳米塑料 | Sun et al., | |||
| 大肠杆菌 Escherichia coli | 0.1, 0.55, 5 μm; 0, 20, 40, 80, 160, 320 mg∙L−1; 24 h | PSMPs (≥160 mg∙L−1) 可以抑制大肠杆菌的细胞生长 | Yi et al., | |||
| 人工湿地微生物群落 | PS NPs: 50‒100 nm PS MPs: 10‒100 μm PS Macro Ps: 500‒1000 μm 10, 100, 1000 μg∙L−1; 1-300 d | (1) MPs/NPs的长期积累诱导微生物丰富度和多样性降低 (2) MPs的积累可能对微生物反硝化过程产生积极影响, 并对湿地系统的固氮产生不利影响 (3) 塑料尺寸对微生物群和氮生物转化的影响大于浓度 | Yang et al., | |||
| PE MPs | 蚯蚓 Earthworm | 250‒1000 μm; 0, 0.01, 0.1, 0.5 g∙100g−1; 56, 180, 208 d | 环境相关浓度 (0.01%－0.5%) 的PEMPs会抑制蚯蚓的繁殖, 造成DNA损伤，具有遗传毒性 | Sobhani et al., | ||
| 纳米Fe3O4 | 斑马鱼 Danio rerio | (1) 0‒1000 mg∙L−1; 0, 2, 12, 24, 36 h (2) 15, 22 nm; 0‒1114.70 mg∙L−1; 0, 24, 48, 72, 96 h | (1) 纳米Fe3O4 (≥100 mg∙L−1, 36 h) 会致使斑马鱼胚胎畸形, 存活率下降 (2) 纳米Fe3O4 (≥20 mg∙L−1, 96 h) 使其体内红细胞损伤、酶活性降低，造成遗传毒性 | Suganya et al., | ||
| 小球藻 Chlorella vulgaris | 约10 nm; 0‒1000 mg∙L−1; 0, 24, 48, 72, 96 h | 低浓度 (10‒250 mg∙L−1) 的纳米Fe3O4会促进细胞生长, 而较高浓度 (≥500 mg∙L−1) 的纳米Fe3O4会抑制细胞生长, 产生细胞毒性 | Yazdanabdad et al., | |||
| 纳米SiO2 | 斑马鱼 Danio rerio | (1) 62 nm; 0, 25, 50, 100, 200 mg∙L−1; 4‒96 h (2) 68 nm; 0, 2.5, 5 mg∙L−1; 7 d | (1) 纳米SiO2 (≥100 mg∙L−1, 24 h) 会诱导斑马鱼产生胚胎毒性, 并对其心血管造成影响 (2) 纳米SiO2 (≥2.5 mg∙L−1, 7 d) 会诱导鱼组织产生氧化应激, 造成DNA片段化损伤 | Ramesh et al., | ||
| 活性污泥微生物群落 | 30 nm; 0, 2, 5, 10, 30 mg∙L−1; 0‒300 d | 纳米SiO2 (5‒30 mg∙L−1) 影响活性污泥的微生物丰富度和多样性, 影响了微生物的硝化过程和除磷功能 | Li et al., | |||
| 新污染物 | 生物 | 处理 (尺寸; 浓度; 时间) | 研究结果 | 文献 | ||
| 纳米炭 | 两栖动物 Amphibalanus amphitrite | 纳米炭黑: 13 nm; 0‒5000 mg∙L−1 氧化石墨烯: 0.5‒5 μm; 0‒1000 mg∙L−1 24, 48, 72 h | 两栖动物仅在非常高质量浓度 (≥500 mg∙L−1, 48 h) 的纳米炭黑和氧化石墨烯下受到抑制 | Mesarič et al., | ||
| 蚯蚓 Earthworm | 纳米炭黑: 20‒70 nm 氧化石墨烯: 厚度0.55‒3.74 nm, 长0.5‒3 μm 碳纳米管: 直径1‒2 nm, 长5‒30 μm 0, 1, 10, 100 mg∙L−1; 12 h | 纳米炭黑、氧化石墨烯、碳纳米管仅在高质量浓度 (100 mg∙L−1) 的条件下才会抑制蚯蚓的生长 | Xu et al., | |||
| 土壤微生物 (古细菌、细菌、真菌) | C60和多壁碳纳米管: 直径50 nm 0, 30, 300 mg∙kg−1; 30 d | 纳米炭 (≥30 mg∙kg−1) 改变了土壤微生物的群落组成和功能 | Wu et al., | |||
表1 废碳粉所含颗粒新污染物的单一生态效应
Table 1 Single ecological effects of particulate emerging contaminants in waste toner
| 新污染物 | 生物 | 处理 (尺寸; 浓度; 时间) | 研究结果 | 文献 | ||
|---|---|---|---|---|---|---|
| PS MNPs | 小麦 Triticum aestivum L. | 0.1, 5 μm; 水培: 0‒200 mg∙L−1; 6 d 土培: 0‒100 mg∙kg−1; 10 d | (1) 水培条件下, 200 mg∙L−1的PSMPs抑制了小麦的生长 (2) 土培条件下, 10 mg∙kg−1的PSMPs对小麦的生长抑制最强 | 廖苑辰, | ||
| 洋葱 Allium cepa L. | 50 nm; 0, 10, 100, 1000 mg∙L−1; 72 h | (1) PSNPs (10－1000 mg∙L−1) 诱导洋葱根部产生细胞毒性、遗传毒性和氧化损伤 (2) 毒性随暴露浓度增大而增大 | Giorgetti et al., | |||
| 水稻 Oryza sativa L. | 50 nm; 0, 100, 1000 mg∙L−1; 96 h | PSNPs被根部吸收并转移到芽上, 影响根细胞超微结构、萌发过程、幼苗生长和根系有丝分裂活性, 诱导细胞遗传学畸变 | Spanò et al., | |||
| 蚕豆 Vicia faba L. | 0.1, 5 μm; 0, 10, 50, 100 mg∙L−1; 48 h | (1) 100 nm PS MPs暴露所产生的氧化损伤和遗产毒性比5 μm多 (2) 100 nm PSMPs可以进入蚕豆根，可能会通过阻塞细胞连接或细胞壁孔、破坏营养物质运输等来产生毒性 | Jiang et al., | |||
| 胡萝卜 Daucus carota L. | 0.1‒5 μm; 0, 10, 20 mg∙L−1; 7 d | (1) 粒径≤0.1 μm的PSMPs可以进入胡萝卜根部 (2) 20 mg∙L−1的PSMPs可导致胡萝卜生长下降并影响其品质 | Dong et al., | |||
| 土壤线虫 Caenorhabditis elegans | (1) 100 nm; 0‒1000 mg∙kg−1; 96 h (2) 50, 200 nm; 0, 17.3, 86.8 mg∙L−1; 24 h (3) 0.1, 0.5, 1, 2, 5 μm; 0, 1 mg∙L−1; 48 h | (1) PSNPs (≥1 mg∙kg−1) 暴露降低了线虫的卵形成和孵化率 (2) PS MNPs会影响线虫的能量代谢、运动、寿命和生殖功能 | Lei et al., | |||
| 水蚤 Daphnia magna | (1) 71 nm; 0, 1 mg∙L−1; 96 h (2) 0.7, 3 μm; 0, 2, 6 mg∙L−1; 6 d | (1) PSNPs诱导了水蚤新生儿的氧化应激, 免疫防御和糖代谢紊乱 (2) PSMPs削弱了捕食者诱导的水蚤防御 | Liu et al., | |||
| 海参 Apostichopus japonicus | 0.1, 20 μm; 0, 100 mg∙kg−1; 60 d | 100 nm和20 μm的PSMNPs对海参的生长性能、消化、免疫系统、细菌病原抗性均有不利影响 | Liu et al., | |||
| 斑马鱼 Danio rerio | 44 nm; 0, 1, 10, 100 μg∙L−1; 30 d | 环境相关质量浓度 (1‒100 μg∙L−1) 的PS-NPs会导致斑马鱼免疫反应功能障碍以及其肠道中微生物组组成和功能的改变 | Teng et al., | |||
| 青鳉鱼 Oryzias melastigma | 2, 200 μm; 0, 0.3, 3 mg∙kg−1; 28 d | PSMPs (3 mg∙kg−1) 显著影响了青鳉鱼的肠道微生态特征 (结构和功能)和宿主代谢特征 | Feng et al., | |||
| 海洋微藻 Heterosigma akashiwo | 1 μm; 0, 1, 2, 5, 10, 30, 75 mg∙L−1; 96 h | 高质量浓度 (≥5 mg∙L−1) 的PSMPs可以抑制藻类细胞的生长, 造成细胞膜损伤、细胞质和细胞器外排和破坏 | Wang et al., | |||
| 原生动物 Ochromonas gloeopar | 0.07, 3 μm; 0, 0.4, 0.8, 1.6, 2 mg∙L−1; 11 d | PSMPs (≥0.4 mg∙L−1, 3 μm) 对原生动物具有显著的生长抑制和藻类清除率降低作用 | Kong et al., | |||
| 原生动物 Uronema marinum | 0.5, 1.07, 2.14, 5 μm; (0, 2, 4, 6, 8, 10)×105 items∙mL−1; 96 h | PSMPs (1×106 items∙mL−1, 0.5‒5 μm) 抑制了原生动物U. marinuma 的丰度、体积和生物量, 影响了海洋食物网 | Zhang et al., | |||
| 嗜碱盐单胞菌 Halomonas alkaliphile | NH2-PS: 50, 1000 nm; PS: 55 nm; 0, 20, 40, 80, 160, 320 mg∙L−1; 2 h | (1) PS MNPs在高质量浓度 (80 mg∙L−1) 下均抑制嗜碱盐单胞菌的生长, 影响了海洋的氮循环 (2) 带正电荷的纳米塑料对细菌的氧化应激高于带负电荷的纳米塑料 | Sun et al., | |||
| 大肠杆菌 Escherichia coli | 0.1, 0.55, 5 μm; 0, 20, 40, 80, 160, 320 mg∙L−1; 24 h | PSMPs (≥160 mg∙L−1) 可以抑制大肠杆菌的细胞生长 | Yi et al., | |||
| 人工湿地微生物群落 | PS NPs: 50‒100 nm PS MPs: 10‒100 μm PS Macro Ps: 500‒1000 μm 10, 100, 1000 μg∙L−1; 1-300 d | (1) MPs/NPs的长期积累诱导微生物丰富度和多样性降低 (2) MPs的积累可能对微生物反硝化过程产生积极影响, 并对湿地系统的固氮产生不利影响 (3) 塑料尺寸对微生物群和氮生物转化的影响大于浓度 | Yang et al., | |||
| PE MPs | 蚯蚓 Earthworm | 250‒1000 μm; 0, 0.01, 0.1, 0.5 g∙100g−1; 56, 180, 208 d | 环境相关浓度 (0.01%－0.5%) 的PEMPs会抑制蚯蚓的繁殖, 造成DNA损伤，具有遗传毒性 | Sobhani et al., | ||
| 纳米Fe3O4 | 斑马鱼 Danio rerio | (1) 0‒1000 mg∙L−1; 0, 2, 12, 24, 36 h (2) 15, 22 nm; 0‒1114.70 mg∙L−1; 0, 24, 48, 72, 96 h | (1) 纳米Fe3O4 (≥100 mg∙L−1, 36 h) 会致使斑马鱼胚胎畸形, 存活率下降 (2) 纳米Fe3O4 (≥20 mg∙L−1, 96 h) 使其体内红细胞损伤、酶活性降低，造成遗传毒性 | Suganya et al., | ||
| 小球藻 Chlorella vulgaris | 约10 nm; 0‒1000 mg∙L−1; 0, 24, 48, 72, 96 h | 低浓度 (10‒250 mg∙L−1) 的纳米Fe3O4会促进细胞生长, 而较高浓度 (≥500 mg∙L−1) 的纳米Fe3O4会抑制细胞生长, 产生细胞毒性 | Yazdanabdad et al., | |||
| 纳米SiO2 | 斑马鱼 Danio rerio | (1) 62 nm; 0, 25, 50, 100, 200 mg∙L−1; 4‒96 h (2) 68 nm; 0, 2.5, 5 mg∙L−1; 7 d | (1) 纳米SiO2 (≥100 mg∙L−1, 24 h) 会诱导斑马鱼产生胚胎毒性, 并对其心血管造成影响 (2) 纳米SiO2 (≥2.5 mg∙L−1, 7 d) 会诱导鱼组织产生氧化应激, 造成DNA片段化损伤 | Ramesh et al., | ||
| 活性污泥微生物群落 | 30 nm; 0, 2, 5, 10, 30 mg∙L−1; 0‒300 d | 纳米SiO2 (5‒30 mg∙L−1) 影响活性污泥的微生物丰富度和多样性, 影响了微生物的硝化过程和除磷功能 | Li et al., | |||
| 新污染物 | 生物 | 处理 (尺寸; 浓度; 时间) | 研究结果 | 文献 | ||
| 纳米炭 | 两栖动物 Amphibalanus amphitrite | 纳米炭黑: 13 nm; 0‒5000 mg∙L−1 氧化石墨烯: 0.5‒5 μm; 0‒1000 mg∙L−1 24, 48, 72 h | 两栖动物仅在非常高质量浓度 (≥500 mg∙L−1, 48 h) 的纳米炭黑和氧化石墨烯下受到抑制 | Mesarič et al., | ||
| 蚯蚓 Earthworm | 纳米炭黑: 20‒70 nm 氧化石墨烯: 厚度0.55‒3.74 nm, 长0.5‒3 μm 碳纳米管: 直径1‒2 nm, 长5‒30 μm 0, 1, 10, 100 mg∙L−1; 12 h | 纳米炭黑、氧化石墨烯、碳纳米管仅在高质量浓度 (100 mg∙L−1) 的条件下才会抑制蚯蚓的生长 | Xu et al., | |||
| 土壤微生物 (古细菌、细菌、真菌) | C60和多壁碳纳米管: 直径50 nm 0, 30, 300 mg∙kg−1; 30 d | 纳米炭 (≥30 mg∙kg−1) 改变了土壤微生物的群落组成和功能 | Wu et al., | |||
| 新污染物 | 生物 | 处理 (尺寸; 浓度; 时间) | 研究结果 | 文献 |
|---|---|---|---|---|
| 纳米Fe3O4+PS MPs [MPS(Fe)] | 小球藻 Chlorella vulgaris 大型蚤Daphnia magna | MPS(Fe)-NH2: 1050 nm; 0.1‒1 mg∙L−1; 72 h MPS(Fe)-COOH: 1831 nm; 1‒20 mg∙L−1; 72 h | 与MPs相比，MPS(Fe) 对小球藻和大型蚤的急性毒性更高 | Zhang et al., |
| PSNPs+纳米Fe3O4 | 生菜 Lactuca sativa L. | PSNPs: 100 nm; 50 mg∙L−1; 21 d 纳米Fe3O4: 10 nm; 50 mg∙L−1; 21 d | PSNPs和纳米Fe3O4的联合暴露会引起更严重的氧化应激，增强对生菜根的损伤 | Gong et al., |
| Graphene-Fe3O4纳米复合材料 | 大肠杆菌 Escherichia coli 金黄色葡萄球菌 Staphylococcus aureus 神经母细胞瘤细胞 (N2A) | 20 nm; 50‒400 mg∙L−1; 48 h | 与纳米Fe3O4相比，Graphene-Fe3O4纳米复合材料对大肠杆菌、金黄色葡萄球菌和细胞的毒性作用更强 | Mahmoodabadi et al., |
| Graphene-Fe3O4纳米复合材料 | 斜生栅藻 Scenedesmus obliquus 莱氏衣藻 Chlamydomonas reinhardtii | 1057‒1344 nm; 0.2, 1 mg∙L−1; 96 h | 与rGO (Graphene) 相比, rGO纳米复合材料表面异质界面有助于其比表面积的变化, 导致生物体氧化应激损伤, 复合暴露下释放更多游离金属离子, 导致细胞致病甚至死亡 | Yin et al., |
| Fe3O4-SiO2纳米复合材料 | 欧洲鳗鱼 Anguilla anguilla | 100 nm; 2.5 mg∙L−1; 0, 2, 4, 8, 16, 24, 48, 72 h | Fe3O4-SiO2纳米复合材料会诱导欧洲鳗鱼大脑、肝细胞产生氧化应激 | Anjum et al., |
| Fe3O4-SiO2纳米复合材料 | pBR322 DNA | (1) (Fe3O4/CA)@SiO2: 20 nm; 0‒1650 mg∙L−1; 10 h (2) (Fe3O4/AA)@SiO2: 30 nm; 0‒520 mg∙L−1; 10 h | ≥330 mg∙L−1的 (1) 和≥260 mg∙L−1的 (2) 均增强了DNA损伤 | Zhang et al., |
表2 废碳粉所含颗粒新污染物的复合生态效应
Table 2 Compound ecological effects of particulate emerging contaminants in waste toner
| 新污染物 | 生物 | 处理 (尺寸; 浓度; 时间) | 研究结果 | 文献 |
|---|---|---|---|---|
| 纳米Fe3O4+PS MPs [MPS(Fe)] | 小球藻 Chlorella vulgaris 大型蚤Daphnia magna | MPS(Fe)-NH2: 1050 nm; 0.1‒1 mg∙L−1; 72 h MPS(Fe)-COOH: 1831 nm; 1‒20 mg∙L−1; 72 h | 与MPs相比，MPS(Fe) 对小球藻和大型蚤的急性毒性更高 | Zhang et al., |
| PSNPs+纳米Fe3O4 | 生菜 Lactuca sativa L. | PSNPs: 100 nm; 50 mg∙L−1; 21 d 纳米Fe3O4: 10 nm; 50 mg∙L−1; 21 d | PSNPs和纳米Fe3O4的联合暴露会引起更严重的氧化应激，增强对生菜根的损伤 | Gong et al., |
| Graphene-Fe3O4纳米复合材料 | 大肠杆菌 Escherichia coli 金黄色葡萄球菌 Staphylococcus aureus 神经母细胞瘤细胞 (N2A) | 20 nm; 50‒400 mg∙L−1; 48 h | 与纳米Fe3O4相比，Graphene-Fe3O4纳米复合材料对大肠杆菌、金黄色葡萄球菌和细胞的毒性作用更强 | Mahmoodabadi et al., |
| Graphene-Fe3O4纳米复合材料 | 斜生栅藻 Scenedesmus obliquus 莱氏衣藻 Chlamydomonas reinhardtii | 1057‒1344 nm; 0.2, 1 mg∙L−1; 96 h | 与rGO (Graphene) 相比, rGO纳米复合材料表面异质界面有助于其比表面积的变化, 导致生物体氧化应激损伤, 复合暴露下释放更多游离金属离子, 导致细胞致病甚至死亡 | Yin et al., |
| Fe3O4-SiO2纳米复合材料 | 欧洲鳗鱼 Anguilla anguilla | 100 nm; 2.5 mg∙L−1; 0, 2, 4, 8, 16, 24, 48, 72 h | Fe3O4-SiO2纳米复合材料会诱导欧洲鳗鱼大脑、肝细胞产生氧化应激 | Anjum et al., |
| Fe3O4-SiO2纳米复合材料 | pBR322 DNA | (1) (Fe3O4/CA)@SiO2: 20 nm; 0‒1650 mg∙L−1; 10 h (2) (Fe3O4/AA)@SiO2: 30 nm; 0‒520 mg∙L−1; 10 h | ≥330 mg∙L−1的 (1) 和≥260 mg∙L−1的 (2) 均增强了DNA损伤 | Zhang et al., |
| 新污染物 | 研究对象 | 处理 (尺寸; 浓度; 时间) | 研究结果 | 文献 | ||
|---|---|---|---|---|---|---|
| 纳米聚丙烯酸酯 | 制造工厂的工人 | 暴露于纳米聚丙烯酸酯的工人可能有呼吸系统疾病的风险 | Tiwari et al., | |||
| PS MNPs | 人肺泡上皮细胞A549、BEAS-2B | (1) 25, 70 nm; 0?300 mg∙L−1; 24 h (2) 1.67?2.17 μm; 1?1000 μg∙cm−2; 24, 48 h | PSNPs (≥25 mg∙L−1, 25 nm; ≥160 mg∙L−1, 70 nm) 和PSMPs (≥10 μg∙cm−2, 48 h; 1000?μg∙cm−2, 24 h) 会引起肺上皮细胞产生细胞毒性和炎症反应, 导致肺屏障功能障碍 | Xu et al., | ||
| 人鼻上皮细胞HNEpCs Sprague-Dawley雄性大鼠 | (1) 细胞: 20, 50,100, 200, 500, 1000, 2000 nm; 0, 10, 125, 500, 1250 mg∙L−1; 48 h (2) 大鼠: 20, 50, 200 nm; 125 mg∙L−1; 10, 20 d | (1) ≥125 mg∙L−1的PSNPs (20、500 nm) 会显著抑制细胞活力, 诱导细胞凋亡 (2) 大鼠鼻腔吸入PSNPs可能会干扰能量代谢并损害上呼吸道、肝脏和肾脏 | Huang et al., | |||
| 神经干细胞NSC | 50, 500 nm; 0?100 mg∙L−1; 25 d | 母体在妊娠期和哺乳期服用PSNPs (≥50 mg∙L−1) 改变了后代NSC、神经细胞组成和脑组织学的功能 | Jeong et al., | |||
| 人脐静脉内皮细胞HUVECs | 50 nm; 0, 5, 10, 15, 20, 25 mg∙L−1; 12, 24 h | NH2-PSNPs (20 mg∙L−1) 对HUVECs表现出较高的细胞毒性，使得细胞活力降低、ROS产生和线粒体膜电位降低 | Fu et al., | |||
| 人和小鼠 体外细胞 | 50, 500 nm; 0?100 mg∙L−1; 24 h | PSNPs和PSMPs (0－100 mg∙L−1) 均没有急性细胞毒性和遗传毒性, 仅具有弱胚胎毒性 | Hesler et al., | |||
| Wistar雄性大鼠 | 25, 50 nm; 0, 1, 3, 6, 10 mg∙kg−1∙d−1; 5 weeks | PSNPs (≥3 mg∙kg−1∙d−1 bw) 会诱导大鼠肾毒性和肾损伤, 引起大鼠甲状腺内分泌紊乱以及代谢缺陷 | Amereh et al., | |||
| C57BL/6、 ICR小鼠 | (1) 5 μm; 0, 100, 1000 μg∙L−1; 6 weeks (2) 0.5, 5 μm; 0, 100, 1000 μg∙L−1; 12 weeks (3) 50, 500 nm; 0?1000 μg∙d−1; 11 weeks (4) 100, 1000 nm; 1 mg∙d−1; 17d | (1) PSMPs (1 mg∙L−1) 改变肠道微生物组, 引起肠屏障功能障碍和代谢紊乱, 引发心脏代谢疾病 (2) PS MNPs (≥500 μg∙d−1) 大脑功能障碍和认知障碍 (3) PS MNPs (1 mg∙d−1) 可穿过血胎盘屏障渗入胎儿丘脑, 对胎儿产生负面影响 | Jin et al., | |||
| 纳米Fe3O4 | RAW巨噬细胞 | 0, 10, 25, 50, 100, 125, 250 mg∙L−1; 37 h | 纳米Fe3O4 (10?250 mg∙L−1) 表现出明显的细胞毒性 | Raguraman et al., | ||
| 人上皮A549肺细胞 | (1) 60?100 nm; 0, 1, 10, 100 mg∙L−1; 24 h (2) ≤100 nm; 0, 10, 50, 100, 250 mg∙L−1; 24,72 h | 纳米Fe3O4 (≥100 mg∙L−1)会产生细胞毒性, 导致肺细胞活性降低、ROS升高、细胞膜电位降低、凋亡率降低、抗氧化能力降低、DNA氧化损伤增加 | Watanabe et al., | |||
| 人中枢神经系统细胞(D384和SH-SY5Y) | 短期: 0?100 mg∙L−1; 4, 24, 48 h 长期: 0?10 mg∙L−1; 2?10 d | 纳米Fe3O4会诱导人中枢神经系统细胞 (D384: 25 mg∙L−1, 4 h、1 mg∙L−1, 48 h、0.05 mg∙L−1, 10 d; SH-SY5Y: 10 mg∙L−1, 48 h) 产生细胞毒性, 影响细胞增殖能力, 损害中枢神经系统的正常功能 | Coccini et al., | |||
| 人脐静脉内皮细胞HUVECs | 10 nm; 0?400 mg∙L−1; 3?24 h | 纳米Fe3O4 (≥100 mg∙L−1, 24 h) 干扰了HUVECs的自噬过程, 最终导致内皮功能障碍和炎症 | Zhang et al., | |||
| LA-9纤维细胞 | 30 nm; 0, 50, 100, 250 mg∙L−1; 24, 48, 72 h | 高质量浓度 (250 mg∙L−1) 的纳米Fe3O4会表现出细胞毒性 | Alves Feitosa et al., | |||
| Fischer 344大鼠 | 0, 0.2, 1, 5 mg∙kg−1; 52 weeks | 纳米Fe3O4会引起大鼠肺部的慢性炎症反应, 高剂量的暴露 (5 mg∙kg−1) 还会引起肺泡增生 | Tada et al., | |||
| Wistar大鼠 | 60 nm; 0, 25, 50, 100 mg∙kg−1; 20 d | 纳米Fe3O4 (25?100 mg∙kg−1) 会使得大鼠染色体畸变、微核形成和DNA损伤, 从而诱导遗传毒性 | Ansari et al., | |||
| 纳米 SiO2 | 人脐静脉内皮细胞HUVECs | 62 nm; 0, 25, 50, 75, 100 mg∙L−1; 24 h | 纳米SiO2 (≥50 mg∙L−1) 诱导细胞毒性、氧化应激和细胞凋亡，造成内皮细胞功能障碍 | Duan et al., | ||
| 人肺A549细胞 | 2?10 nm; 0, 2, 10, 50, 100 mg∙L−1; 24, 72 h | 纳米SiO2 (≥10 mg∙L−1) 对A549细胞有细胞毒性, 导致细胞存活率降低, 线粒体膜电位降低, ROS生成增加, 具有浓度时间依赖性 | Rafieepour et al., | |||
| 人支气管 上皮细胞 | 16 nm; 0, 12.5, 25 mg∙L−1; 6 h | 高剂量纳米SiO2 (25 mg∙L−1) 暴露表现出低细胞毒性和代谢物变化 | Cui et al., | |||
| 肝细胞L-02 | 58 nm; 0, 6.25, 12.5, 25, 50, 100 mg∙L−1; 24 h | 纳米SiO2 (≥25 mg∙L−1) 引起代谢功能障碍, 加剧氧化应激并导致肝损伤, 产生肝毒性 | Zhu et al., | |||
| Caco-2和HT29-MTX共培养物的体外模型 | 20?30 nm; 0, 2×10−4, 0.02, 2 mg∙L−1; 4 h, 5 d | 纳米SiO2 (≥0.02 mg∙L−1) 减少了肠道对营养物质的吸收, 改变了营养转运蛋白的表达水平, 并启动了促炎信号传导 | Guo et al., | |||
| 巨噬细胞系RAW264.7 | 30 nm; 0?20 mg∙L−1; 1, 4 d | 纳米SiO2 (20 mg∙L−1, 24 h；5 mg∙L−1, 4 d) 暴露会引起巨噬细胞反应的改变 | Torres et al., | |||
| Wistar 雄性大鼠 | (1) 10?20 nm; 0, 40, 80 mg∙L−1; 30 d (2) 7, 670 nm; 0?1000 mg∙L−1; 24 h (3) 57 nm; 0, 2, 5, 10 mg∙kg−1; 16 d | (1) 纳米SiO2 (80 mg∙L−1) 会导致大鼠气道高反应性 (AHR) 和气道重塑，使其肺功能受损 (2) 纳米SiO2 (99.5 mg∙L−1) 导致线粒体功能障碍和低能量状态, 诱导心脏毒性 (3) 纳米SiO2 (≥2 mg∙kg−1) 促进高脂肪饮食处理的大鼠的生殖毒性 | Han et al., | |||
| 新污染物 | 研究对象 | 处理 (尺寸; 浓度; 时间) | 研究结果 | 文献 | ||
| 纳米 SiO2 | BALB/c 小鼠 | (1) 70, 300, 1000 nm; 0.8 mg∙pcs−1; 18 d (2) 10?30 nm; 225, 1000, 5000 mg∙kg−1; 28, 84 d | (1) 纳米SiO2 (0.8 mg∙pcs−1)会引起雌性小鼠妊娠并发症 (2) 纳米SiO2 (225 mg∙kg−1) 诱发了小鼠肝脂肪变性、DNA甲基化, 可能会导致脂质代谢紊乱和癌症发展 | Yamashita et al., | ||
| ICR 雄性小鼠 | ≤100 nm; 0?300 mg∙kg−1; 12 d | 纳米SiO2 (300 mg∙kg−1) 会对肠道造成炎症损伤, 导致肠道微生物群的变化 | Yan et al., | |||
| L5178Y/Tk+/−-3.7.2C小鼠淋巴瘤细胞 | 7.172, 7.652 nm; 0?150 mg∙L−1; 12 d | 高质量浓度的纳米SiO2 (≥100 mg∙L−1) 会诱导染色体突变 | Demir et al., | |||
| C57BL/6 J雄性小鼠、Wistar雄性大鼠 | (1) 14?40 nm; 3 g∙kg−1; 28 d (2) 80 nm; 0.15 mg∙ pcs −1; 15, 90 d | 纳米SiO2诱导鼠神经行为障碍和脑损伤 | Parveen et al., | |||
| 纳米炭 | Sprague-Dawley 大鼠 | (1) 14 nm; 9 mg∙m−3; 13 weeks (2) 83.3?87.9 nm; 0?4.2×106 pc∙cm−3; 4 weeks | 纳米炭黑对大鼠具有轻度呼吸毒性和肺部炎症, 但未损害肺组织, 对血液功能也无影响 | Kim et al., | ||
| BALB/c 小鼠嗅球 | 14 nm; 250 μg∙L−1; 11 h | 纳米炭黑可以调节细胞外氨基酸神经递质水平和促炎细胞因子来影响小鼠嗅球细胞 | Win-Shwe et al., | |||
表3 废碳粉所含颗粒新污染物的人体健康效应
Table 3 Human health effects of particulate emerging contaminants in waste toner
| 新污染物 | 研究对象 | 处理 (尺寸; 浓度; 时间) | 研究结果 | 文献 | ||
|---|---|---|---|---|---|---|
| 纳米聚丙烯酸酯 | 制造工厂的工人 | 暴露于纳米聚丙烯酸酯的工人可能有呼吸系统疾病的风险 | Tiwari et al., | |||
| PS MNPs | 人肺泡上皮细胞A549、BEAS-2B | (1) 25, 70 nm; 0?300 mg∙L−1; 24 h (2) 1.67?2.17 μm; 1?1000 μg∙cm−2; 24, 48 h | PSNPs (≥25 mg∙L−1, 25 nm; ≥160 mg∙L−1, 70 nm) 和PSMPs (≥10 μg∙cm−2, 48 h; 1000?μg∙cm−2, 24 h) 会引起肺上皮细胞产生细胞毒性和炎症反应, 导致肺屏障功能障碍 | Xu et al., | ||
| 人鼻上皮细胞HNEpCs Sprague-Dawley雄性大鼠 | (1) 细胞: 20, 50,100, 200, 500, 1000, 2000 nm; 0, 10, 125, 500, 1250 mg∙L−1; 48 h (2) 大鼠: 20, 50, 200 nm; 125 mg∙L−1; 10, 20 d | (1) ≥125 mg∙L−1的PSNPs (20、500 nm) 会显著抑制细胞活力, 诱导细胞凋亡 (2) 大鼠鼻腔吸入PSNPs可能会干扰能量代谢并损害上呼吸道、肝脏和肾脏 | Huang et al., | |||
| 神经干细胞NSC | 50, 500 nm; 0?100 mg∙L−1; 25 d | 母体在妊娠期和哺乳期服用PSNPs (≥50 mg∙L−1) 改变了后代NSC、神经细胞组成和脑组织学的功能 | Jeong et al., | |||
| 人脐静脉内皮细胞HUVECs | 50 nm; 0, 5, 10, 15, 20, 25 mg∙L−1; 12, 24 h | NH2-PSNPs (20 mg∙L−1) 对HUVECs表现出较高的细胞毒性，使得细胞活力降低、ROS产生和线粒体膜电位降低 | Fu et al., | |||
| 人和小鼠 体外细胞 | 50, 500 nm; 0?100 mg∙L−1; 24 h | PSNPs和PSMPs (0－100 mg∙L−1) 均没有急性细胞毒性和遗传毒性, 仅具有弱胚胎毒性 | Hesler et al., | |||
| Wistar雄性大鼠 | 25, 50 nm; 0, 1, 3, 6, 10 mg∙kg−1∙d−1; 5 weeks | PSNPs (≥3 mg∙kg−1∙d−1 bw) 会诱导大鼠肾毒性和肾损伤, 引起大鼠甲状腺内分泌紊乱以及代谢缺陷 | Amereh et al., | |||
| C57BL/6、 ICR小鼠 | (1) 5 μm; 0, 100, 1000 μg∙L−1; 6 weeks (2) 0.5, 5 μm; 0, 100, 1000 μg∙L−1; 12 weeks (3) 50, 500 nm; 0?1000 μg∙d−1; 11 weeks (4) 100, 1000 nm; 1 mg∙d−1; 17d | (1) PSMPs (1 mg∙L−1) 改变肠道微生物组, 引起肠屏障功能障碍和代谢紊乱, 引发心脏代谢疾病 (2) PS MNPs (≥500 μg∙d−1) 大脑功能障碍和认知障碍 (3) PS MNPs (1 mg∙d−1) 可穿过血胎盘屏障渗入胎儿丘脑, 对胎儿产生负面影响 | Jin et al., | |||
| 纳米Fe3O4 | RAW巨噬细胞 | 0, 10, 25, 50, 100, 125, 250 mg∙L−1; 37 h | 纳米Fe3O4 (10?250 mg∙L−1) 表现出明显的细胞毒性 | Raguraman et al., | ||
| 人上皮A549肺细胞 | (1) 60?100 nm; 0, 1, 10, 100 mg∙L−1; 24 h (2) ≤100 nm; 0, 10, 50, 100, 250 mg∙L−1; 24,72 h | 纳米Fe3O4 (≥100 mg∙L−1)会产生细胞毒性, 导致肺细胞活性降低、ROS升高、细胞膜电位降低、凋亡率降低、抗氧化能力降低、DNA氧化损伤增加 | Watanabe et al., | |||
| 人中枢神经系统细胞(D384和SH-SY5Y) | 短期: 0?100 mg∙L−1; 4, 24, 48 h 长期: 0?10 mg∙L−1; 2?10 d | 纳米Fe3O4会诱导人中枢神经系统细胞 (D384: 25 mg∙L−1, 4 h、1 mg∙L−1, 48 h、0.05 mg∙L−1, 10 d; SH-SY5Y: 10 mg∙L−1, 48 h) 产生细胞毒性, 影响细胞增殖能力, 损害中枢神经系统的正常功能 | Coccini et al., | |||
| 人脐静脉内皮细胞HUVECs | 10 nm; 0?400 mg∙L−1; 3?24 h | 纳米Fe3O4 (≥100 mg∙L−1, 24 h) 干扰了HUVECs的自噬过程, 最终导致内皮功能障碍和炎症 | Zhang et al., | |||
| LA-9纤维细胞 | 30 nm; 0, 50, 100, 250 mg∙L−1; 24, 48, 72 h | 高质量浓度 (250 mg∙L−1) 的纳米Fe3O4会表现出细胞毒性 | Alves Feitosa et al., | |||
| Fischer 344大鼠 | 0, 0.2, 1, 5 mg∙kg−1; 52 weeks | 纳米Fe3O4会引起大鼠肺部的慢性炎症反应, 高剂量的暴露 (5 mg∙kg−1) 还会引起肺泡增生 | Tada et al., | |||
| Wistar大鼠 | 60 nm; 0, 25, 50, 100 mg∙kg−1; 20 d | 纳米Fe3O4 (25?100 mg∙kg−1) 会使得大鼠染色体畸变、微核形成和DNA损伤, 从而诱导遗传毒性 | Ansari et al., | |||
| 纳米 SiO2 | 人脐静脉内皮细胞HUVECs | 62 nm; 0, 25, 50, 75, 100 mg∙L−1; 24 h | 纳米SiO2 (≥50 mg∙L−1) 诱导细胞毒性、氧化应激和细胞凋亡，造成内皮细胞功能障碍 | Duan et al., | ||
| 人肺A549细胞 | 2?10 nm; 0, 2, 10, 50, 100 mg∙L−1; 24, 72 h | 纳米SiO2 (≥10 mg∙L−1) 对A549细胞有细胞毒性, 导致细胞存活率降低, 线粒体膜电位降低, ROS生成增加, 具有浓度时间依赖性 | Rafieepour et al., | |||
| 人支气管 上皮细胞 | 16 nm; 0, 12.5, 25 mg∙L−1; 6 h | 高剂量纳米SiO2 (25 mg∙L−1) 暴露表现出低细胞毒性和代谢物变化 | Cui et al., | |||
| 肝细胞L-02 | 58 nm; 0, 6.25, 12.5, 25, 50, 100 mg∙L−1; 24 h | 纳米SiO2 (≥25 mg∙L−1) 引起代谢功能障碍, 加剧氧化应激并导致肝损伤, 产生肝毒性 | Zhu et al., | |||
| Caco-2和HT29-MTX共培养物的体外模型 | 20?30 nm; 0, 2×10−4, 0.02, 2 mg∙L−1; 4 h, 5 d | 纳米SiO2 (≥0.02 mg∙L−1) 减少了肠道对营养物质的吸收, 改变了营养转运蛋白的表达水平, 并启动了促炎信号传导 | Guo et al., | |||
| 巨噬细胞系RAW264.7 | 30 nm; 0?20 mg∙L−1; 1, 4 d | 纳米SiO2 (20 mg∙L−1, 24 h；5 mg∙L−1, 4 d) 暴露会引起巨噬细胞反应的改变 | Torres et al., | |||
| Wistar 雄性大鼠 | (1) 10?20 nm; 0, 40, 80 mg∙L−1; 30 d (2) 7, 670 nm; 0?1000 mg∙L−1; 24 h (3) 57 nm; 0, 2, 5, 10 mg∙kg−1; 16 d | (1) 纳米SiO2 (80 mg∙L−1) 会导致大鼠气道高反应性 (AHR) 和气道重塑，使其肺功能受损 (2) 纳米SiO2 (99.5 mg∙L−1) 导致线粒体功能障碍和低能量状态, 诱导心脏毒性 (3) 纳米SiO2 (≥2 mg∙kg−1) 促进高脂肪饮食处理的大鼠的生殖毒性 | Han et al., | |||
| 新污染物 | 研究对象 | 处理 (尺寸; 浓度; 时间) | 研究结果 | 文献 | ||
| 纳米 SiO2 | BALB/c 小鼠 | (1) 70, 300, 1000 nm; 0.8 mg∙pcs−1; 18 d (2) 10?30 nm; 225, 1000, 5000 mg∙kg−1; 28, 84 d | (1) 纳米SiO2 (0.8 mg∙pcs−1)会引起雌性小鼠妊娠并发症 (2) 纳米SiO2 (225 mg∙kg−1) 诱发了小鼠肝脂肪变性、DNA甲基化, 可能会导致脂质代谢紊乱和癌症发展 | Yamashita et al., | ||
| ICR 雄性小鼠 | ≤100 nm; 0?300 mg∙kg−1; 12 d | 纳米SiO2 (300 mg∙kg−1) 会对肠道造成炎症损伤, 导致肠道微生物群的变化 | Yan et al., | |||
| L5178Y/Tk+/−-3.7.2C小鼠淋巴瘤细胞 | 7.172, 7.652 nm; 0?150 mg∙L−1; 12 d | 高质量浓度的纳米SiO2 (≥100 mg∙L−1) 会诱导染色体突变 | Demir et al., | |||
| C57BL/6 J雄性小鼠、Wistar雄性大鼠 | (1) 14?40 nm; 3 g∙kg−1; 28 d (2) 80 nm; 0.15 mg∙ pcs −1; 15, 90 d | 纳米SiO2诱导鼠神经行为障碍和脑损伤 | Parveen et al., | |||
| 纳米炭 | Sprague-Dawley 大鼠 | (1) 14 nm; 9 mg∙m−3; 13 weeks (2) 83.3?87.9 nm; 0?4.2×106 pc∙cm−3; 4 weeks | 纳米炭黑对大鼠具有轻度呼吸毒性和肺部炎症, 但未损害肺组织, 对血液功能也无影响 | Kim et al., | ||
| BALB/c 小鼠嗅球 | 14 nm; 250 μg∙L−1; 11 h | 纳米炭黑可以调节细胞外氨基酸神经递质水平和促炎细胞因子来影响小鼠嗅球细胞 | Win-Shwe et al., | |||
图3 废碳粉的回收利用技术
Figure 3 Recycling technology of waste toner
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