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药品及个人护理产品(pharmaceutical and personal care products,简称PPCPs)污染正受到越来越多的关注[1]。因其组分具有较强的生物活性、极性和旋光性,PPCPs在环境介质中的迁移转化行为会给环境和人类健康带来潜在风险[2-3]。作为一类重要的PPCPs,β受体阻断剂主要用于人类高血压、心肌梗塞、心律不齐、心力衰竭、婴儿血管瘤和其他心血管疾病的治疗[4-5]。人体对该类药物的不完全吸收以及动物体对该类药物的不完全代谢,使其随着生物体排泄等方式进入到废水中,最终进入城市污水处理厂。但是,目前污水处理厂不能完全去除这些污染物[6-7]。因此,β受体阻断剂就不可避免地进入到自然水体和土壤环境中[8]。研究表明,β受体阻断剂会干扰藻类的光合作用,并影响一些脊椎动物或无脊椎动物的心率[9-11]。因此,研究β受体阻断剂在自然环境中的迁移转化行为十分重要。
针铁矿(goethite,简称Goe)是自然界中广泛存在的一种铁氧化物,常见于土壤、海洋、河流湖泊及沉积物中。之前研究表明,针铁矿对环境中的重金属[12-14]和药物及个人护理产品[15-16]有较强的吸附能力。目前,关于针铁矿对β受体阻断剂吸附的研究鲜有报道。微塑料(microplastics,简称Mps)是环境中常见的外来颗粒污染物,因其具有难降解、粒径小、比表面积大和分布广的特性,可以将环境中污染物吸附并富集在其表面上,对环境中污染物的迁移行为产生影响[17]。目前已有很多学者研究了微塑料对重金属及抗生素类药物的吸附[18-20],同时也有一些文献报道了微塑料对β受体阻断剂的吸附。例如, Razanajatovo等[21]在24 ℃避光条件下研究了聚乙烯微塑料对包括普萘洛尔在内的3种药物的吸附和解吸,实验结果表明,普萘洛尔的吸附率为21.61%。Puckowski等[22]在21 ℃黑暗的玻璃管中水平旋转搅拌24 h研究了4种不同类型的微塑料对9种药物的吸附,实验结果证明微塑料对普萘洛尔的吸附系数最大为2.4 L·kg−1。微塑料对β受体阻断剂的吸附作用很有可能会影响β受体阻断剂在针铁矿上的吸附行为。然而,目前关于微塑料对β受体阻断剂在针铁矿上吸附行为的影响研究尚鲜见报道。
本文以针铁矿、微塑料(聚氯乙烯微塑料)为吸附剂,以β受体阻断剂(普萘洛尔)为吸附质,通过批量吸附实验,考察了微塑料、针铁矿及微塑料共存时针铁矿对普萘洛尔的吸附动力学、吸附等温线,探讨了影响吸附的主要因素如pH、离子强度及腐殖酸,以确定微塑料对β受体阻断剂在针铁矿上吸附的影响。
微塑料对普萘洛尔在针铁矿上吸附的影响
Effect of microplastics on the adsorption of propranolol on goethite
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摘要: 本实验研究了微塑料对新兴污染物普萘洛尔在针铁矿上吸附行为的影响,探讨了针铁矿、微塑料及微塑料共存时针铁矿对普萘洛尔的吸附动力学、吸附等温线,考察了pH、腐殖酸浓度、离子强度对普萘洛尔吸附行为的影响。结果表明,普萘洛尔在3种吸附剂上的吸附动力学均符合伪二阶动力学模型,吸附等温线均符合Langmuir等温吸附模型。对比发现,普萘洛尔的吸附效率顺序为微塑料>微塑料+针铁矿>针铁矿。溶液pH值在2—6时,微塑料对普萘洛尔在针铁矿上吸附的影响较弱,当溶液pH值大于6时,微塑料能显著影响普萘洛尔在针铁矿上吸附。普萘洛尔在3种吸附剂上的吸附量随着腐殖酸浓度的增加而增加,且对普萘洛尔在针铁矿上吸附的促进作用最强。同时,Ca2+的加入对普萘洛尔的吸附抑制较强。本文的研究结果可为全面认识微塑料共存时污染物在环境中的迁移行为提供基础数据。Abstract: This study focused on investigating the influence of microplastics on the adsorption behavior of the emerging pollutant propranolol on goethite. The adsorption kinetics and isotherms of propranolol on goethite, microplastics, and their mixed adsorbents were studied respectively. Besides, the effects of pH, humic acid concentration, and ionic strength on the adsorption efficiency of propranolol were also investigated. Results indicated that the pseudo-second-order model and Langmuir isotherm model fitted the adsorption process well. Moreover, the adsorption efficiency order of propranolol follows microplastics > microplastics + goethite > goethite. Furthermore, compared with the pH range of 2—6, a pH higher than six was more helpful for the adsorption of propranolol on goethite by microplastics. In addition, the adsorption efficiency of propranolol in the above three adsorbents was all promoted with the addition of humic acid, and the goethite exhibited the best. Meanwhile, the adsorption efficiency of propranolol was hampered in the presence of cation, especially for the addition of Ca2+. This study provided basic data for a comprehensively understanding of the migration behavior of propranolol in the environment when microplastics coexist.
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Key words:
- propranolol /
- goethite /
- microplastics /
- adsorption /
- interaction
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表 1 普萘洛尔在3种吸附剂上的吸附动力学参数
Table 1. Adsorption kinetic parameters of propranolol on three adsorbents
吸附剂
Sorbent伪一阶动力学模型
Pseudo-first-order equation伪二阶动力学模型
Pseudo-second-order equationK1/(L·min−1) qe/(mg·g−1) R2 K2/(g·(g·min)−1) qe/(mg·g−1) R2 针铁矿 0.0872 0.2504 0.7371 0.8981 0.2532 0.8524 微塑料 0.0720 1.3564 0.7675 0.1262 1.3754 0.9924 针铁矿+微塑料 0.0936 1.1325 0.7246 0.2211 1.1440 0.9686 表 2 普萘洛尔在3种吸附剂上的吸附等温线参数
Table 2. Adsorption isotherm parameters of propranolol on three adsorbents
吸附剂
SorbentLangmuir Freundlich KL/(L·mg−1) qm/(mg·g−1) R2 KF/ (mg·g−1) n R2 针铁矿 0.1817 0.5124 0.9970 0.1746 3.9432 0.9469 微塑料 0.2325 2.6838 0.9933 0.7480 2.9700 0.9659 针铁矿+微塑料 0.3813 0.9203 0.9835 0.3770 4.3159 0.9164 -
[1] ZHAO X, ZHENG Y, HU S, et al. Improving urban drainage systems to mitigate PPCPs pollution in surface water: A watershed perspective [J]. Journal of Hazardous Materials, 2021, 411: 125047. doi: 10.1016/j.jhazmat.2021.125047 [2] LI L, ZHAO X L, LIU D, et al. Occurrence and ecological risk assessment of PPCPs in typical inflow rivers of Taihu lake, China [J]. Journal of Environmental Management, 2021, 285: 112176. doi: 10.1016/j.jenvman.2021.112176 [3] HAMID N, JUNAID M, WANG Y, et al. Chronic exposure to PPCPs mixture at environmentally relevant concentrations (ERCs) altered carbohydrate and lipid metabolism through gut and liver toxicity in zebrafish [J]. Environmental Pollution, 2021, 273: 116494. doi: 10.1016/j.envpol.2021.116494 [4] 邓月华. 改性凹凸棒土吸附去除水中铅离子、心得安及溶解性有机物[D]. 南京: 南京大学, 2012. DENG Y H. Adsorption and removal of lead ion, propranolol and dissolved organic matter in water by modified attapulgite [D]. Nanjing: Nanjing University, 2012(in Chinese).
[5] NIE W J, LI Y N, CHEN L Y, et al. Interaction between multi-walled carbon nanotubes and propranolol [J]. Scientific Reports, 2020, 10(1): 1025-1029. doi: 10.1038/s41598-020-57894-y [6] KUMAR R, SARMAH A K, PADHYE L P. Fate of pharmaceuticals and personal care products in a wastewater treatment plant with parallel secondary wastewater treatment train [J]. Journal of Environmental Management, 2019, 233: 649-659. [7] VALDES M E, AME M V, BISTONI M D L A, et al. Occurrence and bioaccumulation of pharmaceuticals in a fish species inhabiting the Suquía River basin (Córdoba, Argentina) [J]. Science of The Total Environment, 2014, 472: 389-396. doi: 10.1016/j.scitotenv.2013.10.124 [8] BARBIERI M, LICHA T, NOEDLER K, et al. Fate of β-blockers in aquifer material under nitrate reducing conditions: batch experiments [J]. Chemosphere, 2012, 89(11): 1272-1277. doi: 10.1016/j.chemosphere.2012.05.019 [9] MADUREIRA T V, ROCHA M J, CRUZEIRO C, et al. The toxicity potential of pharmaceuticals found in the Douro River estuary (Portugal): Evaluation of impacts on fish liver, by histopathology, stereology, vitellogenin and CYP1A immunohistochemistry, after sub-acute exposures of the zebrafish model [J]. Environmental Toxicology & Pharmacology, 2012, 34(1): 34-45. [10] VIENO N M, TUHKANEN T, KRONBERG L. Analysis of neutral and basic pharmaceuticals in sewage treatment plants and in recipient rivers using solid phase extraction and liquid chromatography-tandem mass spectrometry detection [J]. Journal of Chromatography A, 2006, 1134(12): 101-111. [11] STANLEY J K, RAMIREZ A J, MOTTALEB M, et al. Enantiospecific toxicity of the beta-blocker propranolol to Daphnia magna and Pimephales promelas [J]. Environmental Toxicology & Chemistry, 2006, 25(7): 1780-1786. [12] DASH B, DASH B, RATH S S. A thorough understanding of the adsorption of Ni (Ⅱ), Cd (Ⅱ) and Zn (Ⅱ) on goethite using experiments and molecular dynamics simulation [J]. Separation and Purification Technology, 2020, 240: 1-14. [13] 尹雪斐, 杨蕊嘉, 刘玉玲, 等. Cd(Ⅱ)与As(Ⅴ)在土壤铁氧化物和细菌表面上的共吸附研究 [J]. 生态环境学报, 2021, 30(03): 614-620. YIN X F, YANG R J, LIU Y L, et al. CO adsorption of CD (Ⅱ) and as (Ⅴ) on soil iron oxides and bacterial surfaces [J]. Journal of ecological environment, 2021, 30(03): 614-620(in Chinese).
[14] ZHAO Y, LIU F, QIN X P. Adsorption of diclofenac onto goethite: Adsorption kinetics and effects of pH [J]. Chemosphere, 2017, 180: 373-378. doi: 10.1016/j.chemosphere.2017.04.007 [15] FILEP T, SZABOÓ L, KONDOR A C, et al. Evaluation of the effect of the intrinsic chemical properties of pharmaceutically active compounds (PhACs) on sorption behaviour in soils and goethite [J]. Ecotoxicology and Environmental Safety, 2021, 215: 112120. doi: 10.1016/j.ecoenv.2021.112120 [16] LI J C, ZHAO L, ZHANG R C, et al. Transformation of tetracycline antibiotics with goethite: Mechanism, kinetic modeling and toxicity evaluation [J]. Water Research, 2021, 199: 117196. doi: 10.1016/j.watres.2021.117196 [17] ALIMI O S, BUARZ J F, HERNANDEZ L M, et al. Microplastics and Nanoplastics in Aquatic Environments: Aggregation, Deposition, and Enhanced Contaminant Transport [J]. Environmental Science & Technology, 2018, 52(4): 1704-1724. [18] GUO X T, HU G L, FAN X Y, et al. Sorption properties of cadmium on microplastics: The common practice experiment and A two-dimensional correlation spectroscopic study [J]. Ecotoxicology and Environmental Safety, 2020, 190: 110118. doi: 10.1016/j.ecoenv.2019.110118 [19] YU F, YANG C F, HUANG G Q, et al. Interfacial interaction between diverse microplastics and tetracycline by adsorption in an aqueous solution [J]. Science of the Total Environment, 2020, 721: 13772-13779. [20] HUANG D F, XU Y B, YU X Q, et al. Effect of cadmium on the sorption of tylosin by polystyrene microplastics [J]. Ecotoxicology and Environmental Safety, 2021, 207: 111255. doi: 10.1016/j.ecoenv.2020.111255 [21] RAZANAJATOVO R M, DING J N, ZHANG S S, et al. Sorption and desorption of selected pharmaceuticals by polyethylene microplastics [J]. Marine Pollution Bulletin, 2018, 136: 516-523. doi: 10.1016/j.marpolbul.2018.09.048 [22] PUCKOWSKI A, CWIĘK W, MIODUSZEWSKA K, et al. Sorption of pharmaceuticals on the surface of microplastics [J]. Chemosphere, 2021, 263: 127976. doi: 10.1016/j.chemosphere.2020.127976 [23] 郭学涛. 针铁矿/腐殖酸对典型抗生素的吸附及光解机理研究[D]. 广州: 华南理工大学, 2014. GUO X T. Study on adsorption and photolysis mechanism of goethite / humic acid on Typical Antibiotics [D]. Guangzhou: South China University of Technology, 2014(in Chinese).
[24] DENGG Y H, LI Y N, NIE W J, et al. Fast removal of propranolol from water by attapulgite/graphene oxide magnetic ternary composites [J]. Materials, 2019, 12(6): 924. doi: 10.3390/ma12060924 [25] LUO Y Y, ZHANG Y Y, XU Y B, et al. Distribution characteristics and mechanism of microplastics mediated by soil physicochemical properties [J]. Science of the Total Environment, 2020, 726: 138389. doi: 10.1016/j.scitotenv.2020.138389 [26] 邓月华, 王文姬, 贺艳, 等. 普萘洛尔在太湖沉积物上的吸附特征 [J]. 环境化学, 2021, 40(1): 263-271. doi: 10.7524/j.issn.0254-6108.2020060104 DENG Y H, WANG W J, HE Y, et al. Adsorption of propranolol on Taihu Lake sediments [J]. Environmental Chemistry, 2021, 40(1): 263-271(in Chinese). doi: 10.7524/j.issn.0254-6108.2020060104
[27] LEUNG K, CRISCENTI L J. Lead and selenite adsorption at water–goethite interfaces from first principles [J]. Journal of Physics:Condensed Matter, 2017, 29(36): 365101. doi: 10.1088/1361-648X/aa7e4f [28] ZHANG Y, LUO Y, GUO X, et al. Charge mediated interaction of polystyrene nanoplastic (PSNP) with minerals in aqueous phase [J]. Water Research, 2020, 178: 115861. doi: 10.1016/j.watres.2020.115861 [29] WANG L, LI Y T, WENG L P, et al. Using chromatographic and spectroscopic parameters to characterize preference and kinetics in the adsorption of humic and fulvic acid to goethite [J]. Science of the Total Environment, 2019, 666: 766-777. doi: 10.1016/j.scitotenv.2019.02.235 [30] CHIANESE S, FENTI A, IOVINO P, et al. Sorption of organic pollutants by humic acids: A review [J]. Molecules, 2020, 25(4): 918. doi: 10.3390/molecules25040918 [31] 许佳瑶, 孙红文, 汪磊. β-受体阻断剂在粘土上的吸附行为 [J]. 环境化学, 2013, 32(11): 2109-2114. doi: 10.7524/j.issn.0254-6108.2013.11.013 XU J Y, SUN H W, WANG L. Adsorption behavior of β-receptor blocker on clay [J]. Environmental Chemistry, 2013, 32(11): 2109-2114(in Chinese). doi: 10.7524/j.issn.0254-6108.2013.11.013