微塑料吸附机制研究进展

陈雅兰; 孙可; 高博

doi:10.7524/j.issn.0254-6108.2021031204

微塑料吸附机制研究进展

1.
北京师范大学环境学院水环境模拟国家重点实验室，北京， 100875
2.
中国水利水电科学研究院流域水循环模拟与调控国家重点实验室，北京，100038

通讯作者: Tel：010-58807493，E-mail：sunke@bnu.edu.cn;

基金项目:
国家自然科学基金（41977299），北京市自然科学基金（JQ19033）和流域水循环模拟与调控国家重点实验室自主研究课题（SKL2020ZY02）资助

Sorption behavior, mechanisms, and models of organic pollutants and metals on microplastics: A review

1.
State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, Beijing, 100875, China
2.
State Key Laboratory of Simulation and Regulation of Water Cycle in River Basin, China Institute of Water Resources and Hydropower Research, Beijing, 100038, China

Corresponding author: SUN Ke, sunke@bnu.edu.cn ;

Fund Project: the National Natural Science Foundation of China (41977299), Beijing Natural Science Foundation (JQ19033) and Open Research Fund of State Key Laboratory of Simulation and Regulation of Water Cycle in River Basin (SKL2020ZY02)

摘要:
微塑料（MPs）广泛存在于土壤和水体环境中，可以充当载体影响污染物的二次释放和生物毒性，对生态环境造成巨大威胁。了解MPs的吸附机制有助于明确MPs对污染物的富集能力和潜在环境风险。本研究总结了MPs与亲水、疏水和重金属污染物之间相互作用机制，探讨了MPs性质、老化过程及环境因素对MPs吸附行为的影响，剖析了现阶段吸附模型及预测模型的发展现状，并针对现阶段研究的不足和未来的研究方向提出展望。本研究认为，MPs与污染物的相互作用机制主要包括疏水、静电、π-π和氢键相互作用；污染物和MPs性质、老化作用和环境因素会影响MPs的吸附行为；混合阶动力学模型、现象动力学模型以及预测模型的发展有助于明晰和快速预测MPs的吸附机制；今后的研究应更加关注复合污染物与MPs的相互作用机制、老化对MPs吸附的影响机制以及MPs吸附和预测模型的应用和开发。
- 微塑料 /
- 吸附 /
- 复合污染 /
- 影响因素 /
- 老化 /
- 预测模型
Abstract:
Microplastics (MPs) are widely distributed in different environmental media and have raised extensive attention as good vectors for pollutants. MPs can either act as secondary sources of adsorbed pollutants to ambient environment or pose joint biological toxicity with carried contaminants. Investigations on sorption behavior and mechanisms of contaminants to MPs help to clarify MPs ability to enrich pollutants and their potential environmental risks. In this study, the interaction mechanisms between MPs and hydrophilic organic contaminants, hydrophobic organic contaminants and heavy metals were summarized. Besides, the effects of MPs properties, aging process and environmental factors on the adsorption behavior of MPs were discussed. Moreover, the development status of the current adsorption and prediction models were analyzed. Last but not least, future research directions were put forward based on the shortcomings of the current researches. The sorption mechanisms between MPs and pollutants mainly include hydrophobic, electrostatic, π-π and hydrogen bond interactions. The properties of MPs and pollutants, aging and environmental factors will affect the adsorption behavior of MPs. The development of mixed-order kinetics model, phenomenological kinetics model and predictive models is helpful to clarify and quickly predict the adsorption mechanism of MPs. Further efforts should be put into the interactions between combined pollutants and combined MPs, the effects of aging on MPs adsorption behaviors, and the application and development of relevant models.
- microplastics /
- adsorption /
- combined contaminations /
- influence factors /
- aging /
- predictive models

图 1 MPs的类型和分子结构（楔形的大小代表相关文献所占比例）

Figure 1. Types and molecular structures of MPs (the size of the wedge represents the proportion of relevant literatures)

下载: 全尺寸图片幻灯片

图 2 MPs对(a)疏水性和(b)亲水性有机污染物的最大吸附容量Q_m与SSA的相关关系

Figure 2. Correlations between the maximum adsorption capacity (Q_m) for (a) hydrophobic and (b) hydrophilic organic contaminants and SSA of MPs

下载: 全尺寸图片幻灯片

图 3 老化对MPs吸附的影响机制

Figure 3. Effects of aging on MPs adsorption behaviors

下载: 全尺寸图片幻灯片

表 1 MPs与有机污染物的相互作用机制

Table 1. Interaction mechanism between MPs and organic pollutants

污染物 Pollutants	MPs	疏水相互作用 Hydrophobic partitioning	静电相互作用 Electrostatic interaction	表面络合 Surface complexation	范德华力 Van der Waals force	氢键相互作用 Hydrogen bond	π-π相互作用 π-π interaction	参考文献 Reference
（1）疏水性污染物
E2	原始/老化PS, PVC, PE	√				√	√	[9]
NAP	PS	√	√				√	[10]
NIT, PHE	PS	√					√	[11]
PAHs	PT, PU, UF					√	√	[12]
PAHs	PS, PCL, PUR, PBS	√				√	√	[13]
9-NAnt	PE, PP, PS	√	√					[14]
双酚类化学品	PVC	√	√			√		[15]
（2）亲水性污染物
AML	PS	√					√	[16]
	老化PS		√
ATV	PS	√					√
	老化PS					√
AMX, CIP, SDZ, TC, TMP	PA, PE, PS, PP, PVC				√	√	√	[17]
PPCPs	PP, LDPE, HDPE, PVC	√	√					[18]
SMT	PA, PE, PS, PET, PVC, PP		√		√			[19]
SMX	PA, PE, PS, PET, PVC, PP		√			√		[20]
TC	PE, PP, PS	√	√				√	[21]
TCS	PVC	√	√			√		[22]
TYL	PE, PP, PS, PVC	√	√	√				[23]
药物	PE	√	√					[24]
离子有机污染物	PVC, PE, PP, PS		√		√			[25]

污染物 Pollutants	MPs	疏水相互作用 Hydrophobic partitioning	静电相互作用 Electrostatic interaction	表面络合 Surface complexation	范德华力 Van der Waals force	氢键相互作用 Hydrogen bond	π-π相互作用 π-π interaction	参考文献 Reference
（1）疏水性污染物
E2	原始/老化PS, PVC, PE	√				√	√	[9]
NAP	PS	√	√				√	[10]
NIT, PHE	PS	√					√	[11]
PAHs	PT, PU, UF					√	√	[12]
PAHs	PS, PCL, PUR, PBS	√				√	√	[13]
9-NAnt	PE, PP, PS	√	√					[14]
双酚类化学品	PVC	√	√			√		[15]
（2）亲水性污染物
AML	PS	√					√	[16]
	老化PS		√
ATV	PS	√					√
	老化PS					√
AMX, CIP, SDZ, TC, TMP	PA, PE, PS, PP, PVC				√	√	√	[17]
PPCPs	PP, LDPE, HDPE, PVC	√	√					[18]
SMT	PA, PE, PS, PET, PVC, PP		√		√			[19]
SMX	PA, PE, PS, PET, PVC, PP		√			√		[20]
TC	PE, PP, PS	√	√				√	[21]
TCS	PVC	√	√			√		[22]
TYL	PE, PP, PS, PVC	√	√	√				[23]
药物	PE	√	√					[24]
离子有机污染物	PVC, PE, PP, PS		√		√			[25]

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表 1 MPs的比表面积（SSA）及其对污染物的最大吸附容量（Q_m）

Table 1. MPs specific surface area and maximum adsorption capacity for pollutants

污染物 Pollutants	MPs	SSA /(m²·g⁻¹)	Q_m /(mg·g⁻¹)	参考文献 Reference
（1）疏水性污染物
PYR	PVC	1.3800	0.0787	[105]
	PS	1.0500	0.1270
	PE	0.9600	0.3330
BPA	PVC	9.7700	0.9230	[15]
BPAF	PVC	9.7700	1.0500
BPB	PVC	9.7700	0.9930
BPF	PVC	9.7700	0.7890
BPS	PVC	9.7700	0.7870
PHE	PVC	1.8700	0.3030	[29]
	PS	2.3500	0.4000
	PE	6.9100	0.7143
PBDEs	PP	0.0004	0.0002	[88]
	PA	0.0017	0.0002
	PS	0.0054	0.0001
E2	PS	0.7183	0.0924	[9]
	PE	0.2367	0.0863
	PVC	0.1339	0.0760
	老化PS	1.7407	0.2290
	老化PE	1.2041	0.1670
	老化PVC	0.9041	0.1090
FIP	PLA	0.4440	0.0040	[116]
	PBS	0.6010	0.0060
	PE	0.0011	0.0110
	PVC	0.0005	0.0120
	PS	0.0037	0.0130
	PP	0.0013	0.0260
（2）亲水性污染物
TYL	PE	0.7506	0.6667	[23]
	PP	1.1961	0.0833
	PS	1.5392	1.4285
	PVC	2.1454	1.6667
TYL	PE	0.5080	1.6667	[117]
	PVC	0.8360	3.3333
TC	PE	0.2341	0.1090	[21]
	PP	0.0365	0.1130
	PS	0.0596	0.1670
TC	PS-SO₃H	72.9200	17.8700	[118]
	PS	49.5200	11.1100
	PS-NH₂	86.3630	21.2700
TC	PA	8.7100	0.0750	[95]
	PS	0.0010	0.0860
	PE	2.1100	0.1540
TCS	PS	0.7300	−0.9800	[119]
	PE	1.1900	6.1100
TCS	PS	2.5300	1.0000	[96]
	PS	1.8800	0.8900
	PS	0.6700	0.7800
	PS	0.5800	0.7200
AMX	PE	1.4444	8.7980	[120]
	PET	0.3429	7.1790
	PS	2.6363	7.6960
	PP	3.2222	4.0280
	PVC	0.5929	6.9830
SMX	PE	0.2341	0.1080	[8]
苯酚	PE	0.1290	−0.1087	[28]
苯酚	PET	0.3429	2.8020	[120]
	PS	2.6363	2.7660
	PP	3.2222	1.2490
	PVC	0.5929	2.2430
OTC	PS	2.0300	1.5200	[76]
*最大吸附容量Q_m基于Langmiur吸附等温线得出。　　The maximum adsorption capacity (Q_m) was obtained based on Langmiur adsorption isotherm.

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表 2 MPs吸附行为的影响因素

Table 2. Factors influencing the adsorption behavior of MPs

污染物 Pollutants	MPs	盐度 Salinity	pH	有机质 Organic matter	温度 Temperature	参考文献 Reference
（1）疏水性污染物
E2	原始/老化PS, PVC, PE		↓		↓	[9]
E2	PVC, PMMA, PC, PS, PE, PA	↑		*		[60]
PAEs	PVC, PE, PS	↑	*	*		[85]
PAHs	PT, PU, UF	↑				[12]
PAHs	PE, PS				↑	[86]
PAHs	PE, PS, PVC			↓		[87]
PBDEs	PE, PP, PA, PS	*	*	↓		[88]
PBDEs	PS	*	*			[89]
	老化PS	↓	*
PBDEs	原始/老化PE, PS	*		↓		[90]
PCBs	PP	↑			↓	[91]
PHCs	PP，PE，PVC	↓			先↑后↓	[92]
9-NAnt	PE	*	*			[14]
	PP, PS	↓	↓
胺微污染物	PE	↑				[93]
（2）亲水性污染物
CBZ, TC	PE	*	*	↓	*	[35]
CIP	原始/老化PS, PVC	↓	先↑后↓			[39]
OTC	原始/老化PS	↓	pH=5最大	↑		[76]
PFASs	HDPE, PS, PS-COOH	↓	↓			[37]
PPCPs	PP	*				[94]
PPCPs	PP, LDPE, HDPE, PVC	↓	复杂			[18]
SMT	PA, PE, PS, PET, PVC, PP	↓	↓			[19]
SMX	PE	*	*	*		[8]
SMX	PA, PE, PS, PET, PVC, PP	↓	↓			[20]
TC	PE, PP, PS	*	pH=6最大	↑		[21]
TC	PA	↓	↑	先↑后↓		[95]
	PE	↓	↑	↓
	PS	↓	↓	先↑后↓
TCS	PS	*	↓		*	[96]
TCS	老化PP	↑				[77]
TCS	PVC	↑	↓			[22]
TYL	PE, PP, PS, PVC	先↑后↓	↓			[23]
“↑”促进作用；“↓”抑制作用；“”无明显影响。“↑” promotion; “↓” inhibition; “” no obvious effect.

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表 3 常见吸附模型表达式及特征

Table 3. Expressions and features of adsorption models

模型 Model	表达式 Expression	特点 Feature
PFO	（1）$ \dfrac{{\rm{d}}{q}_{t}}{{\rm{d}}t}={k}_{1}\left({q}_{e}-{q}_{t}\right) $	可用于描述非平衡条件下高初始吸附物浓度的动力学过程
PSO	（2）$ \dfrac{{\rm{d}}{q}_{t}}{{\rm{d}}t}={k}_{2}{\left({q}_{e}-{q}_{t}\right)}^{2} $	①吸附速率由吸附空位数的平方决定，该空位未被吸附剂表面占据，并且吸附过程涉及电子共享或电子在吸附剂和被吸附物之间转移；②可用于描述低初始吸附物浓度的动力学过程和化学吸附过程，但不能描述在短时间内吸附能力的急剧上升
Elovich	（3）$ \dfrac{{\rm{d}}{q}_{t}}{{\rm{d}}t}={\alpha e}^{-\beta q} $	适用于描述材料在异质表面上的吸附过程
MO	（4）$ \dfrac{{\rm{d}}{q}_{t}}{{\rm{d}}t}={k}_{1}\left({q}_{e}-{q}_{t}\right)+{k}_{2}{\left({q}_{e}-{q}_{t}\right)}^{2} $	适用于描述整个吸附过程
Henrry	（5）$ {q}_{e}={k}_{d}{C}_{e} $	表明存在明显的分配过程
Langmiur	（6）$ {q}_{e}=\dfrac{{q}_{m}b{C}_{e}}{1+b{C}_{e}} $	表明吸附剂在均质吸附剂表面上被单层覆盖
Freundlich	（7）$ {q}_{e}={k}_{f}{C}_{e}^{n} $	表明吸附剂表面的非均质性以及吸附位点及其能量的指数分布，适用于单层和多层吸附
Tempkin	（8）$ {q}_{e}=\dfrac{RT}{{b}_{T}}{\rm{ln}}\left({A}_{T}{C}_{e}\right) $	考虑了吸附剂与吸附剂相互作用的影响，并假设吸附能随表面覆盖率线性降低
Dubinin-Radushkevich	（9）$ {q}_{e}={q}_{s}{\rm{exp}}\left(-B{\epsilon }^{2}\right) $	经验模型，其吸附遵循孔隙填充机制
Redlich-Petersen	（10）$ {q}_{e}=\dfrac{{K}_{R}{C}_{e}}{1+{\alpha }_{R}{C}_{e}^{\beta }} $	兼具Freundlich和Langmuir模型的特征，并将3个参数合并到方程中
*q_t和q_e（mg·g⁻¹）分别是在时间t和平衡时固相中吸附质的浓度；k₁和k₂（min⁻¹）分别是PFO和PSO速率常数；α（ng·g⁻¹·h⁻¹）是初始吸附速率，β（g·ng⁻¹）是解吸常数。吸附等温线模型的参数含义参见原文^{[19, 105]}. 　　q_t and q_e (mg·g⁻¹) are the concentration of adsorbed substance in the solid phase at time t and equilibrium, respectively. k₁ and k₂(min⁻¹) are PFO and PSO rate constants, respectively. α (ng·g⁻¹·h⁻¹) is the initial adsorption rate and β (g·ng⁻¹) is the desorption constant. The parameters of the adsorption isotherm model are given in the original articles^{[19, 105]}.

模型 Model	表达式 Expression	特点 Feature
PFO	（1）$ \dfrac{{\rm{d}}{q}_{t}}{{\rm{d}}t}={k}_{1}\left({q}_{e}-{q}_{t}\right) $	可用于描述非平衡条件下高初始吸附物浓度的动力学过程
PSO	（2）$ \dfrac{{\rm{d}}{q}_{t}}{{\rm{d}}t}={k}_{2}{\left({q}_{e}-{q}_{t}\right)}^{2} $	①吸附速率由吸附空位数的平方决定，该空位未被吸附剂表面占据，并且吸附过程涉及电子共享或电子在吸附剂和被吸附物之间转移；②可用于描述低初始吸附物浓度的动力学过程和化学吸附过程，但不能描述在短时间内吸附能力的急剧上升
Elovich	（3）$ \dfrac{{\rm{d}}{q}_{t}}{{\rm{d}}t}={\alpha e}^{-\beta q} $	适用于描述材料在异质表面上的吸附过程
MO	（4）$ \dfrac{{\rm{d}}{q}_{t}}{{\rm{d}}t}={k}_{1}\left({q}_{e}-{q}_{t}\right)+{k}_{2}{\left({q}_{e}-{q}_{t}\right)}^{2} $	适用于描述整个吸附过程
Henrry	（5）$ {q}_{e}={k}_{d}{C}_{e} $	表明存在明显的分配过程
Langmiur	（6）$ {q}_{e}=\dfrac{{q}_{m}b{C}_{e}}{1+b{C}_{e}} $	表明吸附剂在均质吸附剂表面上被单层覆盖
Freundlich	（7）$ {q}_{e}={k}_{f}{C}_{e}^{n} $	表明吸附剂表面的非均质性以及吸附位点及其能量的指数分布，适用于单层和多层吸附
Tempkin	（8）$ {q}_{e}=\dfrac{RT}{{b}_{T}}{\rm{ln}}\left({A}_{T}{C}_{e}\right) $	考虑了吸附剂与吸附剂相互作用的影响，并假设吸附能随表面覆盖率线性降低
Dubinin-Radushkevich	（9）$ {q}_{e}={q}_{s}{\rm{exp}}\left(-B{\epsilon }^{2}\right) $	经验模型，其吸附遵循孔隙填充机制
Redlich-Petersen	（10）$ {q}_{e}=\dfrac{{K}_{R}{C}_{e}}{1+{\alpha }_{R}{C}_{e}^{\beta }} $	兼具Freundlich和Langmuir模型的特征，并将3个参数合并到方程中
*q_t和q_e（mg·g⁻¹）分别是在时间t和平衡时固相中吸附质的浓度；k₁和k₂（min⁻¹）分别是PFO和PSO速率常数；α（ng·g⁻¹·h⁻¹）是初始吸附速率，β（g·ng⁻¹）是解吸常数。吸附等温线模型的参数含义参见原文^{[19, 105]}. 　　q_t and q_e (mg·g⁻¹) are the concentration of adsorbed substance in the solid phase at time t and equilibrium, respectively. k₁ and k₂(min⁻¹) are PFO and PSO rate constants, respectively. α (ng·g⁻¹·h⁻¹) is the initial adsorption rate and β (g·ng⁻¹) is the desorption constant. The parameters of the adsorption isotherm model are given in the original articles^{[19, 105]}.

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现阶段，塑料由于其耐用性和低成本而被广泛应用于日常生活中。PlasticEurope的最新统计数据显示，2019年全球塑料产量高达3.59亿t^[1]，其中仅有一小部分（约6%—26%）会被回收利用^[2]。据估计，环境中塑料废物的积累量超过49亿t^[3]。未经正确处理/处置的塑料会在自然条件下风化破碎成微塑料（MPs），造成更大的环境风险。

MPs具有良好的疏水性和迁移性，是环境中污染物的优良载体^[4-6]。大量环境监测结果揭示了吸附在MPs上的污染物的时空分布，是MPs作为污染物载体的直接证据^[6-7]。一方面，MPs可以作为二次污染源，源源不断地向周围环境释放已吸附的污染物；另一方面，MPs易被水生生物误食，与吸附的污染物一起对摄食生物造成联合毒性，甚至沿食物链逐级传递，危害生态系统健康。为了有效评估和预防MPs的生态风险，有必要系统地了解其对污染物的吸附机制。

因此，本文系统总结了不同类型MPs与亲水、疏水性有机污染物及重金属的相互作用机制、影响因素及相关模型的研究进展，强调了复合污染物竞争吸附的相关研究的重要性，重点归纳了老化过程对微塑料吸附行为的影响机制，并提出了当前研究领域的关键挑战和对未来研究方向的展望，以期为揭示MPs的环境化学行为和生态风险提供参考。

1. MPs与不同类型污染物的相互作用机制（Interaction mechanism between MPs and different pollutants）

目前，关于MPs与有机污染物的相互作用，研究者们提出了以下几种重要机制：（1）疏水相互作用：指有机化合物在水相和MPs之间的分配过程，通常表现为线性吸附；（2）静电相互作用：当MPs与污染物都带电荷时，会通过静电吸引或静电排斥相互作用，由溶液pH和污染物解离常数（pKa）共同决定；（3）氢键相互作用：指MPs的官能团（如羧基和酯羰基等含氧官能团或酰胺基团）作为质子供体或受体与污染物通过氢键相互作用而影响吸附；（4）π-π相互作用：对于含有苯环结构的MPs（如PS），其能通过π-π相互作用结合含有双键或苯环的污染物分子；（5）范德华力：指分子间的作用力，可用于解释SMX在PE上的线性吸附^[8]。表1总结了不同MPs吸附不同有机污染物时涉及的机制。

1.1. 疏水性有机污染物

一些疏水性有机污染物（如PAHs、PCBs、农药和除草剂）是影响生态系统健康的重要因素。MPs具有较沉积物和天然有机质更强的疏水性及良好的迁移性^[4-5]，容易通过疏水相互作用结合环境介质中已有的疏水性污染物，进而影响其迁移，对生态环境构成了高度威胁^[6]。

MPs和污染物的疏水性是影响其吸附行为的关键因素之一。通常，有机污染物的疏水性遵循HCHs < PCBs < DDTs < PAHs^[26]。与之对应，实验室研究中PCBs和PAHs的吸附量通常高于DDT^[27-29]；现场监测结果也表明，MPs中PAHs和PCBs的浓度高于DDT和HCHs^[30]。Lee等^[31]发现吸附系数与疏水性之间具有良好的线性相关性，进一步证明了疏水性是塑料碎片与PAHs吸附行为的主要相互作用机理。聚合物密度也是影响MPs吸附行为的因素之一。例如，Fries和Zarfl^[32]指出，LDPE比HDPE具有更高的PAHs扩散系数，吸附能力随PAHs分子量的增加而降低，并且吸附速率与MPs和PAHs的密度有关。此外，PE的吸附等温线是高度线性的，这表明污染物倾向于吸附到聚合物内部而非聚合物表面^[32]。相比之下，PS的吸附等温线是非线性的，π-π共轭在吸附中起重要作用^[33]。除了π-π共轭以外，PAHs和MPs的平面度也是影响其吸附行为的因素之一。例如，Liu等^[34]发现，较高的平面度导致了PAHs在PS上的强吸附，PAHs可以轻松到达原始PS上的任意吸附位点。此外，Wu等^[15]还考察了5种更复杂的双酚类化学品在PVC上的吸附行为，深入研究其机理发现，疏水相互作用、静电力和非共价键（氢键和卤素键）都可能对双酚类化学品在PVC上的吸附产生积极影响。总体而言，关于MPs对疏水性污染物吸附机制的研究已取得一定进展，但是相关研究缺乏系统性（如不同研究关注的MPs类型和污染物具有很大差异），仍需进一步地探索以填补对MPs吸附机制理解的空白。

1.2. 亲水性有机污染物

考虑到原始塑料碎片的疏水性，研究者们通常采用疏水性有机污染物进行MPs上的吸附实验。然而，MPs进入环境后，其表面会发生氧化，对亲水性污染物也吸附能力也有所增强。因此，一些研究也开始关注亲水性有机污染物在MPs上的吸附行为。

抗生素是一类典型的持久性有机污染物，包括许多亲水性污染物。Li等^[17]和Shen等^[35]发现MPs可以吸附包括SDZ、AMX、TC、CIP及TMPs在内的亲水性抗生素。除抗生素外，PFAS也是亲水性污染物的典型代表。Wang等^[36]研究了PFOS和FOSA（PFOS的一种前体）在3种典型的MPs（PE、PS和PVC）上的吸附行为。结果显示，PFOS和FOSA在3种MPs上的吸附等温线是高度线性的，这表明主要的相互作用过程可能是分配而不是疏水；且由于污染物官能团的不同，FOSA在PE上的吸附水平高于PFOS。然而，Llorca等^[37]报告称，PFAS在HDPE上的吸附可以解释为疏水相互作用和范德华力共同作用的结果。该研究证明了在PFAS吸附中，疏水力有重要影响，尤其是在疏水吸附剂（例如HDPE）存在的情况下^[38]。可见，关于PFAS在MPs上的吸附机制仍待进一步研究。考虑到环境中的老化过程，Liu等^[39]和Hüffer等^[27]研究发现老化MPs表面有更多的含氧官能团，从而提高了其吸附能力。老化的MPs与亲水性污染物之间的吸附机制主要是含氧官能团之间的氢键相互作用。总体而言，关于MPs吸附亲水性有机物的研究相对较少，其吸附机理尚不明确；同时，老化MPs在环境中普遍存在，其对亲水性污染物的吸附机制也是重要的研究方向。

1.3. 重金属

除有机污染物外，现场实验还发现海洋和淡水MPs表面重金属的累积^[40-41]。Hodson等^[42]进一步强调塑料作为陆地环境中重金属载体的潜力。实际上，由于不同聚合物的化学和物理特性（例如比表面积和分子极性），金属在MPs上的吸附可能存在很大差异^[43]。例如，塑料中Cd和Pb的比率分别为6.9%和7.5%^[44]。大多数关于MPs吸附重金属的研究，均采用吸附等温线和动力学模型来研究吸附过程中的机理。例如，Hodson等^[42]发现金属在MPs上的吸附等温线可以用Freundlich等温线表示，表明发生了多层吸附。而Holmes等^[45-46]发现，Freundlich和Langmuir等温线都能很好描述金属在MPs上的吸附，表明金属也可能在MPs活性部位上发生单层吸附。此外，金属在MPs上的吸附动力学遵循PFO模型^[46]。但是，这些吸附模型几乎是经验模型，并且缺乏特定的物理意义。吸附过程包括3个步骤：①金属在MPs周围薄膜中的扩散；②金属在MPs孔内扩散；③金属在活性部位上的吸附。吸附现象模型的参数（例如传质模型和孔膜扩散模型）具有明确的物理含义，可以描述总体吸附步骤^[47-49]。直到最近，才有很少文献研究金属在MPs上的吸附现象模型^[50]。可见，MPs对重金属的吸附机制尚处于起步阶段，相关工作（如吸附现象模型的应用等）有望进一步开展。

1.4. 复合污染物

在真实环境中往往是多种污染物同时存在的。根据文献数据，全球环境中MPs上积聚的污染物包括PAHs、PCBs、HCHs和DDTs等有机污染物^[30]，以及Cd、Pb、Cu、Zn、As、Ti和Ni等重金属^[51-52]。当它们被MPs吸附时，可能会出现不同的吸附顺序，并且可能发生竞争性吸附^[53-55]。如果某些污染物与一种MPs具有更好的亲和力，它们将可能抑制其他化合物的吸附^[56]；通过中性金属-有机络合物和塑料表面疏水特性的非特异性结合也可以产生吸附作用^[55]。例如，Bakir等^[56]研究了PE和PVC对PHE和DDT的双溶质体系的吸附行为。结果显示，在双溶质系统中，DDT的吸附行为与单溶质系统中没有显著不同。但是，DDT干扰了PHE在塑料上的吸附，表明两者吸附行为的拮抗作用。Zhou等^[57]发现，低浓度的PHE（0.1—1.2 mg·L⁻¹）几乎不影响Cd（II）在MPs上的吸附，这主要是因为Cd（II）和PHE在MPs上的吸附位点不同^[53]。另一种可能的解释是，Cd（II）可以通过阳离子-π相互作用形成新的PHE吸附位点^[53-54]，削弱PHE的抑制作用。Huang等^[55]研究了Cd（II）在不同共存体系中对PS吸附TYL的影响。当Cd（II）和TYL共存时，竞争性吸附占主导地位，从而抑制了PS对TYL的吸附。当PS首先吸附Cd（II），然后再吸附TYL时，TYL和Cd（II）络合物的形成增强了TYL的吸附。

综上，环境中往往是多种污染物同时存在，复合污染带来的环境效应很大程度上区别于单一污染物，但相关研究尚处于起步阶段。研究复合污染物在同种MPs上的竞争吸附和不同MPs间的分配差异，可以为评估复合污染过程中MPs和复合污染物的环境行为和生态风险提供重要依据。

2. MPs吸附行为的影响因素（Factors influencing the adsorption behavior of MPs）

3. 模型模拟（Adsorption and predictive models）

3.1. 吸附模型

现阶段，各种动力学模型已经被应用于描述MPs的吸附过程，例如，准一阶（pseudo-first order，PFO）、准二阶（pseudo-second order，PSO）、Elovich和混合阶（mixed-order，MO）动力学模型，其表达式及特征如表3所示。

大量关于MPs吸附的研究常采用PFO和PSO动力学模型^{[8, 19, 23, 58, 105]}，并通过分析相关系数（R²）或其他统计参数得出其是否能准确描述动力学实验数据的结论。例如，Costa等^[106]比较得出，相较于PSO和Elovich，PFO模型更适合描述OA在EPS（R²=0.956）、PS（R²=0.943）和PET（R²=0.992）上的吸附过程。然而，PFO和PSO的应用局限于特定的吸附条件和某一阶段，无法反映整个吸附过程。实际的吸附过程可能包括PFO和PSO，所以采用MO能更好地描述MPs整个吸附过程的动力学^[107]。Guo等^[107]采用MO模型很好地拟合抗生素在老化的微塑料上的吸附动力学。其中，SMT的k₁=0，表明吸附受PSO动力学控制，即SMT吸附在MPs的活性位点上；而SMX和CEP-C的k₁和k₂均不为零，表明在MPs上的吸附过程可能同时包括外/内扩散和活性位点上的吸附。

常见的吸附等温线模型包括Henrry、Langmiur和Freundlich等，其表达式如表3所示。大量研究比较了不同吸附等温线在MPs吸附中的应用效果。对于TYL在PE、PP、PS和PVC上的吸附，其拟合程度按照Henrry>Freundlich>Langmiur递减^[23]。对于PYR在PE、PS和PVC上的吸附，Wang等^[105]比较Freundlich、Langmiur、Tempkin、Dubinin-Radushkevich和Redlich-Petersen后得出，Langmiur是最佳拟合模型。此外，Henrry还适合描述抗生素在老化PS和PE上的吸附^[19]；Langmiur对三（2,3-二溴丙基）异氰脲酸酯和六溴环十二烷在PP上的吸附具有良好的拟合效果^[108]；非线性Tempkin可以很好地描述Sr²⁺在PA、PS和PP上的吸附^[109]。

3.2. 预测模型

目前，关于MPs对不同污染物吸附机制的研究尚处于初级阶段，所报道的吸附数据害不能满足进一步研究的需求。传统的实验方法需要较长的平衡时间和严格的实验控制以获得吸附实验参数，具有成本高、耗时长等劣势。近年来，一些研究基于定量结构-性质关系模型（QSPR）的机理，将多参数线性自由能关系模型（pp-LFER）应用于预测MPs吸附行为，能够有效解决上述瓶颈^{[27, 110-112]}。pp-LFER模型的表达式如下^[111]：

其中，lgK_i,_p/w表示给定的MPs（i）在有机相（p）和水相（w）之间的对数分布系数。相位描述符E代表过量的摩尔折射；S，双极性/极化率；A，溶质氢键酸度；B，溶质氢键碱度；V，McGowan特征体积。

pp-LFER不仅可以提供预测得到的K_d值，也能促进对吸附机理的分析^[113-115]。Wei等^[110]指出，pp-LFER能够有效预测PCBs、氯苯、PAHs、抗生素、芳烃、脂肪烃、六氯环己烷和PFASs在PE、PP、PS和海水、淡水、纯水中的分配。通过对描述符的进一步分析发现，疏水相互作用是主要的吸附机理，π-π相互作用对含苯环微塑料（PS）的吸附也起着至关重要的作用；氢键碱度和空腔形成能够决定化合物的分配趋势；MPs的结晶度、芳香性和水环境的盐度都会影响其吸附能力。Hüffer等^[27]采用各种内部和外部验证方法测试了pp-LFER模型的稳健性，得出该模型可以有效预测老化PS与有机化合物分子之间的相互作用。Uber等^[111]采用pp-LFER预测了非离子有机化合物在原始和老化PS上的吸附，发现PS的非线性吸附受摩尔体积和相位描述符S控制，且PS的相位描述符与其他MPs存在明显不同（即描述符E和S）。Li等^[112]进一步开发了pp-LFER并应用于不同水环境pH值条件下的MPs吸附行为的预测，成功得到了各种pH值下可电离化合物的lgK_d值。

现阶段，预测模型在MPs吸附中的应用尚处于起步阶段。预测模型能够快速估计不同水环境中有机污染物在MPs上的吸附能力，为MPs进一步的生态风险研究提供必要的机理信息，有待进一步开发.

4. 结论和展望（Conclusions and Prospects）

现阶段，MPs由于其作为污染物载体的能力及潜在的生态风险而广受关注。野外监测和实验室尺度上关于微塑料吸附机理的研究已逐步开展。然而，由于MPs、污染物和环境因子的复杂性，关于不同MPs对单一污染物的吸附机理的认知十分欠缺。其次，环境中往往是多种污染物或多种MPs同时存在，势必会导致其在同种MPs上的竞争吸附和不同MPs间的分配差异。再次，MPs在进入土壤环境前、后势必会经历各种老化过程，其吸附行为也会发生不同程度改变，相关研究尚处于起步阶段。最后，现象动力学和预测模型的应用较少，对吸附机理的解释和广泛预测相对有限。

由此，本文提出以下展望：①开展更广泛且系统的研究，厘清MPs与不同类型污染物的相互作用机制及各影响因子的贡献；②探索复合污染物与MPs的相互作用机制，客观反映MPs的生态风险；③系统开展MPs老化机理及其对吸附行为的影响研究，建立老化程度-MPs特性-吸附能力的关系曲线，逐步解译MPs的长期环境行为；④进一步应用和开发吸附相关的混合阶动力学模型、传质/现象动力学模型及预测模型，实现对MPs生态风险的快速预测评估。

参考文献 (120)

微塑料吸附机制研究进展

通讯作者: Tel：010-58807493，E-mail：sunke@bnu.edu.cn;

Sorption behavior, mechanisms, and models of organic pollutants and metals on microplastics: A review

Corresponding author: SUN Ke, sunke@bnu.edu.cn ;

计量

微塑料吸附机制研究进展

通讯作者: Tel：010-58807493，E-mail：sunke@bnu.edu.cn;

English Abstract

Sorption behavior, mechanisms, and models of organic pollutants and metals on microplastics: A review

Corresponding author: SUN Ke, sunke@bnu.edu.cn ;

全文HTML

1.1. 疏水性有机污染物

1.2. 亲水性有机污染物

1.3. 重金属

1.4. 复合污染物

2.1. MPs类型和性质

2.1.1. 官能团结构

2.1.2. 尺寸或比表面积

2.1.3. 结晶度或玻璃转化温度

2.2. MPs老化

2.3. 环境因素

2.3.1. 有机质

2.3.2. 盐度

2.3.3. pH

3.1. 吸附模型

3.2. 预测模型

目录

微塑料吸附机制研究进展

通讯作者: Tel：010-58807493，E-mail：sunke@bnu.edu.cn;

Sorption behavior, mechanisms, and models of organic pollutants and metals on microplastics: A review

Corresponding author: SUN Ke, sunke@bnu.edu.cn ;

计量

出版历程

微塑料吸附机制研究进展

通讯作者: Tel：010-58807493，E-mail：sunke@bnu.edu.cn;

English Abstract

Sorption behavior, mechanisms, and models of organic pollutants and metals on microplastics: A review

Corresponding author: SUN Ke, sunke@bnu.edu.cn ;

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1.1. 疏水性有机污染物

1.2. 亲水性有机污染物

1.3. 重金属

1.4. 复合污染物

2.1. MPs类型和性质

2.1.1. 官能团结构

2.1.2. 尺寸或比表面积

2.1.3. 结晶度或玻璃转化温度

2.2. MPs老化

2.3. 环境因素

2.3.1. 有机质

2.3.2. 盐度

2.3.3. pH

3.1. 吸附模型

3.2. 预测模型

目录