Further research on the impacts of humic acid in the aggregation of nanoplastics: The roles of molecular weight and surface functionalization

Humic acid (HA) affects the aggregation behavior of nanoplastics. This study examines the adsorption of molecular weight (MW)-fractionated HA onto functionalized polystyrene nanoplastics (PS-Bare, PS-COOH, and PS-NH₂) in NaCl and CaCl₂, characterizes the properties of the adsorbed HA layer, and asse...

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Main Authors: Feng-Yi Li, Gui-Yun Song, Qing-Xin Zhang
Format: Article
Language:English
Published: Elsevier 2025-09-01
Series:Results in Engineering
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Online Access:http://www.sciencedirect.com/science/article/pii/S2590123025028877
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author Feng-Yi Li
Gui-Yun Song
Qing-Xin Zhang
author_facet Feng-Yi Li
Gui-Yun Song
Qing-Xin Zhang
author_sort Feng-Yi Li
collection DOAJ
description Humic acid (HA) affects the aggregation behavior of nanoplastics. This study examines the adsorption of molecular weight (MW)-fractionated HA onto functionalized polystyrene nanoplastics (PS-Bare, PS-COOH, and PS-NH₂) in NaCl and CaCl₂, characterizes the properties of the adsorbed HA layer, and assesses their impact on nanoplastics stability. The results reveal that pristine and MW-fractionated HA form adsorbed layers with comparable functional groups and surface charge. However, the adsorbed layer thickness (ALT) exhibits a positive correlation with the adsorption mass and MW of HA. In NaCl, the maximum ALT values were 0.21∼5.93 nm for PS-Bare, 0.74∼9.43 nm for PS-COOH, and 2.23∼12.1 nm for PS-NH₂, whereas their ranges in CaCl₂ were 0.21∼7.1 nm, 1.05∼12.1 nm, and 2.61∼12.8 nm. The increased ALT elevated the critical coagulation concentration (CCC) values in NaCl from 343 to 426∼1266 mM for PS-Bare and 339 to 467∼1380 mM for PS-COOH, while the hydrodynamic diameter (Dh) of PS-NH₂ stabilized at approximately 143 nm, indicating enhanced steric repulsion and improved nanoplastics dispersion. Similar results were also observed in CaCl2 containing low concentrations of HA. However, in CaCl₂, higher-MW HA at 10 mg C L⁻¹ can counteract steric repulsion through a bridging effect, leading to decreasing CCC to 19.2∼23.1 mM for PS-Bare and to 18.7∼21.6 mM for PS-COOH. Lower-MW HA at 5 mg C L⁻¹ promotes increasing Dh of PS-NH₂ to 600∼900 nm via the synergistic effects of charge neutralization and weak steric hindrance. Additionally, HA<3 kDa induces increasing Dh of PS-NH₂ to 1300 nm through patch-charge attraction, irrespective of concentration.
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spelling doaj-art-b3ac5216ddf641ee8b258bd931cd30502025-08-22T04:57:26ZengElsevierResults in Engineering2590-12302025-09-012710682310.1016/j.rineng.2025.106823Further research on the impacts of humic acid in the aggregation of nanoplastics: The roles of molecular weight and surface functionalizationFeng-Yi Li0Gui-Yun Song1Qing-Xin Zhang2Corresponding author.; College of Grassland, Inner Mongolia Minzu University, Tongliao, 027000, ChinaCollege of Grassland, Inner Mongolia Minzu University, Tongliao, 027000, ChinaCollege of Grassland, Inner Mongolia Minzu University, Tongliao, 027000, ChinaHumic acid (HA) affects the aggregation behavior of nanoplastics. This study examines the adsorption of molecular weight (MW)-fractionated HA onto functionalized polystyrene nanoplastics (PS-Bare, PS-COOH, and PS-NH₂) in NaCl and CaCl₂, characterizes the properties of the adsorbed HA layer, and assesses their impact on nanoplastics stability. The results reveal that pristine and MW-fractionated HA form adsorbed layers with comparable functional groups and surface charge. However, the adsorbed layer thickness (ALT) exhibits a positive correlation with the adsorption mass and MW of HA. In NaCl, the maximum ALT values were 0.21∼5.93 nm for PS-Bare, 0.74∼9.43 nm for PS-COOH, and 2.23∼12.1 nm for PS-NH₂, whereas their ranges in CaCl₂ were 0.21∼7.1 nm, 1.05∼12.1 nm, and 2.61∼12.8 nm. The increased ALT elevated the critical coagulation concentration (CCC) values in NaCl from 343 to 426∼1266 mM for PS-Bare and 339 to 467∼1380 mM for PS-COOH, while the hydrodynamic diameter (Dh) of PS-NH₂ stabilized at approximately 143 nm, indicating enhanced steric repulsion and improved nanoplastics dispersion. Similar results were also observed in CaCl2 containing low concentrations of HA. However, in CaCl₂, higher-MW HA at 10 mg C L⁻¹ can counteract steric repulsion through a bridging effect, leading to decreasing CCC to 19.2∼23.1 mM for PS-Bare and to 18.7∼21.6 mM for PS-COOH. Lower-MW HA at 5 mg C L⁻¹ promotes increasing Dh of PS-NH₂ to 600∼900 nm via the synergistic effects of charge neutralization and weak steric hindrance. Additionally, HA<3 kDa induces increasing Dh of PS-NH₂ to 1300 nm through patch-charge attraction, irrespective of concentration.http://www.sciencedirect.com/science/article/pii/S2590123025028877NanoplasticsHumic acidMolecular weightAdsorbed layer thicknessAggregation
spellingShingle Feng-Yi Li
Gui-Yun Song
Qing-Xin Zhang
Further research on the impacts of humic acid in the aggregation of nanoplastics: The roles of molecular weight and surface functionalization
Results in Engineering
Nanoplastics
Humic acid
Molecular weight
Adsorbed layer thickness
Aggregation
title Further research on the impacts of humic acid in the aggregation of nanoplastics: The roles of molecular weight and surface functionalization
title_full Further research on the impacts of humic acid in the aggregation of nanoplastics: The roles of molecular weight and surface functionalization
title_fullStr Further research on the impacts of humic acid in the aggregation of nanoplastics: The roles of molecular weight and surface functionalization
title_full_unstemmed Further research on the impacts of humic acid in the aggregation of nanoplastics: The roles of molecular weight and surface functionalization
title_short Further research on the impacts of humic acid in the aggregation of nanoplastics: The roles of molecular weight and surface functionalization
title_sort further research on the impacts of humic acid in the aggregation of nanoplastics the roles of molecular weight and surface functionalization
topic Nanoplastics
Humic acid
Molecular weight
Adsorbed layer thickness
Aggregation
url http://www.sciencedirect.com/science/article/pii/S2590123025028877
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