Citation: | HU Tingting, LI Zhixiong, CHEN Jiawei. Quantitative Investigation of the Size-dependent Aggregation of Nanoplastics[J]. Rock and Mineral Analysis, 2024, 43(1): 101-113. doi: 10.15898/j.ykcs.202305020058 |
The geochemical behavior of microplastics (MPs) and nanoplastics (NPs) in the environment has become a global hot topic. Aggregation effect is an important factor controlling the geochemical behavior of NPs, yet there is conflicting evidence regarding the dependence of aggregation on NPs size. Investigating the general patterns and dominant mechanisms governing the aggregation behavior of different-sized NPs under various environmental conditions, will provide help in understanding and predicting the fate of NPs with different sizes. The study has shown that NPs with the same chemical composition but different sizes have different stability and mobility under the same conditions. The critical coagulation concentration (CCC) for NPs increases with the decrease in particle size at a fixed surface ζ potential (CCC=325mmol/L, 296mmol/L, 264mmol/L for 50nm, 100nm, and 200nm, respectively); indicating smaller NPs may transport longer distances. As the pH increased from 5.5 to 7, the negative surface charge of 100 and 200nm NPs allowed them to remain stable even at higher ionic strength. However, 50 nm NPs underwent rapid aggregation because of its smaller ζ potential. Therefore, the effects of pH, ionic strength and NPs sizes should be considered comprehensively in predicting and evaluating the geochemical behavior of NPs in the natural environment. The BRIEF REPORT is available for this paper at
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Characterization of the size-dependent PSNPs: a-c represent the TEM images of PS50, PS100 and PS200, respectively;d-f are the corresponding intensity-weighted hydrodynamic diameter distribution (Dh) of 10mg/L PSNPs determined by DLS;g-i show the ζ potentials as a function of pH in deionized water. The morphology of three PSNPs is all sphericity and has good dispersity. All the data present a good consistency.
Hydrodynamic diameter (Dh) changes of PS50 (a), PS100 (b) and PS200 (c) over 15min in the presence of NaCl(0-800mmol/L) at pH=5.5±0.3. The aggregation cannot happen while NaCl concentration below 200mmol/L;gradually aggregate at 200-400mmol/L; remain the fast aggregation while NaCl concentration above 400mmol/L.
Attachment efficiency (a) and ζ potentials (b) as a function of the concentrations of NaCl (0−800mmol/L) for PS50, PS100 and PS200. The CCC values for PS50, PS100 and PS200 were 325mmol/L, 296mmol/L and 264mmol/L, indicating that larger PSNPs are easier to aggregate.
Effects of pH on aggregation of PS50 (a, d), PS100 (b, e), PS200 (c, f): Hydrodynamic diameter (a-c) and ζ potentials (d-f) (PSNPs concentration was 10mg/L; NaCl concentration was 400mmol/L exceeding the CCC values for the three PSNPs; pH=3, 7, and 10). The aggregation rate decreased with the increase of pH due to the deprotonation.
Total energy profiles obtained by DLVO theory of PS50(a), PS100(b) and PS200(c) in solutions with varied NaCl concentrations. The dominant interaction forces between PSNPs was electrostatic repulsion when the total interaction energy exhibited negativity, while van der Waals attractive forces was responsible to the positive total interaction energies. The energy barrier for limiting PSNPs aggregation vanished when ionic strength was higher than the CCC value.
The linear regression models between attachment efficiency and ζ potential of PS50(a), PS100(b) and PS200(c) under all experimental conditions. The red line zone and blue zone represent the 95% confidence interval and prediction interval,respectively. The correlation coefficients (r2) of PS50, PS100 and PS200 are 0.88, 0.77 and 0.70, respectively, indicating that ζ potential is more favorable for predicting the aggregation behavior of smaller-size PSNPs.