Effects of low-molecular-weight organic acids on the transport of polystyrene nanoplastics: An insight at the structure of organic acids

Plastic nanoparticles are extensively used in various products, leading to inevitable pollution in soil. Understanding their transport in soils where various organic substances exist is crucial. This study examined the impact of low-molecular-weight organic acids (LMWOAs) on the transport of polystyrene nanoplastics (PS-NPs) through saturated quartz sand. The experiments involved three dibasic acids-malonic acid (MA1), 1 ), malic acid (MA2) 2 ) and tartaric acid (TA) - and four monobasic acids- formic acid (FA), acetic acid (AA), propanoic acid (PA) and glycolic acid (GA) -under different pH levels (4.0, 5.5, 7.0) and in the presence of cations (Na+, + , Ca2+). 2 + ). The results demonstrated that in the presence of Na+, + , dibasic acids significantly enhanced PS-NPs transport, with TA being the most effective, followed by MA2 2 and MA1. 1 . This enhancement is attributed to the adsorption of LMWOAs onto the nanoparticles and sand, creating a more negative zeta-potential, which increases the electrostatic repulsion and decreases the PS-NPs deposition, thereby facilitating the transport. Applying the DerjaguinLandau-Verwey-Overbeek theory, higher pH levels increased the energy barrier and secondary energy minimum, decreasing PS-NPs deposition. Moreover, dibasic acids significantly enhanced the hydrophilicity of PS-NPs. Conversely, monobasic acids, except for GA, slightly reduced the hydrophilicity of PS-NPs, as indicated by a small increase in the water contact angle, hereby minimally affecting PS-NPs transport. As for GA, although it is a monobasic acid, the additional-OH group in its molecular structure promoted PS-NPs transport, similar to dibasic acids. For example, GA also significantly enhanced the hydrophilicity of PS-NPs. In the presence of Ca2+, 2+ , the enhancement of PS-NPs transport by LMWOAs was comparable to that with Na+, + , primarily due to the complex-forming and bridging effects of Ca2+ 2+ with the organic acids and PS-NPs. These findings provide important insights into predicting and analyzing the transport behaviors of PS-NPs.