Impact of natural organic matter and inorganic ions on the stabilization of polystyrene micro-particles.

The orthokinetic coagulation of irregularly shaped polystyrene micro-particles (PS-MP) was investigated in solutions of inorganic cations with different valence (NaCl, CaCl2, LaCl3) using a coagulation jar test set-up combined with light extinction particle counting. The stabilizing effect of model natural organic matter (NOM from reverse-osmosis (RO-NOM), humic (HA) & fulvic acid (FA)) and of surface water components (SW-NOM) was studied. Collision efficiencies were calculated from the decrease in particle concentration applying first order reaction kinetics. The coagulation of PS-MP followed Derjaguin-Landau-Verwey-Overbeek (DLVO) theory with regard to ionic charge in solution. Highest collision efficiencies were obtained close to the suspected critical coagulation concentrations for CaCl2 (12 mM) and LaCl3 (5.5 mM) whereas for NaCl no CCC was found within the applied concentration range (10-1000 mM). The addition of NOM effectively stabilized PS-MP at low ionic strength (10 mM NaCl) in the order HA > RO-NOM > FA > SW-NOM at concentrations of dissolved organic carbon (DOC) as low as 0.2-0.5 mg/L DOC through electrostatic repulsion. PS-MP were effectively stabilized in 6.1 mg DOC/L of SW-NOM even at high ionic strength (100 mM MgCl2). Coagulation at intermediate ionic strength (10 mM MgCl2) was only observed for SW-NOM concentrations below 0.6 mg/L DOC. The results showed that even low NOM concentrations prevent PS-MP from orthokinetic coagulation in the presence of high ion concentrations. The study provides further insight in the orthokinetic coagulation behavior of PS-MP in the presence of NOM and highlights the importance of NOM for the stabilization of microplastics in aquatic suspensions. Further research is needed to elucidate the behavior of MP in turbulent systems to predict the mobility MP in aquatic systems such as rivers.

The challenge in preparing particle suspensions for aquatic microplastic research.

The occurrence of small particles consisting of organic polymers, so-called microplastic (MP), in aquatic environments attracts increasing interest in both public and science. Recent sampling campaigns in surface waters revealed substantial numbers of particles in the size range from a few micrometers to a few millimeters. In order to validate sample preparation, identification and quantification and to investigate the behavior of MP particles and potential toxic effects on organisms, defined MP model particles are needed. Many studies use spherical compounds that probably behave differently compared to irregularly shaped MP found in environmental samples. However, preparation and handling of MP particles are challenging tasks and have been systematically investigated in the present study. Polystyrene (PS) as a commonly found polymer with a density slightly above that of water was selected as polymer type for milling and fractionation studies. A cryogenic ball mill proved to be practical and effective to produce particles in the size range from 1 to 200 µm. The yield of small particles increased with increasing pre-cooling and milling durations. Depending on the concentration and the size, PS particles do not completely disperse in water and particles partly creep vertically up along glass walls. Stabilized MP suspensions without use of surfactants that might harm organisms are needed for toxicological studies. The stabilization of PS particle suspensions with ozone treatment reduced the wall effect and increased the number of dispersed PS particles but increased the dissolved organic carbon concentration and changed the size distribution of the particles.