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Formation and stability of NOM-Mn(III) colloids in aquatic environments

Li, Qianqian, Xie, Lin, Jiang, Yi, Fortner, John D., Yu, Kai, Liao, Peng, Liu, Chongxuan
Water research 2019 v.149 pp. 190-201
aquatic environment, biogeochemical cycles, carbon, coagulation, colloidal properties, colloids, electrostatic interactions, humic acids, manganese, nutrients, peat soils, physical properties, prediction, river water, zeta potential
Soluble Mn(III) species stabilized by natural organic matter (NOM) plays a crucial role in a number of biogeochemical processes. To date, current understanding of these phenomena has been primarily concerned on the occurrence and chemistry of soluble NOM-Mn(III) complexes; much less is known regarding the formation and stability of NOM-Mn(III) colloids in the environment. This presents a critical knowledge gap with regard to biogeochemical cycling of manganese and associated carbon, and for predicting the fate and transport of colloid-associated contaminants, nutrients, and trace metals. In this work, we have characterized the chemical and physical properties of humic acid based (HA)-Mn(III) colloids formed over a range of environmentally relevant conditions and quantified their subsequent aggregation and stability behaviors. Results show that molar C/Mn ratios and HA types (Aldrich HA (AHA) and Pahokee peat soil HA (PPSHA)) are critical factors influencing HA-Mn(III) colloidal properties. Both the amount and the stability of HA-Mn(III) colloids increased with increasing initial molar C/Mn ratios, regardless of HA type. The correlation between the critical coagulation concentration (CCC) and zeta potential (R2 > 0.97) suggests that both Derjaguin-Landau-Verwey-Overbeek (DLVO) type and non-DLVO interactions are responsible for enhanced stability of HA-Mn(III) colloids. For a given C/Mn ratio, PPSHA-Mn(III) colloids are significantly more stable against aggregation than AHA-Mn(III) colloids, which is likely due to stronger electrostatic interactions, hydration interactions, and steric hindrance. Further examination in real-world waters indicates that the HA-Mn(III) colloids are highly stable in surface river water, but become unstable (i.e. extensive aggregation) in solutions representing a groundwater-seawater interaction zone. Overall, this study provides new insights into the formation and stability of NOM-Mn(III) colloids which are critical for understanding Mn-based colloidal behavior(s), and thus Mn cycling processes, in aquatic systems.