Effects of soluble organics on the settling rate of modified clay and development of improved clay formulations for harmful algal bloom control

Highlights: • Dissolved organic matter influences the settling rate of MC during HABs control. • "Ionic atmosphere compression" method can improve the MC settling rate by up to 200%. • The high settling rate of MC was caused by large flocs formed in high salinity area. • This study provides a basis for the application of MC in high-organic water. For many years, the dispersal of modified clay (MC) has been used to control harmful algal blooms (HABs) in coastal waters of China. MC flocculation efficiency can be influenced by many factors in variable and complex natural environments, including high concentrations of dissolved organic matter (DOM) in the water to be treated. Since many HABs occur in nearshore waters where DOM concentrations are high, this is a significant problem that requires urgent attention. This study involved the use of humic acid as a representative form of DOM to study the influence of organic matter on the MC flocculation process. At high concentrations, humic acid was adsorbed onto MC particles, resulting in a decrease in surface potential and an increase in electrostatic repulsion between the clay particles; this decreased the MC settling rate and increased the water clarification time. Flocs were characterized by their relatively small particle size, high particle concentration, and low collision efficiency, which together resulted in slow clarification of the water after MC spraying. Based on the mechanism of the DOM-MC interaction and combined with the Derjaguin-Landau-Verwey-Overbeek theory and theoretical considerations of clay surface modification, the "ionic atmosphere compression" method was used to improve MC flocculation efficiency in high-organic water. This method increased the ionic strength of the clay stock solution by adding salt, thereby compressing the ionic atmosphere of MC particles and lowering the potential barrier, allowing the MC particles in the treated water to flocculate rapidly and form large flocs, followed by further floc growth and rapid settling via differential sedimentation. The settling rate of MCs improved by a factor of two and the removal efficiency of the HAB cells increased by 7–28%. This study provides important baseline information that will extend the application of MC to HAB control in water bodies with high organic loadings.