Understanding effect of solution chemistry on heteroaggregation of zinc oxide and copper oxide nanoparticles

The reported presence of mixture of nanoparticles in environmental water warrants developing understanding on their aggregation and fate. This study tried to address this question and focused on understanding effects of pH (3,7 and 10), background electrolyte concentration (1 mM and 10 mM as NaCl) and nanoparticle (NP) concentration (1 and 10 mg/L) on stability of suspension containing mixture of two commonly-found metal oxide-based NP (i.e., ZnO and CuO NPs) in a 6-h study (output variables: aggregation rate constant, settling rate constant, difference in zeta potential, change of metal content in suspension and on aggregates). Two iso-electric point values were obtained: pH 3.08 and 8.33 for mixture suspension in DI (De-ionized) water and pH 5.69 and 8.65 for mixture suspension with 10 mM electrolyte concentration. Settling rate constant and aggregation rate constant values of suspension containing mixture of NPs varied between 0.02 and 0.23 NTU/(NTU-hour) and 0.0002 and 0.03 nm/s, respectively. At natural pH condition, settling rate constant and aggregation rate constant values were obtained to be 0.05 NTU/(NTU- hour) and 0.012 nm/s. The Derjaguin-Landau-Verway-Overbeek (DLVO) analyses indicated that aggregation of mixture of NPs might be happening due to combined effects of ionic layer compression, charge neutralization and van der Waals attraction. Dissolution of nanoparticles was found to be significantly affected by change in pH of suspension. Stability of mixture of nanoparticles was observed to decrease with increasing pH, ionic strength and nanoparticle concentration values. For ZnO and CuO nanoparticles, model equations were developed for predicting their (i) aggregation rate constant, (ii) settling rate constant, (iii) difference in zeta potential, (iv) percentage change of metal in suspension and (v) solid Zn fractions of mixture of nanoparticles as a function of pH, ionic strength and NP concentration. These information are useful in understanding fate of mixture of NPs in suspension as well as in settled solids in natural water bodies and in water treatment systems.