Transport of carboxyl-functionalized carbon black nanoparticles in saturated porous media: Column experiments and model analyses

• Metal (Fe, Al) oxides play a significant role in attachment of CBNPs to porous media.
• CBNP adhesion to quartz sand can be enhanced by increasing electrolyte concentration.
• Ca2+ showed a much stronger effect than Na+ on CBNP transport.
• CBNP adhesion to quartz sand can be enhanced by decreasing pH.

The aim of this study was to investigate the transport behavior of carboxyl-functionalized carbon black nanoparticles (CBNPs) in porous media including quartz sand, iron oxide-coated sand (IOCS), and aluminum oxide-coated sand (AOCS). Two sets of column experiments were performed under saturated flow conditions for potassium chloride (KCl), a conservative tracer, and CBNPs. Breakthrough curves were analyzed to obtain mass recovery and one-dimensional transport model parameters. The first set of experiments was conducted to examine the effects of metal (Fe, Al) oxides and flow rate (0.25 and 0.5 mL min− 1) on the transport of CBNPs suspended in deionized water. The results showed that the mass recovery of CBNPs in quartz sand (flow rate = 0.5 mL min− 1) was 83.1%, whereas no breakthrough of CBNPs (mass recovery = 0%) was observed in IOCS and AOCS at the same flow rate, indicating that metal (Fe, Al) oxides can play a significant role in the attachment of CBNPs to porous media. In addition, the mass recovery of CBNPs in quartz sand decreased to 76.1% as the flow rate decreased to 0.25 mL min− 1. Interaction energy profiles for CBNP–porous media were calculated using DLVO theory for sphere–plate geometry, demonstrating that the interaction energy for CBNP–quartz sand was repulsive, whereas the interaction energies for CBNP–IOCS and CBNP–AOCS were attractive with no energy barriers. The second set of experiments was conducted in quartz sand to observe the effect of ionic strength (NaCl = 0.1 and 1.0 mM; CaCl2 = 0.01 and 0.1 mM) and pH (pH = 4.5 and 5.4) on the transport of CBNPs suspended in electrolyte. The results showed that the mass recoveries of CBNPs in NaCl = 0.1 and 1.0 mM were 65.3 and 6.4%, respectively. The mass recoveries of CBNPs in CaCl2 = 0.01 and 0.1 mM were 81.6 and 6.3%, respectively. These results demonstrated that CBNP attachment to quartz sand can be enhanced by increasing the electrolyte concentration. Interaction energy profiles demonstrated that the interaction energy profile for CBNP–quartz sand was compressed and that the energy barrier decreased as the electrolyte concentration increased. Furthermore, the mass recovery of CBNPs in the presence of divalent ions (CaCl2 = 0.1 mM) was far lower than that in the presence of monovalent ions (NaCl = 0.1 mM), demonstrating a much stronger effect of Ca2 + than Na+ on CBNP transport. Mass recovery of CBNPs at pH 4.5 was 55.6%, which was lower than that (83.1%) at pH 5.4, indicating that CBNP attachment to quartz sand can be enhanced by decreasing the pH. The sticking efficiencies (α) calculated from the mass recovery by colloid filtration theory were in the range from 2.1 × 10− 2 to 4.5 × 10− 1, which were far greater than the values (2.56 × 10− 6–3.33 × 10− 2) of theoretical sticking efficiencies (αtheory) calculated from the DLVO energy by the Maxwell model.