Colloidal properties of aqueous suspensions of acid-treated, multi-walled carbon nanotubes.

Grafting oxygen-containing functional groups onto carbon nanotubes (CNTs) by acid treatment improves their dispersion in aqueous solutions, but there is a lack of quantitative information on the colloidal properties of oxidized CNTs. We have studied the influence that pH and electrolytes have in determining the colloidal stability of oxidized multiwalled carbon nanotubes (O-MWCNTs), prepared by refluxing pristine MWCNTs in nitric acid. The acid-treated MWCNTs contained oxygen predominantly in the form of carboxyl groups. Colloidal suspensions of O-MWCNTs were prepared by low-power sonication and contained negatively charged, individual MWCNTs with an average length of approximately 650 nm. Time-resolved dynamic light scattering revealed that the aggregation rate of O-MWCNTs exhibited both reaction and mass-transport limited regimes in the presence of different electrolytes and as a function of pH. Particle stability profiles constructed from aggregation rate data allowed for the determination of critical coagulation concentrations (CCC), a metric of colloidal stability. The CCC values of O-MWCNTs varied with counterion concentration and valence in a manner consistentwith DLVO theory. Potentiometric measurements of surface charge correlated well with the observed pH-dependent variations in the O-MWCNT's colloidal stability. Electrophoretic mobility was also a diagnostic of particle stability, but only in neutral and acidic conditions.

Riverbank filtration for control of microorganisms: results from field monitoring.

Microbial monitoring was conducted over a period of more than 1 year at three full-scale riverbank filtration (RBF) facilities, located in the United States along the Ohio, Missouri, and Wabash Rivers. Results of this study demonstrated the potential for RBF to provide substantial reductions in microorganism concentrations relative to the raw water sources. Cryptosporidium and Giardia were detected occasionally in the river waters but never in any of the well waters. Average concentrations and log reductions of Cryptosporidium and Giardia could not be accurately determined due to the low and variable concentrations in the river waters and the lack of detectable concentrations in the well waters. Average concentrations of aerobic and anaerobic spore-forming bacteria, which have both been proposed as potential surrogates for the protozoans, were reduced at the three facilities by 0.8 to > 3.1 logs and 0.4 to > 4.9 logs, respectively. Average concentrations of male-specific and somatic bacteriophage were reduced by > 2.1 logs and 3.2 logs, respectively. Total coliforms were rarely detected in the well waters, with 5.5 and 6.1 log reductions in average concentrations at the two wells at one of the sites relative to the river water. Average turbidity reductions upon RBF at the three sites were between 2.2 and 3.3 logs. Turbidity and microbial concentrations in the river waters generally tracked the river discharge; a similar relationship between the well water concentrations and river discharge was not observed, due to the low, relatively constant well water turbidities and lack of a significant number of detections of microorganisms in the well waters. Further research is needed to better understand the relationships among transport of pathogens (e.g., Cryptosporidium, Giardia, viruses) and potential surrogate parameters (including bacterial spores and bacteriophage) during RBF and the effects of water and sediment characteristics on removal efficiency.

Aquasols: on the role of secondary minima.

Experiments are presented that test the hypothesis of deposition into and reentrainment from secondary minima during flow through porous media. The release of deposited particles following a decrease in ionic strength is inconsistent with deposition in the primary minimum of either simple DLVO interaction energy curves (which suggest that deposition is irreversible) or Born-DLVO interaction energy curves (which create a finite primary minimum that deepens with decreasing ionic strength). The observed release of particles is, on the other hand, consistent with deposition in the secondary minimum because this energy minimum decreases and can disappear with decreasing ionic strength. The implications for colloid transport of a reversible deposition process in the secondary minimum are very different from those of a process involving irreversible deposition in the primary minimum. First, particles that are continually captured and released will travel much farther in the subsurface than might be expected if the classic irreversible filtration model is applied. Second, and perhaps more significantly, deposition in the secondary well can increase with increasing particle size. Although particle transport by convective diffusion increases as particle size decreases, particle "attachment" in secondary minima decreases with decreasing particle size. Thus, smaller particles (those with diameters in the order of a few tens of nanometers) would be more effective in the facilitated transport of highly sorbing contaminants such as hydrophobic organic molecules, metals, and radionuclides. Other contaminants are themselves particles, such as viruses (tens of nanometers in diameter) and bacteria (near 1 microm in diameter). Due to this difference in size, viruses could be transported over much larger distances than bacteria. Third, the transport of colloids and, hence, the transport of contaminants associated with them, depends on the Hamaker constant of the particle-water-aquifer media system. Colloids of lower Hamaker constant are likely to be transported farther than colloids of higher Hamaker constant. The extent of adsorption of specific contaminants and the Hamaker constant for the particle-aquifer system are both characteristics of the particles and contribute to the effectiveness of colloid-facilitated transport. Finally, the solution chemistry of the pore waters (through pH, ionic strength, types of solutes, and the valence of the ions) ultimately controls the deposition and release of colloidal particles in porous media. The pH determines the charge density and surface potential of the surfaces. When the surfaces are similarly charged, their interaction can be unfavorable, with an energy barrier and secondary minimum. The ionic strength and valence of the ions determines the shape of the interaction energy curve, including the presence and height of the energy barrier and the presence and depth of the secondary well. Since the subsequent release of a particle depends on the mode in which the particle is deposited (primary or secondary), these factors are particularly important in determining the extent of colloid transport in the subsurface.

Effects of natural organic matter and solution chemistry on the deposition and reentrainment of colloids in porous media.

The role of humic acid in the transport of negatively charged colloids through porous media was examined. Adsorption of humic acid on latex colloids and silica collectors reduced the deposition of suspended particles and enhanced the reentrainment of deposited particles in porous media. These effects are considered to arise from additional electrostatic and steric contributions to the repulsive interaction energy due to the adsorption of negatively charged humic acid on both the suspended particles and the media collectors. At low ionic strength reversible deposition in shallow secondary minima is hypothesized to be the principal attachment mechanism, independent of the presence of humic acid. It is proposed that under these solution conditions, particle deposition and reentrainment are the result of a dynamic process, in which particles are continuously captured and released from secondary minima. At higher ionic strengths, deposition may be regarded as a combination of two mechanisms: capture in the primary well and capture in the secondary minimum. Theoretical calculations of the attachment efficiency were conducted using two existing mathematical models. The first model is based on deposition in the primary well (interaction force boundary layer, IFBL), and the second model is based on the Maxwell kinetic theory and deposition in the secondary minimum (Maxwell model). Simulations conducted with the Maxwell model provide significantly better fits of the experimental results than those conducted with the IFBL model.