Significance of Non-DLVO Interactions on the Co-Transport of Functionalized Multiwalled Carbon Nanotubes and Soil Nanoparticles in Porous Media.

Derjaguin-Landau-Verwey-Overbeek (DLVO) theory is typically used to quantify surface interactions between engineered nanoparticles (ENPs), soil nanoparticles (SNPs), and/or porous media, which are used to assess environmental risk and fate of ENPs. This study investigates the co-transport behavior of functionalized multiwalled carbon nanotubes (MWCNTs) with positively (goethite nanoparticles, GNPs) and negatively (bentonite nanoparticles, BNPs) charged SNPs in quartz sand (QS). The presence of BNPs increased the transport of MWCNTs, but GNPs inhibited the transport of MWCNTs. In addition, we, for the first time, observed that the transport of negatively (BNPs) and positively (GNPs) charged SNPs was facilitated by the presence of MWCNTs. Traditional mechanisms associated with competitive blocking, heteroaggregation, and classic DLVO calculations cannot explain such phenomena. Direct examination using batch experiments and Fourier transform infrared (FTIR) spectroscopy, asymmetric flow field flow fractionation (AF4) coupled to UV and inductively coupled plasma mass spectrometry (AF4-UV-ICP-MS), and molecular dynamics (MD) simulations demonstrated that MWCNTs-BNPs or MWCNT-GNPs complexes or aggregates can be formed during co-transport. Non-DLVO interactions (e.g., H-bonding and Lewis acid-base interaction) helped to explain observed MWCNT deposition, associations between MWCNTs and both SNPs (positively or negatively), and co-transport. This research sheds novel insight into the transport of MWCNTs and SNPs in porous media and suggests that (i) mutual effects between colloids (e.g., heteroaggregation, co-transport, and competitive blocking) need to be considered in natural soil; and (ii) non-DLVO interactions should be comprehensively considered when evaluating the environmental risk and fate of ENPs.

The impact of heteroaggregation between nZVI and SNPs on the co-transport of Cd(II) in saturated sand columns.

This study investigated the co-transport behaviors of nano zero-valent iron (nZVI) and Cd(II) in the presence of soil nanoparticles (SNPs) under various SNPs/nZVI mass ratios. It was illustrated that the mobility of colloidal Cd(II) was highly dependent on the nZVI-SNPs heteroaggregation behavior. In the case of 40 mg/L nZVI with SNPs/nZVI mass ratios > 1, the formation of stable SNPs-nZVI heteroaggregates with hydrodynamic diameters (Dh) < 500 nm facilitated the nZVI and colloidal Cd(II) transport at their effluent mass recoveries of 34.76-37.82 % and 9.81-17.17 %, respectively. However, in the case of 100 mg/L nZVI with SNPs/nZVI mass ratios of 0.4-2, the interception of nZVI-SNPs heteroaggregates with Dh > 1500 nm by quartz sands led to almost complete retention of nZVI and colloidal Cd(II) in the columns. Combined with analytical results of zeta potentials and XRD spectrum, it was revealed that the Cd(II) ions could accelerate nZVI corrosion. The positively charged Fe3O4 and γ-FeOOH on corroded nZVI surface could facilitate the heteroaggregation of nZVI-SNPs by the patch-charge attraction, which further reduced the environmental risk of colloidal Cd(II) transport. These findings revealed the important effects of heteroaggregation between nZVI and SNPs on the transport risk of Cd(II) in groundwater.

The evolution of stable nanohybrids to complex heteroaggregates between nZVI and soil nanoparticles: The influence of ionic strength and soil components.

The heteroaggregation mechanism of nZVI with four types of natural soil nanoparticles (SNPs) extracted from representative soils in northern and southern China was investigated. Heteroaggregation rates between nZVI and SNPs were quantified by dynamic light scattering and evaluated as a function of ionic strength at pH 7. The nZVI-SNPs heteroaggregates were stable with hydrodynamic diameters (Dh) ranging from 400 to 600 nm in 0.1 mM solution. Based on the extended Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, nZVI underwent heteroaggregation with SNPs to form stable nZVI-SNPs nanohybrid due to the attachment of nZVI on the SNPs. However, with enhanced ionic strength, SNPs accelerated the aggregation of nZVI and formed large heteroaggregates with Dh in the range from 1200 to 2000 nm, owing to insignificant electrostatic repulsions and oppositely charged patches. In addition, the differences in the heteroaggregation rates of nZVI with four SNPs were negligible, caused by the negligible impacts of SNPs components such as soil organic matter and Fe/Al oxyhydroxides on the heteroaggregation of nZVI in the 10 mM NaCl solution. These findings are helpful for understanding the interaction between nZVI and SNPs and of significance to groundwater remediation using nZVI.

Co-transport of phenanthrene and pentachlorophenol by natural soil nanoparticles through saturated sand columns.

Mobile colloids such as nanoparticles (NPs) are often considered to affect the fate and transport of various contaminants by serving as carriers. Many studies have focused on the effect of engineered NPs on contaminant transport. To date, very little information is available on the co-transport of natural soil NPs with typical organic contaminants. This study investigated the co-transport of phenanthrene (PHE) and pentachlorophenol (PCP) by three soil NPs through saturated sand columns. Soil NPs with high organic matter and particle concentration were the most effective in transporting PHE through columns. In addition, soil NPs significantly increased the transport of low-level PHE (0.2 mg L-1) but there was no obvious increase at 1.0 mg L-1 PHE. This is attributed to a higher ratio of NP-associated PHE to total PHE at a low-level than at a high-level during transport. In contrast to PHE, the chemical speciation of PCP determined its mobility, which was highly dependent on solution pH. At pH 6.5, anionic PCP became dominant and soluble in the effluent. This could account for the negligible effect of soil NPs on PCP mobility. At pH 4.0, however, neutral molecular PCP dominated and, as expected, decreased mobility of PCP occurred. Soil NPs considerably enhanced the transport of neutral PCP in NP-associated forms compared to controls, due to the high hydrophobicity and sorption affinity of PCP to NPs. The mobility of soil NPs was little affected by PHE and PCP under tested conditions. This study indicated that highly mobile soil NPs may be effective carriers for organic contaminants and give a new direction to polluted site remediation by using a natural material, e.g., soil.

Differences in transport behavior of natural soil colloids of contrasting sizes from nanometer to micron and the environmental implications.

Transport behaviors of nanoparticles (<100nm) and clay fractions (clay particles, <2µm; coarse clay particles, 1-2µm and fine clay particles, 0.1-1µm) extracted from two natural soils (Inceptisol from Jilin and Oxisol from Hainan, China) were investigated in saturated sand columns at 1-30mM NaCl and pH5-9. Increasing NaCl concentrations decreased the mobility, while increasing pH increased the mobility of soil particles of various sizes. At pH5 and 30mM NaCl, nanoparticles and clay fractions exhibited the different transport behaviors, and ripening was observed for Inceptisol nanoparticles while blocking for Oxisol nanoparticles in breakthrough curves (BTCs). The effluent mass recoveries (MRs) of nanoparticles were much more than that of clay particles for both two soils (>1.9-fold) at all tested conditions, except for Inceptisol at pH5 and 30mM NaCl (with comparable MR). According to Derjaguin-Landau-Verwey-Overbeek (DLVO) calculations and particle-collector size ratios, both secondary energy minimum and physical straining led to the retention of clay fractions at pH5 and 30mM NaCl, whereas primary energy minimum and straining induced by simultaneous aggregation caused the retention of nanoparticles. The experimental attachment efficiency between soil particles of various sizes and sand collector for both two soils was in the order nanoparticles