Co-transport of chlordecone and sulfadiazine in the presence of functionalized multi-walled carbon nanotubes in soils.

Batch and saturated soil column experiments were conducted to investigate sorption and mobility of two 14C-labeled contaminants, the hydrophobic chlordecone (CLD) and the sulfadiazine (SDZ), in the absence or presence of functionalized multi-walled carbon nanotubes (MWCNTs). The transport behaviors of CLD, SDZ, and MWCNTs were studied at environmentally relevant concentrations (0.1-10 mg L-1) and they were applied in the column studies at different times. The breakthrough curves and retention profiles were simulated using a numerical model that accounted for the advective-dispersive transport of all compounds, attachment/detachment of MWCNTs, equilibrium and kinetic sorption of contaminants, and co-transport of contaminants with MWCNTs. The experimental results indicated that the presence of mobile MWCNTs facilitated remobilization of previously deposited CLD and its co-transport into deeper soil layers, while retained MWCNTs enhanced SDZ deposition in the topsoil layers due to the increased adsorption capacity of the soil. The modeling results then demonstrated that the mobility of engineered nanoparticles (ENPs) in the environment and the high affinity and entrapment of contaminants to ENPs were the main reasons for ENP-facilitated contaminant transport. On the other hand, immobile MWCNTs had a less significant impact on the contaminant transport, even though they were still able to enhance the adsorption capacity of the soil.

Limited transport of functionalized multi-walled carbon nanotubes in two natural soils.

Column experiments were conducted in undisturbed and in repacked soil columns at water contents close to saturation (85-96%) to investigate the transport and retention of functionalized (14)C-labeled multi-walled carbon nanotubes (MWCNT) in two natural soils. Additionally, a field lysimeter experiment was performed to provide long-term information at a larger scale. In all experiments, no breakthrough of MWCNTs was detectable and more than 85% of the applied radioactivity was recovered in the soil profiles. The retention profiles exhibited a hyper-exponential shape with greater retention near the column or lysimeter inlet and were successfully simulated using a numerical model that accounted for depth-dependent retention. In conclusion, results indicated that the soils acted as a strong sink for MWCNTs. Little transport of MWCNTs is therefore likely to occur in the vadose zone, and this implies limited potential for groundwater contamination in the investigated soils.

Transport and retention of multi-walled carbon nanotubes in saturated porous media: effects of input concentration and grain size.

Water-saturated column experiments were conducted to investigate the effect of input concentration (C0) and sand grain size on the transport and retention of low concentrations (1, 0.01, and 0.005 mg L⁻¹) of functionalized ¹4C-labeled multi-walled carbon nanotubes (MWCNT) under repulsive electrostatic conditions that were unfavorable for attachment. The breakthrough curves (BTCs) for MWCNT typically did not reach a plateau, but had an asymmetric shape that slowly increased during breakthrough. The retention profiles (RPs) were not exponential with distance, but rather exhibited a hyper-exponential shape with greater retention near the column inlet. The collected BTCs and RPs were simulated using a numerical model that accounted for both time- and depth-dependent blocking functions on the retention coefficient. For a given C0, the depth-dependent retention coefficient and the maximum solid phase concentration of MWCNT were both found to increase with decreasing grain size. These trends reflect greater MWCNT retention rates and a greater number of retention locations in the finer textured sand. The fraction of the injected MWCNT mass that was recovered in the effluent increased and the RPs became less hyper-exponential in shape with higher C0 due to enhanced blocking/filling of retention locations. This concentration dependency of MWCNT transport increased with smaller grain size because of the effect of pore structure and MWCNT shape on MWCNT retention. In particular, MWCNT have a high aspect ratio and we hypothesize that solid phase MWCNT may create a porous network with enhanced ability to retain particles in smaller grain sized sand, especially at higher C0. Results demonstrate that model simulations of MWCNT transport and fate need to accurately account for observed behavior of both BTCs and RPs.