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Multi-walled carbon nanotubes (MWCNTs) are increasing used in commercial applications and may be released into the environment with anionic surfactants, such as sodium dodecylbenzenesulfonate (SDBS), in sewer discharge. Little research has examined the transport, retention, and remobilization of MWCNTs in the presence or absence of SDBS in porous media with controlled chemical heterogeneity, and batch and column scale studies were therefore undertaken to address this gap in knowledge. The adsorption isotherms of SDBS on quartz sand (QS), goethite coated quartz sand (GQS), and MWCNTs were determined. Adsorption of SDBS (MWCNTs » GQS > QS) decreased zeta potentials for these materials, and produced a charge reversal for goethite. Transport of MWCNTs (5 mg L-1) dramatically decreased with an increase in the fraction of GQS from 0 to 0.1 in the absence of SDBS. Conversely, co-injection of SDBS (10 and 50 mg L-1) and MWCNTs radically increased the transport of MWCNTs when the GQS fraction was 0, 0.1, and 0.3, especially at a higher SDBS concentration, and altered the shape of retention profile. Mathematical modeling revealed that competitive blocking was not the dominant mechanism for the SDBS enhancement of MWCNT transport. Rather, SDBS sorption increased MWCNT transport by increasing electrostatic and/or steric interactions, or creating reversible interactions on rough surfaces. Sequential injection of pulses of MWCNTs and SDBS in sand (0.1 GQS fraction) indicated that SDBS could mobilize some of retained MWCNTs from the top to deeper sand layers, but only a small amount of released MWCNTs were recovered in the effluent. SDBS therefore had a much smaller influence on MWCNT transport in sequential injection than in co-injection, presumably because of a greater energy barrier to MWCNT release than retention. This research sheds novel insight on the roles of competitive blocking, chemical heterogeneity and nanoscale roughness, and injection sequence on MWCNT retention and release.

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.

Engineered nanoparticles (ENPs) present in consumer products are being released into the agricultural systems. There is little information about the direct effect of ENPs on phosphorus (P) availability, which is an essential nutrient for crop growth naturally occurring in agricultural soils. The present study examined the effect of 1, 3, and 5% doses of Cu0 or Ag0 ENPs stabilized with L-ascorbic acid (suspension pH 2–3) on P ad- and desorption in an agricultural Andisol with total organic matter (T-OM) and with partial removal of organic matter (R-OM) by performing batch experiments. Our results showed that the adsorption kinetics data of H2PO4− on T-OM and R-OM soil samples with and without ENPs were adequately described by the pseudo-second-order (PSO) and Elovich models. The adsorption isotherm data of H2PO4− from T-OM and R-OM soil samples following ENPs addition were better fitted by the Langmuir model than the Freundlich model. When the Cu0 or Ag0 ENPs doses were increased, the pH value decreased and H2PO4− adsorption increased on T-OM and R-OM. The H2PO4− desorption (%) was lower with Cu0 ENPs than Ag0 ENPs. Overall, the incorporation of ENPs into Andisols generated an increase in P retention, which may affect agricultural crop production. [ABSTRACT FROM AUTHOR]

Light expanded clay aggregates (LECA) have been increasingly used as substrate material for constructed wetlands given their phosphate removal capacity, mechanical strength, hydraulic conductivity and their plant rooting and biofilm growth supporting structure. This review summarizes the current literature on LECA-based constructed wetlands. Removal performances for main wastewater parameters phosphate, nitrogen species, suspended solids and oxygen demand are tabulated. Both, physical and biological water purification processes in LECA wetlands are discussed. Additional emphasis is on design and layout of LECA wetlands for different types of wastewater, under different climatic conditions and to improve treatment performance in general. LECA life cycle considerations include sourcing, production energy demand, reuse and recycling options for spent wetland substrates, for example as soil amendment. Research and development opportunities were identified for structural and compositional LECA modification to obtain tailored substrates for the use in water treatment and specific treatment tasks. Beyond traditional wastewater contaminants the fate of a wider range of contaminants, including organic trace contaminants, needs to be investigated as high Fe, Al and Ca oxides content of LECA substrates provide adsorptive sites that may facilitate further biological interactions of compounds that are otherwise hard to degrade. • Gap/strength analysis of LECA as a substrate material in constructed wetlands. • High Fe, Al, and Ca oxides content underpin LECA pollutant removal and adsorbance. • LECA has indirect effects on parameters controlling biochemical efficiency of CWs. • Technical aspects and optimal design considerations for LECA in different CWs evaluated. • Saturated LECA potential use as soil amendment and fertilizer reviewed. [ABSTRACT FROM AUTHOR]

Abstract: We report the adsorption of phenol and dopamine probe molecules, from aqueous solution with NaCl, on commercial multiwall carbon nanotubes (MWCNT) and on their carboxylated derivative. The nanotubes were fully characterized by high resolution transmission electron microscopy (HRTEM), small angle X-ray scattering (SAXS), potentiometric titration, electrophoretic mobility, and nitrogen adsorption (77K) measurements. The experimental pollutant isotherms, evaluated using the Langmuir model, showed that only 8–12% and 21–32% of the BET surface area was available for phenol and dopamine, respectively, which is far below the performance of activated carbons. Influence of the pH was more pronounced for the oxidized MWCNT, particularly with dopamine. The strongest interaction and the highest adsorption capacity occurred at pH 3 with both model pollutants on both types of nanotubes. Although the surface area available for adsorption is far lower in MWCNTs than in activated carbons, it is nonetheless substantial. In particular, delayed release of toxic molecules that are either adsorbed on the surface or trapped in the inner bore of such systems could constitute an environmental hazard. The need for further adsorption studies with regard to their environmental aspects is therefore pressing, particularly for MWCNTs in their functionalized state. [Copyright &y& Elsevier]

Abstract: A column material containing organophilic clay particles was developed for soil remediation. 2,4-dichlorophenol adsorption on aquifer material with an effective particle diameter d <1mm and various partially modified dioctadecyldimethylammonium–montmorillonite/aquifer material mixtures were studied under static and flow conditions. The 2,4-dichlorophenol adsorption on the aquifer material was negligible. On organoclay/aquifer material mixtures the adsorption capacity increased with increasing organoclay content and the adsorption isotherms could be fitted by the Freundlich equation. In columns filled with organoclay/aquifer material mixtures, the 2,4-dichlorophenol retardation increased with increasing organoclay content up to 1% (w / w). Above 1.5–2.0% (w / w) the permeability of the column material decreased. The HYDRUS_1D model, which solves the convection–dispersion equation for solute transport, was used in a forward and inverse mode to simulate 2,4-dichlorophenol breakthrough in the columns. The simulations revealed that 2,4-dichlorophenol transport exhibited an additional kinetic effect not observed in the batch experiments. [Copyright &y& Elsevier]