Fate and Transport of Molybdenum Disulfide Nanomaterials in Sand Columns.

Research and development of two-dimensional transition metal dichalcogenides (TMDC) (e.g., molybdenum disulfide [MoS2]) in electronic, optical, and catalytic applications has been growing rapidly. However, there is little known regarding the behavior of these particles once released into aquatic environments. Therefore, an in-depth study regarding the fate and transport of two popular types of MoS2 nanomaterials, lithiated (MoS2-Li) and Pluronic PF-87 dispersed (MoS2-PL), was conducted in saturated porous media (quartz sand) to identify which form would be least mobile in aquatic environments. The electrokinetic properties and hydrodynamic diameters of MoS2 as a function of ionic strength and pH were determined using a zeta potential analyzer and dynamic light scattering techniques. Results suggest that the stability is significantly decreased beginning at 10 and 31.6 mM KCl, for MoS2-PL and MoS2-Li, respectively. Transport study results from breakthrough curves, column dissections, and release experiments suggest that MoS2-PL exhibits a greater affinity to be irreversibly bound to quartz surfaces as compared with the MoS2-Li at a similar ionic strength. Derjaguin-Landau-Verwey-Overbeek theory was used to help explain the unique interactions between the MoS2-PL and MoS2-Li surfaces between particles and with the quartz collectors. Overall, the results suggest that the fate and transport of MoS2 is dependent on the type of MoS2 that enters the environment, where MoS2-PL will be least mobile and more likely be deposited in porous media from pluronic-quartz interactions, whereas MoS2-Li will travel greater distances and have a greater tendency to be remobilized in sand columns.

Stability and Transport of Graphene Oxide Nanoparticles in Groundwater and Surface Water.

The effects of groundwater and surface water constituents (i.e., natural organic matter [NOM] and the presence of a complex assortment of ions) on graphene oxide nanoparticles (GONPs) were investigated to provide additional insight into the factors contributing to fate and the mechanisms involved in their transport in soil, groundwater, and surface water environments. The stability and transport of GONPs was investigated using dynamic light scattering, electrokinetic characterization, and packed bed column experiments. Stability results showed that the hydrodynamic diameter of the GONPs at a similar ionic strength (2.1±1.1 mM) was 10 times greater in groundwater environments compared with surface water and NaCl and MgCl2 suspensions. Transport results confirmed that in groundwater, GONPs are less stable and are more likely to be removed during transport in porous media. In surface water and MgCl2 and NaCl suspensions, the relative recovery was 94%±3% indicating that GONPs will be very mobile in surface waters. Additional experiments were carried out in monovalent (KCl) and divalent (CaCl2) salts across an environmentally relevant concentration range (0.1-10 mg/L) of NOM using Suwannee River humic acid. Overall, the transport and stability of GONPs was increased in the presence of NOM. This study confirms that planar "carbonaceous-oxide" materials follow traditional theory for stability and transport, both due to their response to ionic strength, valence, and NOM presence and is the first to look at GONP transport across a wide range of representative conditions found in surface and groundwater environments.

Effects of solution chemistry on the transport of graphene oxide in saturated porous media.

A transport study was performed in saturated porous media through a packed bed column to simulate fate of graphene oxide nanoparticles (GONPs) in the subsurface environment. Transport experiments, along with mass balances and column dissections, were conducted as a function of ionic strength (IS, 10(-3)-10(-1) M). Additionally, an extensive evaluation of the electrokinetic properties and hydrodynamic diameters of GONPs were determined as a function of IS and pH. The measured hydrodynamic diameter and the electrophoretic mobility (EPM) of GONPs indicated an insensitivity to pH, although IS did play a role. Results from a stability study indicated that the hydrodynamic diameter of GONPs was stable and unchanging at the lower range of IS (10(-3) and 10(-2) M) then became unstable when IS ≥ 10(-1.5) M KCl was achieved. Specifically, for IS ≥ 10(-1.5) M KCl, the hydrodynamic diameter became greater and showed a larger size range of particles than at the lower IS range (10(-3) and 10(-2) M). In addition, the EPM of GONPs became less negative over the IS range of 10(-3) and 10(-2) M KCl. Furthermore, GONPs were found to be increasingly mobile for IS ≤ 10(-2) M KCl. When GONPs were passed through the packed bed column at 10(-2) and 10(-1) M KCl, 5% and 100% of the GONPs were retained in the column, respectively. Finally, mass balances and column dissections revealed that in the first cm of the column 7% and 95% of the GONPs were deposited at 10(-2) and 10(-1) M KCl, respectively, confirming that the transport of GONPs is a function of IS. The fraction of GONPs eluted during the transport experiments provides insight into the contribution of aggregation and reversibly bound fraction of GONPs in saturated porous media.