He, F., Zhang, M., Qian, T., & Zhao, D. (2009).

Transport of carboxymethyl cellulose stabilized

iron nanoparticles in porous media: Column experiments and modeling. Journal of colloid and
interface science, 334(1), 96-102.

• The overall goal of this study was to investigate the transport behavior of the CMC-
stabilized ZVI nanoparticles (CMC-Fe) in selected porous media. To preliminarily
investigate the transport of CMC-Fe in natural soil matrix for field application, a sandy soil
was selected. The specific objectives were to: (1) test and simulate the transport and
retention of CMC-Fe through 1-D column experiments with four model porous media; (2)
test and simulate the effects of particle size and hydrodynamic conditions on the transport
behavior; and (3) interpret the experimental transport data using the classical filtration
theory.
•
• modified convection–dispersion equation with a first-order removal rate law.
• there has been limited information available on the transport behavior of metallic
nanoparticles in porous media.
• Saleh et al. [16], [17] demonstrated that elevated ionic strength can curb the transportability
of iron nanoparticles.
• The overall goal of this study was to investigate the transport behavior of the CMC-
stabilized ZVI nanoparticles (CMC-Fe) in selected porous media

Materials and methods

• Chemicals
• Preparation and characterization of CMC-Fe nanoparticles
• Porous media
• Column breakthrough tests
• Analytical methods
 • The hydrodynamic dispersion coefficient (D) for each medium was then obtainedby fitting
the classic 1-D convection–dispersion equation (CDE) to the experimental breakthrough
data using the CXTFIT code (STANMOD software, USDA).
• Sorption of CMC to mineral surfaces can occur due to complexation between CMC and
metal oxides [25].
•

• where C (mg/L) is the liquid-phase Fe concentration, V (cm/h) is the pore fluid velocity, R is
the retardation factor, and kd (h−1) is the removal rate coefficient. R is defined by:

• where ρb is the bulk density of the media bed, Kd is the distribution coefficient of the
nanoparticles between the solid and aqueous phases, and f is the porosity of the media. The
retardation factor R is included in Eq

Zhang, M., He, F., Zhao, D., & Hao, X. (2017). Transport of stabilized iron nanoparticles in porous
media: Effects of surface and solution chemistry and role of adsorption. Journal of hazardous
materials, 322, 284-291.
• A mechanistically sounder transport model was proposed by incorporating a Langmuir-type
adsorption rate law into the classic convection–dispersion equation with the adsorption
parameters derived from independent experiments.
• adsorption becomes more significant at elevated velocities.
• high ionic strength (up to 200 mM CaCl2) had negligible effect on the breakthrough profiles
of the nanoparticles
• Transport and deposition of nanoparticles in saturated porous media is typically interpreted
using the classic convection–diffusion equation coupled with the filtration theory [15], [16],
[21], [22], [35], [36].
• The overall goal of this study was to investigate the effects of surface metal oxides and
solution chemistry on transport of CMC-stabilized ZVI nanoparticles and determine the role
of particle adsorption. The specific objectives were to: (1) examine the breakthrough
behaviors of CMC-stabilized ZVI nanoparticles through quartz sand, iron oxide-coated sand
(IOCS), and aluminum oxide-coated sand (AOCS); (2) elucidate the effects of surface metal
oxide coatings on particle transport; (3) simulate the particle transport using a modified
mathematical model that quantifies contributions of adsorption and filtration to the overall
particle deposition; and (4) determine the effects of particle concentration, ionic strength,
natural organic matter (NOM) and polymer stabilizers on the transport of ZVI nanoparticles.

• Material and methods

◦ Chemicals
◦ Preparation of stabilized ZVI nanoparticles
◦ Preparation of porous media
◦ Column transport experiments
Jones, E. H., Reynolds, D. A., Wood, A. L., & Thomas, D. G. (2011). Use of Electrophoresis for
Transporting Nano‐Iron in Porous Media. Groundwater, 49(2), 172-183.

• transport rate of a single species in the pore fluid, vi (cm/s) under an applied electrical field
• where ke is EO permeability (cm2/V‐s),
• n is porosity,
• Ui* is electrophoretic mobility (EPM) (cm2/V‐s) and
• ie is voltage gradient (V/cm).

• The direction of transport for negatively charged species by EP is opposed by the migration
of the bulk pore‐water through EO thereby retarding species transport to the anode.
• Colloid and particulate mobility under EP also depends upon flocculation, sedimentation,
deposition, and sorption/desorption to porous media. Particles with high surface charges
often exhibit sufficient electrostatic repulsion to remain suspended as discrete particles;
conversely, reduced surface charge can cause flocculation and sedimentation.
• The objectives of this study were (1) to ascertain if EP can transport surface stabilized nZVI
through fine grained sand with the intent of remediating a contaminant in situ, (2) to
determine transport rates of stabilized nZVI under different physical and chemical
conditions, and (3) to compare the mass transported to those predicted using Equation 1.
Parameters studied include grain size, volume, and molecular weight of the polymer, the
ionic strength of the solution, and applied voltage gradient. The influence of magnetic
attractive forces between nZVI particles on aggregate formation and its impact on transport
was also investigated through the use of nonmagnetic colloidally stable hematite
nanoparticles, which have similar properties (particle size and stability).

Ben-Moshe, T., Dror, I., & Berkowitz, B. (2010). Transport of metal oxide nanoparticles in
saturated porous media. Chemosphere, 81(3), 387-393.
• In this study we focus on the transport of several metal oxide nanoparticles, namely
magnetite (Fe3O4), copper oxide (CuO), titanium dioxide (TiO2), and zinc oxide (ZnO), in
saturated columns containing glass bead packs. Because of the critical influence of surface
properties on nanoparticle transport and stability in solution, the nanoparticles were not
treated and used as received. The effect of the inlet boundary condition – with nanoparticles
introduced either as a dry powder or as a pulse suspended in aqueous solution – was first
tested using magnetite. Experiments with magnetite nanoparticles were designed to
investigate different factors affecting the transport of the nanoparticles, such as ionic
strength, addition of organic matter (humic acid), flow rate and pH. Subsequent experiments
allowed a comparative analysis of mobility among the four types of metal oxide
nanoparticles, as a function of ionic strength, presence of humic acid, flow rate and pH.
• . Materials and methods
◦ Porous medium
◦ Characterization of nanoparticles
◦ Transport experiments with magnetite
◦ Comparison of mobility among metal oxide nanoparticles

Li, J., Rajajayavel, S. R. C., & Ghoshal, S. (2016). Transport of carboxymethyl cellulose-coated
zerovalent iron nanoparticles in a sand tank: Effects of sand grain size, nanoparticle concentration
and injection velocity. Chemosphere, 150, 8-16.
 • In this study, the spatial and temporal distribution of CMC-stabilized NZVI suspensions
injected into a 2-D Plexiglas sand tank (0.70 m × 0.35 m × 0.02 m) was assessed. The
transport distance in the tank is larger than those employed in the previous studies discussed
above. The changes in concentrations and aggregate sizes of NZVI over time in the aqueous
phase at various locations in the tank were measured during injection and subsequent
aqueous flushing, at nine locations in the tank, as well as in the effluent ports. Such data on
transient and spatial changes in NZVI in a tank system has not been previously reported.
The spatial distribution of deposition of NZVI, and hydraulic conductivity changes resulting
from injection of NZVI suspension were also assessed. Experiments were conducted by
packing either coarse sand, intermediate sand or fine sand into the tank, to study the effects
of sand size on particle transport. The effects of injection velocity, NZVI concentration and
the concentration of the 700K CMC polymer used for coating the NZVI was investigated
with the intermediate sand. The objective was to identify conditions where NZVI could be
transported with high efficiency, and to determine the distribution of NZVI in the porewater
during several PVs of NZVI injection. The hydraulic conductivity changes induced by
injection of CMC-NZVI were also measured.

Esfahani, A. R., Firouzi, A. F., Sayyad, G., & Kiasat, A. R. (2014). Transport and retention of
polymer-stabilized zero-valent iron nanoparticles in saturated porous media: effects of initial
particle concentration and ionic strength. Journal of Industrial and Engineering Chemistry, 20(5),
2671-2679.
• The objective of this study is, therefore, to investigate the transport and retention behavior of
two polymer-stabilized ZVINs which have shown a perfect function in the case of
environmental clean-up. Especially, the influence of initial particle concentrations and
different ionic strengths on ZVIN transport and retention were evaluated. Therefore, particle
transport and retention were carried out by means of injecting both of the stabilized ZVIN
suspensions at various initial concentrations (0.1, 0.5, and 2 g/L) and a wide range of ionic
strengths (1, 10, and 100 mM NaCl plus 1 mM NaHCO3) in some saturated sand columns.
Finally, this research provides some essential information concerning the dominant
mechanisms influencing ZVIN transport and retention in sand packed columns applicable
for in situ remediation.
◦ . Chemicals
◦ The synthesis of bare and polymer-stabilized Fe0
◦ The characterization of nanoparticles
◦ Colloidal stability
◦ Porous media
◦ Transport experiments

McPherson, A. W., Goltz, M. N., & Agrawal, A. (2013). Pollutant Degradation by Nanoscale Zero
Valent Iron (nZVI): Role of Polyelectrolyte Stabilization and Catalytic Modification on nZVI
Performance. Interactions of Nanomaterials with Emerging Environmental Contaminants, 1150,
159-191.

In column studies, the following factors influenced transport of stabilized NP

• Aggregation Tendencies
◦ nZVI is inherently magnetic, whereas its oxides are less so (46). By comparing the
stability and transport of less-magnetic hematite particles to nZVI, it was shown that
magnetic attractive forces between nZVI particles increase agglomeration, significantly
reducing their transport ( 41, 47, 48 )
◦
• Nanoparticle Concentration
 ◦ Phenrat et al. (2009) reported that at a low concentration of 0.3 g/L all particles were
mobile, but at higher nZVI concentrations (1-6 g/L), agglomeration during transport
occurred (48). Raychoudhury et al. (2010) report similar results, with increased
retardation and, in the case of PAA stabilized particles, decreased effluent concentrations
as the nZVI concentration was increased from 0.1 to 3.0 g/L (39). Particle
agglomeration, followed by straining is the most likely mechanism for capture of nZVI
at high concentrations within porous media.
◦
• Ionic Strength
◦ In summary, an increase in ionic strength may cause a decreased in the interparticle
repulsive force, leading to greater nZVI agglomeration thus affecting its transport.
◦
• Transport Velocity
◦ A decrease in pumping rate generally inhibited the transport of stabilized nZVI in bench
scale studies. However, the majority of column studies were conducted at flow velocities
that are artificially high (>1.0 m/day) compared to typical groundwater flow ( 28, 31,
48 ). Lin et al. (2010) showed that even at these high velocities, decreasing the flow-rate
from 38.2 to 6.28 m/day decreased transport by ~5% (32). Raychoudhury et al. (2010)
also demonstrated that decreasing the flow from 14.4 m/day to a realistic value of 0.29
m/day decreased transport 20% to 30% (39). This effect is explained by an increase in
stagnant zones in the pore spaces and decreased drag torques which, when high, result in
captured particle detachment from collector surfaces ( 32, 39, 48 ).
◦
• Reactivity of Polyelectrolyte-Stabilized nZVI
▪ The reactivity of stabilized nZVI toward contaminants may become inhibited due to
polyelectrolyte coatings on the particle surface. Phenrat et al. (2009) examined this
effect for nZVI stabilized with PSS, CMC, and PAP, and found the reactivity toward
TCE decreased between 4 and 25 fold (34), which was attributed to (a) blocking of
reactive sites on nZVI surface, and (b) TCE partitioning to the polyelectrolyte
coatings, effectively decreasing the aqueous TCE concentration. However, such loss
in reactivity is expressed on a nZVI surface-area-normalized basis. Because
polyelectrolyte stabilization of nZVI also decreased mean particle size and prevented
aggregation, both of which dramatically increased the overall reactive surface area
per unit nZVI mass ( 22, 24, 53, 54, 55 ), the net effect of polyelectrolyte
stabilization was an impressive gain in nZVI reactivity on a mass-normalized basis,
making polyelectrolyte-stabilized nZVI a “new class” of particles altogether ( 22, 24,
27, 56, 57, 58, 59, 60 ).