Chemosphere 218 (2019) 1e13

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Co-transport of graphene oxide and heavy metal ions in surface-

modified porous media
Xianqiang Yin a, b, *, Yanji Jiang a, Yuehui Tan a, Xiangmin Meng a, Huimin Sun a, b,
Nong Wang c
a
College of Natural Resources and Environment, Northwest A&F University, Yangling, 712100, China
b
Key Laboratory of Plant Nutrition and the Agri-environment in Northwest China, Ministry of Agriculture, Yangling, 712100, China
c
Agro-Environmental Protection Institute, Ministry of Agriculture of the People's Republic of China Tianjin, 300191, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

HA, smectite, kaolinite, and ferrihy-

drite were used to coating quartz
sand.

The mobility in the coated sand col-
umn is GO > Cd2þ > Pb2þ.

Co-transport mobility of GO and Pb2þ
or Cd2þ in coated sand column was
decreased.

GO released Pb2þ or Cd2þ from
coated sand and smectite is the
smallest.

The DLVO theory could well explain
the transport behavior.

a r t i c l e i n f o a b s t r a c t

Article history: The ability to predict the transport of heavy metal ions in porous media with different surface charac-
Received 16 July 2018 teristics is crucial to protect groundwater quality and public health. In this study, the effects of graphene
Received in revised form oxide (GO) on co-transport and remobilization of Pb2þ and Cd2þ in humic acid (HA), smectite, kaolinite,
19 October 2018
and ferrihydrite-coated sand media were evaluated via laboratory packed-column experiments. Scanning
Accepted 12 November 2018
Available online 15 November 2018
electron microscope and energy dispersive X-ray analysis showed that the surface morphology of the
coated sands was quite different and that ~56.7e89.9% of the surface was covered by the coating and the
Handling Editor: T. Cutright major elemental components were C, O, Si, Al, and Fe. GO exhibited high mobility in HA, kaolinite, and
smectite-coated sand, but showed high retention in ferrihydrite-coated sand. While GO reduced the
Keywords: transport of Pb2þ and Cd2þ, both metal ions also reduced the mobility of GO in coated-sand columns.
Transport Elution experiments revealed that GO led to the remobilization and release of the previously sorbed Pb2þ
Graphene oxide and Cd2þ from the coated sand. However, GO could not release Pb2þ and Cd2þ from smectite-coated sand
Pb2þ columns, probably because smectite has stronger adsorption affinity to the heavy metals than GO.
Cd2þ
Derjaguin-Landau-Verwey-Overbeek calculations were employed and explained the GO transport
Coated sand
behavior in the columns well. Furthermore, the advection-dispersion-reaction equation simulated the
DLVO theory
cotransport of Pb2þ and Cd2þ with GO in the coated sand well. These results are expected to provide
insight into the potential impact of coexisting nanomaterials with contaminants in vulnerable soil and
groundwater systems.
© 2018 Elsevier Ltd. All rights reserved.

* Corresponding author. College of Natural Resources and Environment, North-

west A&F University, Yangling, 712100, China.
E-mail address: xqyin@nwsuaf.edu.cn (X. Yin).

https://doi.org/10.1016/j.chemosphere.2018.11.089
0045-6535/© 2018 Elsevier Ltd. All rights reserved.
2 X. Yin et al. / Chemosphere 218 (2019) 1e13
1. Introduction
Graphene oxide (GO), a carbon-based engineered nanomaterial
with a large specific surface area, contains abundant oxygen-
containing surface functional groups (e.g., hydroxyl, carboxyl,
carbonyl groups, and epoxy groups) and thus has very good water
dispersibility and biocompatibility (Peng et al., 2017). GO has been
applied in numerous fields including electronics, biotechnology,
energy storage, optics, and solar photovoltaic technology (Zang
et al., 2017; Kim et al., 2018). Moreover, it shows promising po-
tential to remove contaminants from aqueous solutions (Sherlala
et al., 2018). GO has strong adsorption capacity for heavy metals
such as Pb(II), Cu(II), Cd(II), Co(II), and Zn(II) and organic contam-
inants (Peng et al., 2017). In addition, its adsorption capacity is
significantly higher than that of activated carbon, carbon nano-
tubes, and other carbon materials (Gan et al., 2015; Konicki et al.,
2017). Considering the massive production and widespread appli-
cations of GO, it is necessary to assess the impact of GO on the
natural environment and global ecosystem.
The presence of complexes of nanoparticles and metals in
dispersed phase can alter the bioavailability and ecotoxicity of
heavy metals (Ma et al., 2016). Previous studies have found that
metal-loaded nanoparticles significantly reduced soil enzyme ac-
tivity, microbial biomass, community structure, and soil biological
processes (e.g., nitrification bacteria) in a relatively short period of
time (Ren et al., 2015; Kim et al., 2017). Moreover, mobile metal-
loaded GOs promotes the absorption and accumulation of metals
in plants because GO can act as their carrier and thus facilitate their
transport in soils (Dwivedi et al., 2015). Consequently, metal-loaded
GOs can enter the food chain, causing various diseases and disor-
ders to public health. At present, research on the transport behavior
of GO is mostly focused on the influence of physical and chemical
factors, including solution chemistry (pH, ionic strength, type of
salt solution, Ca2þ/Naþ, and humic acid), medium properties
(saturation degree, medium size, and surface roughness), and fluid
velocity (Lanphere et al., 2013; Chowdhury et al., 2014; Fan et al.,
2015; Sun et al., 2015; Carstens et al., 2017). However, to the best
of the authors' knowledge, there has been little information about
the cotransport of GO and heavy metal ions in soils. GO can serve as
an effective carrier of Cu2þ to enhance its Cu2þ mobility in porous
media (Zhou et al., 2016). When GO and Pb2þ or Cd2þ are co-
transported in saturated porous media, the migration ability of
Pb2þ or Cd2þ is significantly improved (Jiang et al., 2018). Among
the different toxic metal ions, Pb2þ and Cd2þ have received signif-
icant attention due to their severe toxic effects. Cd is a persistent
pollutant with high neurotoxicity and carcinogenicity, which can
significantly increase brain damage and perturb cell signaling
pathways (Zheng et al., 2017). Pb has serious toxic effects on he-
matopoietic, renal, reproductive, and central nervous systems due
to its ability to interfere with cellular processes and enzyme sys-
tems (Flora et al., 2012). The permissible levels of Pb2þ and Cd2þ in
drinking water stipulated by the World Health Organization are
only 10 and 5 mg L1, respectively (WHO, 2011).
Soil shows differences in structure, particle size distribution,
particle shape, surface charge, and mineral surface types (Zhang
et al., 2012; Zhao et al., 2012). Clays, organic matter, and iron-
oxides, are the most reactive solid constituents in soils and sedi-
ments. These materials play a major role in affecting the fate and
transport of contaminants. However, most studies use quartz sand
or glass beads as a porous medium to simulate soil (Huang et al.,
2016; Lu et al., 2017), which does not reflect the complexity of
the soil. At present, iron-oxides have been successfully coated on
quartz sand and used for studying the transport behavior of heavy
metals (Yang et al., 2010; Ma €hler and Persson, 2013; Han et al.,
2014). Similarly, humic acids (HA) and clay minerals have been
immobilized on quartz sand to obtain porous media suitable for
transport studies (Jerez and Flury, 2006; Yu et al., 2007). The effects
of immobilized clays, organic matter, and iron oxides on nano-
particle and heavy metal transport in porous media have not been
well-studied yet. The options to coat quartz sand with iron-oxides,
HA, and clay minerals offers the opportunity to study the co-
transport of GO and heavy metals in three major soil constituents
using column experiments. Moreover, an understanding of GO and
heavy metal transport in soil constituents coated on quartz sand are
important for the protection of the underground environment.
In this work, a series of column experiments were conducted to
investigate the cotransport of GO and Pb2þ/Cd2þ in quartz sand
coated with HA, ferrihydrite, kaolinite, and smectite. The transport
of GO in Pb2þ or Cd2þ pre-contaminated sand columns was also
studied to understand better the interaction between GO and heavy
metal ions. The specific objectives of the study are: (1) understand
the mutual interaction between GO and Pb2þ/Cd2þ during their
concurrent transport; (2) explore the cotransport mechanisms of
the GO and Pb2þ/Cd2þ in the modified porous media; and (3)
investigate the effect of soil constituents on GO and Pb2þ/Cd2þ
transport in porous media.
2. Materials and methods
2.1. Materials
GO nanosheets used in this work were purchased from the
Pioneer Nano Company (Nanjing, China). They have a lateral
diameter of 1e4 mm and thickness of 0.7e1.4 nm, and were syn-
thesized using a modified Hummers method (Guerrero-Contreras
and Caballero-Briones, 2015). GO stock suspension was prepared
by adding 40 mg GO to 1 L of background electrolyte solution. The
background electrolyte solution contained 0.001 M KCl and its
initial pH was adjusted to 6.5 ± 0.2 with 0.001 M NaOH and 0.001 M
HCl. GO was ultrasonically dispersed in the background electrolyte
solution using an ultrasonic cleaner (KQ-500DE, Kunshan Ultra-
sonic Instrument Company, China) for 2 h PbCl2 and CdCl2 (AR
grade; Aladdin Reagent Company, Shanghai, China) were dissolved
in the background electrolyte solution (pH ¼ 6.5, IS ¼ 0.001 M, KCl)
as stock solution with Pb2þ and Cd2þ concentrations of 40 mg L1. A
mixture of heavy metal and GO was prepared by mixing the same
volume of stock solution. The GO particle size was 72 ± 6 nm as
measured by a Zeta-Plus analyzer (Zetasizer nano ZS90, Malvern
Instruments, UK) and after mixing with Pb2þ or Cd2þ, the particle
size increased to 267 ± 24 or 173.5 ± 9 nm, respectively. The zeta
potential of GO and mixture of heavy metal and GO were also
measured using the Zeta-Plus analyzer.
Humic acid (HA) was purchased from Aladdin Reagent Company
(Shanghai, China). The HA was purified according to Yang's method
(Yang and Koopal, 1999). Then, 10 g of the HA was added to 1 L
deionized (DI) water, and the pH was adjusted to 10 with 0.1 M
NaOH. The solution was stirred overnight and centrifuged at
1500g for 15 min using a low-speed centrifuge (TDL-40B,
Shanghai Anting Scientific Instrument Factory, China) to remove
the precipitate. To the supernatant was added 1 L of DI water and
the pH was adjusted to 2 with 0.1 M HCl, stirred for 24 h, and
centrifuged. Afterward, the precipitate was dialyzed to remove
salts. Finally, the purified HA was collected by freeze-drying.
Ferrihydrite was synthesized by adding 40 g Fe(NO3)3$ 9H2O (AR
grade; Guangdong Guanghua Technology Co., Ltd., Shanghai, China)
to 0.5 L DI water. Then, the pH was adjusted to 7 with 1 M KOH (AR
grade; Guangdong Guanghua Technology Co., Ltd., Shanghai, China)
according to the method of a previous study (Ma €hler and Persson,
2013). After synthesis, the ferrihydrite was centrifuged at 3000 rpm
for 15 min and dialyzed to remove salts, then dried at room
 X. Yin et al. / Chemosphere 218 (2019) 1e13
temperature.
Chemically pure kaolinite and smectite were purchased from
Fuchen Chemical Reagent (Tianjin, China). The clay minerals were
purified by adding 20 g of clay minerals to 1 L DI water, and
removing organic matter using H2O2 (Jerez and Flury, 2006). After
that, the sample was stirred for 4 h and the > 2 mm clay mineral
particle fraction was separated by gravity sedimentation
(Chrysikopoulos et al., 2017). Finally, < 2 mm particles were used in
the experiment without further modification.
2.2. Porous media
Quartz sand (Zhouzhi County Quartz Sand Ltd, China) was
sieved to a homogenized size fraction range of 0.5e0.6 mm. Prior to
the column experiment, the sand was washed with 0.1 M NaOH for
24 h, and then with 0.1 M HCl for 24 h to remove colloidal sub-
stances and metal ions on the surface. Next, the quartz sand was
rinsed with deionized (DI) water and subsequently dried in an oven
at 105  C for 24 h.
HA-coated quartz sand was prepared using a method as re-
ported earlier (Yu et al., 2007). A portion (10 g) of HA was added to
1 L of DI water and the pH was adjusted to 10; then, cleaned quartz
sand was placed in the HA solution. The mixture was acidified by
adding 0.1 M HCl drop-by-drop while stirring; then was dried for
24 h at 105  C. The HA-coated quartz sand was rinsed repeatedly
using DI water, until the supernatant was colorless; then dried
again at 80  C for 24 h.
The quartz sand was coated with ferrihydrite using a modified
method of Ma €hler and Persson (2013). Briefly, all dried ferrihydrites
were added to 1 L of DI water and mixed with 500 g of quartz sand.
The mixture was shaken for 24 h. The pH of the initial solution was
6.5. After one day of shaking and aging, the pH was adjusted to 7.5
with 0.01 M NaOH. After that, the mixture was subjected to mul-
tiple stirring and settling processes for 24 h and was dried in a fume
hood. Finally, the sand was washed repeatedly with DI water until
the supernatant was colorless.
The clay minerals (kaolinite and smectite) were coated onto the
quartz sand using a method described previously (Jerez et al.,
2006). Clay suspensions (40 g L1) were mixed with 200 mg L1
polyvinyl alcohol (98% degree of polymerization, Aladdin Reagent
Company, Shanghai, China) and stirred for 30 min. After the quartz
sand was added to the suspensions; the mixture was stirred for
15 min. Then the mixture was dried at 80  C for 24 h, followed by
washing with DI water to remove all non-attached polyvinyl
alcohol and clay minerals. The sample was then dried again at 80  C
for 24 h.
All the sand samples were parked in a column and then flushed
with electrolyte solution at a flow rate roughly 3 mL min1, so that
loosely bound soil components were flushed out of the sand col-
umn until the concentration of soil components in the outflow fluid
was zero. Afterward, all coated sands were removed from the sand
column and washed with either 1 M NaOH or 1 M HCl. The HA and
clay mineral coated sand samples were washed with 1 M NaOH.
The amount of HA in solution was determined by measuring the
light absorption at 254 nm using UVevisible spectrophotometry
(UV-2800, UNICO Instrument Co., Ltd., USA) and the amount of clay
minerals was measured at the wavelength of 230 nm (Jerez and
Flury, 2006). The absorbance of HA was calibrated by measuring
the TOC (TOC-L, Shimadzu, Japan.). The ferrihydrite coated sand
was washed with 1 M HCl and the amount of ferrihydrite was
measured using a flame atomic absorption spectrometry (Z-2000,
Hitachi, Tokyo, Japan).
Microscopic features and surface morphology of the coated sand
were examined using a scanning electron microscopy (S-4800
Hitachi, Japan) and an energy dispersive spectrometer (SEM-EDS)
3
was used for surface elements. According to the SEM image ob-
tained by randomly scanning five coated quartz sand, the amount
of coverage of humic acid, ferrihydrite, smectite, and kaolinite on
the quartz sand surface was obtained by the pixel histogram
method using Photoshop (Adobe software) (Zhao et al., 2011b).
Briefly, the pixel value of SEM image is recorded in the histogram,
then selecting the coated area and reading the pixel value of the
coated area, the coverage is calculated by the ratio of pixel values.
The specific surface areas of the coated sand were determined using
the BET method with N2 sorption-desorption isotherms. The zeta
potential of the samples was determined using a Zeta-Plus analyzer
(Zetasizer nano ZS90, Malvern Instruments, UK) and a method
described in an earlier study (Johnson et al., 1996). Briefly, all coated
sands were removed from the sand column before and after the
experiment. The sand was sonicated for 10 min and soaked in
background solution for 6 h; then, the zeta potential of the solution
was measured as the zeta potential of the sand in solution. At the
same time, the zeta potential of the HA, ferrihydrite, kaolinite, and
smectite-coated sand was also measured using the Zeta-Plus
analyzer (shown in Table 1).
2.3. Column experiment
Experiments on the adsorption of Pb2þ and Cd2þ by coated
quartz sand were carried out before the column experiment. Pb2þ
or Cd2þ solution (25 mL) of different concentrations (0, 2, 3, 5, 10,
20, 30 and 50 mg L1) was mixed with 5 g coated quartz sand in a
centrifuge tube. The mixture was shaken at 25  C and 170 r min1,
followed by centrifugation at 4000 r min1 for 10 min using a low-
speed centrifuge (TD5A-WS, Shanghai Lu Xiangyi Centrifuge In-
strument Co., Ltd, Shanghai, China). After the centrifugal liquid was
filtered through a 0.45 mm filter, Pb2þ or Cd2þ concentration of the
filtrate was measured using a flame atomic absorption spectrom-
eter (Z-2000, Hitachi, Tokyo, Japan). Langmuir (1918) and
Freundlich (1906) models were also used to describe the sorption
isotherms quantitatively.
Transport experiments were conducted in columns (15 cm,
height and 3 cm, inner diameter) packed with coated quartz sand.
The sand was wet-packed with DI water using a glass stirring rod to
minimize any layering and to remove air entrapped in the column
(Sun et al., 2010). The porosity of the packed column was 0.45 and
the pore volume (PV) was 48 mL.
The column was initially flushed with DI water for 2 h until the
effluent was free of visible impurities. It was then flushed with
background electrolyte solution (pH ¼ 6.5, IS ¼ 0.001 M, KCl) to
stabilize the experimental conditions. Subsequently, two different
types of column experiments were conducted with different
leaching solutions and orders. To investigate the interactions of GO
and the heavy metals in the coated sand column, one set of columns
was sequentially leached with 1.2 PVs of GO-Pb2þ (CGO ¼ 20 mg L1,
CPb ¼ 20 mg L1) or GO-Cd2þ (CGO ¼ 20 mg L1, CCd ¼ 20 mg L1)
mixture solution and then 2 PVs of background electrolyte solution.
The GO suspension (20 mg L1) and Pb2þ and Cd2þ solutions
(40 mg L1) were also separately injected into the column for
comparison. To investigate the ability of GO to release heavy metals
from the coated-sand columns, another set of column experiment
was conducted. In this set, 1.2 PVs of 40 mg L1 Pb2þ or Cd2þ so-
lution and 2 PVs of background electrolyte solution were succes-
sively injected into the coated sand column. Subsequently, the Pb2þ
or Cd2þ- pre-equilibrated sand column was flushed with 1.2 PVs of
20 mg L1 GO suspension, then with 2 PVs of background electro-
lyte solution. The pH was kept constant (6.5 ± 0.2) throughout the
whole experiment and the flow velocity was kept constant at
1 mL min1.
Effluent from the column was continuously collected in test
4 X. Yin et al. / Chemosphere 218 (2019) 1e13

Table 1
Zeta-potential of GO and coated sand in different transport experiments and basic properties of coated sands.

Zeta-potential (mV) Coated sand

Solution of Mixed solution of Mixed solution of Pb-spiked coated Cd-spiked coated Specific surface Amount of Percentage of
GO only GO and Pb GO and Cd sand column sand column area (m2/g) coating (mg/g) Coverage (%)

GO 21.3 ± 0.6 13.9 ± 0.4 15.5 ± 2.1 21.3 ± 0.6 21.3 ± 0.6 / / /
Clean quartz 23.1 ± 0.6 23.1 ± 0.6 23.1 ± 0.6 12.1 ± 0.5 14.2 ± 1.1 0.085 0 0
sand
HA coated sand 26.1 ± 0.7 26.1 ± 0.7 26.1 ± 0.7 15.3 ± 0.5 14.1 ± 0.3 0.231 1.96 68.3
Kaolinite coated 18.6 ± 0.7 18.6 ± 0.7 18.6 ± 0.7 11.3 ± 0.3 20.3 ± 0.5 0.745 8.17 82.6
sand
Smectite coated 13.5 ± 0.3 13.5 ± 0.3 13.5 ± 0.3 9.3 ± 0.3 8.1 ± 0.2 0.955 13.23 89.9
sand
Ferrihydrite 6.7 ± 0.4 6.7 ± 0.4 6.7 ± 0.4 11.1 ± 0.4 13.5 ± 0.4 0.765 3.3 56.7
coated sand

tubes using an automatic fraction collector (BS-16A-LCD, Shanghai
Huxi Analysis Instrument Factory Co. Ltd., China). The GO concen-
tration was determined by measuring the light absorption at a
wavelength of 229 nm using the UVevisible spectrophotometry
(Gupta et al., 2017). The calibration curve for GO was still linear in
the presence of 0.1 mM PbCl2 and CdCl2, and its absorbance was
unaffected by the presence of both metals. The influent and effluent
were subjected to acid digestion to determine the Pb2þ and Cd2þ
concentrations (Wang et al., 2011a). The Pb2þ and Cd2þ concen-
trations in the effluents were measured by the flame atomic ab-
sorption spectrometry (Z-2000, Hitachi, Tokyo, Japan). NaNO3
(20 mg L1) was employed as the tracer solution to determine the
hydraulic properties of the HA, kaolinite, and smectite-coated sand
columns at the same velocity and KBr (20 mg L1) was used to
determine the hydraulic properties of the ferrihydrite-coated sand
column. All column experiments were conducted in duplicate.
2.4. Mathematical model
The Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was
used to calculate the force of interaction between GO and coated
sand under various experimental conditions. The DLVO energy
(Etot) was established as the sum of the energy of two interactions,
namely van der Waals attraction (Evdw) and electric double layer
repulsion (Eedl). For a sphere-plate interaction, these two interac-
tion energies were determined using the expressions reported by
Gregory (1981) and Hogg et al. (1966), respectively:
Etot ¼ Evdw þ Eedl (1)
Ar
Evdw ¼ 
 (2)
6h 1 þ 14h
l governing equations can be written as below (Ding et al., 2014):
permittivity ε0 is 8.85  1012 C2 Jm1; εr is the relative dielectric
permittivity of water (78.5); and x1 and x2 are the surface potentials
of the GO nanoparticles and coated sand, respectively.
The Debye reciprocal length (k) can be calculated from equation
(4):
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2NA e2 I
k¼ (4)
ε0 εr KT
where NA is the Avogadro number (6.02  1023 mol1), e is the
electron charge (1.602  1019 C), I is the ionic strength of the
background electrolyte, K is the Boltzmann constant
(1.38  1023 J K1), and T is the temperature in Kelvins (298 K).
The surface of the coated sand can be chemically heterogeneous
due to incomplete coverage. To account for this effect, modified
DLVO calculations were applied to calculate interaction energy
between GO and soil-component-coated sand. The modified DLVO
energies were determined using expressions reported in other
studies (Bendersky and Davis, 2011; Bradford and Torkzaban,
2013):
B1 B
Etot ¼ E þ 2E (5)
Bt 1 Bt 2
where E1 and E2 are the total interaction energy between GO and
the surfaces of clean quartz sand and soil-component-coated sand,
respectively. B1 and B2 are the surface area of quartz and of soil
components, respectively, and Bt is the total surface area.
Under steady flow conditions and only adsorption, the
advection-dispersion-reaction (ADR) model was used to simulate
solute or colloid transport to explain its retention in the sand col-
umns (Genuchten, 1995; Liu et al., 2013; Zhou et al., 2016). The

  

1 þ expð  khÞ 2 2 vCw v2 C w vCw r vS
Eedl ¼ pε0 εr r 2x1 x2 ln þ x1 þ x2 ln½1 ¼D v  (6)
1  expð  khÞ vt vz2 vz q vt

 expð  2khÞ (3)

where A is the Hamaker constant, and the Hamaker constant of the
GO nanoparticles is 6.26  1021 J in saturated porous media,
1.81  1020 J in the aqueous phase (Feriancikova and Xu, 2012; Fan
et al., 2015), and 5.5  1021 J for clay minerals (Lu et al., 2017),
1.65  1021 J for HA (Lv et al., 2014) and 3.75  1020 J for ferri-
hydrite (Wu and Cheng, 2016). Here, r is the radius of the GO
nanoparticles; h is the separation distance between the GO nano-
particles and the coated sand surface; and l is the characteristic
wavelength of a GO nanoparticle (taken as 100 nm). The vacuum
r vS S
¼k 1 Cw (7)
q vt Smax
where Cw is the GO concentration in the pore water (mg L1) and
reflects the magnitude of the equilibrium reaction in the coated
sand column. D is the dispersion coefficient (cm2 min1), v is the
flow rate (0.1414 cm min1), r is the medium bulk density (g cm3),
and q is the porosity. Here, k is the first-order retention coefficient
(min1), and Smax is the maximum deposited particle concentra-
tion. The model was applied to simulate the experimental break-
through curves. The parameters k and Smax were established using
 X. Yin et al. / Chemosphere 218 (2019) 1e13
HYDRUS-1D, while the recovery values of the heavy metals and GO
were measured with a mass balance.
2.5. Statistical analysis
Energy profile models, breakthrough curves, and standard de-
viation values (represented by error bars) were determined using
Microsoft Excel Software (version 2010, Microsoft Corporation,
USA).
3. Results and discussion
3.1. Coated sand characterizations
The SEM micrographs in Fig. 1 show images of the coated-sand
surfaces. The clean quartz sand surface is depicted as smooth and
tidy, and no coating covered the quartz surface. The coverage of
sand by humic acid, ferrihydrite, smectite, and kaolinite was esti-
mated to be (68.2, 56.7, 82.6, and 89.9) %, respectively, based on the
SEM image. This result is consistent with results from previous
studies (Jerez and Flury, 2006). The HA presents as a whole sheet-
like cover when loaded on the sand, and the HA surface is relatively
smooth. Ferrihydrite exhibits small pieces when loaded onto the
sand surface, but the surface of ferrihydrite is rougher and fluffier
than that of HA. It is not possible to determine whether the Fe
hydroxide is ferrihydrite from the SEM photograph, but goethite is
adsorbed to the surface of the quartz sand as needle structures
(Carstens et al., 2017). The kaolinite coated sand presents as a large
number of small particles of kaolinite stacked on the sand surface,
whereas smectite appears on the surface of the sand as an irregular,
flaky, multilayer covering. The EDS spectra of the coated sands
show high peaks of C, O, Si, Al, and Fe (Fig. 1). These peaks clearly
indicate that the soil components cover the quartz sand surface.
Specific surface areas and amounts of coating on the sands are
listed in Table 1. The amount of HA, ferrihydrite, kaolinite, and
smectite coated onto the sand was around 1.97, 4.4, 8.34, and
14.7 mg g1, respectively (Table 1). The specific surface area of the
coated sand was one order of magnitude larger than that of the
clean quartz sand. The specific surface area of clean sand and sand
covered by kaolinite, smectite, HA, and ferrihydrite was 0.085,
0.745, 0.955, 0.231, and 0.765 m2 g1, respectively. The results of the
specific surface area study are consistent with the surface
morphology and similar to those previously reported (Jerez et al.,
2006; Ma €hler and Persson, 2013).
3.2. DLVO energy
To investigate the mechanism of the inhibition of GO transport
by soil components covering the quartz sand surface, DLVO inter-
action energy profiles between GO and each kind of coated sand
were plotted as a function of separation distance and were given in
Fig. 2. The zeta potential of GO and three kinds of coated sand used
in calculating the DLVO interaction energies are presented in
Table 1. The information in Fig. 2 suggests that transport of GO in
coated sand is determined mainly by the deposition at the sec-
ondary minimum under different conditions. This is due to the
energy barriers between GO and smectite, kaolinite, and HA coated
sand (>10 kT), which are difficult for GO particles to overcome to
deposit on the sand surface at the primary minima (Shang et al.,
2013; Wang et al., 2016). Overall, the energy barrier between GO
and the HA coated sand was the highest under these experimental
conditions (HA coated sand > smectite coated sand > kaolinite
coated sand > ferrihydrite coated sand). The surface charge of
kaolinite, smectite, and ferrihydrite-coated sand is much less than
that of the HA-coated sand (Table 1). However, the energy barrier
5
between GO and clean quartz sand is greater than that of the coated
quartz sand (Jiang et al., 2018). The presence of the heterogeneous
constituents on quartz sand thus can reduce energy barrier and
thus provide additional deposition sites (Lu et al., 2017).
The energy barriers between GO-Pb2þ/GO-Cd2þ and kaolinite,
smectite and HA coated sand were among the highest, followed by
that between GO and coated sand, and finally between GO and
Pb2þ/Cd2þ-spiked coated sand. This trend was not observed for the
energy barries between GO and ferrihydrite-coated sand. The effect
of the heavy metals on the GO interactions with HA, smectite, and
kaolinite coated sand increased the energy barrier between GO and
the sand surface. This is similar to the effect of surfactants (Wei
et al., 2015). However, the energy barrier between GO and the
sand surface decreased in the presence of the heavy metals in
ferrihydrite-coated sand columns, indicating that there is less
repulsive force upon approach to the sand surface. According to
previous studies, when the energy barrier is < 15 kT, the secondary
minimum can be neglected for all these experimental conditions
and GO is mainly attracted at the primary minimum. However,
when the energy barrier is > 15 kT, GO attachment onto the sand
surface commonly occurs at the secondary energy minimum (Wang
et al., 2011b; Mesticou et al., 2014). It has been reported that GO is
permanently deposited on the sand surface at the primary mini-
mum and reversibly deposited on the sand surface at the secondary
energy minimum (Wei et al., 2015). The results also indicate that
GO transport in the coated sand column may be deposit at the
secondary energy minimum due to the presence of heavy metal
ions in the solution. Moreover, the heavy metals retained in the
sand column can significantly reduce GO mobility, at both the
primary and secondary energy minimum.
3.3. Concurrent transport of GO and heavy metal ions in coated
sand
The retention of GO and heavy metal ions (Pb2þ and Cd2þ) in the
coated sand column were evaluated through analysis of the
experimental effluent breakthrough concentrations. The break-
through curves shown in Figs. 3 and 4 were constructed as plots of
the effluent to injection concentration ratios (C/C0). The break-
through curves of GO in the coated sand column were shown in
Fig. 3a. The results indicate that GO exhibits high mobility in HA,
kaolinite, and smectite-coated sand columns and can scarcely be
retained in these porous media. According to mass balance calcu-
lations, the recovery rates of GO in HA, kaolinite, and smectite-
coated sand columns were 99.09%, 94.7%, and 95.3%, respectively
(Table 3). However, the ferrihydrite-coated sand column had a
significant retarding effect on the transport of GO, and the recovery
of GO was only 75%. This might be because the electrostatic force
plays a major role in the migration behavior of GO in the coated
sand column. It can be seen from Table 3 that the zeta potential of
ferrihydrite-coated sand is higher than for the other types of sand.
The recovery of GO in the HA-coated sand column is greater than
that of other coated sand, which proves that the more negative the
charges on the surface of the sand are, the greater is the repulsive
force between GO and sand. This makes it hard for GO to be
deposited on the sand surface, which makes the recovery rate of GO
higher. The migration behavior of GO in the coated sand column is
consistent with the results of the DLVO theory.
The breakthrough curves of Pb2þ and Cd2þ ions in the coated
sand column are shown in Fig. 3b and c. The results show that the
coated sand has a greater retarding effect on Pb2þ and Cd2þ than on
GO because Pb2þ and Cd2þ ions are easily attracted to the nega-
tively charged sand surface. There was a significant difference in the
mobility of Pb2þ and Cd2þ and the recovery of Cd2þ ions was greater
than that of Pb2þ in each kind of coated sand column. This may be
6 X. Yin et al. / Chemosphere 218 (2019) 1e13

Fig. 1. The SEM scanning and EDS spectra of kaolinite, smectite, HA and ferrihydrite coated sand. A is an SEM image of ferrihydrite coated sand after the experiment (GO and Cd
mixture flow through the sand column); B is GO and Pb mixture flow through the sand column. Note that the proportion of micrographs is different to better display the surface
morphology and reflect the uncovered area.
 X. Yin et al. / Chemosphere 218 (2019) 1e13 7

Fig. 2. DLVO energy profiles between GO and quartz sand particles under different conditions. The primary energy barriers for GO and quartz sand (left) and the secondary energy
minimum for GO and quartz sand (right). (CGO ¼ 20 mg L1, CPb ¼ 20 mg L1, CCd ¼ 20 mg L1. pH ¼ 6.5, IS ¼ 0.001 M, KCl).
8 X. Yin et al. / Chemosphere 218 (2019) 1e13

Fig. 3. The transport of GO, Pb and Cd in kaolinite, humic acid, ferrihydrite and smectite coated quartz sand cloumns with pH ¼ 6.5, IS ¼ 0.001 M (a: GO solution; b: Cd solution; c:
Pb solution; d: mixed solution of GO and Pb; e: mixed solution of GO and Cd). KPb and KGO represent the transport of Pb and GO in kaolinite coated sand columns, respectively. HPb
and HGO represent the transport of Pb and GO in humic acid coated sand columns, respectively. FPb and FGO represent the transport of Pb and GO in ferrihydrite coated sand
columns, respectively. SPb and SGO represent the transport of Pb and GO in smectite coated sand columns, respectively. Symbols are experimental data and lines are model
simulations. Error bars represent standard deviation and experiment is in duplicates.

due to different affinities of the soil constituents to Pb2þ and Cd2þ
ions. According to isothermal experiments for adsorption of Pb2þ
and Cd2þ ions on the coated sand (best-fit parameters of the iso-
thermals are shown in Table 2), the maximum adsorption of Pb2þ
on sand coated with HA, smectite, kaolinite, and ferrihydrite was
0.0659, 0.2632, 0.0154, and 0.0414 mg g1, respectively. These
values are significantly larger than those of Cd2þ on the sand.
The retention of Pb2þ and Cd2þ ions on smectite-coated sand
columns was greater than that on other sand columns. This was
particularly true for Pb2þ, which was almost completely trapped in
the sand column. This is mainly attributable to the fact that
smectite has the most coverage of the quartz sand surface and the
adsorption capacity of smectite for Pb2þ and Cd2þ ions is greater
than that of other components. This is also one of the reasons that
the recovery rate of Pb2þ and Cd2þ ions was the highest in the
ferrihydrite coated columns. The other reason is that the ferrihy-
drite coated sand column contains more positive charges.
The breakthrough curves of the concurrent transport of GO with
Pb2þ or Cd2þ ions in the coated sand column are illustrated in
Fig. 3b and c, respectively. The presence of Pb2þ and Cd2þ ions
reduced the mobility of GO and the mobility of Pb2þ and Cd2þ ions
in the sand column coated with HA, smectite, and ferrihydrite was
substantially higher than that of GO-Pb2þ or GO-Cd2þ. The migra-
tion rates of Pb2þ and Cd2þ ions in the kaolinite-coated sand col-
umn were lower than those of GO-Pb2þ and GO-Cd2þ. The results
show that GO promoted the transport of Pb2þ and Cd2þ in the
kaolinite-coated sand column and inhibited the transport of Pb2þ
and Cd2þ in other sand columns. Based on mass balance calcula-
tions, the recovery rates of GO, Pb2þ, and Cd2þ under different
conditions are shown in Table 3. HA contains hydrophobic and
hydrophilic moieties as well as many functional groups such as
carboxyl, phenol, carbonyl, and hydroxyl groups attached to
aliphatic or aromatic carbons (Li et al., 2015). The presence of such
carboxyl and phenol groups results in HA being mainly negatively
 X. Yin et al. / Chemosphere 218 (2019) 1e13 9

Fig. 4. The breakthrough curves of GO in Pb-spiked sand column (a) and Cd-spiked sand column (b) under experimental conditions, pH ¼ 6.5, IS ¼ 0.001 M. KPb and KGO represent
the transport of Pb and GO in kaolinite coated sand columns, respectively. HPb and HGO represent the transport of Pb and GO in humic acid coated sand columns, respectively. FPb
and FGO represent the transport of Pb and GO in ferrihydrite coated sand columns, respectively. SPb and SGO represent the transport of Pb and GO in smectite coated sand columns,
respectively. Symbols are experimental data and lines are model simulations. Error bars represent standard deviation and experiment is in duplicate.

Table 2
Constants and correlation coefficient of isotherm models of Pb or Cd adsorption on coated sand.

Porous media Langmuir Freundlich Temkin

KL Qm (mg$g1) R2 R2 R2

Cd Kaolinite coated sand 0.012 0.0301 0.999 0.954 0.961

Smectite coated sand 0.191 0.1820 0.996 0.961 0.842
HA coated sand 0.269 0.0198 0.826 0.957 0.971
Ferrihydrite coated sand 0.564 0.0170 0.618 0.935 0.868
Pb Kaolinite coated sand 56.2 0.0154 0.461 0.862 0.374
Smectite coated sand 0.974 0.2632 0.905 0.664 0.859
HA coated sand 0.743 0.0659 0.942 0.888 0.951
Ferrihydrite coated sand 36.36 0.0414 0.921 0.885 0.955

KL is the adsorption equilibrium constant (L mg1) related to adsorption capacity; Qm is the maximum amount of Pb2þ/Cd2þ adsorbed on coated sand.

charged in aqueous solution and also provides more sites for the
adsorption of cationic heavy metals (Akbour et al., 2013). When GO
and heavy metals are co-transported in the humic acid-coated sand
column, humic acid can adsorb Pb2þ and Cd2þ by electrostatic
attraction. Moreover, GO can be retained in the sand column by
forming metal p bonds with Pb2þ and Cd2þ on the surface of HA
(Chen et al., 2016; Peng et al., 2017). On the other hand, the zeta
potential of GO increased after adsorption of Pb2þ and Cd2þ, the
repulsive force between GO might decrease and the collision
probability might increase. From the DLVO interaction energy
profiles, the values of the secondary energy minima
were 0.043, 1.05, and 0.37 kT for GO and HA coated sand, GO-
Pb2þ and HA coated sand, and GO-Cd2þ and HA coated sand,
respectively. The results also indicate that GO is easier to deposit at
the secondary energy minimum in the presence of heavy metal
ions. Moreover, this inhibiting effect on GO mobility was more
remarkable with more heavy metal ions passing through or being
retained in the HA coated sand columns. This further confirms that
the transport behavior of GO in the HA-coated sand column is
mainly controlled by the electrostatic force.
The retarding effect of clay minerals on GO transport is attrib-
uted to the positively charged edge of clay minerals. Clay minerals
10 X. Yin et al. / Chemosphere 218 (2019) 1e13

Table 3
Fitted parameter and recovery rate for GO, Pb2þ, and Cd2þ in different transport experiments (pH ¼ 6.5, IS ¼ 0.001 M, KCl).

Solution Porous medium Fitted variable k (min1) Smax (mg g1) Recovery (%) R2

GO HA coated sand GO 7.81E-04 2.08E-02 99.09 1.00

Pb HA coated sand Pb 5.82E-02 1.12Eþ01 23.26 0.98
Cd HA coated sand Cd 5.65E-02 7.23Eþ00 50.97 0.96
GO þ Pb HA coated sand GO 4.94E-03 3.74Eþ00 80.45 1.00
GO þ Cd HA coated sand GO 6.58E-03 8.73Eþ01 73.25 0.99
GO þ Pb HA coated sand Pb 4.01E-02 3.68Eþ02 16.16 0.99
GO þ Cd HA coated sand Cd 2.11E-02 5.30Eþ01 36.35 1.00
GO Cd-spiked HA coated sand GO 2.52E-03 1.01Eþ02 88.11 0.99
GO Pb-spiked HA coated sand GO 4.34E-03 6.44E-01 91.45 1.00
GO Cd-spiked HA coated sand Cd e e 9.78 e
GO Pb-spiked HA coated sand Pb e e 8.04 e
GO Kaolinite coated sand GO 5.36E-03 3.55E-01 94.70 1.00
Pb Kaolinite coated sand Pb 8.01E-02 9.19Eþ00 24.08 0.97
Cd Kaolinite coated sand Cd 1.27E-02 4.24Eþ00 75.09 0.99
GO þ Pb Kaolinite coated sand GO 5.44E-02 3.85Eþ00 28.97 0.96
GO þ Cd Kaolinite coated sand GO 5.77E-02 2.81Eþ02 13.05 0.36
GO þ Pb Kaolinite coated sand Pb 5.77E-02 3.40Eþ00 34.58 1.00
GO þ Cd Kaolinite coated sand Cd 9.29E-03 4.71E-02 82.80 0.99
GO Cd-spiked kaolinite coated sand GO 5.71E-03 1.50Eþ00 89.71 0.99
GO Pb-spiked kaolinite coated sand GO 1.29E-03 1.71E-01 103.73 0.99
GO Cd-spiked kaolinite coated sand Cd e e 21.25 e
GO Pb-spiked kaolinite coated sand Pb e e 4.55 e
GO Smectite coated sand GO 9.21E-04 2.66E-01 95.30 0.99
Pb Smectite coated sand Pb e e e e
Cd Smectite coated sand Cd 2.77E-01 1.27Eþ01 14.45 0.93
GO þ Pb Smectite coated sand GO 7.65E-03 3.31Eþ00 72.42 0.98
GO þ Cd Smectite coated sand GO 1.79E-02 2.38Eþ01 56.91 0.99
GO þ Pb Smectite coated sand Pb 2.62E-02 1.16E-02 4.19 0.98
GO þ Cd Smectite coated sand Cd 4.56E-02 2.90Eþ01 13.55 0.98
GO Cd-spiked smectite coated sand GO 3.62E-03 4.41Eþ00 88.52 1.00
GO Pb-spiked smectite coated sand GO 1.12E-02 1.09Eþ00 88.71 0.99
GO Cd-spiked smectite coated sand Cd e e 0.00 e
GO Pb-spiked smectite coated sand Pb e e 0.00 e
GO Ferrihydrite coated sand GO 6.09E-02 1.91Eþ00 73.23 0.99
Pb Ferrihydrite coated sand Pb 4.74E-02 5.81Eþ00 49.09 0.95
Cd Ferrihydrite coated sand Cd 5.43E-03 5.98E-02 84.12 0.99
GO þ Pb Ferrihydrite coated sand GO 7.52E-02 9.19Eþ02 3.69 0.66
GO þ Cd Ferrihydrite coated sand GO 6.48E-02 6.50Eþ02 5.12 0.64
GO þ Pb Ferrihydrite coated sand Pb 5.67E-02 8.89Eþ00 10.59 0.85
GO þ Cd Ferrihydrite coated sand Cd 4.29E-01 2.97Eþ00 19.90 0.99
GO Cd-spiked ferrihydrite coated sand GO 5.48E-02 2.75Eþ00 66.50 0.97
GO Pb-spiked ferrihydrite coated sand GO 7.14E-03 1.71Eþ00 80.03 0.99
GO Cd-spiked ferrihydrite coated sand Cd e e 7.79 e
GO Pb-spiked ferrihydrite coated sand Pb e e 5.11 e

contain many amphoteric sites, such as Al-OH sites, and have
exposed hydroxyls at the edges of minerals or crystal fractures.
These positively charged edges can provide sites for the deposition
of negatively charged GO. On the other hand, the particle size of GO
increased after adsorption of Pb2þ and Cd2þ on the surface of GO.
The smectite has some exchangeable cations in the middle of the
three-layered sheet structure composed of silica tetrahedron, and
the heavy metal ions in the solution exchange reaction with the
interlayer cations; however, there is no exchangeable cation be-
tween the layers of kaolinite because of hydrogen bonding, which
makes it difficult for heavy metal ions to enter the interlayer
(Mhamdi et al., 2013; Araga ~o et al., 2014). As mentioned earlier,
smectite has a very high affinity for Pb2þ and Cd2þ, which allows
Pb2þ and Cd2þ that has been adsorbed on smectite to further absorb
GO through electrostatic attraction and cationic bridging. The edge
area of kaolinite is much greater than that of smectite, so kaolinite
contains more of the positive charge sites (Lu et al., 2017). In this
work, the recovery rate of Pb2þ and Cd2þ increased when GO and
Pb2þ or Cd2þ were co-transported in kaolinite-coated sand col-
umns. A possible explanation is that the protons on the carboxyl or
hydroxyl functional groups are released into solution after
adsorption of Pb2þ or Cd2þ by GO (Peng et al., 2017), which destroy
the structure of kaolinite. In the acidic condition, the Al3þ ions on
the surface of kaolinite dissolve into the solution (Yang and Steefel,
2008). Pb2þ or Cd2þ are replaced in the process of the combination
of GO and Al3þ due to ion exchange (Mascia et al., 2015). At the
same time, the presence of Al3þ ions also increase the positive
charge on the surface of the kaolinite, making Pb2þ or Cd2þ less
likely to deposit on the sand surface. Which breaks down the
structure of ferrihydrite. Then Fe3þ in the ferrihydrite crystals is
exposed (Yang et al., 2010). GO, in particular, is more easily adsor-
bed at the edge of ferrihydrite, which results in the retention of a
large amount of GO. At the same time, Pb2þ and Cd2þ are more
likely to combine with hydroxyl groups on the surface of ferrihy-
drite due to the destruction of the ferrihydrite structure, resulting
in reduced mobility of Pb2þ and Cd2þ The transport behavior of GO
in clay coated sand column is also consistent with the predictions of
the DLVO theory.
Although the migration trends of GO and Pb2þ or Cd2þ in
ferrihydrite-coated sand columns were similar to those of other
sand columns, the recovery rates of GO and Pb2þ or Cd2þ were all
significantly reduced during co-transport. The recovery rate of GO
only was 73.23%. In the presence of Pb2þ or Cd2þ, the recovery rate
of GO was only 3.73% or 5.12%, respectively. In other words, when
GO was co-transported with Pb2þ or Cd2þ in the ferrihydrite-coated
sand column, their transport capacity significantly reduced.
 X. Yin et al. / Chemosphere 218 (2019) 1e13
Although the ferrihydrite can adsorb GO by electrostatic force, the
uncovered areas of sand grains also have an electrostatic repulsion
effect on the GO. This means that a large amount of GO may not be
deposited on the surface of the ferrihydrite coated sand and the
migration behaviors of Pb2þ and Cd2þ are similar for the same
reason. When GO is mixed with Pb2þ or Cd2þ, the particle size of GO
increases due to its instability. This interaction can increase the
retention of both GO and heavy metals in the ferrihydrite-coated
sand. A large number of half-curled GO particles and their aggre-
gates appeared on the edge of the ferrihydrite in SEM images before
and after transport, suggesting the destabilization of GO by the
metals can increase their deposition. Previous studies have shown
that both Pb2þ and Cd2þ can serve as “bridges” for GO deposition on
the sand surface (refs). On the other hand, GO may also serve as
bridges for the two heavy metals to increase their retention in the
sand columns.
Transport results indicate that several potential mechanisms are
responsible for Pb2þ/Cd2þ adsorption on GO, including electrostatic
attraction, surface complexation, and deposition (Peng et al., 2017).
Surface complexation between the cationic heavy metals and
oxygen-containing functional groups on the GO surface play an
important role in the adsorption process (Beesley. and Marmiroli,
2011; Zhao et al., 2011a). The zeta potential of metal-loaded GO
became less negative due to the adsorption of Pb2þ or Cd2þ, leading
to a decline in repulsive force between metal-loaded GO and coated
sand (Sun et al., 2015). Furthermore, GO aggregation and attach-
ment were enhanced because of cation bridging produced by the
divalent cations Pb2þ and Cd2þ.
Heavy metal ions did not show higher mobility when trans-
ported together with GO in coated sand columns. This indicates
that the mobility of Pb2þ and Cd2þ ions is also closely related to the
surface properties of the media. On the one hand, GO is complexed
with Pb2þ and Cd2þ, which may lead to aggregation of GO and
causes Pb2þ and Cd2þ to deposit on the surface of coated sand (Yang
et al., 2016). Secondly, the covering on the surface of the medium
can first adsorb Pb2þ and Cd2þ, and then adsorb GO through cation
bridge to make the GO new site on the surface of coated sand.
Therefore, GO carries Pb2þ and Cd2þ in the coated sand column, but
GO may also play a role in inhibiting the migration of Pb2þ and
Cd2þ. The ADR model used to simulate the breakthrough curve well
matched the experimental data. Table 3 lists the fitting parameters
(k and Smax) and R2 values. The optimum Smax and the k of GO under
concurrent transport conditions were higher than those under the
individual GO transport condition. The trend of the optimum Smax
and the k of Pb2þ and Cd2þ was similar to that of GO. Model results
confirm that the presence of Pb2þ and Cd2þ in the sand column
enhanced the retention of GO particles and the presence of GO also
enhanced the retention of Pb2þ and Cd2þ.
3.4. Transport of GO in heavy metal contaminated sand columns
Fig. 4 shows the breakthrough curves of GO in Pb2þ and Cd2þ-
spiked coated-sand columns. These curves show that a certain
amount of Pb2þ or Cd2þ was retained in the sand column after the
heavy metal ions were injected and flushed with deionized water.
After the GO suspension was injected, part of previous retained
Pb2þ and Cd2þ were released from most of the columns and the
recovery rate of Pb2þ and Cd2þ ions is shown in Table 3. GO failed to
release Pb2þ and Cd2þ in smectite-coated sand columns, probably
because smectite has stronger affinity for Pb2þ and Cd2þ than GO.
The recovery rate of GO increased in Pb2þ- or Cd2þ-spiked
ferrihydrite-coated sand columns. This result is consistent with the
prediction of the DLVO theory that the repulsive force between GO
and ferrihydrite-coated sand should increase. These results indicate
that previously retained Pb2þ and Cd2þ ions may be grabbed by GO
11
and subsequently flow out of the sand column with their carrier.
The release of GO particles into the soil has an important effect on
the migration of heavy metal ions in underground systems.
GO, with its large specific surface area and numerous functional
groups, has good adsorption capacity for Pb2þ and Cd2þ. This makes
GO a good carrier for heavy metals and thus can facilitate their
migration in soils (Yang et al., 2016). In addition, the great
adsorption capacity of GO can also remobilize previously retained
Pb2þ and Cd2þ in soils, thus allowing them to enter groundwater
systems. Both heavy metal ions and GO are environmentally toxic,
so the co-transport of GO and heavy metals can result in severe
environmental pollution.
4. Conclusions
This study provides new information about the concurrent
transport of GO and heavy metal ions (Pb2þ and Cd2þ) in chemically
heterogeneous porous media: HA, kaolinite, smectite, and
ferrihydrite-coated sand. SEM micrographs showed that approxi-
mately 56.7e89.9% of the quartz sand surface was covered by the
coatings and that the EDS spectra of the coated sands showed that
soil components covered the surface of the quartz sand. The
coexistence of GO and heavy metal ions mutually influenced their
transport behavior in the coated sand. Results from experiments on
concurrent transport indicate that the individual GO in the solution
had high mobility in the sand column. However, the mobility of GO
was significantly reduced when Pb2þ and Cd2þ ions were present in
solution. On the other hand, the mobility of Pb2þ and Cd2þ ions was
also reduced in the presence of GO. The transport behavior of GO in
the coated sand column is consistent with the prediction of the
DLVO theory, indicating that electrostatic force plays a major role in
the transport behavior of GO on the coated sand column. The re-
covery of GO in Pb2þ or Cd2þ-spiked sand columns was less than
that in un-spiked columns except for the ones coated with ferri-
hydrite. In addition, part of the previously retained Pb2þ and Cd2þ
were remobilized and released from the column by GO. Therefore,
when GO is released into the subsurface environment, especially
heavy metal-contaminated soils, it will enhance the mobility of
heavy metals in the soils and thus may impose risks to ground-
water. Although this work simulates soil by coating clay minerals,
ferrihydrite and humic acid on the quartz sand surface, the soil
composition is not single fixed, thus, the influence of different
proportions of soil components on the co-transport of heavy metals
with GO in the coated-sand columns is an important aspect for
future research.
Acknowledgement
This research was partially supported by the National Natural
Science Foundation of China (Grant No. 41877018, 41771260); Na-
tional Key Research and Development Program (Grant No.
2017YFD0801500, 2018YFD0800401); Key research and develop-
ment program of Shaanxi province (Grant No. 2018ZDXM-SF-030,
2017SF-377), Industry University Research Application Cooperative
Innovation Key Program of Yangling Agricultural Hi-tech Industries
Demonstration Zone (Grant No. 2017CXY-10); the Fundamental
Research Funds for the Central Universities (Grant No.
2452017107); and the Chinese Scholarship Council.
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