Journal of Hydrology 618 (2023) 129260

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Journal of Hydrology
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Research papers

Enhanced delivery of remedial reagents in low-permeability aquifers

through coupling with groundwater circulation well
Peng Wang a, b, Jia Li a, b, Pei An a, b, Zheng Yan a, b, Yang Xu a, b, Shengyan Pu a, b, *
a
State Key Laboratory of Geohazard Prevention and Geoenvironment Protection, Chengdu University of Technology, Chengdu, Sichuan 610059, China
b
College of Ecology and Environment, Chengdu University of Technology, Chengdu, Sichuan 610059, China

A R T I C L E I N F O A B S T R A C T

Keywords: Limited dispersion and mass transfer because of hydrogeological heterogeneity make it difficult to deliver
Groundwater circulation well remedial reagents to desired locations. Remediation alternatives that overcome mass transfer limitations are
Remedial reagents required urgently to improve the efficiency of in situ remediation techniques. In this study, a combination of two-
Enhanced delivery
dimensional sandbox experiments and numerical simulations was used to explore the migration process of
Reactive transport
remedial reagents driven by groundwater circulating well (GCW). The influences of the circulating flow rate,
Low-permeability aquifer
concentration of the remedial reagent (H2O2 as a model) and cycle operation mode on the migration of GCW
enhanced remedial reagents were investigated. The flow rate of the pumped water can enhance the concentration
gradient at the interface of different permeation zones. The redistribution of reagents by increased Fick diffusion
significantly increased the dispersion range. The results of parametric sensitivity analysis showed that the ag­
gregation effect of remedial reagents in the low permeability area (~10-7 m/s) and related to the injection site.
Considering remedial reagents attenuation, a reactive transport model can better simulate the concentration
changes in low-permeability regions (R2 > 0.960). The numerical simulation results showed that the principal
component of the hydrodynamic field was tangential to the main axis of the target area. The diffusion coefficient
of the low-permeability region was one order of magnitude lower than that of the high-permeability region (~10-
3
m/s). Thus, the low-permeability region was less affected by the hydraulic action of the GCW and had a longer
retention time for remedial reagents. Specific aquifer parameters and operating modes are key engineering
design factors of a GCW that should be considered in conjunction with other in situ chemical technologies. This
study provides some new insights for in situ remediation of contanminated aquifers with a GCW, and suggests
that (i) the hydraulic circulation driven by GCW can promote the accumulation of injected remedial agents in low
permeability areas, especially injection point is located near wellbore; and (ii) residence time of reagents in
contaminated areas should be comprehensively considered when chemical remediation technology is coupled
with GCW. The results of this study can be used to improve the delivery efficiency of remedial reagents in
contaminated aquifers.

1. Introduction
Groundwater quality worldwide has deteriorated in recent decades
owing to rapid industrialization and the mishandling of hazardous
chemicals (Lin et al., 2018; Němeček et al., 2018; Tawabini and Mak­
kawi, 2018). Especially, the low permeability area as a secondary
pollution source can continue to release pollutants, which results in
incomplete remediation (Tatti et al., 2018; O’Connor et al., 2018). As a
low-disturbance technology to underground environments, in situ
chemical remediation technology makes an important contribution to
groundwater remediation (Siegrist et al., 2011; Lai et al., 2021; Wei
et al., 2022). Such technologies involve the injection of reagents or
redox-manipulating materials, such as H2O2 (Wei et al., 2022), KMnO4
(Lian et al., 2019), ozone (Khan and Carroll, 2020), and persulfate (Zhen
et al., 2014), into the aquifer for in situ chemical oxidation or reduction,
delivering these chemical reagents to target regions and ensuring con­
tact with contaminants. Therefore, the key to the efficiency of in situ
technology is the effective mass transfer of remedial reagents and their
distribution in the contaminated area.
Using hydraulic injection (e.g., gravity feed and pressurized injection

* Corresponding author.
E-mail addresses: pushengyan13@cdut.cn, pushengyan@qq.com (S. Pu).

https://doi.org/10.1016/j.jhydrol.2023.129260
Received 4 December 2022; Received in revised form 1 February 2023; Accepted 6 February 2023
Available online 10 February 2023
0022-1694/© 2023 Elsevier B.V. All rights reserved.
P. Wang et al.
(Schroth et al., 2001)), soluble remedial reagents are typically delivered
to a target treatment zone relying primarily on advective delivery
(Struse et al., 2002; Cavanagh et al., 2014; Head et al., 2020). In fact, in
situ injection technique is only suitable for sandy soils with high
permeability, while the influence on remediation performance is very
limited in low-permeability clays (below 10-7 m/s) (Parker et al., 2008;
Cavanagh et al., 2014; Lian et al., 2019; Head et al., 2020). Reagents
injected into the area creates a preferential flow path in the high
permeability zone (Zhong et al., 2013). Furthermore, the slow hori­
zontal flow rate of groundwater results in limited lateral dispersion of
injected remedial reagents in porous media (Kanzari et al., 2015).
Therefore, migration of remedial reagents into areas with low perme­
ability is problematic. The accurate characterization of the migration
process of soluble reagents in hypotonic heterogeneous medium is
challenging. Groundwater circulation well (GCW) with both pumping
and injecting can extract contaminated groundwater from an aquifer
through one screened section of a dual-screened well, and then inject the
well-treated clean groundwater back into the aquifer through a second
screened section in the same well (Chen and Knox, 1997; Ponsin et al.,
2014).
GCW system can form a crossed circulating flow field with both
longitudinal and vertical circulations between the injection and
extraction screening intervals, which is an important method for pro­
moting mass transfer (Xia et al. 2019; Ciampi et al., 2019; 2021). The
GCW has shown great potential for coupling with other technologies to
enhance aquifer remediation efficiency (Yuan et al., 2021). For example,
GCW can enhance the longitudinal migration of surfactants mainly
because the circulating well can hydraulically control the surfactant
effectively and enhance its effective range of action (Knox et al., 1997;
Alleman et al., 2010). The peripheral multilevel injection wells in
combination with GCW-induced recirculation to inject electron donors
and demonstrated it improves the 3D spread of additives throughout the
treatment area (Ciampi et al., 2022). In particular, GCWs can increase
vertical groundwater flow to pass through low-permeability lenses
(Johnson and Simon, 2007) and facilitate back-diffusion process of so­
lute (Tatti et al., 2018). The circular flow field line generated from the
GCW is orthogonal to the main flow line of the low-permeability zone,
which has high economic utility for the treatment of low-permeability
areas (Tatti et al., 2019). The coupling of GCW and in situ chemical
oxidation may effectively solve the problem of the low efficiency of
remedial reagent transmission. However, the delivery features of
remedial reagents driven by hydraulics in low-permeability aquifers
under conditions of hydraulic excitation of GCW was still unclear.
Numerical model of laplace transform finite difference method was
developed to characterize the spatiotemporal distribution of non-
reactive reagent with advection–dispersion in GCW-induced flow field
(Chen et al., 2010). In fact, low-permeability regions dominated by clay
minerals increase aquifer heterogeneity, thereby adding uncertainty to
the remedial reagent migration process, such as flow around (Lee et al.,
2014), adsorption, reverse diffusion (Tatti et al., 2018) and reactions
(Crincoli et al., 2020). The delivery/migration of remedial reagents is
accompanied by attenuation, adsorption and retardation, which lead to
errors between the numerical simulation results and physical experi­
ments. The attenuation reaction and adsorption of water-soluble re­
agents (H2O2, persulfate and permanganate) may change their
migration in aquifers. Therefore, a migration model with reaction terms
may better reflect the migration process of solute likely remedial reagent
(Zhu et al., 2020; Feng et al., 2022). Moreover, the actual remediation
efficiency of contaminated aquifers is significantly affected by formation
heterogeneity. The dispersion coefficient of heterogeneous strata is
lower than that of homogeneous strata and decreases with the
decreasing of medium particle size (Weill et al. 2017). Aquifer seepage
model constructed based on basic hydrogeological parameters can use to
characterize the remediation efficiency of the GCW, thereby effectively
optimizing its design parameters (Ni et al., 2011; You and Zhan, 2013;
Tu et al., 2019, 2020; Zhu et al., 2020). This process is of great
2
Journal of Hydrology 618 (2023) 129260
significance for developing the application value of GCW in engineering
practice. There is a large gap between the results of physical simulations
based on hydrogeological parameters (dispersion coefficient, hydraulic
conductivity, porosity, etc.) in the laboratory and the simulation results
of mathematical models (Blanford et al., 2001; Yang et al., 2005).
Therefore, the hydrogeological constraints and process parameter opti­
mization scheme of the GCW technology should be explored from the
perspective of combining models and physical simulation tests.
Physical experiments and mathematical model simulations for
describing the groundwater flow and solute delivery regime are
important subjects in subsurface hydrology (Sutton et al., 2000; Goltz
et al., 2008). Previous studies have somewhat weakened the combina­
tion of laboratory testing and numerical simulation. In addition, non-
reactive tracers are mostly used for the migration model, which is
biased for the actual effects of reactive reagent delivery. In this study,
the properties of the remedial reagent concentration field under a GCW-
driven flow field were investigated using a two-dimensional sandbox
experiment and numerical simulation. Water-soluble remedial reagents
(H2O2 and persulfate) were selected as a model solute. The COMSOL
program was used to establish a finite-composition numerical model for
reactive transport of remedial reagents in high/low-permeability region.
The characteristics of migration in low-permeability areas influenced by
the GCW across time scales were analyzed. Furthermore, the effects of
injection concentration, operation modes, and parameters of GCW
technology on the delivery mechanism of the injected remedial reagents
were considered. Sensitivity analysis was performed on the parameters
concerned in GCW system. The concentration field of the remedial re­
agent H2O2 in the vertical circulation flow field was also evaluated. This
study is expected to provide a theoretical reference for GCWs coupling
with in situ chemical remediation technology application of ground­
water remediation associated with low-permeability lenses in contami­
nated aquifer.
2. Materials and methods
2.1. Experimental
2.1.1. Laboratory sandbox experiment
The experimental apparatus used to perform the test is illustrated in
Fig. 1 and consisted of a two-dimensional plexiglass sandbox with di­
mensions of 100 × 6 × 50 cm (length × width × height). Geometric
model parameters of GCW are listed in Table S2. The sandbox consisted
of three parts, with a central part used to reconstruct the aquifer and two
small chambers on both sides. There were 32 sampling points in the last
four rows of the 40 sampling ports on the front of the simulation tank.
Points 10 and 11 were sampled in the low-permeability area. The
diameter of the GCW was 6 cm, and it was wrapped with a filter cloth
and placed in the fifth column of the simulation tank. A peristaltic
closed-pump GCW was used to simulate a constant groundwater flow
rate of 0.045 m/d. The reconstructed aquifer consisted of fine sand as
the high-permeability layer (~10-3 m/s) and illite as the low-
permeability zone (dark grey squares in Fig. 1, ~10-7 m/s). The
porosity of the fine sand was measured and calculated using a one-
dimensional column experiment. The size of illite was estimated using
a reference estimation (Tatti et al., 2018).
2.1.2. Test procedure
Setting of four working conditions under the driving of GCW is
described in detail in Text S1. Briefly, 75 mL of the remedial reagent (10
mM) was injected at the two points corresponding to injection point 2
(Fig. 1b) to ensure that the total volume of each injection is 150 mL. The
transport of H2O2 and persulfate under natural water flow (0.045 m/d)
was separately investigated. In the comparative experiment, the
migration of remedial reagents under GCW with 10 rpm conditions was
introduced in the same state. The effect of GCW on the migration process
of H2O2 as a model remedial reagent was further studied under different
P. Wang et al. Journal of Hydrology 618 (2023) 129260

Fig. 1. Schematic of heterogeneous packing in a two-dimensional sandbox device (a) and simulation model and (b) of a groundwater circulation well (GCW). In­
jection points 1 and 2 represent areas above the low permeability zone and close to wellbore, respectively.

concentrations (5, 10 and 20 mM), pumping flow rates (10, 20 and 30 2.2.2. Groundwater flow model
rpm), and pumping and injection methods with the forward and reverse Considering the homogeneous and anisotropic aquifer, a finite
flows. In all the experiments, 2 mL was sampled from 32 sampling ports element numerical model was established using COMSOL 5.6. The
at set time intervals. Continuous operation of the GCW was guaranteed conceptual model of groundwater flow associated with GCW system is
during the sampling process (the detailed information can be seen in shown in Fig. 1b. To simplify the mathematical model, this section is
Text S1 of Supporting Materials). based on the following assumptions: (1) the aquifer is a confined aquifer
of equal thickness and extends horizontally indefinitely, (2) the aquifer
2.1.3. Chemical analysis is homogeneous anisotropy, (3) the flow field is a stable flow, (4) a cy­
Persulfate concentration was determined using the iodometric lindrical coordinate system is established with the center of the circu­
method (Waclawek et al., 2015). Briefly, the sample solution was diluted lating shaft wellbore as the origin.
10 times, and 5 mL of color developer (KI and NaHCO3 solution) was
added subsequently. The absorbance was measured at 395 nm using a ∂2 H(r, z) Kr ∂H(r, z) ∂2 H(r, z)
Kr + +Kz =0 (2)
UV–vis spectrometer. The concentration of H2O2 was determined using ∂r 2 r ∂r ∂z2
the potassium titanium oxalate colorimetric method (Sellers et al., ⎧
⎪ 0 0 < z < de
1980). Briefly, one mL of sulfuric acid solution (1:3) and 1 mL of 0.05 M ⎪
⎪
⎪
⎪
potassium titanium oxalate solution were added to the sample solution. ⎪
⎪
⎪
⎪
− Q
de < z < le
⎨ 2π Kr R(le − de )
The absorbance of the solution after the reaction was measured using a ∂H(r→∞, z)
= (3)
spectrophotometer at a wavelength of 402 nm. ∂r ⎪
⎪ ⎪ Q
⎪
⎪ li < z < di
⎪
⎪ 2π Kr R(li − di )
⎪
2.2. Data analysis ⎪
⎩0 le < z < D

2.2.1. Accumulated concentration of remedial reagent H(r→∞, z) = 0 (4)

To quantitatively describe the overall characteristics of the reagent
concentration in the low-permeability aquifer, the average concentra­
tion at sampling points in this region was defined as the concentration at
the corresponding time point.
∫∫
− c(x, y, t)dxdy
= (1)
c(t) A
where c(x, y, t) are the reagent concentrations at each spatial point in the
low-permeability region at different times (mol/m3), A is the cross-
sectional area of the low-permeability region (m2), and
−
is the
c(t)
accumulated concentration of the reagent in the low-permeability re­
gion (mol/m3).
A concentration contour map was drawn using Surfer 17 with kriging
interpolation. Each grid node value is based on known data points
adjacent to that node, and then it compensates for clustered data by
giving less weight to the overall prediction. The correlation between the
measured and model-fitted data of various factors (reagent concentra­
tion, pumping water flow rate, and operating mode) was analyzed using
SPSS 23.
∂H(r, z = 0)
=0 (5)
∂z
∂H(r, z = D)
=0 (6)
∂z
where H(r, z) represents the hydraulic head at the location (r, z) (m), r
represents the radial coordinate (m) stretching from the well center and
z indicates the vertical coordinate (m) from the aquifer bottom as shown
in Fig. 1b. Kr and Kz indicate the radial and vertical hydraulic conduc­
tivities (m/s) respectively. R is the well radius (m) and D is the aquifer
thickness (m); le and li are the top coordinates of the injection and
extraction screened intervals (m), respectively; di and de are the bottom
coordinates of the injection and extraction screened intervals (m),
respectively. Equation (4) indicates that there is no drawdown far from
well. Equations (5) and (6) are the upper and lower no-flow boundary
conditions, respectively. The radial and vertical components of the
water flow velocity (eq. (3)) are incorporated into the reagent transport
equation to describe remedial reagent transport in a vertically circu­
lating flow field. The coefficient of determination of the Pearson cor­
relation between the head height fitted by the model and the measured
value was 0.916–0.972 (Fig. S1). Darcy’s law was used to simulate the

3
P. Wang et al. Journal of Hydrology 618 (2023) 129260

hydrodynamic field of the sandbox. The input value used in the model 3. Results and discussion
are listed in Table S2.
3.1. Transport of reagents in natural and vertical circulation flow fields
2.2.3. Reagent mass delivery model
Numerical simulations can provide an effective tool for the design The migration process of the reagents in natural and circulating flow
and implementation of enhanced remediation of contaminated fields was investigated. The time-dependent distributions of the H2O2
groundwater in heterogeneous aquifers owing to advection and hydro­ and persulfate concentrations in the natural flow field are shown in
dynamic dispersion processes using GCW technology. The numerical Fig. S2. Both reagents migrated from the lift-top injection point to the
simulation of reagent delivery in an aquifer was carried out using the right edge of the sandbox within 3 h. Lateral migration occurs with
delivery and diffusion equations. groundwater flow under the action of convection. The remedial reagents
can ideally migrate in the flow field set in this study, ensuring the
∂C ∂C ∂C ( ) ∂C
+ vi = DD,i + De,i + Ri (7) feasibility of subsequent studies in the circulating flow field. The
∂t ∂xi ∂xi ∂xj
migration of the high-concentration centers of the reagents in the
sandbox exhibited different trends with time. The horizontal displace­
Ri = kp ρs C(t) = kp ρs C0 exp(Ki t + b) (8)
ment of the high-concentration center and a limited vertical migration
∂C ∂C ∂C ( ) ∂C ∂C(t) were observed. This indicates that H2O2 migrated mainly in the hori­
+ vi = DD,i + De,i − Ri (9) zontal flow field. Persulfate diffuses both horizontally and vertically and
∂t ∂xi ∂xi ∂xj ∂t
has a relatively fast vertical diffusion rate. By contrast, persulfate could
where C (mmol/L) is the solute concentration, i and j represent r and z, migrate both horizontally and vertically.
respectively. vi are the components of the velocity vector, DD,i is the The retardation factor (R) is defined as the fraction of an analyte in
hydrodynamic dispersion coefficient (m2/s), De,i is the effective diffu­ solute transport in an aquifer system (Glubt and Brusseau, 2021). The R
sion coefficient (m2/s), and Ri is the reaction part (where kp is the sol­ value of H2O2 (R = 1.37) was higher than that of persulfate (R = 1.23) in
id–liquid partition coefficient of the low-permeability area), which the one-dimensional sand column experiment (Fig. S4a), which in­
exists only in the low-permeability region. The decay equation of illite to dicates a faster migration rate of the former. The H2O2 molecules tend to
H2O2 obtained by the batch experiment (Table S3). form hydrogen bonds with water molecules to aggregate, which can
The equations used in the model were numerically solved in two increase the residence time in porous media (Mo et al., 1994; Du et al.,
dimensions using the finite element method. The domain was divided 2005). Conversely, electrostatic repulsion between persulfate and the
into a regular orthogonal grid with a 0.01 m spacing. The Neumann negatively charged quartz sand surface can reduce the adsorption
condition was used for the bottom and side boundaries of the domain. retention and accelerate migration in the aquifer. Moreover, the reme­
The model was validated by reproducing the laboratory test described in dial reagents injected into the aquifer migrated vertically under the
Section 2.1.2 and comparing the experimental results with the numer­ action of gravity. The density effect caused by the larger density of
ical results. The calibration phase was performed by varying the hy­ persulfate can also be used to explain its faster migration in the vertical
drodynamic dispersion coefficient and hydraulic conductivity of the direction (Konz et al., 2009; Lian et al., 2019). Subsequently, the con­
media. The aquifer parameters used in the numerical delivery model are centration of reagents was gradually diluted via hydrodynamic disper­
listed in Table 1. sion along the tortuous channels of the porous medium.
As shown in Fig. 2, an accelerated migration process of both reagents
2.2.4. Parameter sensitivity analysis was observed under the created vertical circulating flow field in the
To further discuss the influence factors of GCW-driven H2O2 migra­ aquifer via the GCW. In a recent study, the biodegradation rate of
tion in different regions, a single factor sensitivity analysis was carried chloroethane was significantly significantly accelerated through GCW
out for its parameters. Low-permeability areas, area around the well and delivery reagents in field scale (Ciampi et al., 2022). In particular, re­
high permeability areas were selected. To concisely and clearly illustrate agents were detected in most sandbox formations within 3 h. The
the influence of various factors on the migration process of H2O2 driven breakthrough curve results show that increasing the flow rate can
by GCW, gray correlation analysis was used to process the data to obtain reduce the retardation factor, thereby accelerating its migration in the
the correlation coefficient. The correlation order of each comparative aquifer (Fig. S4b). In addition to horizontal migration, the concentration
series was established according to the size of the gray weighted cor­ distribution of H2O2 was detected at the bottom of the sandbox. The
relation degree. Sensitivity analysis results of H2O2 migration influ­ intermolecular force for the formation of hydrogen bonds was destroyed
encing factors driven by GCW were listed in Table S4. The greater the with increasing flow rate. The concentration accumulation areas of the
correlation coefficient, the greater the importance of the factor to the reagents were flushed out and vertical migration was enhanced by the
indicator. The more detailed information was shown in text S4 of Sup­ vertical flow field. The lower concentration of remedial reagents near
porting Materials. the wellbore was mainly due to the dilution of more cycles in the vi­
cinity. Because the experimental setup did not involve well construction,
the influence of other factors on the migration of remedial reagents
around the well was not considered here. In fact, the construction of
wells at the site scale causes skin effects, which may accelerate or slow
Table 1 down the migration of solutes. This is mainly owing to an increase or
Specific aquifer parameters involved in the numerical reagent delivery model in
decrease in the permeability of the area close to the circulating well
the aquifer.
(Morozov et al., 2021); hence, the hydrodynamic field is not an ideal
Parameter High permeability zone Low permeability symmetrical flow.
(Fine sand) zone (Illite)
It is worth noting that the concentration distributions of the two
γs (kg/dm3) 2.65 1.20 reagents in right area in the sandbox are relatively uniform in the nat­
Porosity 0.53 0.38
ural flow field (Fig. S2). In left area with the low-permeability region,
Hydraulic conductivity Ki (m/ Kr = 4.90 × 10-3 Kr = Kz = 1.60 × 10-7
s) Kz = 1 × 10-3 migration of the reagent exhibited an obvious “flow around” phenom­
Hydrodynamic dispersion 1.00 × 10-5 5.00 × 10-6 enon, which can be attributed to the hindrance by the low-permeability
coefficient DD,i (m2/s) medium. This result is consistent with findings of other studies, where
Effective diffusion coefficient ar = 5.00 × 10-3 ar = 1.50 × 10-9 permanganate has an obvious bypass phenomenon in the low-
De,i (m2/s) az = 1.00 × 10-3 az = 3.50 × 10-8
permeability area containing the pollutants, and there are many

4
P. Wang et al.
Fig. 2. Concentration distribution of H2O2 (a) and persulfate (b) driven by a groundwater circulation well with a flow rate of 37.6 mL/min (the brown square
indicates the low-permeability area, and the circulating well located in the middle, injection site 2).
accumulations at the boundary of high- and low-permeability areas
(Marble et al., 2010, Tatti et al., 2019). However, reagents tend to
aggregate in the vertical circulating flow field created by the GCW and
even enter low-permeability regions (Fig. 2). The enhanced vertical
migration process during GCW operation may be the key factor driving
the reagent to the low-permeability region. This promising result could
be an advantage for in situ remediation of contaminated low-
permeability aquifers.
3.2. Factors influencing GCW-driven H2O2 delivery
The migration process of a reagent after its injection into an aquifer
determines its remediation scope and effect. In this study, the factors
influencing GCW-driven reagent migration were investigated. Consid­
ering the more obvious vertical migration phenomenon from GCW
(Fig. 2a), H2O2 was selected as the model to further explore the influence
of different factors on the migration of the GCW-enhanced reagent.
Reagents may float or sink during migration in the aquifer owing to
density differences between the injected solution and groundwater
(Swartz and Schwartz, 1998; Konz et al., 2009). First, the effect of
injected reagent concentration should be considered. Density effect is
common in groundwater solute delivery and aquifer remediation. High-
concentration H2O2 (20 mM) preferentially migrates in high-
permeability areas and the time to fill the sand box is shortened
(Fig. S5), which is consistent with the migration properties of perman­
ganate (Lian et al., 2019). The enhanced migration of H2O2 driven by
GCW was affected by higher concentration. The remedial reagent can
better migrate to the bottom of the aquifer under the joint action of
density effect and vertical GCW-driven. In addition, hydroscouring from
GCW can accelerate the back-diffusion process of pollutants from
contaminated medium in pollution source area (Ciampi et al. 2019,
2023). The effective mixing of injected high-concentration remediation
reagents and pollutants can improve the remediation efficiency of
contaminated sites. For example, for sites where pollutants (such as
dense non-aqueous liquids) have accumulated at the bottom of an
aquifer, a strategy of GCW-coupled pulse injection of high-concentration
5
Journal of Hydrology 618 (2023) 129260
remedial reagents could be considered.
In addition to the influence of the concentration of the remedial re­
agents, the technological parameters of GCW also have an important
influence on the migration process (Jin et al., 2015). As shown in Fig. S6,
increasing the flow rate of pumping and injecting into the GCW can
increase the radius of influence. A significant enhancement in intensity
appeared near the wellbore. After the GCW was operated for 1 h at
112.5 mL/min, H2O2 was already distributed in the entire sandbox
(Fig. S7). The result indicates that increasing the flow rate of pumping
and injecting can achieve the expansion of the range of influence in a
relatively short time. A significant diffusion in the high-permeability
region on the right side of the sandbox was observed under a high
flow rate of pumping and injecting (Fig. S7). The longitudinal migration
rate of the concentration centroid was accelerated and was mainly
affected by dispersion (Godoy et al., 2018). The longitudinal dispersion
coefficient increased from 0.005 to 0.05 m with the increase in flow
velocity. Therefore, increasing the flow rate of the pumping water can
effectively enhance the longitudinal migration of the reagent in the
high-permeability area. A higher concentration of aggregation points
was detected at the bottom of the sand box (Fig. S7b), which appears to
be more effective for remediation of similar DNAPL-contaminated sites.
The low-permeability area (illite, ~10-7 m/s) exhibited a marked
significant aggregation and retention of the remedial reagent with the
increase in the flow rate of the pumped water. However, solute transport
in low permeability areas has little effect. This is mainly because the
hydraulic action of the GCW increases the force interface to the main
axis of low permeability. The loss of H2O2 increased with the distance
between the injection point and wellbore (Fig. S8a). This is mainly
attributable to the gradual weakening of the solute capture ability of the
GCW away from the wellbore under the combined action of the
groundwater flow and GCW hydraulics (Chen et al., 2010, 2011; Zhu
et al., 2020). Therefore, both the injection site and circulation method
will affect the transmission process of H2O2, and the injection of reagent
near the circulation well is more conducive to its uniform distribution.
In addition to the common forward flow operation mode, reverse
flow GCW with bottom-up circulation mode is often used for the
P. Wang et al.
treatment of pollutants (Kitanidis and Mccarty, 2012). But the concen­
tration distribution of the reagent in this circulation mode is not clear. In
this study, the results indicated that the range of action of H2O2 was
greatly limited under the action of reverse flow (Fig. S9). Compared with
the forward flow circulation well drive, the water flow disturbance
during the reverse flow from GCW driving is different, in which the
radius of influence is reduced, so the scope of the remediation reagent is
limited, and this is proved by the experimental phenomenon in this
study, which is mainly due to the need to overcome the gravity process
to form vertical upward migration (Fig. S9). Due to the continuous in­
crease of remediation reagents in low-permeability areas (Fig. 4c), the
reverse flow operation mode seems to have a certain positive effect on
the long-term treatment of small-scale pollution points. The operating
mode of forward and reverse flow switching may be a viable strategy to
reduce the treatment time of polluted aquifers.
Fig. 3 shows the correlation degree between each factor and the
correlation coefficient. The migration of H2O2 near wellbore is mostly
affected by the flow rate of the pumped water. This is mainly attributed
to the strong hydraulic disturbance near the wellbore. The slightly
greater concentration coefficient r0i around the wellbore indicates that
the closer distance to wellbore, the stronger the hydraulic driving effect.
The migration of H2O2 in the high-permeability area is mainly affected
by the injection concentration. As shown in Fig. S5, high-concentration
H2O2 has a preferential migration phenomenon in the high-permeability
region (the right area of the sandbox). The concentration gradient
simultaneously accelerates H2O2 longitudinal migration. Therefore, the
concentration and a certain injection distance from the circulation well
to the contaminated area of H2O2 in the actual site should be considered.
The ineffective consumption of the injected remediation reagent caused
by the multiple cycles can be effectively controlled. The migration of
H2O2 in the low-permeability area was mainly affected by the injection
site (r0i = 0.822). The injection above the low permeability area was
more conducive to the migration and aggregation of H2O2 in the low
peroxide area in GCW. In summary, the enhanced migration of H2O2
could be attributed to the high concentration of the reagent, the
increased flow rate of pumping and injecting, and the forward-direction
operating mode of the GCW. These influencing factors should be
designed according to the actual site from the perspective of economics
and environmental effects of the in situ remediation technology.
Fig. 3. Sensitivity analysis of concentration of the reagent, flow rate of
pumping and injecting and operating mode of the GCW. The correlation coef­
ficient of the migration H2O2 in low-permeability areas, area around the
wellbore and high permeability regions of the sand box under GCW driven.
6
Journal of Hydrology 618 (2023) 129260
3.3. Enhanced delivery and accumulation of H2O2 in the low-permeability
aquifer by the GCW system
In the sandbox experiment, the reagents did not reach the bottom of
the aquifer effectively in the simulated natural flow field. The change in
H2O2 concentration in the low-permeability aquifer was compared with
and without being driven by the GCW (Fig. 4). The entire reagent plume
moved downward and then effectively entered the low-permeability
area driven by the GCW (Fig. 4a). Low H2O2 concentrations (over an
order of magnitude) were observed in areas of low permeability during
the four-time intervals, with no driving effect (only natural water flow).
This result indicates that it is difficult for H2O2 to migrate from the high-
permeability region to the low-permeability region, relying solely on
water flow and natural gravity. Remediation of contaminated low-
permeability areas is often very problematic because of the lower hy­
draulic conductivity (<1.6 × 10-7 m/s) of the low-permeability area
than that of the surrounding area (Zinn et al., 2004; Tatti et al., 2016).
The driving force created by the natural water flow is difficult to achieve
in these areas. However, one vertical component of hydraulic excitation
in the low-permeability region could be formed under driven by GCW
(Fig. S9). Considering enhanced migration (Knox et al., 1997) and
effectiveness for remediation (Tatti et al., 2019) of low permeability
formations, one possibility is provided for the reagent enter the low-
permeability region.
A numerical model was used as an effective tool to represent the
accumulation and delivery of solutes from high- to low-permeability
aquifers, thereby simulating possible field scenarios, as shown in
Fig. 5. Driven by the pumping and injection of water, a water circulation
movement formation in aquifer can generate hydraulic excitation. The
reagent at the injection point will migrate to the porous medium and
accumulated in the low-permeability area during the process of pump­
ing and injecting in GCW. The model inversion proves that the diffusion
coefficient of the low permeability region is one order of magnitude
lower than that of near region (Table 1). As reported in the literature, the
pore-scale flow rate of the low-permeability region is less affected by
GCW hydraulics (Mohrlok et al., 2010). The principal component of the
velocity field is tangential to the main axis of a contaminated area (Tatti
et al. 2019). Groundwater flow can enhance concentration gradient at
the interface between different permeability zones increasing redistri­
bution of trapped contaminant by Fick diffusion. Based on the accu­
mulation and release in the low-permeability region, the migration of
H2O2 includes two processes forward and reverse diffusion from the low-
into the high-permeability region (Fig. 6a). Under driven by GCW, the
efficiency of forward diffusion is significantly higher than that of the
reverse diffusion. One positive effect from the actuation of GCW can
form on the migration and retention of reagents, which significantly
accumulates H2O2 in low permeability aquifer.
As shown in Fig. 6, the cumulative concentration of H2O2 region is
further calculated by simulation, which can be used to reflect the change
of the concentration field. Hydrogen peroxide moving into the low
permeability area is less affected by the water flow, but the concentra­
tion is mainly reduced by the decomposition of the aquifer medium. The
effect of concentration is particularly pronounced, a gradual accumu­
lation process around and within these media occurs during the first 6 h,
and then is slowly released or decomposed. High concentrations of H2O2
dissipated rapidly in the region of low permeability media after 3 h
(Fig. 6).
Conversely, low concentration H2O2 is effectively maintained for >8
h after reaching the peak value. This is mainly attributable to the fact
that the decomposition rate constant of H2O2 by the low-permeability
medium increases with its concentration. The reagent concentration in
the low-permeability area is continuously increased until the reagent
cannot be replenished. The accumulation concentration of reagent in the
low-permeability region (Eq.1) indicates that reagent aggregation effect
occurs in low permeation area. That is, at the same time, the higher the
accumulation concentration of reagent in the low permeability area, the
P. Wang et al. Journal of Hydrology 618 (2023) 129260

Fig. 4. Variation in H2O2 concentrations with different injection concentrations (a), pumped water flow rates (b), and circulation methods (c) in the low-
permeability region.

better the effect of pollutant remediation in the low permeability area.

Fig. 5. Distribution field of H2O2 driven by a simulated GCW (10 mM H2O2, Q
= 37.6 mL/min).
The attenuation term of the remedial reagent was added on the basis
of the traditional advection–dispersion equation (ADE) (Tatti et al.,
2019). To validate the model, the concentration of H2O2 (measured
experimentally) in the low-permeability region was compared with the
data obtained from reactive transport model (Eq. (4)). As shown in
Fig. 7, the reactive transport model can better fit the experimental data
(R2 > 0.960). The agreement between the values was considered satis­
factory for demonstrating the suitability of the model for reproducing
the investigated process. The reactive transport model with reaction
terms is reproducible for the migration of the remedial reagents in the
low-permeability region. Considering the high concentration of H2O2
has the phenomenon of self-decomposition, that is, H2O2 will be
consumed by the generated •OH in system (Molamahmood et al.,2022;
Chen et al., 2022). These results further indicated that the migration in
the low-permeability region was mainly affected by the attenuation of
the reactive term of the remedial reagents. Therefore, multiple in­
jections of low concentrations in the actual repair project of GCW
coupled in situ injection of reagents can be considered to ensure stable
oxidation or reduction strength in low-permeability region.
In addition, increasing the water flow rate of the GCW enhanced the
accumulation of H2O2 in the low-permeability region (Fig. 8), which
accelerated the forward diffusion of H2O2. But little effect was observed
in the GCW reverse diffusion system. The dispersion coefficient of the
aquifer was determined to be reverse diffusion. Studies have found that
in soils with small particle sizes, the dispersion coefficient is small (Klotz
et al., 1980; Godoy et al., 2018). Consistent with the simulation results,
the diffusion coefficient in the low-permeability region was six to seven
orders of magnitude lower than that in the high-permeability region
(Table 1). Therefore, the migration and accumulation of H2O2 in the

Fig. 6. Comparison of measured and simulated values of groundwater circulation well (GCW)-enhanced H2O2 in the low-permeability area under the influence of
concentration (a), pumped water flow rate (b) and operating mode (c).

7
P. Wang et al.
Fig. 7. Correlation analysis between measured concentration and simulated concentration in low-permeability area without reaction term (a) and with reaction term
(b). R2 is the coefficient of determination.
Fig. 8. Simulated values of accumulated concentrations of H2O2 in high- and low-permeability areas under 5 mM (a) 10 Mm (b), and 20 mM (c) H2O2 driven by a
groundwater circulation well (GCW) with a flow rate of 37.4 mL/min.
low-permeability region were enhanced by increasing the pumped water
flow rate.
A more obvious enhancing effect can be observed in Fig. 8c, the
highest concentration reached 0.6 mmol/L. To further compare the
enhanced effect in the low-permeability area under the different oper­
ating modes, the reverse flow driven by the GCW under the same con­
ditions was adopted. The delivery of H2O2 mainly migrated in the
vertical direction of the low-permeability region, and gradually accu­
mulated over time (Fig. S8b). The cumulative concentrations of H2O2 in
the high- and low-permeability areas were also simulated (Fig. S10). The
maximum value was reached within the first 3 h under forward flow
driving, and the regional cumulative concentration remained constant
during the following 9 h. The accumulated concentration of H2O2
showed an increasing trend under the influence of the countercurrent
flow and leveled off after 9 h, which is consistent with results of the
laboratory process (Fig. 8c). This was mainly because the reverse flow
changed the direction of the flow field (Fig. S9) such that H2O2 prefer­
entially diffuses into the high-permeability region. The concentration
accumulation of the reagent from the upper well screen under reverse
flow circulation was slower than that under forward flow. The accu­
mulation time of H2O2 in the reverse flow circulation can be prolonged
in the low-permeability area, which has a positive effect on the
continuous and stable treatment of contaminated low-permeability
areas.
Our research was conducted in a two-dimensional sandbox, which is
a simplification of an actual aquifer. Owing to limitations such as high
cost and measurement difficulties of field-scale testing, laboratory-scale
8
Journal of Hydrology 618 (2023) 129260
experiments are the most widely used methods in aquifer remedial re­
agent migration studies and are often used to explain phenomena within
aquifers that cannot be explained by field-scale testing. For scale rea­
sons, the quantitative analysis results of this study cannot be directly
applied to aquifers. In this study, the decomposition kinetics of H2O2 by
other reactive clay minerals in low-permeability aquifers were not
evaluated in detail. Further exploration of this issue will be conducted in
the future. However, the data obtained in this study plays a crucial role
in the upgrading process from the laboratory to field scale. Qualitative
conclusions regarding the effects of circulating flow rate, concentration
of remedial reagents and cycle operation mode on the migration
behavior of reagents in low-permeability areas can be directly used to
guide aquifer green remediation.
4. Conclusions
The remediation efficacy of in situ chemical remediation techniques
is generally limited by the low mobility of reagents in subsurface aqui­
fers. The GCW technology presents an underexplored opportunity to
improve the delivery/emplacement control of reagents in contaminated
aquifers. Under the hydraulic excitation from GCW in a laboratory study
using a sandbox experiment, the transmission range of remedial re­
agents were significantly improved. In particular, the longitudinal
migration of reagents is most pronounced. The evolution of concentra­
tion distribution map showed that remedial reagents can effectively
migrate to the low-permeability zone and retain in here under GCW
driving. The parameter sensitivity analysis results show that injection
P. Wang et al.
above the contaminated low-permeability zone can help improve
remediation efficiency in here. The vertical hydraulic action from
driving role of GCW can improve both the vertical migration of reme­
diation agents and the reverse diffusion of pollutants, and this advantage
will help to improve the remediation efficiency of contaminated aqui­
fers. Vertical transport to cover the bottom area and continuous accu­
mulation in the low-permeability area under driving role of GCW were
observed.
The simulation results show that the migration model with the
addition of reaction items can approach the physical simulation results.
Based on the simulation results, the regional accumulated concentration
reflects the characteristics of enhanced H2O2 migration owing to the
hydrodynamic cycle driven by GCW. The efficiency of forward diffusion
from the high- to low-permeability region is significantly higher than the
reverse diffusion efficiency driven by the GCW. High and low concen­
trations of H2O2 rapidly dissipated and reached the peak value in low
permeability region after injection 3 h and 8 h, respectively. Compared
to the forward flow circulation mode, the reverse flow circulation mode
is suitable for coatings with a small range of pollutant accumulation.
This study provides a basis for understanding the advantages of GCW
in enhancing the migration of remedial reagents, which provides a new
solution for the difficulty of governance in low-permeability areas. The
enhanced remediation efficiency of residual pollutants in low-
permeability regions by coupling GCW with chemical remediation
techniques will be explored further. The results of this study can provide
theoretical guidance for the application of GCW in conjunction with in
situ chemical remediation technology in contaminated aquifers. For
complete remediation of a specific contaminated aquifer, the mecha­
nisms of reactive co-migration of remedial reagents and pollutants
driven by GCW hydraulics need to be carefully studied before being
incorporated into remediation efficiency assessment models. For
example, unresolved questions include the decay kinetic constants of
remedial reagents, as they depend on the depletion of target pollutants,
the ineffective consumption of non-target media, and the relationship
between accelerated hydraulic action and their own decay.
CRediT authorship contribution statement
Peng Wang: Investigation, Methodology, Formal analysis, Writing –
review & editing, Funding acquisition. Jia Li: Investigation, Methodol­
ogy, Formal analysis, Writing – original draft. Pei An: Investigation,
Methodology, Data curation. Zheng Yan: Investigation, Data curation,
Validation. Yang Xu: Software, Formal analysis. Shengyan Pu: Super­
vision, Funding acquisition, Writing – review & editing, Project
administration.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
This work was supported by the National Key Research and Devel­
opment Program of China (2020YFC1808300), the National Natural
Science Foundation of China (42007308, U22A20591), Open Fund of
the National Key Laboratory of Environmental Protection of Water and
Soil Pollution Coordinated Control and Joint Remediation (GHBK-2021-
009), Sichuan Science and Technology Program (10900-20Z16-04) and
Chengdu University of Technology Research Startup Fund Project
(10912-KYQD2019_07699).
9
Journal of Hydrology 618 (2023) 129260
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jhydrol.2023.129260.
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