722

Ying Lu 1,2
Xinqiang Du 1
Research Article
Yuesuo Yang 1,2
Wei Fan 3 Compatibility Assessment of Recharge Water
Baoming Chi 4
Zijia Wang 1
with Native Groundwater Using Reactive
Xueyan Ye 1 Hydrogeochemical Modeling in Pinggu, Beijing
1
Key Laboratory of Groundwater A hydrochemical assessment of the local harvested water and groundwater based on
Resources and Environment, Ministry
field data, lab experiments, and modeling was carried out for a groundwater artificial
of Education, Jilin University,
Changchun, P. R. China recharge (GAR) proposal in the Pinggu Basin aquifer. Harvested water chemically
2
School of Earth and Ocean Sciences, regulated by recharge water standard was chosen as an available recharge source in the
Cardiff University, Cardiff, UK basin. The sediments at the potential recharge site were characterized to determine the
3
Key Laboratory of Wetland Ecology impact of GAR on subsurface hydrochemistry. To model the dynamic hydrochemical
and Environment, Northeast Institute changes during GAR, transport process coupled with the geochemical equilibrium was
of Geography and Agroecology, CAS,
Changchun, P. R. China resolved using PHREEQC and a reverse computing process. These were to simulate
4
Institute of Disaster-Prevention chemical reactions, soil soluble species dispersion, mineral dissolution and precipita-
Science and Technology, Sanhe, tion, and cation exchange in the recharge vadose zone in the Pinggu Basin. The model
P. R. China was validated by a column leaching experiment and applied for field conditions. The
prediction results showed NO3
, SO42
, Cl
, and total dissolved solid had peak
breakthroughs during the first period of recharge indicating a “washout” phenomenon
and then settled down, whilst changes in HCO3
, Ca2þ, Mg2þ, and pH resulted from
carbonate buffering and cation exchange. In the long run, recharge by the harvested
water was unlikely to have a negative impact on groundwater quality. Rather caution
should be taken for potential chemical clogging induced by dolomite precipitation for a
sustainable GAR management.
Keywords: Clogging; Geochemical modeling; Groundwater artificial recharge; Hydrochemistry;
PHREEQC
Received: September 5, 2012; revised: January 3, 2013; accepted: March 2, 2013
DOI: 10.1002/clen.201200482

1 Introduction municipal “gray” water as the recharge source [5–7]. Potential

In an era of global climate change, securing the needed supply of
freshwater is crucial for sustainable development of every country
and community [1, 2]. Groundwater artificial recharge (GAR) has been
considered worldwide as an effective water resources management of
increased water storage in aquifers to save water in periods of water
surplus for use in periods of shortage. Hence, it is becoming
increasingly important in some arid or semiarid regions, where over-
pumping of groundwater has led to underground resources
becoming depleted. Many types of water, such as river water, storm
water, rainfall, roof water, and even municipal wastewater, can be
important water resources but their use must be carefully planned
and regulated to prevent adverse effects.
Water quality issue is therefore one of the forefront considerations
in planning a GAR Scheme [3, 4]. Many studies on impacts of recharge
water quality have been reported, but most focused on reclaimed
Correspondence: Professor X. Q. Du, Key Laboratory of Groundwater
Resources and Environment, Ministry of Education, Jilin University, 2519
Jiefang Road, Changchun 130021, P. R. China
E-mail: duxq77@163.com
Abbreviations: CODCr, chemical oxygen demand; GAR, groundwater
artificial recharge; SI, saturation index; TDS, total dissolved solid
environmental effects of GAR with relative “clean” water have rarely
been considered [8]. However, there may be still a chemical risk of
clean water recharge for following considerations. Firstly, the nature
and processes of water–rock interaction during recharge could be
different with natural recharge and affect the water quality [9, 10]. In
the Florida aquifer system, uranium at >25 ppm was detected, which
was confirmed by studies to be induced by an oxidizing environment
formed after GAR [11]. Secondly, many soils contain naturally
occurring, easily leachable contaminants of relevance to drinking
water quality [12–14]. Extensive recharge water will essentially
dissolve all of the highly soluble salts during infiltration, thus to
increase in salinity in reaching water table [15, 16]. The so called
“clean” water from rain or storm waters harvesting may not be clean
at all subject to the land uses and harvesting processes [17].
Groundwater quality might be deteriorated by such secondary saline
water. Thirdly, disequilibrium between the recharge water and the
native groundwater can lead to mineral dissolution and/or
precipitation in aquifer [18]. Chemical clogging could be induced
during GAR in arid or semiarid regions, which pose an engineering
risk for a successful GAR [19, 20]. More detailed investigation
therefore on chemical evolution of the GAR leaching process using
harvesting water is needed to understand the interactions between
the “clean” recharge water and subsurface environment.

© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.clean-journal.com Clean – Soil, Air, Water 2014, 42 (6), 722–730
 Compatibility Assessment of Recharge Water with Native Groundwater
The chemical processes during GAR are usually complex and it is
difficult to forecast the outcome of the complex reactions by
traditional approaches [16]. The environmental effects of GAR
are usually observed and studied through long-term field
monitoring [21], but this is not suitable at pilot stage because of
data scarcity. Hydro-geochemical processes can, however, be assessed
by numerical modeling tools coupling thermodynamic mechanism,
such as MINTEQA2, EQ3/6, WATEQ4F, Netpath, PHREEQC. Among
these modeling tools, PHREEQC possesses the advantage of including
full geochemical transport phenomena in simulating percolation or
diffusion in some simple systems [16, 22, 23], and is known as a
successful model for water–rock interactions [24, 25]. An interesting
attempt using PHREEQC in GAR was made for water mixing
process [8].
Nowadays, Beijing, as a semiarid region and the political and
cultural centre of China, is facing much severe threat to water
supply [26]. Little precipitation and high evaporation leave burgeon-
ing populations dependent on groundwater for domestic, agricul-
tural, and industrial water needs as a major supply source. Beijing
consumes about two thirds of its water from groundwater every year,
resulting in regional drawdown of ground water level and land
subsidence in some area [27, 28]. To mitigate the aggravating
groundwater stress on the capital city, Ministry of Water Resources
started a GAR program using rain/storm water harvesting in 2007.
The Pinggu Basin, one of the four emergency water supplies for
Beijing, is taken as a pilot site in the GAR program. Serial researches
have been undertaken for rapid and safe technology of GAR and
some of these were reported.
Further on these studies, this paper focuses on chemical evolution
of the relative “clean” water from the harvested rainfall/storm water
during GAR and its interactions with local receiving groundwater in
the Pinggu Basin aquifer. Research followed an overall logic of
framework from field survey, to lab experiment, then to numerical
modeling. Field investigations were required for geologic, hydro-
geological, and hydrochemical background at the proposed recharge
site. Lab experiment was conducted to better understand the
geochemical transformation as the recharge water transport though
the vadose zone. PHREEQC was applied to model the dynamic
transport and reactive hydrochemical processes. The hydrochemical
changes in groundwater during GAR were predicted therefore and
the chemical clogging potential induced by mineral precipitates,
such as calcium and magnesium carbonates was effectively assessed.
2 Materials and methods
2.1 Site description and recharge water resources
Pinggu is located in the north-east of Beijing (Fig. 1), covering about
1075 km2 with 35.5  30.5 km2 in NS and WE dimensions. The region
is surrounded by mountains to the north, east and southeast;
whereas the middle and southwest areas are parts of a pluvial–
alluvial fan. The landform declines gradually from northeast to
southwest, ranging from 12 to 1062 m in elevation (above the sea).
The climate is temperate and continental with an average annual
temperature of 11.5°C and an annual rainfall of 633.8 mm. However,
because rains mostly occur in the wet season (June–September) and
are frequently torrential, much of them are quickly discharged
downstream, then to the sea. Thus, it would be very important to
retain this part of storm water in the area for later use; underground
aquifer space presents a priority to store this water with low
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.clean-journal.com
723
evaporative loss and construction cost for sustainable water
management. Surface water system in this region includes the river
Ju and its tributaries, the rivers Cuo, Jinji, and four seasonal sub-
tributaries in the western region. Since Ju and Cuo are dammed by
Huansuoyu, Haizi, and Xiyu reservoirs, respectively, river flows have
been drastically decreased and even dried out in recent years.
The quaternary deposits in the basin thicken from the margin to
basin center, and the biggest thickness is 557 m. In the northern part,
the piedmont alluvial aquifer is formed of highly permeable coarse-
grained gravels and sands, and then gradually changes to gravels,
coarse and fine sands inter-bedded towards southwest. Pore
groundwater in the basin is the most important groundwater
resource for this region and Beijing with main recharge from
precipitation, and some leakages of surface water and irrigation. Due
to excessive groundwater abstraction over the past 10 years, two
depression cones have developed in the concentrated exploitation
areas of the basin center, with total emptied vadose space of over
0.4 billion m3, which provides a huge potential storage for GAR. The
surface of depression areas is covered by very permeable gravels and
coarse sands that water soaked quickly into deep subsurface.
Therefore, GAR is proposed to be carried out in the depression cones
through surface infiltration as a preferred GAR method using sand
pits along the river. One recharge site in the upstream of the river Ju
in the basin was focused in this study. According to previous field
investigations, infiltration rate around this site is 13.8 m/day on
average, and the water level there is 35–45 m below ground
surface [29].
2.2 Sampling and laboratory analyses
Available recharge water sources within the catchment of our
interested site are reservoir water, runoff originating from the
surrounding mountain area, and the river Ju water during storm
seasons. Thus, samples were collected in Aug. 2008 before and after
rainfalls from the above sources, including eight reservoir water
samples, one mountainous runoff sample and two river water
samples. In order to assess the interactions with local groundwater,
one groundwater sample was also collected from a pumping well just
at the recharge site. These water samples were taken to laboratory for
subsequent chemical analysis for major ions (Ca2þ, Mg2þ, Naþ, Kþ,
HCO3
, Cl
, SO42
, and NO3
) and other related chemical
parameters. The sediments at the recharge site were collected for
X-ray diffraction analysis and mobile solutes testing of the clay size
materials.
2.3 Conceptual model of GAR
Figure 2 shows a schematic diagram of the GAR processes by surface
infiltration method and the major physiochemical mechanisms
involved. When the recharge water infiltrates into subsurface, it is
first in contact with the soil particles, containing minerals and salts
with variable compositions, solubility, and behavior. These phases in
the soil normally react as if fixed in composition (as a metastable
state), but when contacting with water of different composition,
the soil can quickly release most soluble phases and minerals will
recrystallize and adjust their composition in relation to the changing
composition of the contacting water [30]. Thus, the effluent though
vadose zone is influenced by the salt and mineral composition of
the soils, the involving chemical reactions, and the interactions on
the surface of soil particles, e.g. cation exchange [31]. Thereafter, the
Clean – Soil, Air, Water 2014, 42 (6), 722–730
724 Y. Lu et al.

Figure 1. Location and hydrogeological condition of the study area.

Figure 2. Schematic diagram of the GAR system and the major physiochemical mechanisms involved.

© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.clean-journal.com Clean – Soil, Air, Water 2014, 42 (6), 722–730
 Compatibility Assessment of Recharge Water with Native Groundwater
effluent reaches and mixes with local groundwater near the water
table, where the dissolution/precipitation processes may also occur to
reach a geochemical equilibrium with the subsurface environment.
Due to the vast quantity, groundwater in the Pinggu aquifer reacts as
a recipient with an assumed constant chemistry. Overall, these whole
processes take place in a 1D vertical profile, so that GAR here was
conceptualized as 1D transport and reactive model.
2.4 Column leaching experiment
A leaching experiment under controlled laboratory conditions was
undertaken to identify geochemical processes during GAR before
modeling recharge water transport for field conditions. The column
leaching simulating the vadose processes was performed to calibrate
the geochemical model using pH and solutes in the outflow. The
natural sediments collected from the Pinggu recharge site was
packed in a 100 cm long and 14 cm diameter PVC column with a final
bulk density of about 1.56 g/mL and effective leaching length of
94 cm. The leaching experiment was undertaken by pumping water
similar in ionic composition to the recharge water from the bottom
through the column at a constant flow rate of 3.5 mL/min. The
residence time of the water within the column was about 70 h, which
was designed in line with the general vertical and temporal scales in
the field. The discharge was collected at periodic intervals of 12 h at
first and then 24 h. The electric conductivity was measured
immediately. After a stable electric conductivity of the discharge
was reached in 132 h in this instance, the experiment stopped and all
collected samples were analyzed simultaneously for the major ions
(Ca2þ, Mg2þ, Naþ, Kþ, HCO3
, Cl
, SO42
, and NO3
).
2.5 Reactive geochemical modeling
To determine the element speciation through the vadose zone and
saturation degree of mixing water with mineral phases, the reactive
recharge modeling was performed using PHREEQC-2 [32]. Based on
the equilibrium chemistry of aqueous solutions interacting with
minerals, gases, solid solutions, and exchangers, the explicit
mathematical transport and chemical-reactive model was imple-
mented in PHREEQC. The chemical speciation at equilibrium is
defined by thermodynamic activities and mass action equations for
each species, which is resolved by the Newton–Raphson method. To
calculate both transport process and chemical equilibrium during
GAR, the models are run for the advection and dispersion step as an
interactive manner. Based on the conceptual model (Fig. 2) a vertical
transport process in the vadose column in the GAR basin was
modeled. Conservation of mass for a chemical passing through this
column yields the 1D advection–reaction–dispersion equation [32]:
@c @c @2 c
¼
v þ DL 2 þ S ð1Þ
@t @x @x
where t is the time, x is the distance, DL is the dispersion coefficient,
and S is a source/sink term for all dissolved solid species and
dissolution/precipitation reactions implying all interest elements.
The upper and lower boundary conditions are both assumed as
constant: c ¼ c0 of recharge water at the upper face, and c ¼ cg of
groundwater in the aquifer.
Modeling 1D advection and dispersion is achievable using the
keyword data block TRANSPORT in PHREEQC. Data were introduced
in TRANSPORT according to the principle of convective cells.
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.clean-journal.com
725
Therefore, for both lab experiment and proposed field GAR
conditions, the transport column was divided into several cells, in
which the water stayed for a residence time in each cell. The
transport process was coupled with the chemical reactions to meet
the charge balance and equilibrium laws in calculating the species
distribution. For the whole GAR system the core blocks using
in PHREEQC included TRANSPORT, SOLUTION, EQUILIUBRIUM_-
PHASES, and EXCHANGE.
3 Results and discussion
3.1 Characterization of recharge water and local
groundwater
Results of chemical analyses of water samples from reservoir,
mountainous runoff, river, and groundwater around the proposed
GAR site are presented in Tab. 1. The errors in charge balance of all
samples were between
5 and þ5%. The TDS of surface water ranged
from 132 to 423 mg/L, with less salinity than groundwater for most
samples. The pH of surface water ranged from 7.36 to 8.59 as weak
alkaline, which was a little higher in reservoir water whilst lower in
the river water than groundwater. The most abundant cations were
Ca2þ and Mg2þ in all water samples, and those in surface water were
less than groundwater. HCO3
dominated in both groundwater and
surface water, but its proportion in surface water around Huang-
songyu was variable due to rainfalls. Thus, the major ions defined the
water types as Ca–HCO3 for groundwater and Ca–HCO3 or Ca–HCO3–
SO4 for the recharge waters. Both the recharge water and ambient
groundwater had low concentrations of several inorganic species at
or below ppb level, i.e. fluoride, cadmium, chromium, copper,
manganese, arsenic, mercury, nickel, lead, and zinc. The impact of
recharge on these inorganic elements was not investigated in this
study. Overall, although increases of TDS and chemical oxygen
demand (CODCr) in reservoir waters were observed after rainfalls, all
these surface water resources were considered to be clean for surface
infiltration regarding water quality parameters of related water
standards.
3.2 Sediments characteristics
To understand the potential changes in water quality during the GAR
processes through the vadose zone, it was also necessary to
characterize the sediments at the GAR basin. Some chemical
properties of the sediments are shown in Tab. 2. The X-ray diffraction
analysis showed that the primary minerals included several feldspars
(plagioclase and orthoclase), quartz and very little amphibole.
Predominant clays in the study soils were illite, kaolinite, and
smectite. For soil chemical extracts, the concentrations (mg/L) of
major ions sample decrease as an order of sodium > calcium >
potassium > magnesium and bicarbonate > nitrate > sulfate > chloride.
Sodium is the most abundant in salt affected soils, whilst calcium
generally comes from both carbonate dissolution and cation
exchanges. High nitrate may indicate fertilizer use in this area.
The pH of 7.61 is quite consistent with local groundwater.
3.3 Geochemical transformations of recharge
water through the vadose zone
Chemical changes of the recharge water after percolation in the
leaching column were compared to elucidate possible chemical
Clean – Soil, Air, Water 2014, 42 (6), 722–730
726 Y. Lu et al.

NO2

0.10
0.23
0.03
0.08
0.05
0.04
0.04
0.00
0.05
0.89
0.79
0.01
Table 2. Physicochemical properties of the investigated sediments

Mineral compositions (%)

NO3

37.20
13.60

14.60
0.89
0.52
0.56
1.92
0.52
4.00
3.39

2.20

1.35
Quartz 48
Feldspars 33
SO42

Amphibole 2.3
45.0
40.0
30.4
14.6
45.0
30.0
55.5
69.2
60.1
48.3
38.2
10.1
Illite 9
Kaolinite 6
7.0
6.0

7.5

8.8
14.2
15.3

10.0
16.4
15.3
15.3
10.9
20.7
Smectite 4
Cl

Chemical composition in clay size (mg/100 g)

pH 7.61
CO32

Naþ 12.8
n.d.
n.d.

n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
8.2
9.1

9.1
9.1

Kþ 1.5
Ca2þ 4.4
Mg2þ
HCO3

0.48
147.1
172.0
208.0
197.0

169.0
235.0
276.0
73.9
64.1
82.1
51.1
92.0

HCO3
15.7
Cl
3.3
SO42
10.5
NH4þ

NO3

0.73
0.11

0.27
0.09
0.06
1.03
0.49
0.42
n.d.
n.d.

n.d.
n.d.

15
SiO2 2.9
Mg2þ

9.3
3.8

5.4
8.5
29.8
25.0
21.0
24.4
12.1

23.7

21.6
19.7

reactions in soils (Fig. 3). The experiment results showed that the
geochemical evolution of the recharge water could be divided into
Ca2þ
19.0
30.5
47.1
33.1
23.0
18.0
47.1
46.4
38.9
45.6
63.8
69.0

two stages. In the first stage, a “washout” phenomenon occurred for

NO3
, SO42
, Ca2þ, and Mg2þ during a start-up period of the first 36 h.
4.5
6.2
2.9
3.1
4.0
7.0
3.2
0.4
3.1
4.0
4.3
1.2
Kþ

TDS increased from 0.19 to 1.03 g/L at the initial discharge through
the soil columns. Mobile solutes testing showed that the sediments of
7.0
8.2
5.3
5.8

6.3
6.2

7.2
5.8
Naþ

10.0
12.0

18.2
18.6

the GAR site contained high concentration of NO3
(Tab. 2), which is
highly mobile and can contribute to dissolution of the soil base
CODCr
3.8
6.1
3.9

2.3
2.3
0.7

0.6
29.9

30.8
25.2
45.2
20.8

cations (Ca2þ, Mg2þ) [33]. On the other hand, as a source of

acidification, dissolution of nitrate, and sulfate is often companied
with reduction of alkalinity and/or pH over time in shallow
(mg/L)
TDS

192
211
334
297
150
132
233
265
247
320
423
418

groundwater in non-calcareous sandy aquifers [34]. That is a

reasonable explanation that pH and HCO3
slumped at the beginning
and recovered with decrease of NO3
and SO42
dissolved from the
Turbidity
(NTU)
0.0
0.4
1.2
5.5
0.7
0.0
0.8
3.4
3.6
3.9

0.6
13.5

contacted sediments. After the washout period, water evolution

entered the second stage, in which the net gain in HCO3
and SO42

was balanced by increases in Ca2þ and Mg2þ indicating the mineral
dissolution dominated. However, Cl
, Naþ, and Kþ changed little as
8.50
8.55
7.79
7.73
8.56
8.59
7.94
7.92
7.72
7.36
7.46
7.60
pH

water passed through the columns over the entire duration.

Conservative Cl
was due to its low content in soil, whilst Naþ
(mS/cm)
360
360
307
314
280
280
232
304
255
263
435
353
EC

and Kþ were most probably controlled by well-balanced mineral

Table 1. Basic physiochemical data for waters around recharge site

equilibriums as showed in previous studies [35]. In summary, it is

clearly evident that the effluents throughout the soil column are
Huangsongyu_3 (after rain)
Huangsongyu_4 (after rain)

highly dependent on the soil transmission characteristics. Chemical

Huangsuoyu Mountain

changes of the recharge water through vadose zone would bring

Haizi_3 (after rain)
Haizi_4 (after rain)

impact on groundwater.
Huangsongyu_1
Huangsongyu_2

Shangzhizhai

3.4 Transport calculation for leaching experiment

Location
Haizi_1
Haizi_2

The column experiment was simulated using the phase-equilibrium

and cation exchange in combination with transport in PHREEQC. The
Ju
Ju

transport column was divided into 29 cells with water residence time
Groundwater

of 2.4 h each. In the real leaching scenarios, there is a process that the
recharge water enters into the column with soluble species dissolved
Reservoir
Reservoir
Reservoir
Reservoir
Reservoir
Reservoir
Reservoir
Reservoir
Runoff

from soil and other chemical reactions, for which no dedicated

n.d., not detectable.
River
River
Type

module simulates in PHREEQC. To calculate such an initial solution

distribution just after the saturation process in the column, we
Sample no.

developed a reverse process to quantify these composite interactions

during the initial soil saturation. It was assumed that the column was
initially occupied with GAR water and a solution containing the
S10
S11
S12
S1
S2
S3
S4
S5
S6
S7
S8
S9

equivalent amount of the soluble elements from the soil column was

© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.clean-journal.com Clean – Soil, Air, Water 2014, 42 (6), 722–730
 Compatibility Assessment of Recharge Water with Native Groundwater
Figure 3. Breakthrough of the major ions and pH: results of experiment (observed), modeling (modeled) and initial recharge water (RW).
in the ending cell of the column to be reversely interacted hydro-
chemically with the overlying cells in an iterative manner. The
solutions in the transport cells were therefore determined by such a
reverse transport process till the very top recharging cell, i.e. top of
the column. Then, TRANSPORT block was restarted with the defined
recharge water entering into the column. Throughout the column,
solutions in column were assumed to be in equilibrium with CO2 and
related minerals implying the interest elements. The amount of the
reactive minerals contacted with per unit (L) water was estimated
from data of sediments properties (Tab. 2) and column settings in
Section 2.4. The ion diffusion and physical dispersivity were defined
as 4  10
7 m/s and 0.38 m, respectively, according to the leaching
breakthrough curves. The initial cation exchange was determined by
equilibrium with the local groundwater. For the parameterization of
the geochemical model, saturation indexes (SIs) of the detected
minerals were estimated in accordance with those of local
groundwater as we found concentrations of elements were largely
underestimated due to their SIs > 0 in groundwater. The lower
boundary of this leaching model was defined as flux boundary.
The model calibration using pH and key elements in the column
outflow are showed in Fig. 3. The pH simulated with the suggested
mineral assembly was slightly overestimated with observations,
which can be attributed to a NO3- dissoluting process through the
soil [34]. That cannot be simulated in this model unfortunately. An
unwell matching for SO42
at the beginning period can be attributed
to the assumed equilibrium of gypsum SI ¼ 0 which was higher than
that in the local groundwater. Concentrations of Kþ were largely
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.clean-journal.com
727
underestimated due to the low assumed SI of K-feldspar, which was
the only master mineral of potassium in the model, although it had
been defined over 0 according to local groundwater. The underesti-
mation of Naþ suggested the governing chemical reactions were
complex to be accurately described by this simple model since Naþ
was involved in many reactions such as solid solution, cation
exchanges and equilibrium with albite. The overall matching
between measured and modeled effluent composition showed that
the modeling uncertainty existed in setting key mineralogical
properties of the soil, which might be further studied. Also, neglect of
REDOX and kinetics in the modeling might cause a certain disparity
in simulation results of some relevant ions. NO3
and SO42
are the
most possible affected components by REDOX, but their modeled
breakthrough lines were quite consistent with experimental data,
indicating weak biogeochemical reactions within the experimental
period. In contrast, the little overestimations in Ca and Mg more
likely resulted from dissolution/precipitation kinetics. Despite these,
the geochemical model is suitable for estimating the geochemical
evolution of the recharge water for field conditions in capability of
reproducing the major geochemical features and concentrations of
most ions such as Ca2þ, Mg2þ, HCO3
, and NO3
.
3.5 GAR impacts on hydrochemistry under field
conditions
The calibrated leaching model for the vadose zone was applied for the
GAR at the study site by adding one more cell at the end to predict the
Clean – Soil, Air, Water 2014, 42 (6), 722–730
728 Y. Lu et al.
saturated zone during GAR. The bottom boundary was also set to
constant with the local groundwater according to the conceptual
model. Since the available recharge waters mentioned above would
be converged to the GAR site under field conditions, an average of all
the recharge waters was used to predict a general trend of
hydrochemistry after GAR.
The modeled results in Fig. 4 show that hydrochemistry varied
severely at the initial period and then became steady. Similar to the
column leaching experiment, this early transient turbulence could
be impacted by “washout” of the soluble species in the soil zones,
mainly reflected in components of Cl
, SO42
, and NO3
. In the later
steady stage, pH and Mg2þ, SO42
, Cl
, and NO3
increased, whilst
Ca2þ, hardness and calculated TDS decreased due to GAR compared
with initial groundwater chemistry. Most parameters levelled at a
concentration closer to groundwater rather than the recharge water.
It can be inferred that the mixing, interactions and equilibrium with
the assembled minerals govern the evolution of hydrochemistry in
the long term.
To quantify the impact of GAR on groundwater quality, an
evaluation of hydrochemistry was undertaken according to the China
Groundwater Quality Standard (GB/T14848-93) [36]. Despite increase
Figure 4. Modeled breakthroughs of the selected aqueous components and chemical parameters under field condition.
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.clean-journal.com
or decrease of elements in groundwater, the overall quality in the
steady stage remained consistent with present status, indicating that
GAR with the harvested water in Pingu would induce little impact on
hydrochemistry. However, the major concern would remain due to
the disturbances in the first turbulence period, especially for nitrate
contamination. Thus, longer residence time of recharge water in
aquifer is suggested as a safety precaution before water is reused for
supply as some deteriorating components can be naturally degraded
in the subsurface environment.
3.6 Chemical clogging risk during recharge
Dissolution and precipitation processes during hydrochemical
changes after GAR may also change hydraulic conductivity of aquifer
media [19]. Carbonate and calcium minerals are most susceptible to
dissolution or precipitation during GAR [18, 31]. Thus calcite,
dolomite, and gypsum were taken as suspected precipitations in this
study to understand the potential clogging risk.
Since the above model is dependent on SI to assess whether
groundwater is in equilibrium with respect to a certain mineral, SIs
of calcite, dolomite, and gypsum were calculated for groundwater
Clean – Soil, Air, Water 2014, 42 (6), 722–730

Accumulated precipates
SI_Dolomite
Accumulated Precipates
0.3
SI (Calcite/Dolomite)
(mol/L water)
0.2
0.1
0 -2.7
0 48 96 144
Time (hours)
Figure 5. Temporal trends of saturation indices for selected minerals in
groundwater and accumulated.
during GAR as shown in Fig. 5. The Calcite SI increased with GAR,
dolomite SI stayed steady at a level of original native groundwater,
whilst gypsum SI experienced a peak at the beginning and then
gradually settled down. Throughout the calculation period, the
negative SI for gypsum indicated an under-saturated state, and
calcite was also unlikely to precipitate due to its positive but low SI
with respect to equilibrium state in the original groundwater.
The most precipitate during GAR is dolomite, which may cause
clogging of aquifer pores near groundwater table. As shown in Fig. 5,
the dolomite precipitates accumulated to 0.05 mol/L during the
early 24 h, followed by a gradual reduction to 0 till around 200 h
after GAR. This demonstrated that dolomite deposit would be re-
dissolved with the recharge process. Therefore, clogging induced by
dolomite precipitation might just occur in the early period, and then
could be alleviated by re-dissolution reaction later. Accordingly,
aquifer matrix would probably experience a transient reduction of
permeability, but in a low risk for permanent clogging.
4 Concluding remarks
This study presents a quantitative prediction of the dynamic change
of groundwater chemistry during GAR with respect to the
geochemical conditions in Pinggu, Beijing. The results indicated a
“washout” of soluble species in sediments would result in a short
period deterioration of groundwater in 25 h of recharge. The
prediction showed that Cl
, SO42
, NO3
, and TDS reached a peak
at around 5 h after GAR, with concentrations of 9.1, 22.7, 20.9, and
257.7 mg/L, respectively. Since the minerals in subsurface sediments
have a very high buffering capacity and the selected surface water
resource in the catchment of the GAR site are relatively clean with
low TDS, the hydrochemistry would not be significantly altered and
its quality would not be degraded after 50 h of GAR. Due to the
mineral equilibrium in aquifer, clogging was expected to result from
dolomite precipitation in the first 8 days, but not for long due to re-
dissolution under dolomite unsaturation after 24 h of GAR.
This study attempted to model the comprehensive geochemical
reactions along the 1D transport process during GAR. Dissolution of
soluble salts from sediments, mineral equilibrium, cation exchange,
and advective–dispersive transport processes were all achievable in
coupled PHREEQC modeling. Unfortunately, kinetic reactions and
redox transformations in subsurface environment cannot be taken
into consideration in this study due to data availability. Further
field investigations of subsurface environmental characteristics in
the Pinggu aquifer are necessary for better understanding of the
hydrochemical evolution before the proposed GAR is implemented.
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Compatibility Assessment of Recharge Water with Native Groundwater 729
SI_Calcite Acknowledgements
SI_Gypsum
-2.1 This research was financially supported by National Key Technology
R&D Program in the 11th Five Year Plan of China (2006BAB14B04),
National Natural Science Foundation of China (Grant nos. 40902068,
SI (Gypsum)
-2.3 41002077 and 41272255), the China Ministry of Science and
Technology 863 Project (2007AA06Z343), and the Science Frontiers
and Interdisciplinary Innovation Project of Jilin University (grant no.
-2.5 201103112).
The authors have declared no conflict of interest.
192
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