Research Article Compatibility Assessment of Recharge Water With Native Groundwater Using Reactive Hydrogeochemical Modeling in Pinggu, Beijing
Research Article Compatibility Assessment of Recharge Water With Native Groundwater Using Reactive Hydrogeochemical Modeling in Pinggu, Beijing
Research Article Compatibility Assessment of Recharge Water With Native Groundwater Using Reactive Hydrogeochemical Modeling in Pinggu, Beijing
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
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Compatibility Assessment of Recharge Water with Native Groundwater 723
The chemical processes during GAR are usually complex and it is evaporative loss and construction cost for sustainable water
difficult to forecast the outcome of the complex reactions by management. Surface water system in this region includes the river
traditional approaches [16]. The environmental effects of GAR Ju and its tributaries, the rivers Cuo, Jinji, and four seasonal sub-
are usually observed and studied through long-term field tributaries in the western region. Since Ju and Cuo are dammed by
monitoring [21], but this is not suitable at pilot stage because of Huansuoyu, Haizi, and Xiyu reservoirs, respectively, river flows have
data scarcity. Hydro-geochemical processes can, however, be assessed been drastically decreased and even dried out in recent years.
by numerical modeling tools coupling thermodynamic mechanism, The quaternary deposits in the basin thicken from the margin to
such as MINTEQA2, EQ3/6, WATEQ4F, Netpath, PHREEQC. Among basin center, and the biggest thickness is 557 m. In the northern part,
these modeling tools, PHREEQC possesses the advantage of including the piedmont alluvial aquifer is formed of highly permeable coarse-
full geochemical transport phenomena in simulating percolation or grained gravels and sands, and then gradually changes to gravels,
diffusion in some simple systems [16, 22, 23], and is known as a coarse and fine sands inter-bedded towards southwest. Pore
successful model for water–rock interactions [24, 25]. An interesting groundwater in the basin is the most important groundwater
attempt using PHREEQC in GAR was made for water mixing resource for this region and Beijing with main recharge from
process [8]. precipitation, and some leakages of surface water and irrigation. Due
Nowadays, Beijing, as a semiarid region and the political and to excessive groundwater abstraction over the past 10 years, two
cultural centre of China, is facing much severe threat to water depression cones have developed in the concentrated exploitation
supply [26]. Little precipitation and high evaporation leave burgeon- areas of the basin center, with total emptied vadose space of over
ing populations dependent on groundwater for domestic, agricul- 0.4 billion m3, which provides a huge potential storage for GAR. The
tural, and industrial water needs as a major supply source. Beijing surface of depression areas is covered by very permeable gravels and
consumes about two thirds of its water from groundwater every year, coarse sands that water soaked quickly into deep subsurface.
resulting in regional drawdown of ground water level and land Therefore, GAR is proposed to be carried out in the depression cones
subsidence in some area [27, 28]. To mitigate the aggravating through surface infiltration as a preferred GAR method using sand
groundwater stress on the capital city, Ministry of Water Resources pits along the river. One recharge site in the upstream of the river Ju
started a GAR program using rain/storm water harvesting in 2007. in the basin was focused in this study. According to previous field
The Pinggu Basin, one of the four emergency water supplies for investigations, infiltration rate around this site is 13.8 m/day on
Beijing, is taken as a pilot site in the GAR program. Serial researches average, and the water level there is 35–45 m below ground
have been undertaken for rapid and safe technology of GAR and surface [29].
some of these were reported.
Further on these studies, this paper focuses on chemical evolution
2.2 Sampling and laboratory analyses
of the relative “clean” water from the harvested rainfall/storm water
during GAR and its interactions with local receiving groundwater in Available recharge water sources within the catchment of our
the Pinggu Basin aquifer. Research followed an overall logic of interested site are reservoir water, runoff originating from the
framework from field survey, to lab experiment, then to numerical surrounding mountain area, and the river Ju water during storm
modeling. Field investigations were required for geologic, hydro- seasons. Thus, samples were collected in Aug. 2008 before and after
geological, and hydrochemical background at the proposed recharge rainfalls from the above sources, including eight reservoir water
site. Lab experiment was conducted to better understand the samples, one mountainous runoff sample and two river water
geochemical transformation as the recharge water transport though samples. In order to assess the interactions with local groundwater,
the vadose zone. PHREEQC was applied to model the dynamic one groundwater sample was also collected from a pumping well just
transport and reactive hydrochemical processes. The hydrochemical at the recharge site. These water samples were taken to laboratory for
changes in groundwater during GAR were predicted therefore and subsequent chemical analysis for major ions (Ca2þ, Mg2þ, Naþ, Kþ,
the chemical clogging potential induced by mineral precipitates, HCO3, Cl, SO42, and NO3) and other related chemical
such as calcium and magnesium carbonates was effectively assessed. parameters. The sediments at the recharge site were collected for
X-ray diffraction analysis and mobile solutes testing of the clay size
materials.
2 Materials and methods
2.1 Site description and recharge water resources 2.3 Conceptual model of GAR
Pinggu is located in the north-east of Beijing (Fig. 1), covering about Figure 2 shows a schematic diagram of the GAR processes by surface
1075 km2 with 35.5 30.5 km2 in NS and WE dimensions. The region infiltration method and the major physiochemical mechanisms
is surrounded by mountains to the north, east and southeast; involved. When the recharge water infiltrates into subsurface, it is
whereas the middle and southwest areas are parts of a pluvial– first in contact with the soil particles, containing minerals and salts
alluvial fan. The landform declines gradually from northeast to with variable compositions, solubility, and behavior. These phases in
southwest, ranging from 12 to 1062 m in elevation (above the sea). the soil normally react as if fixed in composition (as a metastable
The climate is temperate and continental with an average annual state), but when contacting with water of different composition,
temperature of 11.5°C and an annual rainfall of 633.8 mm. However, the soil can quickly release most soluble phases and minerals will
because rains mostly occur in the wet season (June–September) and recrystallize and adjust their composition in relation to the changing
are frequently torrential, much of them are quickly discharged composition of the contacting water [30]. Thus, the effluent though
downstream, then to the sea. Thus, it would be very important to vadose zone is influenced by the salt and mineral composition of
retain this part of storm water in the area for later use; underground the soils, the involving chemical reactions, and the interactions on
aquifer space presents a priority to store this water with low the surface of soil particles, e.g. cation exchange [31]. Thereafter, the
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724 Y. Lu et al.
Figure 2. Schematic diagram of the GAR system and the major physiochemical mechanisms involved.
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Compatibility Assessment of Recharge Water with Native Groundwater 725
effluent reaches and mixes with local groundwater near the water Therefore, for both lab experiment and proposed field GAR
table, where the dissolution/precipitation processes may also occur to conditions, the transport column was divided into several cells, in
reach a geochemical equilibrium with the subsurface environment. which the water stayed for a residence time in each cell. The
Due to the vast quantity, groundwater in the Pinggu aquifer reacts as transport process was coupled with the chemical reactions to meet
a recipient with an assumed constant chemistry. Overall, these whole the charge balance and equilibrium laws in calculating the species
processes take place in a 1D vertical profile, so that GAR here was distribution. For the whole GAR system the core blocks using
conceptualized as 1D transport and reactive model. in PHREEQC included TRANSPORT, SOLUTION, EQUILIUBRIUM_-
PHASES, and EXCHANGE.
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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
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
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
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
192
211
334
297
150
132
233
265
247
320
423
418
0.6
13.5
impact on groundwater.
Huangsongyu_1
Huangsongyu_2
Shangzhizhai
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
equivalent amount of the soluble elements from the soil column was
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Compatibility Assessment of Recharge Water with Native Groundwater 727
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- underestimated due to the low assumed SI of K-feldspar, which was
chemically with the overlying cells in an iterative manner. The the only master mineral of potassium in the model, although it had
solutions in the transport cells were therefore determined by such a been defined over 0 according to local groundwater. The underesti-
reverse transport process till the very top recharging cell, i.e. top of mation of Naþ suggested the governing chemical reactions were
the column. Then, TRANSPORT block was restarted with the defined complex to be accurately described by this simple model since Naþ
recharge water entering into the column. Throughout the column, was involved in many reactions such as solid solution, cation
solutions in column were assumed to be in equilibrium with CO2 and exchanges and equilibrium with albite. The overall matching
related minerals implying the interest elements. The amount of the between measured and modeled effluent composition showed that
reactive minerals contacted with per unit (L) water was estimated the modeling uncertainty existed in setting key mineralogical
from data of sediments properties (Tab. 2) and column settings in properties of the soil, which might be further studied. Also, neglect of
Section 2.4. The ion diffusion and physical dispersivity were defined REDOX and kinetics in the modeling might cause a certain disparity
as 4 107 m/s and 0.38 m, respectively, according to the leaching in simulation results of some relevant ions. NO3 and SO42 are the
breakthrough curves. The initial cation exchange was determined by most possible affected components by REDOX, but their modeled
equilibrium with the local groundwater. For the parameterization of breakthrough lines were quite consistent with experimental data,
the geochemical model, saturation indexes (SIs) of the detected indicating weak biogeochemical reactions within the experimental
minerals were estimated in accordance with those of local period. In contrast, the little overestimations in Ca and Mg more
groundwater as we found concentrations of elements were largely likely resulted from dissolution/precipitation kinetics. Despite these,
underestimated due to their SIs > 0 in groundwater. The lower the geochemical model is suitable for estimating the geochemical
boundary of this leaching model was defined as flux boundary. evolution of the recharge water for field conditions in capability of
The model calibration using pH and key elements in the column reproducing the major geochemical features and concentrations of
outflow are showed in Fig. 3. The pH simulated with the suggested most ions such as Ca2þ, Mg2þ, HCO3, and NO3.
mineral assembly was slightly overestimated with observations,
which can be attributed to a NO3- dissoluting process through the 3.5 GAR impacts on hydrochemistry under field
soil [34]. That cannot be simulated in this model unfortunately. An
conditions
unwell matching for SO42 at the beginning period can be attributed
to the assumed equilibrium of gypsum SI ¼ 0 which was higher than The calibrated leaching model for the vadose zone was applied for the
that in the local groundwater. Concentrations of Kþ were largely GAR at the study site by adding one more cell at the end to predict the
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.clean-journal.com 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 or decrease of elements in groundwater, the overall quality in the
constant with the local groundwater according to the conceptual steady stage remained consistent with present status, indicating that
model. Since the available recharge waters mentioned above would GAR with the harvested water in Pingu would induce little impact on
be converged to the GAR site under field conditions, an average of all hydrochemistry. However, the major concern would remain due to
the recharge waters was used to predict a general trend of the disturbances in the first turbulence period, especially for nitrate
hydrochemistry after GAR. contamination. Thus, longer residence time of recharge water in
The modeled results in Fig. 4 show that hydrochemistry varied aquifer is suggested as a safety precaution before water is reused for
severely at the initial period and then became steady. Similar to the supply as some deteriorating components can be naturally degraded
column leaching experiment, this early transient turbulence could in the subsurface environment.
be impacted by “washout” of the soluble species in the soil zones,
mainly reflected in components of Cl, SO42, and NO3. In the later
3.6 Chemical clogging risk during recharge
steady stage, pH and Mg2þ, SO42, Cl, and NO3 increased, whilst
Ca2þ, hardness and calculated TDS decreased due to GAR compared Dissolution and precipitation processes during hydrochemical
with initial groundwater chemistry. Most parameters levelled at a changes after GAR may also change hydraulic conductivity of aquifer
concentration closer to groundwater rather than the recharge water. media [19]. Carbonate and calcium minerals are most susceptible to
It can be inferred that the mixing, interactions and equilibrium with dissolution or precipitation during GAR [18, 31]. Thus calcite,
the assembled minerals govern the evolution of hydrochemistry in dolomite, and gypsum were taken as suspected precipitations in this
the long term. study to understand the potential clogging risk.
To quantify the impact of GAR on groundwater quality, an Since the above model is dependent on SI to assess whether
evaluation of hydrochemistry was undertaken according to the China groundwater is in equilibrium with respect to a certain mineral, SIs
Groundwater Quality Standard (GB/T14848-93) [36]. Despite increase of calcite, dolomite, and gypsum were calculated for groundwater
Figure 4. Modeled breakthroughs of the selected aqueous components and chemical parameters under field condition.
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Compatibility Assessment of Recharge Water with Native Groundwater 729
0.3 -2.1 This research was financially supported by National Key Technology
SI (Calcite/Dolomite)
SI (Gypsum)
0.2 -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.
0.1 -2.5 201103112).
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730 Y. Lu et al.
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