Geosciences Journal

DOI 10.1007/s12303-014-0059-x
The Association of Korean Geoscience Societies and Springer 2015

Geochemical properties of groundwater affected

by open loop geothermal
heat pump systems in Korea
ABSTRACT: This study was performed to examine the chemical
and isotopic compositions of groundwater used in open loop GHP
systems and natural groundwater around the open loop GHP systems
and to evaluate the influence of open loop GHP systems operation
on groundwater chemistry in Korea. The water temperature of
groundwater used in open loop GHP systems ranged from 6.0 to
37.1 C and decreased by 6.7 to 11.6 C compared with that of natural
groundwater around the open loop GHP systems. The pH,
EC, Eh, Fe2+, and Mn2+ of the groundwater were not significantly
affected by open loop GHP systems operation. The groundwaters
used in open loop GHP systems showed various water types, such
as Ca-HCO3, Ca-Cl, Ca-SO4, and Na-HCO3. Although HCO3
and
Cl concentrations were slightly influenced by open loop GHP systems
at some sites, the groundwater chemistry used in the open loop GHP
systems did not significantly change at most sites. In addition, carbonate
and silica minerals and minerals containing Mn were in
undersaturated condition, which indicates that the precipitation of
these minerals will not occur. However, some minerals containing
Fe, such as Fe(OH)3, goethite, and hematite can be precipitated as
scale within these system. In the open loop GHP systems selected
in this study, the influence of open loop GHP systems on groundwater
chemistry is not revealed sufficiently because of short-term
monitoring of groundwater chemistry. However, integrated longterm
monitoring is necessary to evaluate influence of open loop GHP
systems on groundwater chemistry and to improve our understanding
of the environmental impacts related to these systems.
Key words: groundwater, open loop geothermal heat pump system,
Langelier saturation index, Ryznar stability index, saturation indexes,
PHREEQC

1. INTRODUCTION
Global warming has become a major social issue in many
countries. The increase in greenhouse gases is one of the main
causes of global warming. Most of the greenhouse gases have
been emitted by the combustion of fossil fuels. In recent times,
renewable energies have been used as an alternative energy
source to reduce the level of greenhouse gases in the atmosphere
(Abesser, 2010). Geothermal heat pumps (GHPs) make
use of a renewable energy source and have been growing
rapidly over the past 20 years (Lund et al., 2004; Lee, 2009;
Abesser, 2010). GHP systems for cooling and heating are
mainly used in Germany, Switzerland, Austria, Sweden,
Denmark, Norway, France, USA, Canada, Netherlands, and
China (Sanner et al., 2003; Gao et al., 2009; Abesser, 2010;
Lund and Bertani, 2010; Bonte, 2013).
The use of GHPs has increased by 10% since 1994 in
developed countries (Lund et al., 2004; Curtis et al., 2005;
Self et al., 2013). As of 2005, USA had the most GHP systems
in operation among developed countries; the capacity and
number of GHP installations in the USA were 6,300 MW and

600,000, respectively (Lund et al., 2004; Curtis et al., 2005).

However, GHP growth has been relatively slow compared
with other renewable energy fields, and this is attributed to
non-standardized system designs, significant capital cost,
and a lack of understanding of GHPs (Self et al., 2013).
In Korea since 2004, GHP systems have been considered
to be alternative heating and cooling systems. GHP systems
have been mainly used in fishery (29.5%), agriculture (25.9%),
dwelling (9.1%), public (6.7%), and education facilities (6.3%)
(Kwon et al., 2012). As of 2008, 29.3% of the total GHP
systems were open loop type (mainly standing column well
type) (Lee, 2009). Open loop GHP systems were installed in
107 facilities from 2004 to 2013 (Fig. 1). The installed capacity
of an open loop GHP is 55,665 kW. The number of installations
of open loop GHP facilities increased gradually from
2004 to 2007. However, installations decreased steadily after
2007; this is attributed to apprehension about contamination
of groundwater and depletion of groundwater resources. Conversely,
the capacity of open loop GHP systems installed at
each facility has increased gradually.
Open loop GHP systems can have influences on the thermal
budget of groundwater, local ecology, underground structure,
hydraulic gradient, and groundwater chemistry because groundwater
is directly used in the GHP system (USEPA, 1997; Simpson
et al., 1989; Guimer et al., 2007; Kelly, 2009; Abesser, 2010;
Zhu et al., 2011; Possemiers et al., 2014). These influences vary
depending on the local geology, hydraulic conductivity, and
groundwater discharge and have been assessed using chem-

Youngyun Park
Namju Kim
Jin-Yong Lee*

Department of Geology, Kangwon National University,

Korea
Department of Geology, Kangwon National University,
Korea
Geoengeering Co. Ltd., Chuncheon 200-956, Republic
Department of Geology, Kangwon National University,
Korea
*Corresponding author: hydrolee@kangwon.ac.kr

Chuncheon 200-701, Republic of

Chuncheon 200-701, Republic of
of Korea
Chuncheon 200-701, Republic of

Youngyun Park, Namju Kim, and Jin-Yong Lee

ical compositions of groundwater and numerical modeling

of groundwater flow and heat transport (Ferguson and Woodbury,
2004; Guimer et al., 2007; Banks, 2009; Abesser, 2010;
Gropius, 2010). These influences are slowly being revealed.
Therefore, long-term monitoring of groundwater level and
chemistry is necessary.
According to previous studies, serious problems such as
groundwater contamination and scale formation can occur
caused by open loop GHP systems operation. When groundwater
used in open loop GHP systems is injected into an aquifer,
contaminants such as metals leached from the open loop

GHP system, microorganisms, and precipitations containing

Fe and Mn (scale formation) are introduced into the aquifer
(USPEA, 1999; Abesser, 2010; EA, 2011; Possemiers et al.,
2014). In addition, change in pressure and groundwater temperature
may cause changes in dissolved O2 and CO2 levels, solubility
of minerals, reaction kinetics, redox processes, and
sorption-desorption of dissolved components (Holm et al.,
1987; Brons et al., 1991; Griffioen and Appelo, 1993; Hoyer
et al., 1994; Sowers et al., 2006). Formation of scale of carbonate
and silica minerals and minerals containing Fe and
Mn may occur by these processes (Rafferty, 1999; Abesser,
2010). Of the minerals forming scale, carbonate minerals are
most common. The Langelier Saturation Index (LSI) and
Ryznar Stability Index (RSI) have been used to predict carbonate
scaling inside open loop GHP systems (CACC, 1965; Rafferty,
1999). In addition, silica minerals and minerals containing
Fe and Mg as well as carbonate minerals can precipitate
(Possemiers et al., 2014). Saturation index (SI) has been used
to evaluate precipitation of these minerals. Saturation index
(SI) for these minerals can be calculated with geochemical
modeling by software such as MINTEQA2 (Allison et al.,
1991) and PHREEQC (Parkhurst and Appelo, 1999).
In this study, chemical and isotopic compositions of groundwater
used in open loop GHP systems and natural groundwater
around the open loop GHP systems were examined to
understand their geochemical properties. In addition, the
influence of open loop GHP systems on groundwater chemistry
was evaluated using methods such as variations of dissolved
components levels, LSI, RSI, and SI.
2. MATERIALS AND METHODS
2.1. Measurement of Field Parameters
Groundwater used in open loop GHP systems (GG) were
sampled 3 times at CJ, CS, DL, GJ, GR, and YG, 2 times
at BS and SJ and 1 time at HA (Fig. 2). All samples were
collected after finish of heat exchange between groundwater
and open loop GHP systems during the recovery period
between the cooling and heating mode from November 2012
to November 2013. In addition, the natural groundwater (NG)
around the facilities operating open loop GHP systems in
Yeonggwang (YG) and Gangjin (GJ) were sampled 3 times
(Fig. 2). The collected samples were filtered with a 0.45 m
membrane filter. A part of the filtered samples was acidified
with HNO3 (pH~2). Prior to groundwater sampling, water
temperature, pH, electrical conductivity (EC), and Eh were
Fig. 1. Status of open loop GHPs installed in Korea from 2004 to
2013.
Fig. 2. Sampling sites in this study (BS = Busan; CJ = Cheongju;
CS = Cheongyeong; DL = Seoul; GJ = Gangjin; GR = Guri; HA =
Haman; SJ =Wonju; YG = Yeonggwang).
Influence of open loop GHP on groundwater

measured in the field using portable meters (HORIBA, D54,

55). Fe2+ and Mn2+ concentrations were also measured in the
field using a portable spectrophotometer (HACH, DR-2800).

Fe2+ and Mn2+ concentrations can be detected from 0.02 to

3.00 mg/L and 0.006 to 0.700 mg/L, respectively.
2.2. Chemical and Isotopic Analysis
The concentrations of cations (Ca2+, Mg2+, Na+, K+, H4SiO4,
and total Fe, and Mn and anion (Cl, NO3
, SO4
2, and HCO3
)
were analyzed using inductively coupled plasma (VISTAMPX
model, VARIAN) and ion chromatography (DX-120
model, Dionex Corporation) at the National Science Research
Supporting Center of Sangji University in Wonju, Korea.
Alkalinity was measured using the Gran method and HCO3

concentrations were calculated from the measured alkalinity

(Stumn and Morgan, 1996). Oxygen and hydrogen isotopic
compositions were analyzed with an isotopic ratio mass spectrometer
(Isoprime model, GV Instruments Ltd) at the Ochang
Center of Korea Basic Science Institute, Korea. Oxygen and
hydrogen isotopic compositions are reported in notation
relative to the VSMOW (Vienna standard mean ocean water)
standard. The notation is defined as follows,
() = [(Rsample/Rstandard) 1] 1000, (1)
where Rsample is the isotopic ratio 18O/16O or D/H of water
samples and Rstandard is the isotopic ratio 18O/16O or D/H of
VSMOW standard. The reproducibility of oxygen and hydrogen
isotopic compositions is 0.1 and 0.5, respectively.
2.3. Evaluation of the Influence of Open Loop GHP System
on Groundwater Chemistry
Use of open loop GHPs can influence groundwater chemistry
(Rafferty, 1999, 2003, 2004; Zia et al., 2008; Abesser, 2010;
Park et al., 2013a, 2013b). However, the influence of open
loop GHP systems on groundwater chemistry is not fully
understood. In this study, the chemical compositions of groundwater
were not obtained when the open loop GHP systems were
installed. Therefore, the variation ratios of the concentrations
of major ions were used to evaluate the influence of open loop
GHP systems on groundwater chemistry. Variation ratios of
the concentrations of major ions can be calculated as follows:
[A] = ([A]measured [A]0)/[A]0, (2)
where [A]measured is the concentration of the dissolved component
A measured in a sample. [A]0 is the concentration of
dissolved component A measured in a sample collected first.
In this study, [A]0 was used as end-member when change
of chemical compositions of GG was evaluated by open loop
GHP systems operation. The positive (+) and negative ()
signs represent increase and decrease in concentration, respectively,
compared with the initial concentrations of component
A.
2.4. Saturation and Stability Index
Carbonate minerals can frequently be observed as scale in
the pipe line and some equipment parts of open loop GHP
systems, such as the heat exchanger and heat pump (Rafferty,

1999). Therefore, the LSI and RSI have been mainly used
to predict the precipitation of carbonate minerals inside the
open loop GHP systems because the accuracy of predicting
the formation of scale is greater than that of corrosion (CACC,
1965). The LSI and RSI can be calculated as follows:
LSI = pH pHs, (3)
RSI = 2pHs pH, (4)
where pH is the value measured directly from samples and
pHs is the calculated pH of saturation of calcium carbonate.
CACC (1965) suggested indications for each value (Table 1).
The pHs value can be calculated as follows (Rafferty, 2004;
Zia et al., 2008):
pHs = (9.3 + A + B) (C + D), (5)
where A = (Log[TDS] 1)/10, TDS represents total dissolved
solid (unit = ppm); B = (13.12Log(C 273)) + 34.55;
C = (Log(calcium hardness)) 0.4, calcium hardness is in ppm
as CaCO3; D = Log(alk), alk represents alkalinity (unit = ppm
as CaCO3).
SI is used to predict precipitation and dissolution of minerals
and can be calculated using geochemical modeling programs.
In this study, SI for carbonate and silica minerals and
minerals containing Fe (Fe(OH)3, goethite, hematite, melanterite
and siderite) and Mn (hausmannite, manganite, pyrochroite,
pyrolusite and rhodochrosite) was calculated using PHREEQC.
SI is defined as follows (Parkhurst and Appelo, 1999):
SI = Log(IAP/Ksp), (6)
where IAP represents ionic activity products and is calculated
from activities of dissolved components of groundwater.
Ksp is the constant of reaction at equilibrium and can
be obtained from thermodynamic data. In this study, IAP
and Ksp were also calculated using PHREEQC. When SI <
0 (IAP < Ksp), groundwater is undersaturated with minerals.
Therefore, if the reaction time is enough, dissolution of minerals
can occur. In contrast, when SI > 0 (IAP > Ksp), groundwater
is oversaturated with minerals, and the minerals can be
precipitated. Groundwater chemistry can be altered by dissolution
and precipitation of minerals, and the operation of
open loop GHPs can accelerate these reactions (Holm et al.,
1987; Griffioen and Appelo, 1993; Rafferty, 1999, 2003, 2004).
3. RESULTS AND DISCUSSION
3.1. Physical Parameters
During the study period, water temperatures of the GG
ranged from 6.0 to 37.1 C (Table 1). However, in most of
Youngyun Park, Namju Kim, and Jin-Yong Lee

the GG, the water temperatures ranged from 6.0 to 24.2 C

except CJ sampled in May 2013. The water temperature of
GG sampled at CJ in May 2013 was 37.1 C because of operation
in the heat storage mode. Water temperature of GG at
GJ using both cooling and heating was lower by 3.5 to 5.6 C
than that of NG. Groundwater obtain heat from open loop
GHP system in cooling mode and give heat to open loop
GHP system in heating mode. The variations of water temperature
of GG in the cooling mode was larger than those

in the heating mode because the energy used by an open loop

GHP system in cooling mode was greater than that in the
heating mode (EA, 2011; Park et al., 2013b). The water temperature
of GG at YG using only heating mode was lower by
6.7 to 11.6 C than that of NG. These results indicate that
operating strategies have to be considered when variations
of water temperature, caused by open loop GHP systems, are
evaluated. The water temperature of GG shows wider range
as compared to that of NG because of the operation of open
loop GHP systems (Fig. 3a) (Rafferty, 2003; Abesser, 2010;
Park et al., 2013a, 2013b).
The pH of GG ranged from 6.7 to 9.1, and gradually
increased at most samples except SJ (Table 1). Degasing of
dissolved CO2 can be influenced on pH of GG (Abesser, 2010).
These results were also observed in NG of GJ and YG. These
results represent that pH of GG did not significantly influenced
by open loop GHP systems operation in this study.
Park et al. (2013a) observed that pH of GG gradually decreased
by approximately 1 in GHP system operated over 6 years.
However, the influence of open loop GHP systems on GG
may be differently observed because of a complex relationship
among various factors such as groundwater chemistry,
local geology, aquifer property, and strategy of open loop
GHP systems operation. According to the previous studies
(Abesser, 2010, Park et al., 2013a), pH of GG generally shows
Table 1. Physical parameters of groundwater used open loop GHP systems (GG) and
natural groundwater around open loop GHP systems
(NG)
Sample Type Sampling date Temperature (C) pH EC (S/cm) Eh (mV) Fe2+ (mg/L) Mn2+
(mg/L)
BS GG
May 2013 21.0 8.1 284 307 1.39 0.09
Nov. 2013 24.2 8.6 274 166 0.02 0.06
CJ GG
Nov. 2012 11.1 6.9 403 351 0.02 0.06
May 2013 37.1 7.6 418 384 0.01 0.04
Nov. 2013 18.8 7.9 383 235 0.01 0.05
CS GG
Nov. 2012 16.5 7.8 181 351 0.06 0.03
May 2013 17.0 8.4 156 334 0.04 0.02
Nov. 2013 17.0 9.1 138 254 0.02 0.02
DL GG
Nov. 2012 12.7 6.9 539 367 0.07 0.04
May 2013 6.9 7.0 503 403 0.03 0.04
Nov. 2013 6.0 7.5 447 237 0.01 0.04
GJ
GG
Nov. 2012 12.4 7.2 198 383 0.06 0.13
May 2013 15.4 7.7 187 349 0.03 0.08
Nov. 2013 12.8 7.6 221 201 0.02 0.11
NG
Nov. 2012 18.0 7.1 228 364 n.d. n.d.
May 2013 18.9 7.7 172 341 0.02 0.07
Nov. 2013 17.8 8.3 180 175 0.02 0.06
GR GG
Nov. 2012 17.0 6.7 628 381 0.14 0.18

May 2013 15.6 7.1 548 413 0.06 0.27

Nov. 2013 17.4 8.6 193 327 0.03 0.03
HA GG Nov. 2012 19.0 7.0 6,080 178 0.06 0.90
SJ GG
May 2013 15.4 7.5 426 354 0.02 0.04
Nov. 2013 13.4 7.0 450 265 0.01 0.04
YG
GG
Nov. 2012 8.4 7.3 572 365 0.02 0.04
May 2013 7.0 7.4 388 345 0.02 0.03
Nov. 2013 7.3 7.9 465 205 0.01 0.04
NG
Nov. 2012 15.1 7.1 118 321 n.d. n.d.
May 2013 18.6 7.8 490 352 0.02 0.04
Nov. 2013 16.3 7.8 427 258 0.01 0.03
n.d.: not detected.
Influence of open loop GHP on groundwater

wide range compared to that of NG. However, pH of GG had

relatively narrow range compared to that of NG at GJ and
YG (Fig. 3b). In this study, these cause did not revealed.
The EC is a good parameter to easily monitor groundwater
chemistry. The EC of GG ranged from 138 to 6,080
S/cm (Table 1). The initial EC (local background levels)
measured at each sampling site showed wide range. In particular,
the EC was very high (6,080 S/cm) at HA. In this study,
GG at HA was sampled once. Therefore, the influence of
open loop GHP systems on groundwater was not evaluated
at this site. Although the groundwater quality was not good, the
energy efficiency of the open loop GHP system was excellent.
At GJ and YG, the EC of GG showed higher values and
narrower range compared with that of NG (Fig. 3c). These
results indicate that EC of GG did not significantly affected
by open loop GHP systems operation at GJ and YG. Therefore,
the variation of EC of GG and NG may be attributed to
not open loop GHP systems operation but other factors such
as precipitation and agricultural activities. Through additional
studies, understanding for variation of EC in GG and NG can
be improved.
The Eh is an indicator of redox conditions. According to
classification suggested by Garrels and Christ (1965), redox
condition of most GG is environmental in contact with the
atmosphere or transitional environment. The Eh of GG ranged
from 178 to 413 mV. Fe2+ concentrations in GG ranged from
0.01 to 1.39 mg/L. Fe2+ concentrations had a wider range.
The Fe2+ concentration at BS was the highest (1.39 mg/L)
(Table 1). When GG of BS was sampled, compounds containing
Fe that had a red color were observed. However, these
compounds were not observed after GG was pumped out for
approximately 10 min. These compounds may be the result
of reactions between GG stored in the open loop GHP systems
and certain parts of the equipment. In addition, groundwater
can be contaminated when these compounds flow into groundwater
(Abesser, 2010). The Mn2+ concentrations in GG ranged
from 0.02 to over 0.90 mg/L (Table 1). The Mn2+ concentrations

in GG at HA were the highest (over 0.90 mg/L). HA

is located at a river bank, and it is known that the Mn 2+ concentrations
are very high (over 0.3 mg/L) in this area (Hyun
et al., 2006). At GJ and YG, the Eh and concentrations of
Fe2+ and Mn2+ of GG showed wide ranged compared to those
Fig. 3. Comparison of water temperature, pH, EC, Eh, Fe2+, and Mn2+ of groundwater used in
open loop GHP systems and natural
groundwater around open loop GHP systems at GJ and YG.
Youngyun Park, Namju Kim, and Jin-Yong Lee

of NG (Figs. 3df). These results represent that open loop

GHP systems operation can be influenced on redox conditions
of groundwater.
3.2. Chemical Compositions
Figure 4 shows the chemical compositions of GG and NG.
The groundwater chemistry at sites where open loop GHP
systems are installed was varied. The GG at GR, YG, HA,
and BS were Ca-Cl types, GJ and DL were Ca-SO4 types, SJ
and CJ were Ca-HCO3 types, and CS was Na-HCO3. The NG
at GJ and YG were Ca-Cl and Ca-SO4 types. Therefore, the
influence of open loop GHP systems on groundwater chemistry
can appear differently at each facility. Contributions of
major dissolved components in GG at each site did not show
significant differences during the study area. At GJ, Ca 2+, Na+,
HCO3
, and HCO3
concentrations in GG were higher than
in NG. K+, Mg2+, Cl, NO3
, and SO4
2 concentrations in GG were
lower than in NG. However, the concentrations of all dissolved
components showed variation within approximately
2 mg/L. At YG, the concentrations of cations in GG and NG
did not show significant variations, but those of anions had
distinct variations. In particular, Cl, NO3
, and SO4
2 concentrations
showed significant variations. These components can
mainly come from agricultural activities in the rural area.
Evaluating influence of open loop GHP systems operation
on GG is very difficult in agricultural areas. While chemical
compositions of GG can show rapid change caused by agricultural
activities, those of GG can be slowly changed by open
loop GHP systems operation. Therefore, to exactly assess influence
of open loop GHP systems operation, selecting endmember
is very important. In this study, samples collected
first were selected as the end-member.
3.3. Isotopic Compositions
Oxygen and hydrogen isotopic compositions in GG ranged
from 9.6 to 6.8 and 70 to 46, respectively (Fig. 5).
The isotopic compositions showed a wide range because of
the latitude effect. The regression line for the isotopic compositions
is D = 7.3118O + 1.94. In this regression line, the
slope shows a little difference as compared with the slope

of the regression line for the local meteoric water (slope = 8.05
to 8.15) (Lee and Chung, 1997; Lee and Lee, 1999). The isotopic
compositions of the meteoric water and groundwater
can show a little difference because the meteoric water could
slightly experience evaporation during runoff and recharge
(Clark and Fritz, 1997). If groundwater experiences heavy
evaporation, the slope of the regression line can be lower than
6. Figure 5 indicates that GG was supplied from the meteoric
water and did not experience heavy evaporation loss.
The concentration of dissolved components can increase by
evaporation loss. In this study, water temperature increased
to 31.7 C at CJ. However, the isotopic compositions of GG
at CJ were plotted around its regression line because evaporation
loss did not occur at CJ. These results support that
there was no increase in the concentration of dissolved
components caused by evaporation.
3.4. Variation of water quality of the used groundwater
by open loop GHP systems
Figure 6 shows the variation ratios of the concentration of
major ions in GG;. [H4SiO4] and [HCO3
] ranged from
0.07 to 0.15 and 0.25 to 0.11, respectively, at all sampling
Fig. 4. Chemical compositions of natural groundwater and groundwater
used in open loop GHP systems.
Fig. 5. Isotopic compositions of natural groundwater and groundwater
used in open loop GHP systems.
Influence of open loop GHP on groundwater

sites except at some of GR ([H4SiO4] = 0.89 and [HCO3

] =
0.72) (Figs. 6e and f). These results show that H4SiO4 is
not influenced by the operation of open loop GHP systems,
and the decrease in HCO3
concentrations may be attributed
to degasing of dissolved CO2 at sites showing negative values,
except GR. In cooling mode, HCO3
concentrations can
be reduced by degasing of dissolved CO2 (Bouwer, 2002;
Abesser, 2010).
[Ca2+], [Mg2+], [Na+] and [SO2
2] ranged from 0.67
to 0.25, 0.83 to 0.34, 0.58 to 0.31and 0.63 to 0.44, respectively
(Figs. 6a, b, c, and h). Variations in the concentration
of these components are not influenced by the operation of
open loop GHP systems. The operating period of the open
loop GHP systems was short less than 2 years at most sampling
sites except CJ, which was in operation over 6 years.
However, variations in Ca2+, Mg2+, Na+
, and SO4
2 concentrations
showed relatively narrow ranges at CJ as compared
with the other sampling sites. Therefore, Ca2+, Mg2+, Na+
, and
SO4

concentrations may be controlled by external factors

of open loop GHP systems such as precipitation and inflow
of these components from soil.
[K+] and [Cl] ranged from 0.39 to 0.59 and from 0.77
to 0.57, respectively (Figs. 6d and f). The concentrations of
K+ and Cl showed a wide range as compared with those of
Ca2+, Mg2+, Na+, and SO4
2. The increase of K+ concentrations
was significant at GJ, YG, and CJ. In this study, the reasons
for these were not demonstrated and additional studies are
necessary to determine the reasons. A distinct increase in Cl
concentrations was observed at CJ, which may be attributed
to the influence of open loop GHP systems (Park et al., 2013a).
2

Fig. 6. Variation of dissolved components levels in groundwater used in open loop GHP
systems.
Youngyun Park, Namju Kim, and Jin-Yong Lee

The average concentrations of Cl increased gradually at 11

facilities installed at CJ.
[NO3
] ranged from 1.00 to 4.21 (Fig. 6g). Increase in
NO3
concentrations was significant at GJ, which may be
attributed to agricultural activities around the facility. NO3

concentrations increased slightly at GR and are not attributed

to agricultural activities unlike GJ. The facility at GR was
installed in the downtown of the city. These reasons are not
explained in this study. In addition, to understand the influence
of installation and operation of open loop GHP systems,
hydrogeochemical surveys around the facility should
be conducted.
3.5. Saturation and Stability Index
The LSI and RSI of GG ranged from 1.86 to 0.10 and
7.73 to 10.9, respectively (Fig. 7). All the samples did not
show precipitation of carbonate minerals because the LSI
values were lower than 0.5, and the RSI values were higher
than 7.73 (see Table 2). At GJ and YG, the LSI of GG and NG
ranged from 1.86 to 0.80 and 1.79 to 0.43, respectively.
The RSI of GG and NG ranged from 9.48 to 10.9 and 8.66
to 10.7, respectively. The LSI and RSI values of GG did not
distinguish from those of NG. These results indicate that GJ
and YG did not influence by used in open loop GHP systems,
which is attributed to the short operating and monitoring
period. According to previous studies, the LSI and RSI are
influenced by open loop GHP systems operation, and this
influence occurs very slowly (Rafferty, 1999, 2003; Zia et
al., 2008).
The saturation indexes for carbonate and silica minerals
and minerals containing Fe and Mn are summarized in Table 3.
GG and NG were undersaturated with aragonite, calcite, and
dolomite in most samples, except BS collected in November
2013. Therefore, carbonate minerals did not precipitate
in GG and NG. The saturation indexes for quartz and chal-

Fig. 7. Langelier saturation index and Ryznar stability index for groundwater used in open
GHP systems. Violet and green colors represent
groundwater used in open loop GHP systems and natural groundwater around open loop
GHP systems, respectively.
Table 2. Indication of LSI and RSI values (CACC, 1965)
Index Values Indication
LSI
(Langelier saturation index)
2.0 Scale forming but non corrosive
0.5 Slightly scale forming and corrosive
0.0 Balanced but putting corrosion possible
0.5 Slightly corrosive but non-scale forming
2.0 Serious corrosion
RSI
(Ryznar stability index)
4.05.0 Heavy scale
5.06.0 Light scale
6.07.0 Little scale or corrosion
7.07.5 Corrosion significant
7.59.0 Heavy corrosion
>9.0 Corrosion intolerable
Influence of open loop GHP on groundwater

cedony are higher than 0 in most samples. Thus, silica minerals

can be precipitated slightly, but the H4SiO4 concentration
did not significantly decrease (see Fig. 6e). Therefore, precipitation
of silica minerals did not occur.
Fe(OH)3 is a compound containing Fe. Goethite, hematite,
melanterite, and siderite are minerals containing Fe. The saturation
indexes of Fe(OH)3, goethite, and hematite were higher
than 0 in all GG and NG samples.GG and NG were underTable 3. Saturation indexes of carbonate and silica minerals and minerals including Mn and
Fe calculated from PHREEQC
Mineral Formula
Natural groundwater Groundwater used in open loop GHP
Maximum Minimum Mean Std. Maximum Minimum Mean Std.
Carbonate
minerals
Aragonite CaCO3 0.43 1.82 1.02 0.6 0.05 2.22 1.00 0.6
Calcite CaCO3 0.28 1.67 0.87 0.6 0.19 1.72 0.77 0.5
Dolomite CaMg(CO3)2 1.46 4.33 2.62 1.1 0.10 4.26 2.25 1.1
Silica
minerals
Quartz SiO2 0.61 0.36 0.49 0.1 0.62 0.94 0.22 0.4
Chalcedony SiO2 0.16 0.09 0.04 0.1 0.15 1.37 0.24 0.4
Minerals including
Fe
Fe(OH)3(a) Fe(OH)3 1.32 0.68 1.08 0.2 2.07 0.18 1.28 0.4
Goethite FeOOH 6.85 6.35 6.70 0.2 7.39 6.34 6.78 0.3
Hematite Fe2O3 15.7 14.7 15.4 0.4 16.7 14.6 15.5 0.7
Melanterite FeSO4:7H2O 8.66 11.7 10.3 1.3 8.28 12.9 10.2 1.6
Siderite FeCO3 3.15 5.46 4.42 0.9 2.79 7.28 4.41 1.2
Minerals including
Mn
Hausmannite Mn3O4 8.10 12.5 10.2 1.8 5.73 17.9 11.3 4.3
Manganite MnOOH 2.68 4.18 3.59 0.7 1.56 6.79 3.82 1.6
Pyrochroite Mn(OH)2 5.08 7.24 6.13 0.9 4.69 7.63 6.25 0.8
Pyrolusite MnO2 6.19 9.84 8.06 1.5 4.75 13.8 8.75 3.1
Rhodochrosite MnCO3 0.85 1.89 1.34 0.4 0.44 2.36 1.33 0.5

Std.: standard deviation.

Fig. 8. Relationship between pH and
Fe* (a), pH and saturation index for
minerals including Fe (b) and between
Fe* and saturation index (c) in groundwater
used in open loop GHP systems.
Fe* represents total Fe including Fe2+
and Fe3+.
Youngyun Park, Namju Kim, and Jin-Yong Lee

saturated with melanterite and siderite (Table 3). Therefore, Fe

in GG and NG can be precipitated to form of Fe(OH)3, goethite,
and hematite. Precipitation of material containing Fe is mainly
controlled by Fe levels, pH, and redox condition (Grassian, 2005).
In this study, there was no relationship observed between pH
and Fe* (total Fe including Fe2+ and Fe3+) concentrations
(Fig. 8a). The saturation index of minerals containing Fe did
not show a significant relationship with pH and Fe * concentrations
(Figs. 8b and c). These results are attributed to the
low concentration of Fe*.
Hausmannite, manganite, pyrochroite, pyrolusite, and rhodochrosite
are minerals containing Mn. The GG and NG were
undersaturated with respect to these minerals (Table 3). The
saturation indexes for these minerals in GG were similar to
those of NG. Mn* (total Mn including Mn2+ and Mn3+) concentrations
showed a negative relationship with pH (Fig. 9a).
Mn* concentrations can increase in the future because the
pH of GG can decrease from the operation of the open loop
GHP systems (Park et al., 2013a). Like Fe*, the saturation
indexes did not show a significant relationship with pH and
Mn* concentrations (Figs. 9b and c). Consequently, the open
loop GHP systems operation can cause scale formation mainly
by minerals containing Fe rather than from carbonate and
silica minerals and mineral containing Mn. Therefore, monitoring
for Fe concentrations has to also be conducted when
the influence of open loop GHP systems on groundwater
chemistry is evaluated.
4. CONCLUSION
Use of open loop GHP systems has been limited by lack
of understanding of these systems and that of the environmental
risks, such as groundwater contamination and depletion
of groundwater even though the open loop GHP systems
have high efficiency of energy and cost. This study was performed
to examine chemical and isotopic compositions of
GG and NG and to evaluate the influence of open loop GHP
systems on GG by using the LSI, RSI and SI for carbonate and
silica minerals and minerals containing Fe and Mn. Variations
of water temperature of GG were larger than that of
NG. The water temperature of GG increased by 6.7 to 11.6 C
compared with that of NG. However, pH, EC, Eh, Fe2+, and
Mn2+ did not show significant influence by open loop GHP
systems operation. GG showed various chemical compositions
at each open loop GHP system and had various water types
(Ca-HCO3, Ca-SO4, Ca-Cl, and Na-HCO3 types). Even though
variations of HCO3

and Cl concentrations caused by open

loop GHP systems operation were observed at some sites, chemical
compositions did not seem to be influenced by open loop
GHP systems operation at most sites. These results are attributed

Fig. 9. Relationship between pH and

Mn* (a), pH and saturation index for
minerals including Mn (b) and
between Mn* and saturation index (c)
in groundwater used in open loop
GHP systems. Mn* represents total Fe
including Mn2+ and Mn3+.

Influence of open loop GHP on groundwater

to the short monitoring period (less than 2 years) at most facilities.

Variations of LSI, RSI, and SI caused by open loop GHP
systems operation were not observed. Precipitation of carbonate
and silica minerals and minerals containing Mn are
going to be not predicted because of undersaturation for these
minerals. However, scale formation of minerals in the form
of Fe(OH)3, goethite, and hematite can be induced. Therefore,
Fe concentrations have to be monitored because they
have influence on the effectiveness and lifetime of open loop
GHP systems. In this study, the influence of open loop GHP
systems on groundwater chemistry was not revealed sufficiently
because monitoring period was not sufficient. Integrated
long-term monitoring of groundwater used in open loop GHP
systems is necessary to maintain the efficiency of open loop
GHP systems. Hydrogeological characteristics are sufficiently
understood to reduce the environmental risks related to open
loop GHP systems operation. In addition, optimal system design,
operation strategies, and post management need to be considered.
ACKNOWLEDGMENTS: This study was supported by the New &
Renewable Energy of the Korea Institute of Energy Technology Evaluation
and Planning (KETEP) grant funded by the Ministry of Knowledge
Economy of Korea government (No.20123040110010). In addition,
we would like to deeply appreciate anonymous reviewers for helpful
comments.

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