Analytica Chimica Acta 631 (2009) 189–195

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Analytica Chimica Acta

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Characterizing the origins of bottled water on the South Korean market

using chemical and isotopic compositions
Yeon-Sik Bong a,b , Jong-Sik Ryu a , Kwang-Sik Lee a,∗
a
Division of Earth & Environmental Sciences, Korea Basic Science Institute, 113 Gwahangno, Yusung-gu, Daejeon 305-333, Republic of Korea
b
Department of Geology and Earth Environmental Sciences, Chungnam National University, Daejeon 305-764, Republic of Korea

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

Article history: We analyzed the major elements and stable isotopes of oxygen, hydrogen, and carbon (dissolved inorganic
Received 12 July 2008 carbon: DIC) in various types of bottled water (domestic and foreign) commercially available in South
Received in revised form 10 October 2008 Korea to classify the water types and to identify their origins. Only marine waters and some sparkling
Accepted 10 October 2008
waters could be discriminated by their physicochemical compositions. Oxygen and hydrogen isotopes
Available online 1 November 2008
made marine waters more distinguishable from other water types. The determination of the carbon iso-
tope composition of DIC was clearly useful for distinguishing between naturally and artificially sparkling
Keywords:
waters. In addition, statistical analysis also appeared to aid in the discrimination of bottled water types.
Bottled water
Chemical composition
Our results indicate that a method that combines chemical and stable isotope composition analysis with
Dissolved inorganic carbon statistical analysis is the most useful for discriminating water types and characterizing the origins of
Stable isotopes bottled water.
Statistical analysis © 2008 Elsevier B.V. All rights reserved.

1. Introduction
Bottled water consumption has grown steadily over the past
few decades. In 2003, bottled water became the second largest
commercial beverage category by volume in the United States, and
despite its already significant stature, bottled water consumption
continued to grow rapidly in 2007 (International Bottled Water
Association: www.bottledwater.org). Bottled water is an increas-
ingly important component of human dietary intake worldwide,
with many consumers believing it to be a safe product that orig-
inates from remote sources and unpolluted environments [1,2].
However, given the widespread increase in nonpoint anthropogenic
pollutant sources arising from rapid urbanization and development
in production areas, the actual quality and origin of bottled water
should be carefully evaluated [3,4].
Deep ocean water (hereafter, marine water) is very cold and
salty water, found approximately 200 m below the ocean surface
layer. Marine water that is brought to the surface has a number
of uses, including use as a beverage. A number of features make
marine water attractive in the beverage market. It is said to contain
very few trace elements and to have a mature and stable chemical
composition. Some consumers also believe that it will cure certain
diseases [5]. Recently, the amount of marine water has increased
∗ Corresponding author. Tel.: +82 42 865 3447; fax: +82 42 865 3963.
E-mail address: kslee@kbsi.re.kr (K.-S. Lee).
significantly in the bottled water market, despite its high costs.
Many South Korean and Japanese consumers, in particular, consider
marine water to be the most contaminant-free bottled water.
Although a number of studies have examined various types
of bottled water, including still and sparkling water, using sta-
18
ble isotopes (␦ OH2 O , ␦DH2 O , and ␦13 CDIC ) or chemical elements
[1,2,6–10], few studies have combined both techniques. In addition,
no previous study has examined bottled water of marine origin.
Thus, we analyzed the chemical and stable isotope compositions
of various types of bottled water that are commercially available
in South Korea to classify the water types and to identify their
sources. Statistical analyses were also conducted to confirm the
classifications.
2. Materials and methods
2.1. Materials
In total, 35 brands and 15 replicates of bottled water (29
domestic and 21 foreign brands) commercially available from
supermarkets in South Korea were randomly collected in early
2008. Several brands of bottled water were sampled as duplicates
from different supermarkets. Information on the sampling location
and origin of the bottled water was taken from the bottle labels,
when indicated. The bottled water was divided into the following
three main groups based on its origin: (1) still water (water without
the presence of dissolved gaseous CO2 ), (2) sparkling water (water

0003-2670/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.aca.2008.10.032
190 Y.-S. Bong et al. / Analytica Chimica Acta 631 (2009) 189–195
in which dissolved gaseous CO2 was present), and (3) marine water
(desalinized seawater).
2.2. Sample analyses
Samples for cation and anion analyses were passed through
0.45-␮m pre-cleaned membrane filters and kept refrigerated at
approximately 4 ◦ C before analyses. All analyses were done just
after opening the bottles of water. Samples for cation analysis were
acidified in the laboratory with ultrapure HNO3 to pH < 2. Cations
were analyzed by Inducitively Coupled Plasma Atomic Emission
Spectroscopy (ICP-AES; PerkinElmer Optima 4300DU, USA) at the
Korea Basic Science Institute (KBSI). Anions were analyzed by ion
chromatography (IC; Dionex ICS-1500, USA) at the Korea Institute
of Geoscience and Mineral Resources. The analytical uncertainties
ranged from 2 to 5% for cations and anions.
For oxygen isotope analysis, ∼0.3 mL of each water sample was
equilibrated with carbon dioxide gas at 25.0 ± 0.1 ◦ C [11]. The car-
bon dioxide was then extracted and cryogenically purified. For
deuterium isotope analysis, metallic chromium was applied to pro-
duce hydrogen gas using an automatic on-line sample preparation
system (GV Instruments Euro PyrOH, UK) [12]. For ␦13 CDIC analy-
sis, water samples were transferred into evacuated glass septum
vials pre-filled with 85% phosphoric acid [13]. The CO2 gas was then
extracted using a gas evolution technique and cryogenically puri-
fied. The oxygen, hydrogen, and carbon isotope compositions of the
samples were determined using Isotope Ratio Mass Spectrometers
(IRMS; GV Instruments IsoPrime and Micromass Optima, UK) at the
KBSI. The stable isotope compositions are expressed in ␦ notation
relative to Vienna Standard Mean Ocean Water (VSMOW) for oxy-
gen and hydrogen isotopes and Vienna Pee Dee Belemnite (VPDB)
for carbon isotopes:
 
Rsample
ı(‰) = −1 × 1000
Rstandard
where R represents 18 O/16 O, D/H, or 13 C/12 C. The analytical repro-
ducibility for each standard and sample was ±0.1‰ for ␦18 O, ±0.5‰
for ␦D, and ±0.2‰ for ␦13 CDIC . During the sample analysis, the lab-
oratory standards for each isotope were run every nine samples.
2.3. Statistical analyses
To classify the bottled water, we performed multivariate sta-
tistical analyses. We used SAS Version 8 for Windows (USA) to
perform R-mode factor analysis of the standardized data, includ-
ing principal components analysis (PCA) to determine interactions
among the variables. Before PCA, each variable was standardized
to a mean of zero and variance of one to avoid misclassification
arising from the different orders of magnitude of the measures.
We attempted to simplify the complex and diverse relationships
that existed among the observed variables by revealing common
and unobserved factors that linked them to seemingly unrelated
variables [14].
3. Results and discussion
3.1. Physicochemical characteristics
Table 1 summarizes the sample brands, origins, and physic-
ochemical parameters, including pH, major ions, stable isotopes
(18 O, D, and 13 C), and Calcite Saturation Index (CSI). The pH of
the still water brands ranged widely from 6.73 to 10.1, with an
average of 7.35. In comparison, sparkling and marine water brands
had narrower pH ranges of 5.60–6.70 and 6.38–7.40, respectively.
The higher pH of still water was likely due to its isolation from
atmospheric CO2 . In contrast, the lowest pH of the sparkling water
might reflect high levels of CO2 through carbonate dissolution
and/or artificial CO2 injection. Interestingly, the pH of marine water
(6.38–6.93), except for one sample labeled Bingha (Japan) (7.40),
was much lower than that of natural seawater (7.40–8.35) [15]; this
could have been due to the desalinization process.
The concentrations of all dissolved major elements displayed
large variation (Table 1), which likely arose from the different geo-
logical origins of the waters. Numerous factors control the chemical
composition of natural water, including atmospheric and anthro-
pogenic inputs, lithology, and groundwater residence time [16]. Of
the types of bottled water, sparkling water had the highest mean
concentrations of all major elements, with the exception of Mg2+
and Cl− (Table 1). The elemental ratios of sparkling water to other
water varied from 1.4 to 22, except for Mg2+ and Cl− , and were cal-
culated by dividing the mean concentration of sparkling water by
the mean concentrations of still and marine waters. The maximum
ratio occurred for HCO3 − because of carbonate dissolution and/or
the artificial addition of CO2 .
We attempted to identify the water types using a Piper diagram
(Fig. 1), which was drawn by plotting the proportions (in equivalent
values) of the major cations (Ca2+ , Mg2+ , and Na+ + K+ ) on one tri-
angular diagram, the proportions of the major anions (HCO3 − , Cl− ,
and SO4 2− ) on another diagram, and then combining the informa-
tion from the two triangles on a quadrilateral field [17] to obtain
information about the natural diversity of the chemical composi-
tion of bottled water brands. The frequently observed water types
were Ca–Mg–HCO3 and Ca–Na–HCO3 in still water, Ca–Mg–HCO3 in
sparkling water, and Mg–Na–Cl in marine water (Table 1). However,
the bottled water, especially the still water, was quite scattered in
Fig. 1 and did not form distinct clusters. Still water and sparkling
water could not be distinguished from each other in Fig. 1, whereas
marine water was clearly distinguished from other types of bottled
water. Three samples of sparkling water were well grouped because
of their high SO4 2− content.
One still water (Siana, Korea) and one marine water (Bingha,
Japan) had quite different water types and plotted in foreign regions
compared to other brands of their respective water types (Fig. 1).
Fig. 1. Piper diagram of the chemical composition of various brands of bottled water.
Rather than forming distinct clusters, the data are quite scattered, especially among
still water brands. Three samples of sparkling water and five samples of marine
water are well grouped due to enriched SO4 2− and Cl− , respectively.
Table 1
Physicochemical and stable isotopic compositions of bottled waters used for the study.

Brand Origin Water type pH Ca2+ (␮M) K+ (␮M) Mg2+ (␮M) Na+ (␮M) Cl− (␮M) NO3 − (␮M) SO4 2− (␮M) HCO3 − (␮M) ␦18 O (‰) ␦D (‰) ␦13 CDIC (‰) CSIa

Still water
Waterline Korea Ca–Mg–HCO3 7.23 573 23.3 200 187 105 76.2 108 1570 −9.0 −64 −15.3 −0.8
Waterline Korea Ca–Mg–HCO3 7.44 617 24.3 211 228 115 66.6 129 1661 −9.1 −62 −15.5 −0.5
Soonsoo Korea Ca–Na–HCO3 7.49 338 19.5 107 406 102 95.1 49.8 1186 −9.0 −63 −16.4 −0.9
Soonsoo Korea Ca–Na–HCO3 –SO4 7.45 530 6.3 30.5 547 157 19.0 304 1093 −8.3 −56 −15.9 −0.8
Seoksu Korea Ca–HCO3 7.18 546 31.5 113 174 157 118 71.1 1313 −9.0 −62 −15.2 −0.9
Seoksu Korea Ca–HCO3 7.23 557 32.0 116 171 151 109 70.8 1310 −9.0 −61 −15.1 −0.9
Samdasoo Korea Na–Mg–Ca–HCO3 6.90 73.5 43.5 102 232 170 30.4 21.3 495 −7.0 −43 −16.0 −2.5
Samdasoo Korea Na–Mg–Ca–HCO3 6.89 75.8 43.7 105 245 171 28.4 20.0 469 −7.2 −45 −15.7 −2.5
Icis Korea Ca–Mg–HCO3 7.08 311 16.0 193 65.6 76.3 33.1 47.4 965 −9.0 −62 −16.2 −1.4
Icis Korea Ca–Mg–HCO3 7.23 315 16.2 197 65.3 83.5 31.9 55.6 961 −9.2 −65 −16.1 −1.2
Sammool Korea Ca–Mg–HCO3 7.27 309 15.9 191 65.4 82.2 33.0 46.4 962 −9.1 −63 −15.8 −1.2
Sammool Korea Ca–Mg–HCO3 7.25 311 16.1 196 64.7 76.5 23.4 45.6 984 −9.2 −62 −16.1 −1.2

Y.-S. Bong et al. / Analytica Chimica Acta 631 (2009) 189–195

Sammool Korea Ca–Mg–HCO3 7.30 335 16.0 210 67.0 80.2 28.7 49.3 993 −9.4 −64 −15.9 −1.2
Elumgol Korea Na–Ca–HCO3 7.33 262 18.3 39.3 1006 170 100 137 1096 −8.5 −58 −19.1 −1.2
Elumgol Korea Na–Ca–HCO3 7.37 194 16.1 29.4 1017 184 90.2 128 983 −8.4 −58 −19.2 −1.3
Bongpyong Korea Ca–Na–HCO3 7.21 386 15.2 124 291 174 120 38.5 1011 −10.3 −72 −19.7 −1.2
Odaesan Korea Ca–Na–HCO3 7.34 429 15.1 114 387 83.4 131 86.7 1171 −9.6 −68 −10.9 −0.9
Dongwon Korea Ca–HCO3 –SO4 7.33 783 30.1 156 274 150 47.2 358 1318 −9.3 −67 −18.8 −0.7
Yaksan Korea Ca–Na–HCO3 6.98 300 8.0 55.3 253 61.1 65.0 38.9 802 −9.6 −68 −17.2 −1.6
Soo Korea Ca–Na–HCO3 6.94 369 15.0 114 287 171 115 33.8 947 −10.4 −73 −20.0 −1.5
Soo Korea Ca–Na–HCO3 6.92 353 14.6 114 275 161 112 34.1 958 −10.3 −73 −19.4 −1.5
Evian France Ca–Mg–HCO3 7.38 1963 27.4 1095 305 203 60.2 133 6572 −10.1 −73 −11.0 0.4
Evian France Ca–Mg–HCO3 7.68 2066 26.3 1135 304 205 61.0 135 6554 −10.2 −75 −11.1 0.7
Volvic France Mg–Ca–Na–HCO3 –Cl 7.91 299 137 344 502 438 119 88.5 1323 −8.5 −58 −9.6 −0.5
Volvic France Mg–Ca–Na–HCO3 –Cl 7.78 334 145 379 541 442 120 89.6 1352 −8.4 −59 −9.4 −0.6
Whistler Canada Ca–HCO3 7.01 311 14.7 53.8 109 166 13.6 73.7 556 −15.7 −121 −11.4 −1.7
Aqua panna Italy Ca–Mg–HCO3 7.38 912 22.1 302 355 241 69.7 228 1975 −7.9 −48 −11.0 −0.4
Tŷnant England Ca–Mg–Na–HCO3 –Cl 7.41 586 23.0 553 929 393 11.8 76.2 2705 −6.4 −41 −20.1 −0.4
Siana Korea K–HCO3 10.1 10.8 2359 8.47 77.9 298 16.7 5.85 1740 −8.2 −59 −37.4 −0.2
Power O2 Germany Mg–Ca–HCO3 7.54 1088 28.5 1288 549 634 31.1 281 4575 −10.6 −76 −11.9 0.2
Keumgangsoob Korea Na–HCO3 –Cl–NO3 6.74 22.6 7.13 7.67 182 82.0 39.4 16.8 164 −8.3 −55 −19.3 −3.7
Keumgangsoob Korea Na–Ca–NO3–Cl 6.73 52.9 7.36 21.6 104 113 75.1 33.8 41.6 −9.3 −57 −20.2 −3.9

Mean 7.35 488 101 247 321 184 65.3 94.9 1556 −9.2 −64 −16.3 −1.1

Sparkling water
Chojung Korea Ca–Na–HCO3 5.60 597 35.9 220 938 480 225 127 1488 −8.2 −59 −26.6 −2.5
Solé Italy Ca–Mg–HCO3 6.41 2610 10.5 1447 144 127 171 184 7262 −8.2 −55 −38.7 −0.4
Solé Italy Ca–Mg–HCO3 6.21 2991 11.6 1319 161 135 182 167 7353 −8.2 −55 −23.0 −0.6
Gerolstenier Germany Ca–Mg–HCO3 6.63 8157 443 4056 4309 1059 86.7 407 28331 −8.7 −59 −2.6 0.7
Montes Austria Ca–Mg–SO4 –HCO3 5.98 2864 105 2258 1285 521 11.8 3193 3321 −12.2 −89 −47.6 −1.3
Perrier France Ca–HCO3 6.12 4538 27.4 254 535 747 103 424 7135 −6.3 −42 −5.4 −0.5
Heidiland Swiss Ca–Mg–SO4 5.65 2941 14.2 1642 189 42.3 33.4 2682 1405 −12.8 −91 −40.9 −1.9
S. Pellegrino Italy Ca–Mg–SO4 –HCO3 6.08 4701 74.5 2361 1596 1810 50.6 4277 3495 −9.0 −61 −6.8 −1.0
San Benedetto Italy Ca–Mg–HCO3 6.16 1334 26.6 1313 325 91.3 139 49.6 4815 −8.6 −58 −48.8 −1.1
Tŷnant England Ca–Mg–Na–HCO3 –Cl 5.81 601 21.7 551 948 390 D.L. 75.2 2033 −6.6 −42 −38.7 −2.1
Tau England Ca–Mg–Na–HCO3 –Cl 5.86 584 21.7 541 956 385 D.L. 72.1 2062 −6.6 −42 −35.3 −2.1
Apollinaris Germany Na–Mg–HCO3 6.70 2762 893 5999 23226 3660 78.1 1023 31778 −9.3 −62 −7.9 0.3

191
192 Y.-S. Bong et al. / Analytica Chimica Acta 631 (2009) 189–195

For the still water sample (Siana), the K–HCO3 type was not nor-

−3.3
−3.3

−2.5

−0.6
−2.0
−1.0

−2.3
CSIa

–
mal because stoichiometric balance could not be formed. This
result suggests that the water was artificially produced to create
␦13 CDIC (‰) an alkaline water. The marine water (Bingha) might also have been
produced by a different desalinization method or might not have

−11.8
−10.7
−15.3

−7.4
−17.5
−6.0
−26.9

−11.5
been real marine water. More detailed descriptions of this sample
are provided in the stable isotope section [3,2].
In short, the different types of bottled water could not be dis-
␦D (‰)

criminated exactly using the Piper diagram. Therefore, other tools

−60

−3
−5
−2
−2
−2
−64

−13
such as stable isotopes and statistics are needed to discriminate the
water samples more clearly.
␦18 O (‰)

−0.3
−0.4
0.0
−0.1
−0.2
−10.3
−8.7

−1.9 3.2. Oxygen and hydrogen isotopes

HCO3 − (␮M)

The isotope composition of water varies greatly by temperature,

latitude, altitude, and precipitation amount [2,16]. Therefore the
47.6

oxygen and hydrogen isotope compositions of bottled waters pre-

8373

116
130

148
339
1460

373

serve important information about the water source, production

location, and natural processes in the hydrological cycle.
SO4 2− (␮M)

The measured hydrogen and oxygen isotope ratios of the

bottled water ranged from −120.6 to −1.7‰ for ␦D (average
11.9
1057

391
392

800
577
284

409

−56.5‰, n = 50) and from −15.71 to −0.05‰ for ␦18 O (average

−8.18‰, n = 50; Table 1). More specifically, the oxygen and hydro-
gen isotope ratios for still water brands ranged from −120.6
NO3 − (␮M)

to −41.3‰ (mean = −63.5‰, n = 32) and from −15.71 to −6.39‰

18.2
23.8
9.7
9.8
11.2
71.3

24.0

(mean = −9.16‰, n = 32), respectively. For sparkling and marine

108

waters, the ␦18 O compositions ranged from −12.75 to −6.32‰ and

–10.30 to −0.05‰, respectively, and the ␦D compositions ranged
Cl− (␮M)

from −91.5 to −41.8‰ and −64.5 to −1.7‰, respectively.

787

4177
3374
1201
10572
10344
1436

5184

In the plot of ␦D and ␦18 O (Fig. 2), water samples were clustered
along the Global Meteoric Water Line (GMWL, ␦D = 8 × ␦18 O + 10)
of Craig [18]. Here, the GMWL represents the global relationship
Na+ (␮M)

between 18 O and 2 D in meteoric waters. This implies that the iso-

2884

1650
1698
1314
3052

959

1919
2838

tope values of the bottled water reflect relatively unaltered source

water signatures [1]. Among the samples, marine water showed
a prominent feature; except for one sample (Bingha, Japan). The
Mg2+ (␮M)

marine water brands had similar values reported for Korean seawa-
11.0
1830

1273
1367

4398

660

2107
4933

ter (␦D = −1‰ and ␦18 O = 0.1‰) by Kim et al. [19], within analytical
error. Isotope compositions of some marine waters were slightly
depleted, as compared to normal seawater, indicating that the pro-
K+ (␮M)

cess of desalinization can cause small isotopic fractionation. The

32.8
32.6
44.6
91.2
89.1
48.0

56.4
140

Bingha (Japan) marine water sample had quite different isotope val-
ues (␦D = −64.5‰ and ␦18 O = −10.30‰). If this water was produced
by seawater distillation (even though its low energy efficiency
Ca2+ (␮M)

2890

186
205
0
529

685

355
526
6.38
6.38
6.52
6.79
6.93
7.40

6.73
6.10
pH

Ca–Mg–Na–HCO3 –Cl

D.L. below detection limit; – not calculated.

Water type

Mg–Na–Cl
Mg–Na–Cl

Mg–Na–Cl
Mg–Na–Cl
Na–Cl

Calcite Saturation Index (CSI).

Origin

Korea
Korea
Korea
Japan
Japan
Japan
Table 1 (Continued )

Spring water.

Fig. 2. A plot of the ␦D vs. ␦18 O values for various brands of bottled water. Except
Marine power
Marine power
Marine water

for marine water, the oxygen and hydrogen isotope compositions plotted around
Donghaesoo
Minewater
Minewater

the global meteoric water line (GMWL) of Craig [18]. Most marine water samples,
with one exception (Bingha, Japan), had the same value as natural seawater, within
Bingha
Brand

Mean

Mean

analytical error. Refer to the text for more information on the Bingha sample. The
a

symbols are the same as in Fig. 1.

 Y.-S. Bong et al. / Analytica Chimica Acta 631 (2009) 189–195 193

makes this method uncommon in commercial applications), the

isotope values could be reasonable because the distillation pro-
cess can cause relatively high isotopic fractionation [1]. Whether
this bottled water actually originated from marine water cannot
be clearly resolved with the available information. However, we
cautiously suggest that this water sample does not appear to have
originated from marine water because the concentrations of dis-
solved major ions differ from those in the other marine water
samples (Table 1).
The oxygen and hydrogen isotope compositions of one still water
sample (Whistler, Canada) were significantly lower than those of
the other samples. The bottling location of this water was Whistler
Mt., Canada, which is an area with glaciated peaks of nearly 2464 m
in elevation. Such high-elevation terrain is a likely source for the
D- and 18 O-depleted sample. For sparkling water, in contrast, we
identified three subgroups (Fig. 2). Group 1 had the lowest isotope
values, indicating that these samples were very old water that infil-
trated during a past climatic regime; such water usually originates
from deep aquifers. Group 2 had isotope ratios similar to those of
still water. In contrast, group 3 had relatively higher isotope values,
suggesting different conditions in the recharge area compared to
the other samples; such higher isotope values generally suggest a
shallow groundwater origin. However, because we lacked informa-
tion on the origin and geographical features of these bottled water
brands, we cannot draw any conclusions.
As shown in the previous section, the use of both oxygen and
hydrogen isotopes and major ion chemistry was not sufficient to
discriminate the origins of the bottled water types, especially for
natural and artificial sparkling waters. Fig. 3. Plots of ␦13 CDIC vs. pH (a) and the Calcite Saturation Index (b) for various
brands of bottled water. The CO2 gas of most brands of sparkling water was not
3.3. Carbon isotopes of DIC natural. Values for natural sparkling water are from Redondo and Yélamos [7]. The
symbols are the same as in Fig. 1.
The origins of sparkling water could not be determined from
water brands was likely an artificial gas that originated from the
the information on source characteristics, the bottle labels, major
combustion of fossil fuels [7]. Similarly, the highly negative ␦13 CDIC
ions, or oxygen and hydrogen isotopes. Fortunately, the ␦13 CDIC has
value of sparkling waters (<−23‰) indicates that their CO2 was of
recently been used to successfully determine the origin of CO2 in
artificial origin.
both natural and artificial sparkling bottled water [7,8].
The measured ␦13 CDIC of all of the bottled water brands ranged Table 2
from −48.8 to −2.6‰, with an average of −18.3‰; by heaviness, Rotated patterns of factors after varimax rotation. A and B represent the results of
the averages were ordered as follows: marine water (−11.5‰), still factor analysis for the major elements only and the combined data set, respectively.
water (−16.3‰), and sparkling water (−26.9‰). The large isotopic A. Variable Factor 1 Factor 2 Factor 3
variation in sparkling water brands probably reflects the different
Ca 2+
0.31 0.83 −0.28
origins of CO2 in the water, that is, artificial (<−13.0‰) or natural
K+ 0.65 −0.25 0.07
(−8.0 to +7.0‰) [7]. Mg2+ 0.62 0.58 0.44
In a plot of ␦13 CDIC versus pH (Fig. 3a), the three types of water Na+ 0.84 0.23 0.16
are relatively well identified. Sparkling water had the lowest pH Cl− 0.28 0.18 0.79
and highly scattered ␦13 CDIC values, whereas still water had the NO3 − 0.09 0.08 −0.75
SO4 2− −0.10 0.80 0.27
highest pH and a narrow range of ␦13 CDIC values. Marine water had HCO3 − 0.82 0.45 −0.25
pH and ␦13 CDIC values intermediate to those of the sparkling and
Eigenvalues 3.30 1.54 1.20
still waters. One still water sample (Siana, Korea) had the highest pH
Proportion (%) 41.2 19.2 15.0
(10.1) and very light ␦13 CDIC (−37.4‰). Based on the available results
and label information, this sample was most likely alkaline water B. Variable Factor 1 Factor 2 Factor 3
produced by the injection of industrial CO2 during its production
Ca2+ 0.76 −0.21 0.16
(Table 1; Figs. 1 and 3). Such extremely negative values of ␦13 CDIC K+ 0.33 0.00 0.06
in bottled water result from the artificial introduction of CO2 . Only Mg2+ 0.82 0.44 0.19
four sparkling water brands plotted within the range of ␦13 CDIC val- Na+ 0.80 0.21 −0.15
ues for natural sparkling water [7]; these brands were probably Cl− 0.29 0.84 0.15
NO3 − 0.13 −0.41 −0.55
naturally sparkling water, namely water fortified with CO2 gases of
SO4 2− 0.42 −0.06 0.78
geogenic origin or produced from the action of acid on carbonate HCO3 − 0.93 −0.10 −0.23
rocks. Therefore, the high ␦13 CDIC value of sparkling waters (>−8‰) ␦18 O −0.08 0.94 −0.07
indicates that their CO2 was of natural origin; these results are ␦D −0.08 0.92 −0.09
␦13 CDIC 0.19 0.37 −0.47
consistent with the label information. However, the ␦13 CDIC values
of the other sparkling water brands were highly negative, ranging Eigenvalues 3.50 2.74 1.29
from −48.8 to −23.0‰. Considering that the ␦13 CDIC of industrial Proportion (%) 31.8 24.9 11.8
CO2 gases is more negative than −18‰, the CO2 in these sparkling Bold numbers indicate highly positive correlation.
194 Y.-S. Bong et al. / Analytica Chimica Acta 631 (2009) 189–195
The diagram of ␦13 CDIC versus the CSI in Fig. 3b was calcu-
lated using the computer program PHREEQC (USA) [20]. With the
exception of two samples, most sparkling water plotted to the neg-
ative CSI region, indicating that these brands were undersaturated
with calcite. However, two sparkling water brands (Gerolstenier
and Apollinaris, Germany) were supersaturated with calcite, which
might reflect strong water–rock interactions in carbonate aquifers.
Therefore, the ␦13 CDIC value can clearly show whether the CO2 gas
in bottled sparkling water is natural or artificial.
3.4. Statistical approach: factor analysis
PCA is generally used to reduce the number of dimensions
present in a data matrix, to select the most discriminating param-
eters, and to investigate the overall variation in the data [9]. We
performed factor analysis for both the major elements only, and
Fig. 4. Plots of PCA factor 1 vs. factor 2 scores (a) and factor 1 vs. factor 3 scores (b)
using a factor analysis for major elements only, and factor 1 vs. factor 2 scores (c)
using a factor analysis for combined data set including stable isotope compositions,
explaining the grouping of various brands of bottled water. The symbols are the
same as in Fig. 1.
the combined data set including stable isotope data. On the basis of
the eigenvalues calculated from rotated factors, three factors were
selected for all bottled waters (Table 2). To simplify the interpre-
tation, we used only two factors, which explained over 68% of the
total variance (Table 2). For the former case of the major elements,
the first factor, which accounted for 41.2% of the total variance,
was characterized by highly positive loadings for K+ , Mg2+ , Na+ ,
and HCO3 − , mainly indicating hardness. The second factor, which
accounted for 19.2% of the total variance, was characterized by Ca2+
and SO4 2− , suggesting the dissolution of gypsum. Lastly, the third
factor, accounting for 15.0%, was marked by only Cl− , representing
salinity.
In contrast, for the latter case of the combined data set, the first
factor explaining 31.8% was typified by Ca2+ , Mg2+ , Na+ , and HCO3 − ,
mainly indicating hardness and dissolution of carbonate. The sec-
ond factor accounting for 24.9% was characterized by Cl− , ␦D, and
␦18 O, clearly suggesting marine water. The indication of the third
factor, marked only by SO4 2− , was unclear.
In a plot of each of the two factor scores (Fig. 4a and b), most
still waters grouped at point (0,0), with the exception of one sam-
ple (Siana, Korea). Similarly, some of the other two water types
seemed to be grouped at the same point. Even though Fig. 4a and b
illustrates differences among the three water types, it seems to be
difficult to completely discriminate different water types through
a factor analysis using the major elements only.
In contrast Fig. 4c which was drawn from the results of fac-
tor analysis using the combined data set, including isotope data,
marine water was completely distinguishable from the other water
types. Similarly, sparkling water was much better discriminated.
However, clearly distinguishing between natural and artificial CO2
still appeared to be difficult. To achieve complete discrimination
between all the water types, further, more detailed, statistical stud-
ies are needed.
Thus, factor analysis, combined with both chemical and stable
isotope compositions, appears to be a much more useful technique
for discriminating between the water types of bottled water.
4. Conclusions
To classify water types and to identify the origins of bottled
water, we analyzed major elements and stable isotopes (oxygen,
hydrogen, and carbon) in 50 brands of bottled water commercially
available in South Korea. Our results indicate that use of the dis-
solved major ions alone was not effective for discriminating the
water types of bottled water. Stable oxygen and hydrogen iso-
topes of bottled water clearly discriminated marine water from
other types of bottled water, showing similar values with seawater.
Oxygen and hydrogen isotopes also provided important informa-
tion about the hydrological conditions of the bottled water such as
recharge temperature, residence time, and water–rock interaction;
a few subgroups were thus identified among the sparkling water
brands. Natural and artificial sparkling water could be clearly distin-
guished by the carbon isotope composition of DIC. Our results show
that a combined method involving chemical and stable isotope
compositions and statistical analysis is better for discriminating
water types and characterizing the origins of bottled water than is
the use of one of these methods alone. The stable isotope compo-
sition of bottled water can thus be used as a good quality control
tool for market regulators.
Acknowledgements
We would like to thank H.S. Shin, D.C. Koh, Y. Park, A.R. Jang,
Y.A. Bong, S.Y. Han and W.J. Shin for their help in chemical analysis
 Y.-S. Bong et al. / Analytica Chimica Acta 631 (2009) 189–195
and sample preparation. This work was supported by a KBSI grant
(N28052) to K.S. Lee.
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