Environmental Pollution 267 (2020) 115409

Contents lists available at ScienceDirect

Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Human health risk assessment of some bottled waters from Romania*

Thomas Dippong a, *, Maria-Alexandra Hoaghia b, Cristina Mihali a, Elena Cical a,
Mihai Calugaru c
a
Technical University of Cluj-Napoca, North University Centre at Baia Mare, Faculty of Science, 76 Victoriei Street, 430122, BaiaMare, Romania
b
INCDO-INOE 2000, Research Institute for Analytical Instrumentation, 67 Donath Street, 400293, Cluj-Napoca, Romania
c ^nca
Research Centre for Instrumental Analysis, 1 Petre Ispirescu Street, Ta beşti, 077167, Ilfov, Romania

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

Article history: The paper presents the quality status of 14 brands of bottled water, with sources of groundwaters from
Received 29 February 2020 different mountain areas alongside the Carpathian Mountains from Romania. A number of 12 physico-
Received in revised form chemical parameters (ammonium, bicarbonate, electrical conductivity, carbonate, chemical oxygen de-
8 August 2020
mand, chloride, nitrate, nitrite, pH, sulphate, total hardness, turbidity), 9 metals and metalloids (Li, B, Na,
Accepted 10 August 2020
Available online 1 September 2020
Mg, Al, K, Ca, Sr, Ba) and 17 heavy metals (V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Mo, Ag, Cd, In, Tl, Pb, Bi)
were determined and studied. The quality status, the potential contamination and the health risk
assessment of bottled waters were assessed, by using the drinking water quality index, the heavy metal
Keywords:
Bottled water
pollution index, the heavy metal evaluation index, the degree of contamination and the human health
Heavy metals risk indices. Hierarchical cluster analysis was applied, indicating similarities among the studied bottled
Health risk waters based on their metal content. The Piper diagram reveals that the majority of bottled water
Quality index samples fall into the Ca, Mg, Na, K, Cl
, SO2
2


4 , CO3 , HCO3 categories. The quality of bottled waters based
Pollution indices on the indices results indicated marginal, poor and very-poor quality status of the studied water samples,
Piper diagram while the health risk assessment indices presented potential risks at aluminium, chloride and nitrate for
the inhabitants who used those water samples with the purpose of drinking. The pollution indices with
respect to metals generally reflected a low pollution status. This study represents the first attempt in
assessing the overall quality of some bottled water collected from the mountain area, Romania, likewise
assessing the comprehensive human health risk due to several chemical elements determined in water in
amounts around and exceeding the maximum allowable concentrations. This research can be useful for
development of potential strategies for risk control and management in the field of drinking water.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction indicating significant challenges in the system modelling, respec-

Globally, in the last decay, the use and demand of bottled water
has been increasing, which rises concerns regarding the quality of
the bottled water and also the used packaging material (most used
polyethylene terephthalate (PET) playing an important role as an
adequate barrier against humidity, oxygen and carbon dioxide
(Chapa-Martínez et al., 2016). Sources for the bottled water are
represented by groundwater (13%e30% of the total freshwater
volume). The groundwaters are sources of drinking water for more
than 50% of the population worldwide (Chen et al., 2016).
Groundwaters (aquifers) are complex and heterogeneous systems
*
This paper has been recommended for acceptance by Eddy Y. Zeng.
* Corresponding author.
E-mail address: dippong.thomas@yahoo.ro (T. Dippong).
tively in the quantification of sustainable management of water
resources (Chang et al., 2017). The chemical composition of
groundwater is influenced and altered by the fast development of
society (urbanism, industrialization, mining activities, radioactive
activities, domestic and agricultural sources), and also by natural
processes (volcanism, weathering of rocks, evaporation processes)
implicitly affecting the human health and the natural environment.
Pollution refers to changes in the biological and physico-chemical
characteristics of all water bodies, groundwater as well, such as
the increase and presence of diverse hazardous materials (heavy
metals, polyaromatic hydrocarbons, nitrates, nitrogen, chloride)
and pathogens (Qiao et al., 2020; Udhayakumar et al., 2016).
Due to its polarity, water has the capacity to suspend, dissolve,
absorb and adsorb many different compounds, therefore contam-
ination could appear (Deeba et al., 2019).

https://doi.org/10.1016/j.envpol.2020.115409
0269-7491/© 2020 Elsevier Ltd. All rights reserved.
2 T. Dippong et al. / Environmental Pollution 267 (2020) 115409
According to Zhao et al. (2020), one of the most significant
pollution of the environment, respectively of the water sources are
represented by the heavy metals, due to their serious toxicity at low
levels, persistence ability, biomagnification and bioaccumulation.
Sources of heavy metals are the municipal emissions (coal burning
and exhaustion gases) for Zn and Ni, while the metal industry
(emissions and discharges) and sewerage are sources of B, Co, Cu,
Ag, Cd (Xiao et al., 2019; Belkhiri et al., 2017; Chen et al., 2016; Devic
et al., 2014).
Heavy metals could cause health problems after accumulating
into the body system through the food chain, water ingestion,
inhalation, epidermal absorption (Zhao et al., 2020; Belkhiri et al.,
2017). As results, severe implications and different disorders may
appear (cardiovascular and skeletal diseases, infertility and
neurotoxicity) (Chabukdhara et al., 2017; Chang et al., 2017).
Chemical carcinogens caused about 90% of the cancer cases (Zhao
et al., 2020). These substances could enter into human organisms
through the drinking water ingestion pathway.
A source for drinking water has to be free of pathogens and its
quality has to be identified with the help of physico-chemical and
biological parameters (Chabukdhara et al., 2017). In order to assess
the quality of a proper drinking water source, different mathe-
matical tools are used all over the world, such water quality index
or heavy metal pollution index. For example, the arithmetic
drinking water quality index (DWQI(A)) and DWQI convert the data
regarding the water quality into numerical expressions, indicating
the quality status of water sources (Ponsadailakshmi et al., 2018).
Heavy metal pollution indices (HPI) are efficient tools in assessing
the pollution status, based on the heavy metal contents
(Ghaderpoori et al., 2018). The importance of these methods is
given by the possibility to convert quantitative data into qualitative
data, improving the quality assessment of water and offering clues
regarding the degree of contamination.
The Romanian inhabitants from rural and urban areas use
groundwater and bottled water as sources of drinking water. The
groundwater originates from alluvial deposits and presents high
amounts of nitrogen compounds due to agricultural activities
(Dippong et al., 2019; Hoaghia et al., 2019). Thereby, the ground-
water ecosystems and the human health must be frequently
assessed, by monitoring the heavy metals content and other
chemical contaminants (Belkhiri et al., 2017). In this direction, in
order to evaluate the potential human health risk, the chronic daily
intake (CDI) through water ingestion and the hazard quotient (HQ)
are calculated.
Multivariate analysis is widely used in assessment of complex
data (differentiation and classification of waters with different
composition based on major trace elements and/other chemical
parameters) (Belkhiri et al., 2017; Devic et al., 2014). Among the
different multivariate techniques, cluster analysis (CA) has become
accepted in classifying the samples by indicating different degrees
of similarities based on their chemical characteristics.
There are several studies regarding the chemical composition of
spring and mineral bottled water from Romania, such as Konczyk
et al. (2019) or Carstea et al. (2016). Although the requirement for
the drinking water obtained by the supply systems is increasing in
Romania, there are regions in the country where the inhabitants
have no access to a drinking water source except the bottled water.
These findings represent only a small part of the study research; the
drinking water obtained by the supply system is an important so-
lution from the economical part of view as well (the price of 1 L of
bottled water is comparable with the price of 1 m3 of drinking
water).
The novelty and originality of the study consists on the
following specific aspects: (I). Developing and improving a chem-
ical model based on the distribution of significant physico-chemical
parameters, such as 26 elements (including elements as Li, B, V, Ga,
Mo, Ag, In, Tl, Bi Sr, Ba which were not sufficient studied in other
studies) for different 14 bottled water brands from Romania; (II).
Applying for the first time a quality, pollution and risk assessment,
by using comprehensive indices, offering scientific evidence and
basic data (water environment risk management and water pollu-
tion prevention) regarding the 14 bottled waters brands.
This study is significant and valuable from the point of view of
environmental protection, identifying diverse and toxic metals in
small and high amounts in the content of the groundwater
presuming potential effects on the human health trough ingestion.
The study is important for research in medicine, offering informa-
tion regarding the concentration of each type of water, creating
perspectives for future studies on effects on organs or even iden-
tifying some diseases.
2. Materials and methods
2.1. GIS distribution of bottled water site
Geostatistics is used in spatial distribution of contaminated
drinking water sources with heavy metals; starting with the sam-
pling sites, those methods became one of the modelling methods
used in sustainability studies and water resources management
(Belkhiri et al., 2017).
A number of 14 bottled water brands (AP1-AP14, AP- Apa
Potabila meaning Drinking Water) which utilize the groundwater as
source of drinking water, distributed in all mountain areas from the
Romanian Carpathian Mountain Chain were collected in this study
(Fig. 1).
The origin of bottled water is significant to be established and
assessed, as well as the natural conditions of the parent water in
order to control the quality of water for market regulators. The
natural sources of waters confirm the similarities between the
bottled waters (Dotsika et al., 2010). Generally, groundwater is the
source for bottled waters, which is pumped or directly bottled at
the source. In order to make accurate interpretation via the data
regarding the quality of water, a significant role is played by the
information regarding the hydrogeology and geology of the West-
ern and Eastern Carpathian Mountains from Romania. Precipitation
infiltrates through the fault system to the granite or altered rocks
feeding the primary aquifer. As water flows deeply, aquifers are
enriched by minerals (Petrovic et al., 2010). The Romanian Carpa-
thians are part of the Carpathian Mountains Chain, situated in the
Central and Eastern Europe. The groundwater sources originate
from all three main divisions of the Carpathians: Orientali Carpa-
thians (volcanic mountains, such as Oas, Gutai, Calimani, Gurghiu
and Harghita Mountains; characterized by a complex structure
mostly made up by siliciclastic, calcareous and limestones), Occi-
dentali Carpathians (having mosaic structure represented by
limestone, conglomerate, volcanic and crystalline rocks) and Mer-
idionali Carpathians (are typical Alpine chain with the highest
peaks from the Romanian mountains represented by Moldoveanu
Peak- 2544 m; characterized by complex structure generally made
up by metamorphic rocks and deeply eroded structures). The main
rock formations are represented by crystalline, metamorphic and
also volcanic rocks (Negm et al., 2020; Stefanescu et al., 2006). In
volcanic areas the geological formations are represented by ancient
rocks (proterozoic) and newer rocks (neogene). The ancient rocks
are represented by sedimentary rocks such as sandstone, lime-
stone, marl, clay while the igneous rocks are basalt, granite, and
volcanic tuffs. The new rocks are the product of volcanic activities of
volcanic mountains: flows of andesitic pyroclastic breccias, dacitic
intrusions, dioritic and microdioritic lava (Ion et al., 2019). The
rocks hosting the aquifers used as water sources for bottled
 T. Dippong et al. / Environmental Pollution 267 (2020) 115409
Fig. 1. Location map of the studied bottled waters.
drinking water are usually carbonate rocks (limestone, calcareous
conglomerates), pyroclastites, andesites, detrital sedimentary de-
posits, sandstones or crystalline shale (Feru, 2012).
The brands of bottled waters as well as their sources and data
regarding the geochemistry (details regarding the beds of different
rocks of the studied bottled waters samples) are presented in table
5. (Supplementary material). Generally, the quality of water is
influenced by the geological structure (Petrovic et al., 2010).
The bottled waters (volumes of 2.0 and 2.5 L) were bayed from
stores in April, May and July of 2019. Samples were transported and
kept at low temperature to the laboratory until the chemical
analysis. Before the analysis, the bottles were homogenised and
transferred into clean beakers. Water was filtered by using 0.45 mm
acetate cellulose filters in order to determine the elements and
anions. Distribution maps were used in order to show the varia-
tions of chemical parameters (11 physico-chemical parameters and
13 elements) specific for diverse areas of the Romanian Carpathian
Mountains. The maps were elaborated by using ArcGIS software.
We used the mean values for each brand of bottled water (obtained
from the three lots collected in the three months), due to the
purpose of the study which was to analyse in a detailed manner as
many physico-chemical parameters as it could; also, comparing
diverse water brands that could offer more information regarding
the water quality and about the potential effects on health. No
temporal distribution was followed, because the aim was to high-
light the critical maximum and minimum values with direct impact
on human health. We consider the obtained results regarding the
metal content novelty and interests for other research studies. The
main reason why such a consistent number of elements were
studied is due to the dependence of the quality of water to the
technological processes of purification and bottling. Nowadays,
3
there is no technology for neutralize and eliminate many of those
metals from the sources of waters used by the inhabitants for the
drinking purpose. Natural neighbour interpolation was used in
order to obtain the distribution maps. The interpolations algorithm
applies weights to the closest subset of input samples to a query
point (Dippong et al., 2019). The geographic information system
(GIS) was used for obtaining the spatial distribution maps of the
physico-chemical parameters. The maps delineate the areas with
low and high amounts of concentrations of the chemical parame-
ters. ArcGIS software was used for interpolation and elaborating the
spatial distribution maps (Dippong et al., 2019). This method does
not extrapolate minimum and maximum values, which means that
the values represented on the maps fit in a minimum-maximum
ratio of the parameters. Also, it highlights growing and lowering
values of the parameters into coloured areas around the sampling
sites. For each map, the true north and the scale (constant elements,
such as the legend, and variable elements, such as the minimum
and maximum values of each indicator) were represented.
2.2. Experimental methods
A number of 12 physico-chemical parameters (ammonium, bi-
carbonate, electrical conductivity, carbonate, chemical oxygen de-
mand, chloride, nitrate, nitrite, pH, sulphate, total hardness,
turbidity), 9 elements (Li, B, Na, Mg, Al, K, Ca, Sr, Ba) and 17 heavy
metals (V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Mo, Ag, Cd, In, Tl, Pb, Bi)
were analysed. A variety and relatively high number of elements
was studied with the aim of creating a vision concerning the
possible effects of elements on the quality of water. On the other
hand, we could consider Li, Sr and Ga as elements presented for the
first time, so contributing to the originality of the paper. The quality
4 T. Dippong et al. / Environmental Pollution 267 (2020) 115409

indicators, as well as the constituents of bottled water samples correlation between the analysed metals. CA was formulated based
were analysed using standard procedures. The pH and the electrical on the Ward-algorithmic method and the Euclidean distances were
conductivity (EC) were determined immediately after opening the employed for measuring the distance between the water samples
bottles. The EC was measured with WTW INOLAB 740 conductivity in the multidimensional space of metals content. This is a widely
meter according to SR EN 27888-1997. pH was measured following used method in the cluster analysis of environmental data with
the standardized method SR ISO 10523-2012, using HI 253 Hanna correlated variables (Belkhiri et al., 2017). The data were statisti-
Instruments pH meter, equipped with a combined pH electrode. cally analysed using the Statgraphics software and Excel facilities.
Turbidity was determined with a WTW turbidimeter according to Due to significant departures from a normal distribution of metals
SR EN ISO 7027/2001 method. Bicarbonate (HCO
3 ) and carbonate concentrations in the bottled water samples, before the cluster
(CO2

3 ) anions according to the methodology described by the analysis a logarithmic operator was used.
American Public Health Association APHA (American Public Health
Association APHA, 1992). The total hardness (ht) was determined by
EDTA titrimetric method in the presence of the complexometric 2.4. Drinking water quality index (DWQI) and the arithmetic
indicator Eriochrome Black T according to SR ISO 6059-2008. DWQI(A)
Chemical Oxygen Demand (COD) was established by SR EN ISO
8467-2001 method. Chloride anion (Cl
) was analysed by precipi- The DWQI (Drinking Water Quality Index) and the arithmetic
tation titration according to ISO 9297-2001. Ammonium (NHþ 4 ) was DWQI(A) represent efficient mathematical instruments in convert-
analysed by a standardized spectrophotometric method according ing significant data quantities (regarding the water quality) into a
to SR ISO 7150-1:2001 using a Specord 50 Analytik Jena UV-VIS number, reflecting an objective quality status of drinking water or
spectrophotometer (detection limit of the method is 1.0 mg/L). Ni- bottled water (Ponsadailakshmi et al., 2018). This methodologies
trates (NO
3 ) were analysed by SR ISO 7890-3-2000 spectrophoto- were calculated in four steps: 1. selection of the chemical param-
metric method with sulfosalicylic acid in alkaline medium. The eters with significant impact to health and potability affinity; 2.
concentration of nitrites (NO
2 ) was measured according to SR ISO sub-index development, where different units of the physico-
6777-2002, using a Specord 50 Analytik Jena UV-VIS spectropho- chemical indicators are converted to a common scale and for
tometer. Concentrations of sulphate anion (SO2
4 ) were measured each and every chemical indicator a rating value (0e100) is given,
with a Perkin Elmer Lambda 25 spectrophotometer in comparison established by comparison with the acceptable limits according to
with the standard sulphate solutions. The detection limits for the Romanian Law 311 from 2004; 3. weightage assignment for the
anions were: 2.0 mg/L for HCO
3 ; 0.2 mg/L for SO4
2

and Cl
; physico-chemical indicators, calculated according to equation (1);



0.02 mg/L for NO3 and 0.4 mg/L for NO2 . 4. the last step is represented by the use of the aggregation func-
Elements were determined by inductively coupled plasma mass tion, which groups the weight factors and sub-indices of all
spectrometry using a Perkin Elmer NexlON 300S Inductively physico-chemical parameters, by using the aggregation index (Ai)
Coupled Plasma Mass Spectrometry (ICP-MS) following a stan- calculated with the help of the group physico-chemical parameters
dardized protocol (SR EN ISO 15586-2004). For the extraction of (GQ1-4), as equation (2) shows (Ponsadailakshmi et al., 2018;
elements, Suprapure 65% HNO3 (Merck) and ultrapure water Boyacioglu, 2007):
(Merck Millipore) were used. Calibration was performed with
multi-elements calibration standards (starting from a Multi- Wt
W ¼ Pn (1)
i¼1 ðWt Þi
element standard solution, 1000 mg/L, Merck) prepared by serial
dilutions of the stock solution. Quality assurance of analytical data
was realized by using internal standards for the control of signal where, W represents the weight factor of the chemical indicator, Wt
drifts. Also, accuracy was established by measuring quality control is the temporary weight and n represents the total number of the
samples immediately after calibration and after every ten samples. chemical parameters; the values were adapted according to
The detection limits of metals were 0.25 mg/L for Al and K, 0.9 mg/L Ponsadailakshmi et al. (2018).
for Ga and Li, 1.0 mg/L for Cu and Mn, 1.1 mg/L for Sr, 1.25 mg/L for Fe; nh i nh i nh i
1.5 mg/L for Ba, 2.0 mg/L for As, Ag, Bi, Cd, Crt, Co, In, Mo, Ni, Pb, Tl, Zn Ai ¼ ðGQ 1Þ0:147  ðGQ 2Þ0:132  ðGQ 3Þ0:206
and V and 2.5 mg/L for B, Ca, Mg, Na. nh io (2)
All the reagents were high purity (Merck). Ultrapure water was  ðGQ 4Þ0:279
used for reagent preparation and analysis. Each sample from each
brand was analysed for the same physico-chemical parameters where, GQ 1 ¼ ½ðSIpH Þ0:180   ½ðSIEC Þ0:200   ½ðSINa Þ0:200  
(ammonium, bicarbonate, electrical conductivity, carbonate,
½ðSICl Þ0:200   ½ðSISO4 Þ0:220 
chemical oxygen demand, chloride, nitrate, nitrite, pH, sulphate,
total hardness, turbidity), elements and metalloids (Li, B, Na, Mg, Al, h 0:188 i h i h i
K, Ca, Sr, Ba) and heavy metals (V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, GQ 2 ¼ SIHCO3  ðSITh Þ0:188  ðSICa Þ0:188
Mo, Ag, Cd, In, Tl, Pb, Bi). The measurements of each standard so- h 0:188 i h i
 SIMg  ðSIFe Þ0:250
lution or sample were realized in triplicate. Standard solutions
were used for quality control of the determination of elements and
h 0:213 i h 0:213 i h i
anions both for calibration and checking. Blank test were carried GQ 3 ¼ SINO3  SINO2  ðSIMn Þ0:191
out for each parameter and each set of samples. h i
 ðSIZn Þ0:191
2.3. Cluster analysis
h i h i h i h i
Cluster analysis (CA) was performed to group the water samples GQ 4 ¼ ðSICd Þ0:228  ðSICr Þ0:228  ðSICu Þ0:158  ðSINi Þ0:158
that show similarity regarding the metals content. Cluster analysis h i
was performed both in Q-mode and in R-mode. Q-mode CA was  ðSIPb Þ0:228
performed to identify clusters of similar sites on the basis of simi-
larities within a class, whereas R-mode CA was used to show the
 T. Dippong et al. / Environmental Pollution 267 (2020) 115409 5

   indicated by the Contamination factor (Cf), which are calculated by

Ai using equations (8) and (9) (Biswas et al., 2017; Backman et al.,
DWQI ¼ Ai þ 10 
0:5 (3)
Min þ Max 1998):

X
n X
n
DWOI:ðAÞ ¼ ðSIi  Wi Þ (4) Cd ¼ Cf (8)
i¼1 i¼o

In this study, DWQI and DWQI (A) were computed with the help
CA
of two different equations (3) and (4), according to Cude (2001) and Cf ¼
1 (9)
CN
Ramesh et al. (2010), in order to avoid misinterpretation of the
results. The minimum and the maximum quality among the four where, CA is the measured concentration of the heavy metal and CN
GQ is represented by Min and Max, which were applied in order to is the MAC of the heavy metal, according to the Romanian
optimize any environmental conditions and the deviation with Ai. Legislation Law 311/2004, regarding the drinking water (Biswas
The drinking water quality status, according to the DWQI scores et al., 2017).
is classified into six categories, such as: excellent (DWQI ¼ 95e100), The Cd classifies the water into one of three pollution degrees,
good (DWQI ¼ 85e94), fair (DWQI ¼ 75e84), marginal namely low (Cd < 40), medium (Cd ¼ 40e80) and high (Cd > 80)
(DWQI ¼ 60e74), poor (DWQI ¼ 59-40) and very-poor (DWQI< 40) (Biswas et al., 2017; Bhuiyan et al., 2010).
(Ponsadailakshmi et al., 2018).

2.7. Human health risk assessment

2.5. Pollution indices (heavy metal pollution index (HPI) and heavy
metal evaluation index (HEI)) A straight and short pathway of the toxic chemicals into the
human or animal body are the inhalation, food chain and dermal
The overall quality of the drinking water with respect to heavy contact (Demir et al., 2015; Muhammad et al., 2011). For non-
metals was indicated by using pollution indices, such as the heavy carcinogenic risk, the hazard quotient (HQ) can be calculated, as
metal pollution index (HPI), heavy metal evaluation index (HEI) and equation (10) shows:
the degree of contamination (Cd) (Ghaderpoori et al., 2018;
Sobhanardakani, 2016; Prasanna et al., 2012). The HPI is calculated CDI
HQ ¼ (10)
with the help of equations (5) and (6), as it follows: RfD
Pn
i¼1 Wi  Qi C  DI
HPI ¼ Pn (5) CDI ¼ (11)
i¼1 Wi BW

X
n
Mi ð
ÞIi
Qi ¼  100
Si
I i
i¼1
where, n is the total number of the heavy metals concentrations, Wi
represents the unit weightage and Qi the sub-index of the ith in-
dicators. The sign (
Þ specifies the numerical variances of the two
values, overlooking the algebraically meaning. The monitored
heavy metals are represented by Mi, while Ii and Si signify the ideal
and the maximum allowable concentrations (MACs) of the heavy
metals. The HPI values reflect the pollution status with respect to
heavy metals, classifying the water samples into three pollution
categories, such as high (HPI> 100), indicating a source of water
with no drinking purpose; second category is the threshold risk
where, CDI represents the chronic daily intake through water
(6) ingestion, RfD is the oral toxicity reference dose, C is the concen-
tration of the chemical indicator (mg/L), DI is the daily intake (2 L/
day) and BW indicates the body weight (72 kg). The HQ results
specify if the exposed individuals are safe or could be exposed to
health risks (HQ > 1.0) (Demir et al., 2015; Muhammad et al., 2011).
3. Results and discussion
3.1. Spatial distribution analysis
Table 1 exhibited the physico-chemical parameters (ammonium
- NHþ

4 , bicarbonate - HCO3 , electrical conductivity - EC, carbonate -

(HPI ¼ 100) and the third category is the low pollution (HPI < 100) CO3 , chemical oxygen demand - COD, chloride - Cl
, nitrate - NO



3,

(Ghaderpoori et al., 2018). nitrite -NO
2

2 , pH, sulphate -SO4 , total hardness - ht, turbidity - T,

This index offers as well a water quality grade based on the
heavy metals contents, according to the study of Edet and Offiong
(2002) and Biswas et al. (2017); it can be calculated by using
equation (7):
Xn
HC
HEI ¼
i¼0
H MAC
where, HC and HMAC are the obtained concentrations and the MAC
of the studied heavy metal. HEI results indicate low (HEI < 40),
medium (HEI ¼ 40e80) or high (HEI > 80) degree of pollution
(Biswas et al., 2017; Bhuiyan et al., 2010).
2.6. The degree of contamination (Cd)
The Cd summarizes the combined effects of heavy metals,
the elements (Li, Na, Mg, Al, K, Ca, Sr, Ba) and the heavy metals (Mn,
Fe, Cu, Zn, Ga). The B, V, Cr, Co, Ni, As, Mo, Ag, Cd, In, Tl, Pb, Bi). The
amount of contaminants present in the water sample was generally
low. Thus, the drinking water samples show values higher than the
MACs only for few parameters and few cases (bolded in Table 1).
The standardized skewness and kurtosis indicated whether the
(7) water samples have a normal distribution. CO2
3 were found only in
AP2, with an amount of 88 mg/L. Fig. 2 shows the distribution maps
for the quality of the bottled water (EC, COD, pH, T, ht, chloride,

þ


SO2

4 , HCO3 , NH4 , NO3 , NO2 , Cu), while Fig. 3 indicates the distri-
bution maps for the metal content (Li, Na, K, Ca, Mg, Ba, Sr, Al, Ga,
Fe, Mn, Zn).
The pH distribution (Fig. 2a) characterizes the biological and
chemical processes and showed values between 6.65 and 8.03
(except AP2, situated in the northern part of the country, which has
a 9.52 pH, exceeding the MAC), indicating that the waters are
neutral and weak basic. A different pH values as 7.0, could be caused
6 T. Dippong et al. / Environmental Pollution 267 (2020) 115409

by the hydrolysis of strong base salts, weak acids and dissolved

3.78
1.88
3.00
14.4
14.6
2.29
4.31
13.3
2.46
4.84
34.5

1.79
1.38
1.38

15.9
31.4

4.99
8.57
mg/L mg/L mg/L mg/L mg/L mg/L

121

121

197
gases (carbon dioxide, hydrogen sulphide and ammonia)
Ga

e
(Chabukdhara et al., 2017). The pH has the ability to influence most

5000
4.33
1.75
1.08
1.33
0.89
1.74
6.17
1.95
6.71
1.74
1.14
2.72
1.34
0.80
0.80
6.70
2.40
1.90
80.5
2.36
0.94
of the chemical and biological reactions, but no direct impacts on
Zn

the human health (Adimalla and Qian, 2019; Udhayakumar et al.,

3.02
1.69
1.74
1.66
1.38
1.64
1.33
1.64
16.7
1.56
1.06
1.42
1.38
1.19
1.06
16.7
2.67
4.06

5.59
10.4
152

100
Cu

2016). The dissolved carbon dioxide, forming the carbonic acid in

1.45
1.84
5.43
5.15
5.15
4.03
1.39
7.81
17.5
4.88
10.0

3.44
7.67
1.39

26.4
76.9

5.69
10.6
a water system, determines the pH (Udhayakumar et al., 2016).

293

293

292

200
Fe

Generally, the pH values increase with the altitude from weak acid

55.8
5.01
1.46
2.26
1.74
1.94
1.65
1.44
1.38
39.3
1.28
1.68

1.71
1.05
1.05
55.8
8.40
16.9

3.75
3.88
50.0
201
Mn

to weak base. So that sample AP1 localized at the lowest altitude

has a pH of 6.65, while sample AP13 situated at the highest altitude
12.9
1.90
10.4
49.2
3.60
8.20
14.8
48.2
8.50
16.9

1.90
3.40
1.90

85.9

5.53
10.2
126
896

896

235
274

700
Ba

(almost 1200 m) is characterized by a pH of 7.88.

7000
A significant characteristic of water is represented by the EC,
35.3
8.49

41.4
46.2
11.8

38.4
64.0

4.87
47.8
28.6
4.87

97.2

5.64
10.5
mg/L

158
254

360

262

360
114

288
Ca mg/L Sr

helping measuring the ionic amounts. A high value of EC indicates a

high amount of total dissolved solids and salinity (Adimalla and
0.90
0.10
3.56
4.00
0.06
2.37
0.67
5.00
0.71
2.37
4.81
22.8
1.15
1.49
0.06
22.8
3.57
5.79
0.16
4.92
8.54
Qian, 2019). A high value for the EC (Fig. 2b) was found in the

100
adjacent mountain area of the Carpathian Mountain Chain (AP8
10.1
6.19
0.30
1.04
0.52
1.26
2.97
2.15
2.91
2.53
1.86
5.86

0.42
0.83
0.30
10.1
2.78
2.81

2.52
1.95
10.0
mg/L mg/L

101 and AP10 characterized by EC ranging from 585 to 691 mS/cm),

K

directly proportional to the total dissolved matter. EC depends on

1.04
10.6
13.9
1.40
2.44
1.38
1.12
0.82
77.2
1.74
0.64
6.97
1.34
0.72
0.64
77.2
8.66
20.1

5.33
9.58
233

200
Na mg/L Mg mg/L Al

the mobility, relative and total concentrations of ions and their

availability (Shah et al., 2019; Udhayakumar et al., 2016). A high
Quality index parameters, metals and heavy metals characteristics and summary statistics of the studied bottled water samples from groundwater sources.

0.33

value for the EC is the effect of geochemical processes and

7.98
0.09
2.87
1.25
2.06
11.0
2.85
7.30
1.48
0.12
10.1
0.12
0.76
1.58
0.09
11.0
3.54
3.85
0.11

50.0
1.6

anthropogenic activities and is the result of salts enrichment in

water, due to the evaporation process followed by dilution caused
by the infiltrated rain water in the groundwater (Chabukdhara
0.05
0.04
10.3
0.72
2.20
0.61
0.46
4.90
2.80
1.06
0.05
0.05
0.56
0.85
2.20
10.3
1.76
2.80
0.16
3.89
5.31
200

et al., 2017; Adimalla and Qian, 2019). A high value of EC in-

83.7
14.1
13.6
1.82
1.62
1.44
1.38
9.86
1.22
3.91
18.6

1.17
0.94
0.90

19.1
34.8

3.52
3.40
30.0
NTU mg/L

creases the values of the quality index, giving the water unsuitable
114

114

182
Li

purpose for drinking (Shah et al., 2019).

11.1
0.08
0.12
0.60
0.14
0.08
0.09
0.12
0.08
0.46
0.16

0.11
0.09
0.16
0.08
11.1
0.97
2.92

5.69
0.62
5.00
306

The COD (Fig. 2c) represents an indicative measurement of

T

organic matter and inorganic oxidic compounds such as nitrites,

min 5
6.61
1.35
2.71
8.75
5.94
12.0
3.81
16.7
16.3
16.3
88.6
8.40
7.95
7.85
1.35
88.6
14.5
21.9

5.22
9.37
151

sulphur and ferrous salts (Dippong et al., 2019; Li et al., 2020). The
d
4 mg/L ht

MAC ¼ Maximum allowable concentration in drinking water, according to Law 311/2004 and NGU Report 2012.073.


high COD values in samples AP7 and AP10 are result of the
organically and inorganically leaching from contaminated under-
SO2

layers, leading to groundwater contamination, thus to contamina-

4.34
7.19
103

250
2.5
2.0
1.8
0.7
0.3
0.7
2.5
9.2
0.9
2.8
0.7
1.3
2.5
2.0
0.3
9.2
2.1
2.2

tion of the bottled water (Brenton-Deval et al., 2019; Varol, 2020).

6.5e9.5

Suspended matter (fine inorganic particulate, micro-organisms,

9.52
6.65

6.87
8.03
7.29
7.52
7.54
7.40
7.50
7.50
6.67
7.55
7.88
7.79
6.65
9.52
7.55
0.70
9.31
2.39
3.42

suspensions) gives the turbidity of water (Dippong et al., 2019). The

3 mg/L NO2 mg/L pH

turbidity (Fig. 2e) is the reduction of transparency due to the

presence of particulate matter, such as clay or slit, finely divided

0.25
0.002
0.008
0.004
0.005
0.007
0.005
0.004
0.002
0.005
0.004
0.002
0.005
0.002
0.002
0.002
0.008
0.004
0.002

47.7
0.84

0.50

organic matter, plankton or other microscopic organisms. Due to

the attachment of the microorganisms to the particles, the low
values of the turbidity indicated a reduced microbial contamination
degree (WHO, 2011). Generally, the turbidity distribution for
COD mg/L Cl
mg/L NO

50.0
1.85
0.20
2.66
11.6
5.35
3.18
1.65

5.90
20.8
0.16
1.76
2.06
1.81
0.16
50.0
7.78
13.6

4.35
6.56
50.0
172

studied bottled waters is uniform and low, except for AP11, which
exceeded twice the MAC, probably caused by organical or inor-
21.3
20.6
0.70
18.4
2.12
2.83
14.2
26.6
5.67
30.5

22.0
21.3
1.41
0.70

22.9
33.3

4.81
8.36

ganical particles of colloidal matters. A high value of turbidity

133

133

146

250

(presence of suspended matter e support for germs) could be a

source for epidemiological hazards. This parameter is influenced by
high volumes of precipitations, by carrying the deposited sedi-
2.40
3.20
0.85
1.28
0.96
0.48
5.44
1.68
0.64
5.12
2.24
1.60
1.60
1.28
0.70
0.48
4.96
2.06
1.55
75.4
2.14
5.00

ments through the water body.

mS/cm

High chloride content (Fig. 2g) was observed in more populated

0.59
2500
61.9

90.6

61.9

58.6
0.48
485
261

295

472
105
585
472
691
373
305
236
171

691
329
193

areas, inducing a salty taste, as in sample AP11. Groundwater is rich

4 mg/L HCO3 mg/L EC

in chloride due to the content of salts in the rocks and sediments,

precipitations or due to the use of CaCl2 in roads defrosting. In cases

of low alkalinity and high chloride content, the corrosion of water

62.9
50.0

53.7

77.3

50.1

72.9
1.37
307

258

291

486
429
466
755
285
214
165

755
278
203

0.6
e

enhances electrical conductivity. Sample AP11 is characterized by a

high value of chloride (133 mg/L), which could corrode the iron
pipes or plates, affect the crops and could induce laxative effects if it
0.013
0.160
0.006
0.011
0.005
0.006
0.012
0.080
0.007
0.009
0.005
0.007
0.013
0.012
0.005
0.160
0.025
0.043
Altitude m NHþ

4.34
6.15
0.50
176

is consumed (Adimalla and Qian, 2019). Furthermore, people with

kidney and heart diseases may be affected by a drinking water rich
in chloride (Udhayakumar et al., 2016).
1030

1170
1150

1200
1100

Sulphate is a significant water quality indicator, especially when

280
760
825

870

660
900
980
590
610

e
e
e
e
e
e
e
e

high amounts could induce negative effects on human health, such

Std.Kurt
Sample

as laxative effects, respiratory disorders, gastric cancer, birth mal-

CV(%)
Mean

MACa
Table 1

Skew
AP10
AP11
AP12
AP13
AP14

Max
Min
AP1
AP2
AP3
AP4
AP5
AP6
AP7
AP8
AP9

formations of arterial hypertension in cases of high concentrations

SD

of nitrates (Chabukdhara et al., 2017; Varol, 2020). The highest

 T. Dippong et al. / Environmental Pollution 267 (2020) 115409 7

Fig. 2. Distribution maps for the pH (a), EC (b), COD (c), Cu (d), T (e), ht (f), Cl
(g), SO2

þ


4 (h), HCO3 (i), NH4 (j), NO3 (k) and NO2 (l) content.
8 T. Dippong et al. / Environmental Pollution 267 (2020) 115409

Fig. 3. The Li (a), Na (b), K (c), Ca(d), Mg(e), Ba(f), Sr(g), Al(h), Ga(i), Fe(j), Mn(k), Zn(l) distribution maps for bottled water samples from groundwater sources.
 T. Dippong et al. / Environmental Pollution 267 (2020) 115409
amounts of sulphates were found in AP8, situated in a mountain
area. Samples AP8 is characterized by a noticeable amount of sul-
phate, having as source the input of sulphur due to the volcanic
activity (Frengstad et al., 2010). Sources for sulphates are also sul-
phate minerals and gypsum solution, while for the rest of the water
samples are the medicinal and high mineralised waters (Fugedi
et al., 2010 and Petrovic et al., 2010).
The total hardness of water is given by the amount of calcium,
magnesium, bicarbonates, carbonates and sulphates, having the
ability of increasing the boiling point of water (Udhayakumar et al.,
2016). A ht value was found in sample AP11, which can be consid-
ered a very hard water (88.6 d), while samples AP2, AP3 and AP7
have a lower ht than 5 d, being considered soft waters, while me-
dium ht characterized the rest of the samples. The ht content could
lead to other hard soluble compounds which could cause deposits
in plastic flasks, but also in ceramic containers from which the
water is consumed.
An unpleasant taste of water is given by a high value of ht,
causing deposits of salt at the bones, kidneys, hypertension, stroke,
osteoporosis, and colorectal cancer (Dippong et al., 2019; Adimalla
and Qian, 2019). Long exposure to hard water could lead to car-
diovascular disorders, parental mortality or cancer (Chabukdhara
et al., 2017). Sources of high ht are represented by industrial and
urban waste waters or rock leaching, which could lead to foaming
or calcium carbonate deposits in the metal installations (Nedeau
et al., 2003). Soft waters have a low buffer capacity, and could be
more corrosive in metal installations (WHO, 2011).
Calcium has important properties in bone growth. Sources of
calcium in water are represented by limestone, but also by indus-
trial discarded and waste waters (Udhayakumar et al., 2016). A high
amount of calcium (in case of AP12) increasing the pH up to 7.55,
acting like a buffer (un-carbonated water) against carbonated wa-
ters (Frengstad et al., 2010). Magnesium is another element with
important benefits, ensuring the well-functioning of cells in the
enzyme activation, although a high amount of magnesium has
negative effects on the human body, such as laxative effects, nausea
or even paralysis (Udhayakumar et al., 2016; Adimalla and Qian,
2019). Also, high amount of Mg could help in preventing diverse
diseases, such as heart arrhythmia, hypertension, nervous system
and endocrinologic diseases and in regulation of the levels of blood
sugar (Petrovic et al., 2010). Mg is present in a relatively high
amount (AP6 - 11 mg/L), due to minerals transferred from
groundwater sources or anthropogenic activities (use of chemical
fertilizers, household effluents, due to the serpentine) (Petrovic
et al., 2010; Dinelli et al., 2012; Devic et al., 2014).
In most of the regions, bottled waters have a relatively high
amount of bicarbonates, due to the natural dissolution of rocks and
soil (Devic et al., 2014), while sulphates and chlorides are lower
than the MACs.
Dissolved CO2was distributed among the weak acids of the
carbonate system, as reaction R1 indicated; the HCO
3 is the most
frequent anion in water, and indicated the ionization (dissociation)
in CO2, as the most important proton source. Reaction R2 indicated
the release of Ca2þ and HCO
3 in the groundwater. The alkalinity has
two main sources, namelly the disolved CO2 and CO2
3 content
(Albu et al., 1997). The CO2
3 hardness is given by the sum of the


CO2

3 and HCO3 , which could be removed by precipiation or boiling.
The carbonates content depends on the pH, temperature, cations,
dissolved CO2 and dissolved salts (Shah et al., 2019).
H2 O þ CO2 %H2 CO3 %Hþ þ HCO
þ 2
3 %2H þ CO3 (R1)
CaCO3 þ H2 O þ CO2 %Ca2þ þ 2HCO

3 (R2)
Limestone influences the water properties by enriching it with
9
bicarbonate and calcium, resulting HCO3eCa type of waters
(Frengstad et al., 2010). High concentrations of HCO3 (AP11-
755 mg/L) and Ca (AP12e22.8 mg/L) are due to the weathering of
calcium feldspars in magmatic rock sand limestone (Petrovic et al.,
2010).
A nitrogen source could be the intense use of fertilizers in the
agricultural activities (difference in fertilizer application rate and
pesticides), organic degradation of the waste and infiltration of the
untreated waste water directly into the soil texture, hydrological
conditions (rainfall) and local pedo-climatic variability (Devic et al.,
2014). On the opposite side, enrichment with ammonium, nitrate
and nitrite occur due surface pollution; certain nitrogen com-
pounds are characterized by sensitivity at oxidation throughout
different processes, which make differences between the bottled
water, such as between AP2, AP4, AP8, AP10 or AP11 (Fugedi et al.,
2010). The high amount of NHþ 4 indicated that the origin of water is
represented by areas rich in oil and gas resources (Petrovic et al.,
2010). Ammonia results after incomplete degradation of nitrogen
compounds (Dippong et al., 2019). Generally, the ammonia content
is lower than the MAC; AP12 presents the highest concentrations of
ammonia which could induce negative health effects, because it
could easily react with chlorine, reduce the free chlorine and form
chloramines (WHO, 2011). AP8 presents the highest nitrate content
(Fig. 2), exceeding the MAC, which by consumption reduces the
oxygen from water. Sources of nitrates are represented by agricul-
tural activities (use of animal wastes, fertilizers) and domestic
practices (septic tanks leakage, household waters) (Adimalla and
Qian, 2019). A high amount of nitrate causes hypertension, can-
cer, congenital malformations, thyroid disorders and goitre
(Dippong et al., 2019). Sources of nitrite are chemical and animal
manure fertilizers, degradation of organic waste, industrial dis-
charges and leaching from waste deposits (Chabukdhara et al.,
2017). A lower concentration of nitrite is reflected in a short
range distribution. The mineralization of organic compounds is a
source for nitrites, which could action as raw material in the protein
synthesis or other nitrogen compounds (Dippong et al., 2019).
A high amount of metals (Fig. 3) in groundwater has different
sources, such as the landfill discharges, urban leakage, contami-
nated surface waters, chemical fertilizers, herbicides and pesticides
leakage (Belkhiri et al., 2017; Chang et al., 2017; Huang et al., 2008).
Some of the metals are considered essential for human health, yet
the use for consumption of water characterized by a poor-quality
could lead to different health problems, and the use for irrigation
could lead to reduction in agricultural productivity (Devic et al.,
2014). Other contamination causes with heavy metals are the
anthropogenic activities amplified by natural factors, such as pre-
cipitations, geology, slope and water withdrawal, solid waste and
different strong polluted areas leaching (Deeba et al., 2019; Belkhiri
et al., 2017; Chang et al., 2017; Cadar et al., 2015). The levels (in
terms of mass concentration) of metals in the bottled water sam-
ples that were tested herein, showed the following sequence:
Ca>Mg>Na>Sr>Ba>Fe>Li>Ga>Al>Mn>K>Cu>Zn. All metals pre-
sented large variability due to natural and anthropogenic causes.
The presence of heavy metals (Ni, Cu, Zn, Cd, Sb, Pb) is due to the
anomalies caused by the interactions between the water and the
plumbing system, especially in the cases of Pb and Ni, which are
particularly soluble in acid water (Dinelli et al., 2012). The highest
variability was found for Fe, Sr and Ba (above 250%), while Zn, Mg
an K displayed the lowest coefficients of variation (80% for Zn and
about 100% in the cases of Mg and K).
Lithium is the lightest alkali-metal element and it is used as a
reactive salinity tracer and as water/rocks interactions (Frengstad
et al., 2010). The lithium amount decreases with the increase of
the altitude, so that sample AP12 at altitude 610 m has a lithium
content of 225 mg/L, samples AP1 (altitude 280 m) has 83.7 mg/L Li
10 T. Dippong et al. / Environmental Pollution 267 (2020) 115409
and sample AP13 (altitude of 1200 m) has 1.17 mg/L Li. Micas and
amphiboles are typical mineral hosts for Li (AP 13), while schists
and granites enrich the water with Li as well (AP1 and AP12)
(Frengstad et al., 2010). The high content of Li in these samples
indicated strong water/rock interactions. Almost all the Li con-
centrations in water were low, except in AP1 that showed a high
content of Mg and also characterized by one of the highest electric
conductivity values, and AP12 that contains high concentrations of
Ca and Fe.
The most dominant cation in water is represented by sodium,
which is an imperative nutrient and extremely important in the
domestic use of water and in agricultural activities. Sources of so-
dium are represented by the weathering processes or by geological
structure represented by alkali feldspar. Though, it presents nega-
tive effect to people with circulatory, renal or cardiac illnesses or
vomiting and hypertension if it exceeds the thresholds
(Udhayakumar et al., 2016; Adimalla and Qian, 2019). Sodium dis-
tribution (Fig. 3b) is relatively uniform. The highest values were
obtained in AP3, suggesting a water-aquifer strong interaction,
caused by the direct cation exchange between the groundwater and
the clay fraction of the aquifer or caused by infiltration of septic
tanks and dissolution of the soil salts of silicate weathering (due to
anthropogenic and agricultural practices, poor drainage, evapora-
tion) (Shah et al., 2019). Water rich in sodium is characterized by a
significant number of micro-components, due to the acidic igneous
intrusions near by the water source and due to the rich minerali-
zation processes (Petrovic et al., 2010). The presence of Na (AP3 -
10.3 mg/L) is due to the water-rock interactions (alkaline volcanics)
as well.
Potassium has a uniform distribution (Fig. 3c), which does not
exceed the MAC; the highest values were obtained for AP1, AP11
and AP12, caused by anthropogenic activities, especially animal
manure used as fertilizers and human wastes (Devic et al., 2014;
Huang et al., 2008). The presence of potassium in water is due to
natural processes and water pollution, although potassium amount
is lower as the sodium amount because of the low solubility and
higher resistance to clay formation and weathering (Udhayakumar
et al., 2016).
Strontium (Sr) is a natural element, ubiquitous in the environ-
ment and occurs in water, food, air, and soils (Jo Melnyk et al., 2019).
Strontium in water is toxic when the concentration surpasses the
limit of 7000 mg/L due to its ability to substitute calcium in bones.
The toxicity is considered more dangerous especially when the Ca
water content is low. All the water samples have lower Sr content
than the MAC (WHO, 2011). AP8 has the highest Sr amount of
360 mg/L, as a result of human activities or natural processes (rock
and soil weathering).
Ga plays no decisive role in the biological cycle, has moderate
toxicity and has no MAC (WHO, 2011). The presence of colloids
enriches the water with Ga, while the water-rock interactions
(amphiboles, micas, schists) and the granite intrusion enrich the
water with Li and B (AP12) (Dinelli et al., 2012; Frengstad et al.,
2010).
AP12 is characterized by high Ba content, higher than the MAC,
with natural sources such as granite (igneous rocks), alkaline
igneous, volcanic rocks and manganese (rich sedimentary rocks)
and lower pH (WHO, 2011).
According to Fig. 3, generally the water samples present uniform
distribution for Al, except AP9 (77 mg/L), which is characterized by
the highest Al content. A possible source of Al is the water treat-
ment plant, due to the use of adjective agent based on aluminium
sulphate.
The distribution of iron and manganese is normal (Fig. 3j and k),
but in AP12 the MACs are exceeded; the high amounts have three
possible sources, namely the industrial effluents, sewerage and
waste leaching (Devic et al., 2014). The high amount of Fe (AP12-
293 mg/L) and Mn (AP12, 55.8 mg/L), exceeding the MACs are results
of the presence of basic rocks or due to the granite rocks weath-
ering (Petrovic et al., 2010). The atmospheric exposure leads to
oxidation of the ferrous iron to ferric iron, imprinting a brown-red
colour to the water (WHO, 2011). The exposure to Mn could affect
the nervous system, inducing muscular pains, weakness, anorexia,
apathy, slow speech, emotional facial expression, trembling, slow
motion of arms and legs (Michalke and Fernsebner, 2014). AP12 has
the highest Mn content, exceeding the MAC, followed by AP9 which
presents a metallic taste and a specific odour of mud, easily
confused with H2S.
Main sources of Cr, Cu and Zn are the smelting and mining ac-
tivities, machinery and electroplating industry, while for Ni and Zn
the agricultural activities (the use of fertilizers) (Mazhar and
Ahmad, 2020; Zhao et al., 2020). Generally low Cu concentrations
were measured with the highest concentration obtained for AP9,
due to its mobility influenced by the P content and pH. A declining
trend of the Cu mobility is due to the increase of P, and an increased
mobility for Cu is due to the decrease of the pH (Turner et al., 2016).
Gastrointestinal stress, kidney and heart disorders are generated by
high Cu content (Dippong et al., 2019; WHO, 2011).
An essential element is represented by Zn, characterized by a
high mobility in the surface environments (Dinelli et al., 2012). The
zinc distribution (Figure 3l) is uniform for all samples, with the
highest amount obtained for AP7 and AP9. High zinc content could
give to the water an astringent taste and induce opalescence.
Although it plays a main role in physiological, metabolically and
growing processes, as one of the essential microelements it could
be toxic to the organisms in high amounts (Mazhar and Ahmad,
2020; WHO, 2011). Agriculture practices (wheat and rise cultures)
are sources of the Zn enrichment, due to its lack of absorption, by
using micronutrients based on ZnSO4 (Mazhar and Ahmad, 2020).
3.2. Cluster analysis
In Fig. 4a and b cluster diagrams are presented, as a statistical
tool for the classification of complex data based on their similarity
or their difference in Q-mode as spatial distribution and also in R-
mode as resemblance between the characteristics of metals con-
centration in water. The Ward method was used in the clustering
analysis for clusters generation, based on the R-mode Euclidian
distance. Fig. 4c shows the distribution of location of bottled water
samples while Fig. 4d shows their total metal content.
Thus, four main clusters were established: C1- which includes 6
elements grouping waters with a medium content of minerals from
the North-Western, North-Eastern and Curvature Carpathian
Mountains areas (Fig. 4c), C2 with 6 elements which groups the
waters characterized by a low content of minerals (Fig. 4d), located
in North-Eastern and South-Eastern parts of Romania, and C3
which contains a single element, water AP9 being the richest water
in Ca and Cu. C4 contains only AP12 characterized by a high amount
of salts, especially Ba, Ga, Mn and Fe salts. Both clusters C1 and C2
included 42.86% of the bottled water samples while C3 and C4
included 7.14% of samples.
As is indicated in Table 2, the waters included in cluster C1 are
richer in metals than those included in cluster C2, characterized by
metals with low amount. The water samples included in cluster C3
had the highest content of Ca, Cu, Na, Zn, Al and Fe compared to the
other groups. The water samples from cluster C4 is distinguished by
the highest concentrations of Li, Fe, Mn, Ba, Ga and K.
R-mode cluster analyses showed 2 groups: C1 containing 9
metals at low to medium level, some of them strongly correlated:
(Ba linked to the pair Ga-Li); Mn linked to Sr and to K and the group
of Cu, Zn and Al. C2 groups 4 metals found at relative high levels,
 T. Dippong et al. / Environmental Pollution 267 (2020) 115409 11

Fig. 4. Cluster analysis of bottled water samples from Romania: a) Q-mode cluster analysis of bottled water from groundwater samples based on their metal content; b) R-mode
cluster analysis of similarities of metal based on their level in the samples of bottled water from different areas; c) Distribution of analysed bottled water samples from Romania in
different clusters; d) Concentrations of metals in bottled water samples and the symbol of the cluster.

namely Ca eFe and Mg eNa. (structure, stratigraphy and tectonic) (Petrovic et al., 2010).
Piper diagram (Fig. 5), represents the average milli-equivalent
3.3. Piper diagram percentage of major anions (HCO2- 2-
3 -SO4 ) and cations (Ca -
2þ

Mg2þ). With the help of this graphical representation, differences

In a Piper diagram, similarities between waters with the same and similarities among the chemical parameters of waters are
origin (geotectonic unit) are impossible to find, due to the litho- studied. Also, waters are classified into specific chemical types and
logical diversity and geological properties of groundwaters the processes and hydrochemistry can be studied as well. Studied

Table 2
Average values of element concentrations in the clusters.

Ba Cu Ca Ga K Li Mg Mn Na Sr Zn Al Fe

mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L
Cluster C1
min 8.20 1.00 0.67 2.30 1.04 1.40 2.85 1.38 0.05 11.8 1.10 0.64 1.39
max 126 3.00 481 34.5 6.19 83.7 11.0 5.01 10.3 360 6.20 13.9 10.0
mean 36.7 1.70 82.2 10.2 3.52 21.4 7.02 2.24 2.73 145 2.73 3.15 5.02
Cluster C2
min 1.90 1.20 0.06 1.40 0.30 0.90 0.09 1.05 0.04 8.49 0.80 0.72 1.84
max 49.2 1.70 4.00 14.6 1.86 14.1 2.06 1.94 2.20 254 1.80 10.6 7.67
mean 12.8 1.50 1.53 6.48 0.87 3.92 0.98 1.53 0.91 74.0 1.30 3.04 4.69
Cluster C3 (AP 9)
8.50 16.7 705 2.50 2.53 1.20 1.48 39.3 2.80 38.4 6.70 77.2 17.5
Cluster C4 (AP 12)
896 1.40 22.8 121 10.1 114 0.12 55.8 0.05 4.87 2.70 6.97 293
12 T. Dippong et al. / Environmental Pollution 267 (2020) 115409
anions and cations are plotted into two ternary plots, projected up
as a diamond (Mazhar and Ahmad, 2020; Shah et al., 2019). The
trilinear diamond diagram indicates that generally the samples are
characterized as Ca2þ-Mg2þ-HCO2- 3 , concluding that alkalies
represent the majority of the samples (Mazhar and Ahmad, 2020).
The Piper diagram shows the water type, with respect to certain
chemical parameters (Ca, Mg, Na, K, Cl
, SO2
2


4 , CO3 , HCO3 ). Ac-
cording to the diagram, except sample AP3, which is a mixed Ca-
Na-HCO-3 type, the rest of the samples are characterized as Ca-Mg-
HCO
3 type (Fig. 5). The quality of water depends on diverse natural
factors, as soil atmosphere, nature bedrock, air precipitation and
topography (Shah et al., 2019).
The interactions between the water and rocks and the precipi-
tation of calcite are assessed by the chloride plot (Varde et al., 2019).
Water are enriched with calcium, due to the interactions among
water and rocks (dolomite or calcite), with magnesium due to the
water-minerals (olivine and biotite) interactions, while sulphate
derives after the dissolution of gypsum or pyrite (Varde et al., 2019).
3.4. Drinking water quality index- DWQI and arithmetical DWQI(A)
and pollution indices (HPI, HEI)
By using the drinking water quality indices, the quality of water
is assessed, based on the series of important physico-chemical
parameters for the drinking purpose of water, namely the bi-
carbonates, EC, pH, sulphates, turbidity, sodium, magnesium, po-
tassium, calcium. The main purpose of this techniques is to indicate
relevant and significant data regarding the suitability of the used
water (agricultural, industrial or for the drinking purpose). In order
to calculate the DWQI and the DWQI(A) each physico-chemical in-
dicator was assigned with a specific weight, based on their priority
(Shah et al., 2019). The maximum acceptable and negligible risk
levels and the risk assessment standard level were presented.
Fig. 5. Piper diagram for the drinking water samples.
In this study 19 parameters were classified and grouped into
four classes, namely G1 and G2, representing the potability groups
(G1-pH, EC, chloride, sodium, sulphate and G2 - ht, calcium, mag-
nesium, iron, bicarbonates), G3 and G4, indicating the health in-
dicators (G3 - nitrate, nitrite, manganese, zinc and G4 - cadmium,
cooper, chromium, lead and nickel). According to the DWQI results
(Table 3), all water samples are characterized as having a marginal
drinking water status, which indicates that the threshold limits are
sometimes exceeded (in the case of NO
3 , Mn, Fe, Zn), showing a
threatened quality (Ramesh et al., 2010).
The highest values were obtained for samples AP3, AP5, AP13
and AP14, indicating that certain samples present the best quality
among the studied samples. On the other hand, samples AP8 has
the lowest DWQI value, due to the relatively high NO
3 content,
followed by AP11 (correlation with the high HCO
3 content) >AP9
(correlation with the highest Cu and high Mn contents) >AP7
(correlation with of the highest Zn concentration). Comparable data
and interpretation are applied to water samples according to the
DWQI(A) results, with the only difference regarding the drinking
water quality status. The DWQI(A) results classifies the studied
water samples into two quality categories, namely poor and very
poor-quality status (Table 3). Other studies indicated different
status, such as poor, very-poor, marginal, good and fair quality in
India, excellent water in Turkey, although the increase of the pop-
ulation induces a high amount of nitrates, nitrites, phosphorus, as
well as total coliform (Ponsadailakshmi et al., 2018; Boyacioglu,
2007; Xing et al., 2020). According to the HPI, samples were clas-
sified into two pollution classes: high and low pollution. From the
first category, samples AP1 and AP12 take part, due to the high
value which exceeds 100; the high amount of Li and Fe lifted the HPI
results. The rest of the samples were characterized by a low
pollution status, with values ranging between 2.44 (AP14) and 29.3
(AP11). The HEI and Cd values were ranging between 0.32 and 9.19
 T. Dippong et al. / Environmental Pollution 267 (2020) 115409 13

Table 3
Ai, Min-Max, DWQI, and DWQI(A), HPI, HEI and Cd results of studied water samples results of studied water samples.

Sample Ai Min-Max DWQI Drinking water status DWQI(A) Drinking water status HPI HEI Cd

AP1 27.6 45.7 73.4 marginal 63.5 poor 127 3.99 ¡9.01
AP2 27.5 45.4 72.9 62.2 22.3 0.93
12.1
AP3 28.1 46.6 74.8 64.4 22.2 1.01
11.9
AP4 28.1 46.6 74.7 64.4 4.26 0.59
12.4
AP5 28.1 46.6 74.8 64.4 3.92 0.39
12.6
AP6 28.1 46.5 74.7 64.3 3.52 0.74
12.2
AP7 27.3 45.0 72.3 63.2 3.43 1.42
11.5
AP8 22.7 37.3 60.0 57.9 very-poor 16.0 1.15
11.8
AP9 27.0 44.6 71.5 62.3 poor 28.4 2.88
10.1
AP10 27.8 46.2 74.1 63.4 7.02 0.62
12.2
AP11 26.6 44.7 71.3 59.7 very-poor 29.3 1.42
10.3
AP12 28.1 46.6 74.7 64.3 poor 211a 9.19a ¡3.81a
AP13 28.1 46.6 74.8 64.4 3.06 0.42
12.6
AP14 28.1 46.6 74.8 64.4 2.44 0.32
11.7
a
The highest values obtained for the pollution indices.

and
12.6 to
3.81, indicating a low degree of pollution. HPI results Table 4
were correlated with the HPI and Cd values. Other studies from Iran Risk indices (CDI, HQ) results.

and Malaysia characterized the studied water samples with low Chronic daily intake (CDI) Hazard quotient (HQ)
and medium pollution status (Cd, Cr, Cu, Pb and Zn pollution), the mg/kg-day
HPI and HEI results ranging from 28.9 to 53.9 (HPI) and 0.44e5.74 Min Max Min Max
(HEI) (Ghaderpoori et al., 2018).
Al 2*10
5 2.4*10
3 4.6*10
2 5.9
Ba 6*10
5 2.7*10
2 3.0*10
4 1.4*10
1
3.5. Human health risk assessment Cu 3*10
5 5.2*10
4 8.0*10
4 1.3*10
2
Fe 4*10
5 9.0*10
3 1.0*10
4 1.3*10
2
Mn 3*10
5 1.7*10
3 2.0*10
4 1.2*10
2
Human health risk was calculated for heavy metals, two nitro-
Sr 3.1*10
4 1.5*10
1 5.0*10
4 2.5e10
1
gen compounds and chloride, based on their toxically levels in Zn 2.4*10
2 2.1*10
1 7.9*10
2 6.9*10
1
considerable amounts and their imminent presence in the water NO¡2 6*10
5 2.5*10
4 2.1*10
2 8.2*10
2
composition, namely for Al, Ba, Cu, Fe, Mn, Sr, Zn, NO


2 and NO3 . The NO¡3 4.9*10
3 1.54 3.1*10
3 9.6*10
1
¡
reference dose (RfD) for the studied chemicals were used according Cl 2.1 *10
2 4.1 2.2*10
1 41

to EPA IRIS, list (1997): 0.0004 mg/kg-day for Al, 0.20 mg/kg-day for
Ba, 0.04 mg/kg-day for Cu, 0.70 mg/kg-day for Fe, 0.14 mg/kg-day
for Mn, 0.60 mg/kg-day for Sr, 0.30 mg/kg-day for Zn, 0.003 mg/kg-
day for NO


2 , 1.60 mg/kg-day for NO3 and 0.10 mg/kg-day for Cl .

A drawback of the study is the relative low number of samples.
The CDI for all metals were below 1.0 mg/kg-day, while for NO

and Cl
, the maximum values were 1.53 mg/kg-day and 4.10 mg/kg-
day, for samples AP8 and AP11. The ascendant trend for the CDI
based on the content of metals is the following Zn>Sr>Ba>-
Fe>Al>Mn>Cu (Table 4).
The HQ results indicated relatively high results for Al, Cl
and
NO
3 contents, results which exceeded the unity, showing a po-
tential risk at the respective chemicals. Sample AP9 was charac-
terized with the highest HQ values obtained for Al (5.94), Cu (0.01)
and Zn (0.69) and for the sample AP8 at NO
3 (0.96). Sample AP2
was characterized with the highest HQ calculated for the
NO


2 content (0.08) and the lowest HQ for Ba, Mn, Sr and NO3 , while
sample AP12 was presenting the highest HQ results at Ba, Fe, Mn
and Sr. Samples AP13 and AP14 were characterized with the lowest
HQ for NO
2 and Zn. Sample AP11 was considered the problematical
sample due to the highest HQ value for Cl
, although it has the
lowest results for Al and for the nitrogen compounds. More than
70% of the samples present considerable high HQ values, exceeding
the unity (HQ > 1.0), which indicates a potential risk at chloride,
especially for sample AP11, which exceeded the unity almost forty
times. Recent studies in Romania indicated potential health risks at
nitrates (values ranging from 0.003 to 4.058), but no risks at nitrite
and heavy metals, such as Cr, Mn, Ni, Cu, Zn, Cd, Pb and (values
below 1.0) (Hoaghia et al., 2019). Different studies from Pakistan
and Turkey indicated that studied drinking water sources are safe
for consumption, but also could present risk at As and Cu, due to
plumbing and pipe corrosion; the HQ values were lower than in
Pakistan and ranging from 1.0 to 8.7, in Turkey (Demir et al., 2015;
Muhammad et al., 2011).
3
Also, we did not take into account groundwater characteristics
across the locations from which the groundwater samples were
collected. Possible local particularities or specific local pollution
sources could also influence the pattern of distribution maps of
water characteristics. Additionally, some water characteristics
especially the pH, nitrates and EC might vary due to influences from
weather factors such as precipitation, lack of precipitation and local
source of pollutants (such as agriculture practice, animal hus-
bandry, use of fertilizers, erosion and weathering of rocks, munic-
ipal waters, household waters). The oxidability can be influenced by
the alluvium on the slopes of the Carpathian Chain caused by the
melting of the snow, abundant and successive precipitation, espe-
cially in the rainy seasons.
While this study was based on a relatively low number of
samples, we proposed that future studies should expand our
approach to larger number of water samples, validating and
updating the distribution maps based on larger number of samples.
Such enhanced models represented by distribution maps of
groundwater characteristics could be further validated with tests at
intermediate locations.
Further investigation on the sources of these contaminants will
be carried out. Generally, the sources of contaminants in water are
the rocks with which the groundwater interacts and also the sur-
rounding soil. Therefore, the water sources used for bottled waters
are analysed before starting the water extraction and from time to
time (usual monthly) during the exploitation of the water resource.
The future tendencies will consist of the comparison between
the bottled water and the drinking water obtained in centralized
systems.
14 T. Dippong et al. / Environmental Pollution 267 (2020) 115409
4. Conclusion
This study has a multidisciplinary approach aiming to show the
spatial variations of elements and the main physico-chemical in-
dicators in the 14 studied bottled waters from groundwater sour-
ces. The distribution maps showed that the levels of parameters
were over an extended area along the Western and Eastern Car-
pathian Mountains. Generally, the maps indicated that all studied
bottled water samples comply with legal requirements, except for
one samples (AP11) for which the turbidity exceeds twice the MAC.
According to the Piper diagram, the studied waters are classified in
the Ca-Na-HCO-3 and Ca-Mg- HCO
3 water categories. The amounts
of Li, Sr and Ga were generally low, except two samples for which Li
exceeded the MAC. The metals distribution analysis showed that
AP12 is not suited for drinking purposes, due to the higher contents
of Ba, Fe, Li and Mn as the MACs. Although, this type of water could
be used in a limited amount as medicinal water. Generally, the
amount of elements and heavy metals is due to the water-rock
interactions, with limestone causing enrichment with bicarbonate
and calcium, with micas and amphiboles causing enrichment with
lithium and boron. Granite rocks weathering enriched the waters
with iron and manganese, while the weathering of limestone and
calcium feldspars enriches the waters with calcium and bicarbon-
ate. The anomalies caused by the interactions between the water
and plumbing enrich the waters with lead, nickel, cooper, cad-
mium, antimony or zinc. Water samples were characterized by high
values of total hardness, richness in chloride, bicarbonates and
nitrates, but not exceeding the MAC, according to the Romania
legislations applied for the drinking water sources. Cluster analysis
indicated 4 groups of bottled water samples with dissimilarities
among the metals and heavy metals content. Every bottled water
sample from the cluster showed high similarities regarding the
chemical composition. AP 9 and AP12 showed no similarities to the
rest of the water samples, forming separate clusters.
According to the DWQI and DWQI(A) results the studied drinking
water samples were classified as waters with marginal, poor and
very poor quality. According to the HQ values, a potential risk at Cl
,
Al and NO
3 can be induced, due to exceeding the unity for certain
indicators. Due to the high Fe and Li content, HPI results exceeded
100, indicating a high pollution status for 2 samples (AP1 and
AP12). The rest of the two pollution indices (HEI and Cd) showed a
low pollution status for all the studied drinking water samples.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.envpol.2020.115409.
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