Journal of Environmental Protection, 2011, 2, 97-108
doi:10.4236/jep.2011.21011 Published Online March 2011 (http://www.SciRP.org/journal/jep)
Natural Contaminants in Drinking Waters
(Arsenic, Boron, Fluorine and Vanadium) in the
Southern Pampean Plain, Argentina
Martín E. Espósito1, Juan D. Paoloni4, Mario E. Sequeira2,3, Nilda M. Amiotti1,3, María del C. Blanco1
1Epto. de Agronomía-UNS; 2Depto. de Ingeniería-UNS; 3CERZOS-CONICET; 4CONICET.
Received October 14th, 2010; revised November 19th, 2010; accepted December 28th, 2010
ABSTRACT
This research aims at making a diagnosis of the presence of arsenic, boron, fluorine and vanad ium in the waters from
the basin of El Divisorio stream, tributary of Paso de las Piedras reservoir, in the southwest of Buenos Aires Province.
This storage is used to provide water to the cities of Bahía Blanca and Punta Alta with a population of approximately
400,000 inhabitants. A selective and specific samp ling of wells, perforations and superficial watercourses was made in
46 points, in an area of nearly 400 km2. Groundwaters had arsenic (max. 0.114 mg/l) exceeding the reference guideline
in 97.3% of the samples, boron (max. 1.42 mg/l), vanadium (max. 0.8 mg/l) and fluorine (max. 6.6 mg/l), being respect-
tively, 91.9%, 82.9%, and 67.6%. Regarding the superficial flow, while arsenic concentrations were higher than the
limit in 100% of the cases (max. 0.072 mg/l), 88 .9% corresponded to elevated boron (max. 1 mg/l) and vanadium (max.
0.23 mg/l) and only 22.2% to fluorine (max. 3.18 mg/l) ones. In all these cases, concentrations exceed the reference
guideline values sug gested by the World Health Organ ization , the Argentine Food Code and the Environmental Protec-
tion Agency. The pr esence of these contaminants tha t finally could determine the qua lity of the water resource entering
the reservoir is attributed to the natural characteristics of the environment since contributions by anthropic actions
have not been detected in the area. The most critical sectors in th e basin were identified in order to stress the possible
negative influence of consuming these waters on the community’s health, with the purpose of reporting the results to
institutions, authorities and the population and applying them to preventive medicine.
Keywords: Arsenic, Fluorine, Vanadium, Hydrochemistry, Risk
1. Introduction
The continuous demographic growth and the increase of
food production boosted by technology have intensified
the pressure on water usage for producing food, goods
and services. Because of this, the rising demand of
groundwater has grown exponentially alongside prob-
lems regarding the availability and quality of the provi-
sion sources and risks posed for human health [1].
Groundwaters are becoming an increasingly scarce
resource for humanity. In addition, water quality is im-
paired by the presence of natural contaminants derived
from the contact of water with weathered materials that
compose the crust of the Earth, thus raising ion levels in
water. This situation affects millions of people around
the world and represents a real threat to health.
Among the most relevant natural contaminants due to
their toxicity and dangerousness are arsenic, boron, fluo-
rine and vanadium, which reduce the qu ality of the water
resource, especially when their concentrations are higher
than the reference gui deli ne values [2-4].
The most significant consequence of a chronic expo-
sure to arsenic (As) is the occurrence of carcinogenic
pathologies in different soft organs such as the skin,
lungs, pancreas and intestine [5,6] as well as disorders of
the nervous system [7]. In Argentina, this syndrome is
known as Regional Chronic Hydroarsenicism (HACRE,
for its Spanish acronym) [8]. The coexistence of the As
ion with other elements present in water like bo ron, fluo-
rine, vanadium and other ones [9] increases the degree of
severity of the condition.
Boron (B) is an important micronutrient for superior
plants [10]. In 2003, both the Subsecretaría de Recursos
Hídricos de la Nación (National Office of the Under-

Natural Contaminants in Drinking Waters (Arsenic, Boron, Fluorine and Vanadium) in the 98 Southern Pampean Plain, Argentina
Secretary for Water Resources) [11], in its guideline of
water quality for human consumption, and the World
Health Organization (WHO) specified that different
studies in laboratory animals had evidenced several toxic
effects of the oral exposure to boron such as testicular
atrophy, spermatogenesis disorders and decrease of body
mass, among others. According to available information
and due to the lack of evidence on human carcinogenesis,
the Environmental Protection Agency (US EPA) (1994)
classified boron in group D, which corresponds to sub-
stances that cannot be classified as carcinogens.
Fluorine (F) is a microcomponent that can accumulate
in human beings, plants and animals [12]. The ingestion
of water with high levels of F may lead to an increase in
its total content, particularly in calcified tissues; its solu-
ble forms may also be absorbed through the gastrointes-
tinal tract [2,13]; and, in even more acute cases, it can
cause different types of cancer [14]. When F concentra-
tions in water are approximately 1.2 mg/l, the first
symptoms of dental fluorosis may appear [15,16].
In nature, vanadium (V) participates in chlorophyll
synthesis in photosynthetic organisms and it is a micro-
nutrient for several marine and terrestrial species [17,18].
Water consumption is one of the routes of entry into the
human body, where vanadium is absorbed and trans-
ported to several tissues through the blood stream [19]
and accumulates in the liver, kidneys, bones, lungs, etc.
[20,21]. Vanadium is a carcinogenic compound with
mutagenic and genotoxic properties for the human being
when it is present in high concentrations in drinking wa-
ter and periods of exposure are long [22,23].
The presence of arsenic and other trace elements in
superficial and groundwaters could be associated to the
presence of glass, volcanic ash and other minerals
As-bearers in the loess sediments, interfering in the hy-
drochemical characteristics [24-28].
The WHO (1995) suggests as guideline values that
concentrations of arsenic, fluorine and boron for human
consumption should not exceed the contents of 0.01, 1.5
and 0.3 mg/l respectively. For its part, the Argentine
Food Code (3) coincides with the limit established for
arsenic; as for fluorides, it recommends a table where
tolerance values vary according to water temperature;
and finally it differs on the value for boron, raising the
level to 0.5 mg/l. Regarding the limit of vanadium, the
value of 0.05 mg/l proposed by the US EPA was consid-
ered.
In the southwest of Buenos Aires Province, there is
precedent of contaminated superficial and groundwaters
with simultaneous high levels of arsenic, boron, fluorine
and vanadium which greatly exceed the values estab-
lished by the different abov emention ed en tities, being th e
groundwater resource one of the main provision sources
for human consumption and agricultural and farming
uses. Because of this, our research work carried out in El
Divisorio stream, tributary of Paso de las Piedras reser-
voir, in Buenos Aires Province, is aimed at making a
diagnosis of the presence of these elements, identifying
the most critical areas in the study region and reporting
on their negative influenc e on human health. In addition,
our study is intended to provid e health care systems with
information that can be applied to preventive medicine.
2. Materials and Methods
This research work was conducted in the endorheic basin
of El Divisorio river (Figure 1), located in the hilly sys-
tem corresponding to the Sierras Australes hill range, in
the south of Buenos Aires Province [29]. The main wa-
tercourse drains the western slope of Pillahuincó hill,
chain which corresponds to the westernmost separation
of Ventania system [30]. The surface of the basin is ap-
proximately 400 km2, its bed has an extension of 40 km
and it flows into Paso de las Piedras reservoir (61˚45" W
and 38˚25" S), water storage provides drinking water to
Punta Alta and Bahía Blanca cities and Bahía Blanca’s
Petrochemical Complex [31].
The system that constitutes the basin corresponds to a
seasonal rainfall pattern, the annual average being ap-
proximately 750 mm [32]. The mean temperature in the
coldest month (July) is 7˚C and in the hottest month
(January), 23.5˚C. Winds are irregular in their direction
and speed.
The main productive activities in this area are agricul-
ture and farming, which determine a strong presence of a
residing and stable rural population [33]. The area and its
surroundings also have several tourism development
centres which gave recently acquired significance at the
local, provincial and national levels.
Maps of the Instituto Geográfico Militar (Military Geo-
graphical Institute) in scales of 1:50 000 and 1:100 000
with their respective mosaic photographs and satellite
images, as well as the field survey, were used to deter-
mine the study area and demarcate the geographical loca-
tion in the corresponding cartography. The heights above
sea level of the sampling points were established using
the Global Positioning System (GPS) Garmin etrex vista
HCx.
In order to study water quality, a selective and specific
sampling was conducted in the winter of 2008 in 46
points among wells, perforations and superficial water-
courses used for exploiting the resource within the study
area (Figure 1). Groundwater extraction was carried out
in 37 points by means of tradition al piston pumps, driven
by wind energy (windmills), and in some cases using

Natural Contaminants in Drinking Waters (Arsenic, Boron, Fluorine and Vanadium) in the
Southern Pampean Plain, Argentina
99
-61.8-61.75-61.7-61.65 -61.6 -61.55 -61.5 -61.45 -61.4
-38.45
-38.4
-38.35
-38.3
-38.25
-38.2
01020
km
RESERVOIR
N
Location of sampling sites in the phreatic a quifer and i n superficial watercourses
Locatio n of sampling sites in the phreatic aquifer and in superfi cia l water cou rses
BUENOS
AIRES
N
Figure 1. Geographical location of the study area and wa te r sampling points.
electrically-driven centrifugal pumps. In wells which are
discontinuously exploited, the extraction system was kept
in operation during a given time so that decanted or de-
posited impurities did not obstruct the system. As for
superficial waters, 9 samples were taken along the main
watercourse and its affluents. Water samples were col-
lected in hermetically-sealed, plastic bottles with a ca-
pacity of a half-litre volume, also labelled for identifica-
tion before being placed in coolers for their later trans-
port to the laboratory.
During water extraction, the depth of the phreatic level
was determined with a Spohr probe. In all cases, water
temperature was recorded and samples with replicates
were collected. Quantitative determination of arsenic in
waters was done by a Hydride Generator and by Induc-
tively-Coupled Plasma and Atomic E mission Spectrome-
try (ICP-AES) based on Halicz and Russell’s method
(1986), which consists in the continuous generation of
arsine (AsH3) using three of the four channels of a peri-
staltic pump (Cole Palmer Instruments Company, Mas-
terflex). The sample solution and a solution of sodium
tetrahydroborate plus potassium iodide were transported
to a modified liquid-gas separator. Arsine and hydrogen
were collected from the separator to th e plasma by a con-
tinuous flow of argon. Arsenic was determined according
to its main wavelength at 193.69 nm. Boron and vana-
dium were analyzed with ICP equipment and fluorine,
with a specific electrode. Quality control of th e chemical
analyses was performed by means of ICP standard solu-
tions. The treatment was supplemented with other routine
analyses such as anions, cations and some trace elements.
The concentrations of arsenic, boron, fluorine and va-
nadium in the different sampling points which cover the
area (Table 1) were used to draw thematic maps of iso-
concentrations and vulnerability employing the software
Surfer V. 8. On the other hand, the software InfoStat was
used to perform a Principal Component Analysis (PCA)
with the standardized data of the studied variables.
3. Results
Waters from the river courses, wells and perforations in
the area are used for consumption by the stable rural
population, for fulfilling farming requirements and in
some cases for supplementary irrigation. No waste dis-
charge from tanneries, mines, metallurgical plants, etc.,
which could be evaluated as possible contaminant sources,
has been observed in the study and neighbouring areas.
Herbicides and fungicides applied as technological
packages in the basin for the production of cereal crops
do not contain these active ingredients. Moreover, fertil-
izers are used in small doses, providing only nitrog en and
phosphorus. Rural farms of the basin began to adopt this
technology in the last two decades as a consequence of
the change underwent by production systems which
caused this farming region to start turning into one more
related to agricultural production. Thus, after this lapse
of time the degree of anthropic contamination is not very
high.

Natural Contaminants in Drinking Waters (Arsenic, Boron, Fluorine and Vanadium) in the 100 Southern Pampean Plain, Argentina
Table 1. Concentration of arsenic, bor on, fluorine and vanadium in superficial water s (grey) and gr oundwaters of the basin.
Longitude Latitude Arsenic Boron Fluorides Vanadium
ppm ppm ppm ppm
–61.65225 –38.41882 0.068 1.01 3.93 0.55
–61.63482 –38.40879 0.114 0.72 3.23 0.74
–61.62932 –38.44197 0.027 0.93 0.67 0.27
–61.56575 –38.44847 0.053 0.91 2.56 0.49
–61.51277 –38.30398 0.031 0.36 1.05 0.12
–61.51943 –38.30541 0.051 0.63 2.35 0.46
–61.52689 –38.29328 0.022 0.33 0.68 0.10
–61.6071 –38.33512 0.055 0.61 2.50 0.30
–61.58091 –38.3522 0.083 0.69 3.24 0.74
–61.54281 –38.38494 0.107 1.24 4.60 0.68
–61.54294 –38.40554 0.076 0.97 2.36 0.66
–61.60184 –38.38104 0.069 0.81 2.75 0.59
–61.62704 –38.38098 0.032 0.76 2.28 0.14
–61.63905 –38.38335 0.039 0.54 1.61 0.21
–61.59681 –38.49197 0.056 0.89 2.00 0.54
–61.60647 –38.47748 0.085 0.85 3.09 0.65
–61.58481 –38.41873 0.099 1.10 4.40 0.32
–61.50587 –38.36866 0.088 0.74 3.00 0.80
–61.53058 –38.35495 0.056 0.84 3.21 0.24
–61.53935 –38.32513 0.055 0.55 1.51 0.31
–61.59761 –38.33051 0.072 0.45 1.18 0.21
–61.42482 –38.267 0.071 0.31 0.59 0.15
–61.41075 –38.25573 0.043 0.51 0.69 0.15
–61.45931 –38.27826 0.013 0.29 0.66 <0.05
–61.47797 –38.25602 0.018 0.13 0.39 0.04
–61.47302 –38.22964 0.026 0.22 0.4 < 0.05
–61.65167 –38.3801 0.072 0.83 3.16 0.15
–61.68635 –38.40771 0.054 0.95 1.73 0.45
–61.65687 –38.40077 0.052 0.56 1.44 0.23
–61.52431 –38.26066 0.030 0.67 1.32 0.19
–61.5154 –38.24776 0.019 0.88 0.9 0.14
–61.48995 –38.23871 0.010 0.12 0.2 <0.05
–61.54416 –38.27581 0.021 0.60 0.98 0.13
–61.60498 –38.33753 0.024 0.57 1.13 0.14
–61.57752 –38.3572 0.027 1.00 3.18 0.06
–61.64474 –38.3111 0.012 0.60 1 < 0.05
–61.61879 –38.28918 0.029 0.64 1.57 0.23
–61.58342 –38.27105 0.026 0.66 1.24 0.22
–61.56069 –38.29111 0.024 0.66 1.28 0.15
–61.6924 –38.41359 0.018 0.51 0.9 0.07
–61.6628 –38.36362 0.049 1.42 4.63 0.54
–61.68781 –38.35052 0.056 0.82 4.86 0.51
–61.62051 –38.34701 0.058 1.00 6.6 0.51
–61.65316 –38.32424 0.055 0.82 4.28 0.50
–61.69243 –38.385 0.036 1.18 2.04 0.29
–61.70991 –38.42303 0.054 0.99 4.88 0.58

Natural Contaminants in Drinking Waters (Arsenic, Boron, Fluorine and Vanadium) in the 101
Southern Pampean Plain, Argentina
The movement of the phreatic flow responds to char-
acteristics typical of the basins of this hilly system, water
levels in wells and perforations emphasizes variations
ranging from 1.4 m deep at the bottoms of valleys and
near beds to 41 m in the interfluve of the southeastern
sector. The development of the phreatic surface mor-
phology shows a significant symmetry with a significant
hydraulic gradient of approximately 6.06‰, exhibiting a
substantial parallelism between the isohypses, which
determines a clear orientation of the discharge towards
the reservoir (Figure 2).
The presence of arsenic was detected in groundwaters
in the 37 analyzed samples, 36 of which showed values
higher than the established limits, being the frequency
distribution of concentrations irregular and asymmetric
(Figure 3) with the greatest concentration points situated
in the southeastern sector of the lower basin (Figure 4).
In superficial waters, the reference value was exceeded in
all the samples and the highest value was found in the
middle basin, not responding to a given distribution pat-
tern. Making a generalization about the entire basin, ar-
senic concentrations found in waters widely range from
0.01 mg/l at the headwaters of the basin to 0.114 mg/l
near the river mouth .
Values obtained for boron show that 34 samples of
phreatic waters exceed the established limit, and also
present an irregular frequency distribution (Figure 5),
which demonstrates a high variability for this ion. B
concentration increases downstream direction, this spa-
tial behaviour is demonstrated by a more tight grouping
of equal concentration isolines (Figure 6). In addition,
maximum values are identified in locations very close to
the mouth of the main watercourse, almost over the res-
ervoir. Regarding superficial water, 8 out of the total
number of samples are beyond the guideline value, lo-
cated in the same sector as the high concentrations of
arsenic. The minimum concentration of boron in water is
0.12 mg/l and coincides with the well where the mini-
mum value of arsenic was found. The highest value, 1.42
mg/l, was recorded in the lower sector of the basin.
Figure 2. Map of the groundw ate r flow hydrodynamic s.

Natural Contaminants in Drinking Waters (Arsenic, Boron, Fluorine and Vanadium) in the 102 Southern Pampean Plain, Argentina
Figure 3. Distribution of accumulated frequencie s of ar se nic conc entrations in groundwater.
-61.8-61.75-61.7-61.65 -61.6-61.55 -61.5-61.45-61.4
-38.45
-38.4
-38.35
-38.3
-38.25
-38.2
01020
km
RESERVOIR
0.0 1
0.0 2
0.0 3
0.0 4
0.0 5
0.0 6
0.0 7
0.0 8
0.0 9
0.1
As (mg/l)
The concentration nucleusThe concentration isoline s
N
Figure 4. Map of isoconcentration and distribution of arsenic in groundwater.

Natural Contaminants in Drinking Waters (Arsenic, Boron, Fluorine and Vanadium) in the 103
Southern Pampean Plain, Argentina
Figure 5. Distribution of accumulated frequencie s of bor o n concentrations in gr oundwater.
-61.8-61.75-61.7-61.65 -61.6 -61.55 -61.5-61.45-61.4
-38.45
-38.4
-38.35
-38.3
-38.25
-38.2
01020
km
RESERVOIR
0
0.3
0.6
0.9
1.2
B (mg/l)
The concentration nucleusThe concentration isolines
N
Figure 6. Map of isoconcentration and distribution of boron in the phreatic layer.

Natural Contaminants in Drinking Waters (Arsenic, Boron, Fluorine and Vanadium) in the
Southern Pampean Plain, Argentina
104
Analyzing the variability of ions concentration data
matrix showed in the graph of the first two Principal
Components (Figure 11), the upper right quadrant (quad-
rant I) illustrates the samples with the highest concentra-
tion of boron and fluorine in the middle and lower basins.
The high contents of arsenic and vanadium located in the
lower right quadrant (quadrant IV) belong mainly to the
middle basin. It is worth noticing that the middle basin
presents a clear heterogeneity regarding the chemical
composition of the waters since their values are distrib-
uted in the four quadrants. Unlike the previously de-
scribed quadrants, the left sector (quadrants II and III)
exhibits values with the lowest concentrations of all the
analyzed elements are located, which indicates a better
quality of the water belonging mainly to the up per basin,
partly to the middle basin and in very few cases to the
lower basin.
Regarding fluorine, the samples in the groundwater
flow showed concentration levels higher than the guide-
line value in 25 of the analyzed points, presenting an
asymmetric and irregular frequency distribution (Figure
7) and being located in the southwest of the middle sec-
tor of the basin, as reflected by the morphology of the
concentration isolines (Figure 8). Superficial waters
showed a smaller proportion of points beyond the limit.
Only 2 samples exceed it, the high est concentration level
being located at the same point where the maximum
concentration of boron was detected. Fluorine concentra-
tions in the basin range from 0.2 mg/l, the lowest record,
which belongs to the same sample where the lowest con-
centrations of the abovementioned elements were found,
to the highest value with a mag nitud e of 6.6 mg/l, located
in the middle sector of the study area.
As for vanadium, the results of groundwater analyses
proved that it is contaminated in 33 of the collected sam-
ples. A complex distribution of frequencies and an
asymmetric distribution of the variable concentration
(Figure 9) were also observed. Zones with higher con-
tent of the contaminant ion are emphasized in the south-
east of the middle sector of the basin (Figure 10). In the
superficial water resource, this element is present in 8 out
of the total number of determinations and its concentra-
tion increases from the headwaters towards the mouth.
Vanadium values in the study area vary between 0.04
mg/l for a sample obtained from a bed of a tributary at
the catchment and 0.80 mg/l in a sector of the middle
basin.
4. Conclusions
Groundwaters had arsenic (max. 0.114 mg/l) exceeding
the reference guideline in 97.3% of the samples. Similar
values were found for boron (max. 1.42 mg/l), vanadium
(max. 0.8 mg/l) and fluorine (max. 6.6 mg/l), respect-
tively, 91.9%, 82.9%, and 67.6%. Regarding the super-
ficial flow, while arsenic concentrations were higher than
the limit in 100% of the cases (max. 0.072 mg/l), 88.9%
corresponded to elevated boron (max. 1 mg/l) and vana-
dium (max. 0.23 mg/l) and only 22.2% to fluorine (max.
3.18 mg/l) ones. According to obtained results, the hy-
drochemical characteristics of the basin could determine
Figure 7. Distribution of accumulated frequencies of fluorine concentrations in groundwater.

Natural Contaminants in Drinking Waters (Arsenic, Boron, Fluorine and Vanadium) in the 105
Southern Pampean Plain, Argentina
-61.8-61.75 -61.7-61.65-61.6 -61.55-61.5 -61.45 -61.4
-
38.45
-38.4
-
38.35
-38.3
-
38.25
-38.2
01020
km
RESERVOIR
0
1.5
3
4.5
F (m g/l)
The concent ration nuc leusThe concentrati on isolines
N
Figure 8. Map of isoconcentration and distribution of fluorine in the groundwater aquifer.
Figure 9. Distribution of accumulated frequencie s of vanadium c oncentrations in groundwater.

Natural Contaminants in Drinking Waters (Arsenic, Boron, Fluorine and Vanadium) in the 106 Southern Pampean Plain, Argentina
-61.8-61.75 -61.7 -61.65-61.6 -61.55-61.5 -61.45 -61.4
-
38.45
-38.4
-
38.35
-38.3
-
38.25
-38.2
01020
km
RESERVOIR
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
V ( mg/l)
The conc entration nucl eusThe concent ration isolines
N
Figure 10. Map of isoconcentration and distribution of vanadium in groundwate r .
Figure 11. BIPLOT graph of the first two Principal Components.

Natural Contaminants in Drinking Waters (Arsenic, Boron, Fluorine and Vanadium) in the
Southern Pampean Plain, Argentina
107
the water quality of the reservoir due to the observed
degree of co n centration of natural contam inants.
The PCA of the four chemical variables under study
indicates that the upper basin is not affected by high con-
centrations of these elements. On the contrary, the points
containing the highest arsenic, boron, fluorine and vana-
dium values were detected in the lower and middle ba-
sins.
In addition, considering the evaluation of land utiliza-
tion and the technology adopted in the production sys-
tems in the studied area, the high contents of these con-
taminants in the water resources may not be ascribed to
anthropic actions.
Mapping of contaminants highlighted the areas at the
highest risk. Maps are proposed as a simple tool to easily
understand the interpretation of our results not only for
professionals who practise preventive medicine but also
to the community and authorities related to water man-
agement, in view of their responsibility for delivery and
distribution of drinking water to urban areas.
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