Environ Earth Sci (2013) 70:30673084
DOI 10.1007/s12665-013-2367-2
ORIGINAL ARTICLE
Arsenic anomalies in shallow Venetian Plain (Northeast Italy)
groundwater
A. Carraro P. Fabbri A. Giaretta
L. Peruzzo F. Tateo F. Tellini
Received: 23 October 2012 / Accepted: 28 February 2013 / Published online: 16 March 2013
 Springer-Verlag Berlin Heidelberg 2013
Abstract A pilot area within the Venetian Plain was
selected to assess the arsenic (As) contamination of
groundwater. The area represents a typical residential,
industrial and agricultural organization representative of
most western countries, and is also devoid of lithologies
with high or anomalous As content. Hydrogeological and
chemical data have been collected, the latter spatialized by
a geostatistical approach. The unconfined aquifer reservoir
varies from a predominantly gravel composition in the
north to a sandy and siltclay composition further south,
including peat layers. The hydrochemical features of the
waters are rather homogeneous, featuring low mineral
content and a Ca-bicarbonate signature. In contrast, the
redox state is highly variable; oxidizing conditions are
predominant in the northern and coarse parts of the aquifer,
whereas reducing potentials prevail in the southern and
siltclay parts. Several well waters contain arsenic in
excess of drinkable limits (=10 ppb), and most of these
wells are located in the southern area. A large portion of
the studied area has a high probability of containing non-
potable water (up to 150 ppb As). Remarkably, As hot
spots (As [ 300 ppb, up to 431 ppb) were identified at
the transition from gravel to siltclay sediments. No
industrial or agricultural source of As has been found.
A. Carraro (&)  P. Fabbri  A. Giaretta  L. Peruzzo 
F. Tateo  F. Tellini
Institute of Geosciences and Earth Resources, National Research
Council (CNR) of Italy, c/o Department of Geosciences,
University of Padova, 35131 Padova, Italy
e-mail: a.carraro@unipd.it
P. Fabbri
Department of Geosciences, University of Padova,
35131 Padova, Italy
Keywords Arsenic  Contamination  Geostatistics 
Hydrochemistry  Venetian Plain (Italy)
Introduction
Arsenic concentration in the natural environment has
always been considered a risk factor for human disease.
The occurrence of arsenic (As) in water directly designed
for drinking, agricultural uses and livestock breeding is of
particular interest. Numerous studies have evaluated As
anomalies on Southeast Asiatic Plains (e.g., Bangladesh),
which have been well known for many decades (Welch and
Stollenwerk 2003; Ahuja 2008; Ravenscroft et al. 2009). In
Italy, there have been studies of groundwater As concen-
trations, but these studies have mainly considered volcanic
reservoirs (Angelone et al. 2009). The consequences of As
occurrence in drinking water are very severe, and some
diseases are directly related to the concentration of this
element in water (Tseng 1977; Chen et al. 1988; Tseng
et al. 1996; Chiou et al. 1997; Wang et al. 2002, 2009).
Interest in As drinking water contamination has increased
over time (Alerts and Khouri 2004) due to two main fac-
tors: (1) a widespread decrease in the drinkable water
resources as a consequence of increasing pollution of
anthropogenic origin; and (2) a continuous lowering of
legally allowable As concentrations in the West due to the
hazard posed by As. In Europe and the USA, an As con-
centration of 10 micrograms per liter (ppb) is currently
considered acceptable for drinking.
In Italy, the Po and Venetian Plains represent a contin-
uous region where industrial activities are concentrated and
where millions of people live and work. There are occa-
sional reports of As contamination in groundwater in dif-
ferent parts of the plains (Scialoja 2005). The Venetian
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Plain is a highly populated area. There are no localized
emissions of hydrothermal and volcanic As, but a variety of
industrial and farming activities involving a significant
amount of water for food uses (directly for drinking,
agriculture and animal nutrition) are present. In the past, As
anomalies in water and groundwater have been identified
only sporadically. The first signal was given by results of a
survey that began in 1992 (Baldantoni and Ferronato
1995), which showed the presence of an area with As
concentrations exceeding 50 ppb, ranging as high as
480 ppb. However, these data are related to six different
superimposed aquifers, ranging from zero to approximately
300 m in depth over a fairly wide area (about
20 km 9 15 km), that includes the area considered in this
work.
The main goal of this study is to evaluate the distribu-
tion of As in shallow groundwater within a pilot area of
70 km2, which was selected according to the following
features: (1) the study area shows a residential and indus-
trial composition typical of most western countries; (2) a
sampling survey was performed that took the hydrostrati-
graphical situation into account; (3) samples were collected
in a narrow time interval; (4) wells were located in a well-
defined stratigraphical context; and (5) known pollutant
sources of As were not present.
Study area
Hydrogeological framework
The Bacchiglione, Brenta, Piave and Leogra Rivers are
responsible for the deposition of a significant portion of the
material, hundreds of meters thick, which forms the subsoil
of the Venetian Plain.
Along the piedmont belt of the plain, fans from adjacent
rivers laterally penetrate gravelly alluvial fans. The result is
entirely gravelly subsoil throughout the thickness of the
high Venetian Plain. Because deeper fans often invade
further areas of the high plain from the undifferentiated
gravel cover, the terminal parts of the fans extend down-
stream for various distances, producing an alluvial cover
that is no longer uniformly gravely, but is instead com-
posed by alternating layers of gravel and silty clay of
swampy, lagoon or marine origin (Bondesan and Meneghel
2004; Fontana et al. 2008). The stratigraphical framework
produces a large, unconfined aquifer extending 1520 km
south, from the Pre-Alps to the southeast. The water table,
in a band that is 25 km wide and several kilometers long,
intersects the topographic surface, creating numerous
characteristic plain artesian springs referred to as fonta-
nili (Fig. 1; Vorlicek et al. 2004). This natural drainage
system supplies numerous perennial streamflows (e.g., the
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Environ Earth Sci (2013) 70:30673084
Sile River, 56 m3/s). This configuration is a characteristic
structure that is present throughout the northern Po Plain
(Cucchi et al. 2008; Pilla et al. 2006).
The unconfined aquifer is 200300-m thick and is
intensively exploited for water supply. The relatively
homogeneous, unconfined hydrogeological unit changes
into a multi-layered confined or semi-confined aquifer
system south of the fontanili belt. Impervious or semi-
pervious layers, which may be more than 10-m thick, are
interbedded with sand and gravel, as shown in Fig. 1.
Many public wells of different depths (100300 m)
were drilled in the southern part of the high plain and
screened in a multilayered aquifer system for water supply
purposes.
The unconfined aquifer is mainly recharged from irri-
gation, surface water infiltration and rainfall. These pro-
cesses are only effective in the high part of the Venetian
Plains, where surface water infiltration can reach the
unconfined aquifer and the artesian aquifers linked to it.
The study area is located in the central part of the
Venetian Plain, on the Brenta megafan (on the right bank
of the actual Brenta River), including the municipal terri-
tories of Carmignano di Brenta, Grantorto, Gazzo and
Piazzola sul Brenta (Northern Padova district, Northeast
Italy; Fig. 1).
Hydrostratigraphy
About thirty lithostratigrafies from local and regional
administrative technical authorities, were used in this
study. The original stratigraphies were simplified to con-
form the data to stratigraphical reconstructions. The max-
imum depth of the lithostratigraphic investigation using
private wells was approximately 200 m, and three-dimen-
sional aquifer hydrostructures were constructed for six
hydrostratigraphic profiles, both in the northsouth and
eastwest directions (Fig. 1a). The hydrostratigraphical
profiles are presented in Fig. 2.
In Fig. 1, the position of two boreholes specifically
drilled in this zone to a depth of 30 m (RB1 and PM1) is
also shown along cross-section 1L. Note that the two
boreholes demonstrate a more complex and variable lith-
ostratigraphy with respect to the cross-sections reported in
Fig. 2. In particular, the organic matter is concentrated in
peat layers and scattered in clays, silts and sands, either as
small fragments or as a thin and discontinuous lens. Most
of the materials plotted as clay in the cross-sections are silt
and clay with a minor sandy component (Fig. 3).
Besides the hydrostructural aspects, particular attention
was placed on the presence of peat deposits, considering their
debated role in As concentration (see, for example, Yama-
zaki et al. 2003; Zaccone et al. 2008). There is a visible peat
layer approximately 2030 m below ground level (from -5
Environ Earth Sci (2013) 70:30673084
Fig. 1 Sketch of the study area. The inset map shows the location of
the six cross-sections reported in Fig. 2 and the position of two
boreholes. The upper limit of the Fontanili belt and the location of
to 5 m with respect to the sea level, Fig. 2). This layer is
visible in cross-sections 1T, 2T, and 1L and partially visible
in cross-sections 3T and 4T. In the area between 3T and 4T,
the continuity of this layer is not clear. However, strati-
graphical details (such as the peat layer) are sometimes lost
due to the procedure used during drilling (most of the wells
were finalized to groundwater exploitation). The RB1
borehole confirms the presence of this layer. Furthermore, at
a depth of approximately 90100 m (from -70 to -80 m
with respect to the sea level, Fig. 2), the presence of a second
peat layer is visible, but most of the cross-sections are not this
3069
the schematic geological profile are also shown (a); schematic
geological profile of the Venetian alluvial plain from north to south
(b)
deep. Thus, it is impossible to speculate about the actual
continuity of this deeper peat layer. This peat horizon is
visible in cross-sections 4T and 1L.
From a strictly hydrogeological perspective, analysis of
lithostratigraphic cross-sections has identified one uncon-
fined aquifer and three superimposed aquifers ranging from
0 m to more than 170 m in depth. The typical quantitative
and qualitative characteristics of each aquifer are reported
in Table 1 and are described as follows.
Unconfined aquifer (024 m.b.g.l.). This aquifer is vis-
ible on all of the shown cross-sections, where a shallow
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3070 Environ Earth Sci (2013) 70:30673084

BRENTA
RIVER
BRENTA
RIVER
BRENTA
RIVER

BRENTA
RIVER

BRENTA RIVER
BRENTA
RIVER

Fig. 2 Cross-sections of the study area (see Fig. 1)

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Environ Earth Sci (2013) 70:30673084 3071

Fig. 3 Pictures from the PM1 borehole: organic matter concentrated in thin peat layers (arrows) approximately 13.5 m below ground level (a);
and disseminated as isolated small plaques (arrows) within claysilt sediments approximately 17.5 m below ground level (b)

Table 1 Aquifer range of depth in meters below ground level (m.b.g.l.)

Aquifer Number of wells Depth Head (m.a.g.l.) Flow ratemean (l/s) Flow ratemax (l/s) Cond. (lS/cm) Temp. (C) pH
(m.b.g.l.)

Unconfined 43 024 / / / 600 16.2 7.3

I confined 27 2560 1.3 0.08 0.6 314 14.0 8.0
II confined 8 6585 1.3 0.20 0.6 400 16.3 7.5
III confined 24 140180 1.5 0.17 2.1 450 17.0 8.3
The principal parameters for the unconfined and three confined aquifers are also reported (head data measured using a manometer, chemical
physical data acquired by portable instruments)

layer of gravel is observed with decreasing thickness from
north to south. Cross-sections 1L and 2L exhibit a different
lithological setting that consists of mainly gravel in the
north and sand in the south. This aquifer is exploited for
domestic, irrigation and farming purposes. The water table
is near the surface. The unconfined aquifer hydrostratig-
raphy is comparable in the right and left river banks.
First confined aquifer (2560 m.b.g.l.). The first aquifer
is highly visible on the 1T profile, in the western part of 4T,
and in the longitudinal cross-section 1L. This aquifer is
artesian, and the potentiometric level is above ground level
(m.a.g.l) (Table 1). In this aquifer, the most ancient wells
are present, but intense exploitation of this aquifer occurred
during the second post-war period. This aquifer is intensely
exploited, and our estimation of the total extraction in the
studied area is approximately 200 l/s, with an increase of
55 l/s in the last decade. This aquifer is also exploited for
commercial purposes as mineral water. Along the right
bank of the Brenta river, this aquifer reduces its hydraulic
head and thickness.
Second confined aquifer (6585 m.b.g.l.). The three-
dimensional reconstruction of this aquifer is less known
because the stratigraphies available in the left Brenta bank
are rarely deeper than 50 m. The information contained in
cross-sections 1T, 2T, 3T and 4T shows that the thickness
of this aquifer is very variable. The water presents a higher
electrical conductivity than the first aquifer (Table 1). This
aquifer is poorly known in the left Brenta because only a
few wells reach this depth, due to the good productivity
and quality of the first aquifer. The exploitation of this

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aquifer ended in the 1990s, and its only current use is
ornamental (fountains). This aquifer shows high concen-
trations of ammonium, iron and manganese, and it is not
potable (Mion et al. 2009). Most of the wells were drilled
in the left Brenta.
Third confined aquifer (140180 m.b.g.l.). This aquifer
is visible in cross-sections 2T and 3T. Unfortunately, in the
middle part of the study area, only stratigraphies shallower
than 50 m (first aquifer) are available; thus, the third
aquifer is not geometrically defined. All of the wells were
drilled in the right Brenta. All the hydrogeological char-
acteristics of these artesian wells present consistent dif-
ferences (Table 1). In our study, the exploitation of this
third aquifer visibly increased from 1995 to 2000.
In Table 1, the principal parameters of the aquifers are
presented. These parameters include depth and thickness,
the value of the potentiometric level (i.e., the height at
which the water flows without a pump), the average and
maximum flow rates (without a pump), the electrical con-
ductivity of the water, the temperature and the pH.
Methods
Hydrochemical methods
All of the samples were collected between June 2010 and
November 2010, which is during the dry season and before
the beginning of the heavy autumn rains. A sample survey
was planned to collect water samples with a homogeneous
spatial distribution throughout the entire study area, which
is elongated along the flow direction of the Brenta River,
approximately from northwest to southeast.
Most of the samples (44) were obtained from the
unconfined aquifer, which is preferentially exploited in this
area (Mion et al. 2009). Samples from deeper aquifers were
also collected (16 from aquifer I, 3 from aquifer II and 2
from aquifers deeper than 180 m), representing artesian
aquifers up to 330 m in depth.
The boreholes were purged for 30 min before sam-
pling. Water temperature, Eh, pH, dissolved oxygen (DO)
and electrical conductivity parameters were measured in
the field, collecting the samples in a beaker. The redox
potential was measured after prolonged immersion of the
electrode (at least 20 min) and assuring measurement
stability. Other parameters that were measured in the field
include alkalinity (titration with HCl using phenolphtha-
lein and methyl orange and calculating the total alkalinity
as HCO3-), sulfides (excess iodine titrated with thiosul-
fate), free CO2 (Na-carbonate titration), ammonium
ion, fluoride, nitrite and sulfate (using an Hanna
spectrophotometer).
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Environ Earth Sci (2013) 70:30673084
In the laboratory, the untreated water samples were stored
in the refrigerator and analyzed within 24 h for nitrate,
chloride and phosphate with a Perkin Elmer UVVIS
spectrophotometer. All of the other elements considered in
this study (Si, Na, K, Mg, Ca, Fe and As) were determined on
untreated waters (as for all the other parameters), but on a
subsample that was acidified with HNO3 immediately after
sampling, to get pH \ 2. A Perkin-Elmer 5000 atomic
absorption spectrometer (AAS) was used for the Na and K
measurements, and a JobinYvon JY 38Plus inductively
coupled plasma optical emission spectrometer (ICP-OES)
was used to measure the other elements.
The total dissolved solids (TDS) were measured by
evaporating the sample in a platinum crucible at 180 C
(Hem 1985).
Geostatistical method
The data concerning the As concentration in the ground-
water from the unconfined aquifer (up to 24 m in depth)
were used to study its statistical and spatial distribution.
The dataset is represented by original data collected by
CNR in 2010 and by additional data collected from 1992 to
2005 by ARPAV, the Environmental Protection Agency
for the Veneto Region (a total of 445 data points, from the
two datasets).
Geostatistical analyses were conducted by R code (R
Development Core Team 2012) using the Gstat package in
particular (Pebesma 2004).
Many different spatial continuity indices and graphical
tools can be used to quantify spatial continuity. A classical
(semi-) variogram (Isaaks and Srivastava 1989) of the
arsenic values was used, which is given by:
1 X n
c h zxi  zxi h2 1
2N h i1
The experimental variogram demonstrates how the
mean squared differences between pairs of samples z(xi)
and z(xi ? h) varies according to h (modulus and
direction).
The variographic analysis can also be used to analyze
the differences in spatial variability of an indicator variable
I(xi; z) with respect to a particular threshold, z. In this
study, the arsenic potability limit will be used as z:

1 if zxi  z z cutoff
I xi ; z 2
0 otherwise
The indicator variograms obtained with this procedure
can be also interpreted as a frequency of transition from
one state (above the threshold) to another (below the
threshold) and can thus inform the spatial clustering of
values above or below the chosen threshold.
Environ Earth Sci (2013) 70:30673084
Although experimental variograms are useful explor-
atory tools, variogram structure identification is important
but not sufficient to achieve this studys goals. The next
step is the inference process, which is necessary for every
chosen kriging procedure. To synthesize a spatial conti-
nuity structure, it is necessary to infer a mathematical
function called a theoretical variogram, which can syn-
thetically represent an experimental variogram. During the
inference process, in which the theoretical variogram
model and its parameters are chosen, hydrogeological
information should be taken into account to support the
data analysis. Moreover, to conduct prediction using both
ordinary and indicator kriging (Journel 1983), the theo-
retical variograms must satisfy a definite-positive condition
(Chiles and Delfiner 1999).
Hydrochemistry results
Hydrochemical characteristics
Most of the samples (88 %) have low mineral content
(average TDS of approximately 400 mg/l, conductivity of
0.6 mS/cm), and only a few (12 %) of the samples have
TDS higher than 500 mg/l. The mineral content is always
below the limit for waters rich in mineral salts (Council
Directive 80/777/EEC 1980).
The Pipers diagram reported in Fig. 4 summarizes the
major element chemistry of the waters under consideration.
Table 2 reports the average, standard deviation, maximum
and minimum values of all analyzed parameters. The entire
dataset shows a rather monotonous chemistry, with 2 sit-
uations (4 samples) representing remarkable exceptions.
Most of the samples fall near the Ca-bicarbonate corner of
the Pipers diagram, which corresponds with the carbonate
abundance in the aquifers found in Brenta sediments
(Jobstraibizer and Malesani 1973; Venzo and Gajo 1998;
Monegato et al. 2010). Two samples that had high Na
contents are located far from the others in the plot (black
squares in Fig. 4) but still have a bicarbonate anionic sig-
nature. These samples represent the deepest waters of the
entire dataset (200 and 330 m), and their composition is
consistent with the evolution of Ca-bicarbonate water
undergoing cation exchange reactions (CaNa), as quanti-
tatively shown by Cheng (1988). Two other samples are
outside the main population in the plot (grey squares in
Fig. 4). These samples come from two neighboring shallow
wells (\10 m in depth and 1,200 m apart) that are lower in
Ca and Mg and slightly higher in Na; thus, their shifted
position in the Pipers diagram likely reflects local
conditions.
The variability of the chemical data was evaluated
according to two parameters: (1) the depth (Fig. 5); and (2)
3073
Fig. 4 Piper diagrams showing the main hydrochemical composition
of the groundwater under consideration
the geographic position of the wells (Fig. 6). The well
positions are expressed by the distance between the wells
and the apex of the Brenta megafan (i.e., the town of
Marostica). This distance approximates the position of the
wells along the flow direction of groundwater within the
study area (from northwest to southeast) and is indicated by
the parameter DW (measured in meters). The Brenta
megafan, as defined by Fontana et al. (2008), covers the
entire study area.
Figure 5 shows some parameters that are more sensitive
to variations in depth. The conductivity ranges from an
average value of 603 lS/cm in the unconfined aquifer to an
average value of 437 lS/cm in the first confined aquifer.
As expected, the conductivity and TDS parameters are
strongly correlated each other (r = 0.987, 52 observa-
tions). The decrease in conductivity with depth is coupled
by an increase in pH, which is rather variable in the
unconfined aquifer and becomes slightly alkaline below it.
Furthermore, the CaMg ratio shows significant variations
between the unconfined aquifer and first confined aquifer,
up to a depth of 67 m.
In Fig. 5, two historical datasets are plotted with the
original data (2010 survey) to increase the number of
samples. The trends described for the 2010 survey are
supported by historical data, even though the older dat-
abases were collected over a considerably larger time
interval (from 1987 to 1993 and from 1999 to 2008). The
more scattered data points in the external dataset can be
accounted for by data collection spanning several hydro-
logic years. Historical datasets allow for the appreciation of
the higher NO3- content in the north (Carmignano), as well
as its decrease in depth.
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3074 Environ Earth Sci (2013) 70:30673084

Table 2 Summary of depth, chemical and physical analyses of well water

n Average Standard deviation Min Max Detection limits

Depth (m) 65 31 47 6 330

T (C) 65 16 2 13 24 0.1
TDS (mg/l) 52 408 117 205 630 1
Cond (lS/cm) 65 556 155 253 873 1
pH 65 7.3 0.3 6.7 8.1
Eh (mV) 65 -44 149 -285 203
DO (ppm) 65 2.1 1.8 0.0 6.0 \0.01
CO2 (mg/l) 64 42 28 7 114 \0.2
HCO3- (mg/l) 65 396 114 171 773 1
-
Cl (mg/l) 65 11.9 13.4 \0.3 59.9 0.3
SO42- (mg/l) 65 21 21 \5 95 5
NO3- (mg/l) 65 8.7 10.6 \0.5 66.1 0.5
PO43- (mg/l) 65 0.18 0.21 0.01 1.00 \0.01
F- (mg/l) 65 0.23 0.14 0.02 0.65 \0.01
?
NH4 (mg/l) 61 2.8 4.6 0.01 29.0 0.01
SiO2 (mg/l) 65 16.2 7.1 5.9 32.1 0.02
Na? (mg/l) 65 14 27 2 166 0.03
K? (mg/l) 65 3.1 5.0 0.6 29.4 0.05
Mg2? (mg/l) 65 23 8 12 40 0.001
2?
Ca (mg/l) 65 82 29 23 147 0.01
Fe (lg/l) 65 842 1,768 2 [13,000 0.1
As (lg/l) 65 35 86 \0.4 431 0.4
A few values (less than 25 %) below the instrumental detection limits have been substituted by half of the detection limit (Farnham et al. 2002).
TDS total dissolved solids, Cond conductivity, DO dissolved oxygen. The sensitivity of pH and Eh is \0.01 and 0.1, respectively

In addition to the variations in depth described above,
many chemical parameters are observed to change from
northwest to southeast. Nevertheless, such variations can
only be clearly identified for the unconfined aquifer
because most of the wells are very shallow in the
southern part of the study area. In Fig. 6, the measured
parameters are plotted against the DW values, to
emphasize that several analytical parameters are con-
trolled by the position of the wells (unconfined aquifer)
along the approximately 20 km extension of the study
area. The relationships between the DW parameter and
water chemistry (Fig. 6) are mainly expressed by changes
in the slope of linear trends (Na?, Mg2? and pH) or by a
more-or-less sharp transition from a clear linear rela-
tionship in the north to more scattered values towards the
south (conductivity, HCO3- and SiO2). Other parameters
(NH4? and Fe) change when Eh becomes negative,
shifting from almost undetectable to appreciably high
values.
Arsenic in groundwater
The concentration of arsenic in the water samples varies
significantly, ranging from \0.4 ppb to 431 ppb (Table 2).
With respect to the quality of the water resource, the most
relevant feature is the high concentration of this element in
the groundwater. In particular, the limit for drinkable water
(10 ppb, Council Directive 98/83/EC 1998) is far below the
average value measured in the area (35 ppb), even if the
median is considerably lower (5 ppb). When considering
the variability of As concentrations, the number of wells
that pass the drinkable limit can be considered instead of
the average and of the median concentration. In this case,
considering that 32 % of the samples are above the
drinkable limit, the occurrence of a significant As anomaly
is confirmed.
According to both the original data and older data from
ARPAV (Environmental Protection Agency for the Veneto
Region, sampling from 1992 to 2005), significant vari-
ability in As concentration characterizes both the vertical
profile and spatial distribution of the element (Fig. 7a, c).
In general, low As concentrations can be found irrespective
of the well depth. However, it is very interesting to note
that the As anomaly decreases from shallow to greater
depths (dashed line in Fig. 7a).
In Fig. 7b, data from Bangladesh (BGS and DPHE
2001) are reported for comparison purposes. Naturally
occurring As in groundwater (up to 2,500 ppb) is well

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Conductivity (S/cm) pH
0 400 800 1200 6.5 7 7.5
0
50
100
150
200
250
300
Depth (m)
350
Fig. 5 Chemical variation of selected parameters with depth. The
dataset provided by the municipalities of Carmignano and Piazzola is
also reported (small empty symbols). The dashed line indicates the
documented in a wide Bangladeshi area of approximately
150 000 km2, where the relevant aquifers consist of allu-
vial/deltaic sediments with abundant organic matter. It is
evident that samples from Bangladesh show a behavior
similar to that of the samples from the Venetian Plain, with
As anomalies that also decrease with depth. Another sim-
ilarity is the positive relationship between As and NH4?
observed in Bangladesh (BGS and DPHE 2001) and the
Venetian Plain (Pearson correlation coefficient = 0.50, 50
observations). Such similarities allow to consider analogue
mechanisms responsible for elevated groundwater As
concentrations.
Because data are available for a continuous DW range,
the distribution of As values versus the DW parameter has
been considered for the unconfined aquifer. The distribu-
tion of As concentrations along DW distance follows a
rule: concentrations are rather low for DW distances less
than 17,000 m but become higher and more variable with
increasing DW (Fig. 7c).
A remarkable anomaly can be detected at approxi-
mately 21,500 m DW, where 3 samples (2010 sampling
survey) show very high As concentrations of up to
431 ppb. Such a small cluster of samples can be consid-
ered a hot spot (see Smedley 2006) that is character-
ized by the highest As contents (2010 survey) and by a
strong threshold with respect to adjacent points (Fig. 8a).
At the same DW distance, another well demonstrated
similar features (330 ppb As in 1993, 24 m depth), and
one of the hot spots recognized in the 2010 survey was
sampled previously in 1995, yielding very similar results
(318 ppb As).
3075
NO3- (mg/l) Ca/Mg
8 8.5 0 20 40 60 80 1 2 3 4 5 6
CNR survey 2010
CNR survey 2010
CNR survey 2010
Piazzola dataset (1987-1993)
Carmignano dataset (1999-2008)
transition from the unconfined to confined aquifer approximately
24 m below ground level
Geostatistical results
A preliminary statistical analysis, reported in Fig. 8b,
shows a lognormal distribution of As in the unconfined
aquifer, with a skewness value of 6.5. Such an As distri-
bution is often observed in datasets (Angelone et al. 2009;
Hosono et al. 2011), and a data transformation is frequently
conducted before geostatistical analysis, mainly when a
gaussian kriging (Digger and Ribeiro 2007) is used. In this
case, it is preferable not to transform the As data because,
when confronted with a more difficult variogram inter-
pretation, the actual As concentration previsions are
obtained directly in As concentrations.
Before calculating the experimental variograms, it is
useful to analyze the variogram cloud (Ploner 1999). The
variogram cloud is an extremely helpful tool for checking
spatial continuity and detecting outliers. Figure 9 illustrates
how the variogram cloud increases with h and the presence
of outliers, as suggested by the initial statistical analysis.
According to Isaaks and Srivastava (1989), a convenient
tool to visualize experimental variograms is to also analyze
the variogram simultaneously in all directions with a sur-
face variogram. The surface variogram in Fig. 10a reveals
an anisotropy in the continuity structure of arsenic in the
study area. In particular, the experimental surface vario-
gram detects an anisotropy with a maximum continuity at
55. Thus, directional experimental variograms related to
the arsenic along and orthogonal to the principal anisotropy
(along 10, 55, 100 and 145) are shown in Fig. 10b.
Analysis of Fig. 10b confirms the anisotropy visible in the
experimental surface variogram of Fig. 10a.
123
3076
Fig. 6 Variations in the main analytical parameters as a function of DW values for the unconfined aquifer (DW well distances respect to the apex
of Brenta megafan, expressed in meters)
The variographic analysis can also be used to analyze
the differences in spatial variability with respect to a par-
ticular threshold, which is the guideline value for As in this
case. This type of elaboration allows for the identification
of the local probability that the arsenic concentration in
shallow groundwater exceeds the potability threshold of
10 ppb.
With this in mind, the surface experimental indicator
variogram is shown in Fig. 10c, where an anisotropy at
approximately 90 is notable. Thus, to complete the spatial
anisotropy analyses, directional experimental indicator
variograms along the direction of maximum continuity and
its perpendicular are shown in Fig. 10d. The indicator
variogram analysis also demonstrates the maximum con-
tinuity at 90.
123
Environ Earth Sci (2013) 70:30673084
The variogram of arsenic (Fig. 10b) and the indicator
variogram related to the arsenic threshold of 10 ppb
(Fig. 10d) are fitted using exponential models. The com-
parison between experimental and theoretical variograms
suggests a good reproduction of the spatial structure of As
data (Fig. 10b and d). According to Davis (1987), the
cross-validation procedure cannot confirm that a particular
variogram model is or is not the optimum. Then, the
resulting theoretical variograms will be used while apply-
ing different kriging procedures.
The first variogram related to As values, reported as a
continuous line in Fig. 10b is:
  
3h
ch 100 700 1  exp  3
1300
Environ Earth Sci (2013) 70:30673084 3077

Fig. 7 Arsenic concentration with respect to well depth (a study area, b Bangladesh, BGS and DPHE 2001) and the DW parameter (c,
unconfined aquifer only)

Fig. 8 Geographic distribution

of the As concentration in the
groundwater of the unconfined
aquifer (a). Map coordinates are
shown in metric units WGS84.
Lines showing DW distances of
17,000 and 21,500 m are
reported. The histogram
showing the lognormal
distribution of As data is also
reported (b)

123
3078
Fig. 9 Variogram cloud. The initial statistical analysis indicates an
increase with h and the presence of outliers
where 100 is the nugget effect (12.5 %), 700 is the
sill (87.5 %) and 1,300 is the range of the variogram,
with a geometrical anisotropy of 0.46 at 55.
The second variogram, related to the potability threshold
and reported as a continuous line in Fig. 10d is:
  
3h
ch 0:009 0:035 1  exp  4 water in the study area is in agreement with the subsurface
1000
where 0.009 is the nugget effect (20.5 %), 0.035 is the
sill (79.5 %) and 1,000 is the range. This model
presents a geometrical anisotropy (0.5) at 90.
After completing a detailed variogram analysis and the
inference process, the next step is to apply kriging pre-
dictions. One of the main objectives of this process is the
spatial prediction of arsenic distribution in the study area
using an ordinary kriging. An additional result is the spatial
prediction of the probability that the arsenic concentration
in shallow groundwater exceeds 10 ppb (the arsenic pota-
bility threshold), using an indicator kriging.
In Fig. 11a, the predicted distribution of arsenic in
shallow groundwater is shown. The inset shows the pre-
diction error variance in more detail, clearly showing that
the reliability of the prediction varies throughout the study
area.
A preliminary analysis of Fig. 11a reveals a wide zone
in the northwest part of the study area with low arsenic
values and high kriging result reliability (Fig. 11b),
accordingly to the high datapoint density. This zone is
roughly delimited by a DW parameter of 17,000 m (which
has been established according to several geochemical
parameters). In the central part (DW between 17,000 and
123
Environ Earth Sci (2013) 70:30673084
21,500 m), the kriging result is more heterogeneous
because domains with low and intermediate As values are
side by side but can still be predicted (Fig. 11b). In con-
trast, southeast of the 21,500 m DW line, the kriging pre-
diction shows domains with very high and very low As
concentrations. Nevertheless, most of these low As
domains are characterized by lower reliability due to the
lack of wells. Moreover, the domains characterized by the
highest As anomaly show a lenticular shape that matches
the anisotropy at 55 (Fig. 10a, b).
In Fig. 11c, the probability that arsenic concentration in
shallow groundwater exceeds 10 ppb is shown, and its
prediction error variance is reported in the related inset
(Fig. 11d). The southeastern part of the studied area is
characterized by a high probability ([51 %) of encoun-
tering non-potable water. However, within this southeast-
ern part, the small zones with a low probability of
exceeding the potability threshold must still be interpreted
with caution if they are located in areas where the well
density is very low (very low reliability). A different
condition is typical of the band along the right bank of the
Brenta River in the southeast, where the As concentration
is low and the prediction reliability is good.
Discussion
The widespread Ca-bicarbonate composition of ground-
geology and sediment composition (Monegato et al. 2010),
which is characterized by abundant amounts of calcite and
dolomite. The unconfined aquifer shows a larger variation
of selected parameters, such as conductivity, pH, NO3- and
the CaMg ratio, as compared to the deeper aquifers. In
particular, the high nitrate content in the northern part of
the unconfined aquifer was already known to be attributed
to anthropogenic actions (Boscolo and Mion 2008).
In confined aquifers ([24 m.b.g.l.), the effect of
anthropogenic activity (NO3-) is minimized, and the
CaMg ratio decreases to as low as 2, which was almost
reached by the deepest samples. The variation of the
CaMg ratio has been evaluated using a geochemical
modeling approach (Visual MINTEQ; Gustafsson 2012)
along the transition from the unconfined aquifer to the first
confined aquifer. The main forcing variables are pH, the
progressive attenuation of the atmospheric buffer for CO2
and the continuous presence of calcite and dolomite in the
aquifers. These conditions cause the water from the
unconfined aquifer to become more oversaturated in calcite
approaching the first confined aquifer, thus promoting
calcium carbonate precipitation (that is, lowering of the
CaMg ratio, as observed). Geochemical modeling predicts
a value of 2.2 for the CaMg ratio at equilibrium, which is
Environ Earth Sci (2013) 70:30673084
Fig. 10 Experimental surface variograms and related directional
experimental variograms for the unconfined aquifer: experimental
surface variogram for As concentration (a); directional experimental
variograms for As concentration (b); experimental surface indicator
in agreement with the measured trend and also accounts for
the lowering of TDS and conductivity.
Despite the homogeneous Ca-bicarbonate composition
of waters, strong variations in redox conditions occur from
north to south and such redox variability is quite remark-
able, ranging from 172 mV (in the north) to -272 mV (in
the south), and is accompanied by changes of other
master variables (such as pH and conductivity; Fig. 6). south agrees with stratigraphical data that indicate the
Approaching the distal areas of the Brenta depositional
megafan, along the flow direction (DW parameter; Fig. 6),
a stronger importance of the organic matter decay is sug-
gested by increasingly negative Eh values, the increase in
3079
variogram for the drinkable limit threshold of 10 ppb As (c); and
directional experimental indicator variograms for the threshold of
10 ppb As (d)
NH4? and the decrease in pH (both aerobic or anaerobic
decay determine a decrease in pH; Langmuir 1997). The
effect of lowering the Eh and pH is an enhanced dissolution
of carbonates, oxides and hydroxides, shifting the TDS and
conductivity to higher values, as demonstrated by the
increased DW parameter (Table 2; Fig. 6).
Such a chemical evolution of groundwater from north to
disappearance of gravel and the presence of thick clay
deposits towards the south (Fig. 2). Owing to the formation
of peat in wet depressions, fine-grained sedimentation in
the Venetian alluvial plains is characterized by abundant
123
3080 Environ Earth Sci (2013) 70:30673084

Fig. 11 Predicted distribution of As (a) and related error variance (b); probability that As concentration in shallow groundwater exceeds 10 ppb
(c); and related error variance (d). Map coordinates are shown in kilometric units WGS84 (OK ordinary kriging, IK indicator kriging)

123
Environ Earth Sci (2013) 70:30673084
organic matter (Miola et al. 2006; Fontana et al. 2008;
Zecchin et al. 2011). Both peat deposits and disperse
organic matter are detectable in boreholes (Fig. 3). As
suggested by the positive relationship between As and
NH4?, the role of organic matter in the study area has
direct effects on the specific problem of As occurrence in
groundwater. Similar conditions are well known worldwide
(Varsanyi et al. 1991; BGS and DPHE 2001; Dowling et al.
2002; Ahmed et al. 2004; Dangic and Dangic 2007; Berg
et al. 2008; Deng et al. 2009; Reza et al. 2010; Winkel et al.
2011; see also several examples shown by Ravenscroft
et al. 2009 and the review by Smedley 2006). Another
similarity between the Venetian Plain and other areas
affected by As groundwater contamination (such as Ban-
gladesh; BGS and DPHE 2001) is the decrease in the
maximum As content at certain depths (Fig. 7). In partic-
ular, at intermediate depths (100200 m), the variation in
As content is less pronounced, and maximum values are
significantly lower (average in Bangladesh:
As = 45 49 ppb; see Fig. 7 for the Venetian Plain).
Below 200 m.b.g.l., the groundwater As content is still
lower (average in Bangladesh: As = 4 10 ppb; see
Fig. 7 for the Venetian Plain), implying an increasing
probability of finding water with acceptable As content.
Furthermore, this feature can be explained by considering
the role of labile organic matter, which loses its reducing
capability with aging (BGS and DPHE 2001; Ravenscroft
et al. 2009), as well as the effect of flushing (more pro-
longed in deeper aquifers), which has been identified as a
key factor (BGS and DPHE 2001; Ravenscroft et al. 2005).
According to the chemical data reported in Figs. 6 and
7c (including the master variables pH and Eh) and the As
distribution (see ordinary kriging predictions in Fig. 11), an
important change in water chemistry occurs from north-
west to southeast, between a DW parameter of 17,000 and
21,500 m. This trend represents a transitional discontinuity
in the area and marks a northern and southern domain
featuring different likelihoods of finding potable water with
respect to As concentration (Fig. 11c). In particular, the
southern domain is clearly characterized by an anomalous
background identified by diffuse high As values up to
150 ppb, which is considerably higher as compared to the
drinkable limit of 10 ppb (Figs. 7c, 8a and 11c). Never-
theless, the main environmental and health concern goes
beyond such diffuse anomalous background and is rep-
resented by the As hot spots (As [ 300 ppb) punctuat-
ing the distance reference of 21,500 m DW (Fig. 8a). A
speculative explanation for the peculiar locations of the
hot spots considers the abrupt increment of the retar-
dation factor (Rd) for As. The increased As concentration
is consistent with lithological variations (from coarser to
finer sediments) that determines an increase in Rd due to
changes in sediment texture and the distribution coefficient
3081
of As for clays. A similar mechanism accounts for the
occurrence of As hot spots in South and East Asian
countries (The World Bank 2005) and also as a general rule
(Smedley 2006). In the study area, a lithological variation
appropriate to account for the occurrence of these hot
spots corresponds to 21,500 m DW. Such lithological
discontinuity of the unconfined aquifer is emphasized by
matching the DW parameter (that represents a simple
geometric expression of the sediment dispersion) with the
kriging arsenic predictions. In further lithostratigraphic
detail, cross-sections 1L and 2L (Fig. 2) show that the
thinning of gravel deposits towards the south (unconfined
aquifer) gives rise to a fine-grained aquifer passing through
the 21,500 m DW.
The abundance of clay-silt materials in the southern part
of the unconfined aquifer appears to be a main constraint
for water quality with respect to As concentration. In
particular, the probability of exceeding the threshold limit
of 10 ppb (Fig. 11c) reflects this condition. An example is
the southern part of the study area, where the probability is
often very high but where the easternmost side is charac-
terized by a low probability. The lithostratigraphic
arrangement is represented by cross-section 4T (Fig. 2),
where the unconfined aquifer (024 m.b.g.l.) is mainly
sandy west of the Brenta River for approximately 2 km and
where the probability of encountering non-potable water is
low. In contrast, the aquifer becomes silty-clay to the West,
where it contains peat material and where the probability
increases by over 50 %.
A final consideration relates to the origin of As anom-
alies and their stationary or stable areal distribution. No
significant variation can be found between the most recent
analytical survey (2010) and historical data covering the
last 20 years. In particular, both the anomalous back-
ground in the southern area and the hot spots appear to
be very stable in space and intensity. Because the distri-
bution of industrial plants does not match the distribution
of As in groundwater, an anthropogenic origin should be
considered cautiously. Furthermore, the possible input of
As salts as pesticides before 1976 (which was the ban year
in Italy; Celli 1995) does not agree with the traditional
agricultural practice of the area (Bittante et al. 1985;
Celetti 2008; Varini 2008).
The alternative hypothesis, a natural origin of As in
groundwater, cannot be completely assured but is consis-
tent with the geology of the area. In particular, the soils
developed on the Brenta fan (including the study area) and
Adige fan have As contents much higher than the adjacent
depositional systems (such as the Piave and Tagliamento),
which are similar in age and tectono-stratigraphic setting
(average values for topsoils: Brenta = 21 ppb, Adige =
19 ppb, Piave = 8 ppb, Tagliamento = 10 ppb; Giandon
et al. 2011). The high As concentration in the Brenta and
123
3082
Adige soils (in a large area extending over thousands of
square kilometers) can be accounted for, at least qualita-
tively, by the occurrence of sulfide ore deposits in the
catchments, several tens of kilometers from the study area
(see the compilation by De Vivo et al. 2009). A prevailing
geogenic origin of As in the Brenta soils has been identified
by Ungaro et al. (2008), who studied an area in the
southern Brenta fan.
Summary and conclusions
The study area represents a typical northern Italian plain
area where industrial, agricultural and economic activities
have been well developed for a long period of time. The
social and economic wellness reaches high standards
respect to the western countries and rural activities are also
prosperous. This condition requires the use of local
groundwater for private purposes (low volumes), social and
economic activities (large volumes). In this context, the
results of the present study are as follows:
several water wells (32 %) from the most exploited
aquifer (the unconfined one) have been found to contain
As in excess of drinkable limits;
the kriging arsenic prediction map (Fig. 11a) shows
that most of these high As values are located in the
southern part of the study area, where reducing
groundwater conditions occur;
the indicator kriging prediction map (Fig. 11c) demon-
strates the high probability of encountering non-potable
water in a large part of the unconfined aquifer, which is
the most frequently exploited aquifer in the area;
the most remarkable groundwater As anomalies
([300 ppb) are found at the transition from a gravel to a
silty-clay reservoir in the unconfined aquifer. These
anomalies have the characteristics of so-called hot-
spots, which are observed worldwide and are character-
ized by very high As concentrations and a strong threshold
with respect to adjacent wells from the same aquifer;
a rapid decrease in As concentration with depth was
observed, allowing for the prediction that more favor-
able water quality (at least with regard to As) can be
found below a depth of 150200 m.
An anthropogenic source of As appears to be unlikely in
the study area. In fact, soils on silty-clay Brenta sediments
have higher As concentrations than most common soils, but
the positive relationship between As and NH4? suggests
that sedimentary organic matter is the first candidate to
determine As anomalies in groundwater.
The likely natural origin of As contamination suggests
that the problem goes well beyond the area considered in
this study. In western countries, health effects are
123
Environ Earth Sci (2013) 70:30673084
minimized by the provision of potable water to the public.
However, the pipe network is not as pervasive as it needs to
be. The health effects of As pollution in groundwater are
generally very severe, including chronic exposures occur-
ring at relatively low concentrations (see the review by
EFSA 2009), particularly among the elderly (see, for
example, Tseng 1977). Accordingly, geochemical, litho-
stratigraphical and geostatistical analyses are powerful
tools for the study of the environment and healthcare.
Acknowledgments This study has been funded by National
Research Council (CNR) of Italy, Veneto Region, the Brenta Aut-
orita` dAmbito Territoriale Ottimale (AATO) and Carmignano
municipality. The Agenzia Regionale per la Prevenzione e Protezi-
one Ambientale (ARPAV), Carmignano and Piazzola municipalities
are greatly appreciated for providing historical datasets. Anonymous
reviewers are acknowledged for improving the manuscript.
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