Applied Geochemistry xxx (2013) xxx–xxx

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Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem

Dissolved nitrates in the groundwater of the Cecina Plain (Tuscany,

central-western Italy): Clues from the isotopic signature of NO
3

B. Nisi a,⇑, O. Vaselli b,c, A. Delgado Huertas d, F. Tassi b,c

a
CNR-IGG, Institute of Geosciences and Earth Resources, G. Moruzzi, 1, 56124 Pisa, Italy
b
Department of Earth Sciences, Via G. La Pira, 4, 50121 Florence, Italy
c
CNR-IGG, Institute of Geosciences and Earth Resources, G. La Pira, 4, 50121 Florence, Italy
d
Instituto Andaluz de Ciencias de la Tierra IACT (CSIC-UGR), Avda. de las Palmeras, 4, 18100 Armilla, Granada, Spain

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

Article history: Anthropogenic NO 3 is one of the most serious pollutants in the groundwaters from the multi-aquifer sys-
Available online xxxx tem of the Cecina Plain (Tuscany, central-western Italy). According to the EC Directive (91/676/CEE), the
local administration of Tuscany has declared the Cecina Plain as ‘‘vulnerable by nitrates’’. Determining
the origin and the source(s) of NO 3 contamination is an important step prior to any remediation program.
In the present work a geochemical survey was carried out on 92 groundwater samples collected in June
and October 2006 to highlight the natural and anthropogenic features that concur with the observed
chemical composition. The geochemical facies of the water samples is dominated by Ca(Mg)–HCO3 and
Ca(Mg)–SO4(Cl) and, subordinately, by Na(Ca)–Cl(SO4), likely resulting by water–rock interaction pro-
cesses between meteoric-derived groundwaters with the sedimentary formations characterizing the
Cecina Plain, at which ingression of seawater in the coastal area is also added. A mixing model, based
on ionic ratios (NO3/Na, Cl/Na, Cl/Br), was applied to distinguish the anthropogenic sources (e.g. sewage,
agriculture input) from natural sources (e.g. seawater intrusion). Selected samples were analyzed for the
isotopic composition of NO 15 18
3 (d N–NO3 and d O–NO3) to formulate hypotheses on its origin and the pro-
cesses this component may suffer in the water system. Nitrate concentrations range from 0.01 to
354 mg/L. About 35% and 19% of the sampled wells in June and October 2006, respectively, had levels
of NO 3 higher that those recommended by the World Health Organization (<50 mg/L). The d O–e
18

d15N–NO3 values in the Cecina Plain groundwaters are between 7.5‰ and 22.6‰ and from 2.8‰ to
14.9‰, respectively, indicating that synthetic fertilizers are the main source of NO3 pollution in the study
area. Nevertheless, sewage/manure inputs and denitrification processes were also recognized.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction
The multi-aquifer system in the coastal area between Rosignano
and San Vincenzo (hereafter Cecina Plain), located in Tuscany (cen-
tral-western Italy), includes the terminal courses of the Cecina and
Fine rivers (Fig. 1), and is affected by several natural and anthropo-
genic contaminants that contribute to spoil the water quality of the
area. Overall, the main processes affecting this portion of the coast-
al side of the Tyrrhenian Sea can be summarized, as follows: (i) sea
water intrusion due to both the over-exploitation of the water re-
sources and the intense tourism activity in summer time (Pranzini,
2004; Grassi et al., 2007); (ii) boron contamination of the Cecina
River, deriving by both the geothermal power generation at Larde-
rello and B-rich mineral processing (Pennisi et al., 2006), and (iii)
nitrate pollution whose source is apparently related to the agricul-
tural practices.
⇑ Corresponding author. Tel.: +39 050 3152320; fax: +39 050 3152323.
E-mail addresses: b.nisi@igg.cnr.it, barbara.nisi@unifi.it (B. Nisi).
The presence of high NO 3 contents (up to about 300 mg/L;
Grassi et al., 2007) represents a major issue for groundwater man-
agement in the Cecina Plain. Despite increasing efforts to reduce
NO 3 inputs from intensive agriculture at national and European
(EC Directive 91/676/CEE) levels, NO 3 is still one of the main
contaminants, with about 35% of the well waters characterized
by values >50 mg/L (Pranzini, 2004) (maximum admissible con-
centration for drinking water according to the EC Directive
98/83/CEE). As a consequence, according to the EC directive the
local administration of Tuscany has declared the Cecina Plain as
‘‘vulnerable by nitrates’’. According to Grassi et al. (2000, 2007)
and ARPAT (2003), the main source of NO 3 in the Cecina Plain
groundwater system is the use of fertilizers.
A powerful tool to distinguish different sources of NO 3 is the
determination of stable isotope ratios of N and O (e.g. Wassenaar,
1995; Böhlke et al., 1997; Kendall, 1998; Bleifuss et al., 2000;
Kendall and Aravena, 2000; Panno et al., 2001, 2008; Burns and
Kendall, 2002; Campbell et al., 2002; Fukada et al., 2004; Nisi
et al., 2005; Kwang-Sik et al., 2008; Xue et al., 2009; Fenech

0883-2927/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apgeochem.2012.12.004

Please cite this article in press as: Nisi, B., et al. Dissolved nitrates in the groundwater of the Cecina Plain (Tuscany, central-western Italy): Clues from the
isotopic signature of NO 3 . Appl. Geochem. (2013), http://dx.doi.org/10.1016/j.apgeochem.2012.12.004
2 B. Nisi et al. / Applied Geochemistry xxx (2013) xxx–xxx

Fig. 1. Schematic geological map of the Cecina Plain and locations of the sampling sites. LEGEND: (1) alluvial (Holocene-present) and clastic deposits of the coastal plain
(Upper Pleistocene); (2) Pleistocene sands, clayey sands and conglomerates, and marine deposits (Pliocene) with some Miocene evaporites; (3) Flysch formations made up of
clays, marls and sandstones (Cretaceous–Paleocene) (Ligurian units); (4) Upper Jurassic allochtonous ophiolites; (5) flysch formations made up of clays, marls and sandstones
(Eocene) (sub-Ligurian units); (6) turbiditic sandstones (Cretaceous/Eocene–Oligocene) (Tuscan units); (7) Mesozoic limestone (Tuscan units).

et al., 2012), particularly when coupled with water chemistry and
NO3 concentrations (e.g. Nisi et al., 2005, 2008; and reference
therein). The d15N–NO3 values tend to show overlapping ranges
which do not differentiate the sources NO 3 (e.g. Kendall, 1998;
Widory et al., 2004, 2005). By coupling the d18O–NO3 values as
an additional isotopic parameter the origin of dissolved NO 3 can
be constrained more precisely (Clark and Fritz, 1997; Kendall,
1998; Mayer et al., 2002; Nisi et al., 2005). Overuse of fertilizers
has resulted in high concentrations of NO3 , which has resulted in
changes in the N–NO3 isotopic composition in superficial and
groundwaters. Nitrate from synthetic fertilizers have d15N values
varying from 6‰ to +6‰ (Kendall, 1998; Xue et al., 2009), while
those of d18O are +22 ± 3‰ (Amberger and Schmidt, 1987), because
they are produced from atmospheric N (d15N = 0‰) (Mariotti,
1983) and O (d18O = +23.5‰) (Kroopnick and Craig, 1972). Nitrate
derived from manure and sewage is isotopically distinct from that
of fertilizers in both d15N (from 5‰ to 25‰, Kendall, 1998; Clark
and Fritz, 1997; Xue et al., 2009) and d18O (<15‰, Kendall, 1998)
values. However, during microbial denitrification, i.e. during the
stepwise conversion of NO 3 to N2, N and O isotopes are fraction-
ated; the lighter isotopes (14N and 16O) are preferentially parti-
tioned into the products, while the heavier ones (15N and 18O)

Please cite this article in press as: Nisi, B., et al. Dissolved nitrates in the groundwater of the Cecina Plain (Tuscany, central-western Italy): Clues from the
isotopic signature of NO 3 . Appl. Geochem. (2013), http://dx.doi.org/10.1016/j.apgeochem.2012.12.004
 B. Nisi et al. / Applied Geochemistry xxx (2013) xxx–xxx
becomes concentrated in the residual reactants (Mariotti et al.,
1988; Böttcher et al., 1990). As a consequence, NO 3 from fertilizers
affected by partial denitrification has more positive d15N values,
which could cause misleading interpretations for the origin of
the dissolved NO 3.
Several studies have employed both d15N and d18O in NO 3 to
indicate the occurrence of denitrification in the water system, be-
cause during this process, the residual NO 3 increases its N isotopic
value at about twice the rate as that of O (e.g. Olleros, 1983; Bött-
cher et al., 1990; Voerkelius and Schmidt, 1990). Therefore, if a bin-
ary diagram of d15N vs. d18O is plotted, a denitrification trend has a
slope of approximately 0.5.
In this work, water chemistry and N and O isotopic data for NO 3 domestic and tourism practices, the latter being particularly in-
are, for the first time in an international journal, presented with
the aim of (i) assessing the anthropogenic sources that contribute
to the high NO 3 values recorded in the groundwater system of
the Cecina Plain and (ii) recognizing the presence of possible pro-
cesses that may affect the pristine anthropogenic NO3 isotopic sig-
nature. Mixing models of ionic molar ratio was an additional tool
to provide further evidence and support for the conclusions
achieved through d18O–NO3 and d15N–NO3 isotope studies. It is
to be noted that in Capri et al. (2009) some preliminary diagrams
of the Cecina Plain waters were displayed in the framework of a re-
search project of national interest (PRIN-2006) funded by the Ital-
ian Ministry of Education, University and Research and aimed at
assessing the contamination risks of NO 3 in several Italian sites.
The paper by Capri et al. (2009) was merely a summary of the main
scientific activities carried out within the previously mentioned
project.
2. Study area
2.1. Hydrogeological background
The Cecina Plain, located in central-western Italy, represents the
coastal area between Rosignano and San Vincenzo, which includes
the lower courses of the Cecina and Fine rivers. The study area is
oriented N–S and is approximately 40 km long and 6 km wide
(Fig. 1). From a geological point of view, Lower Pleistocene to Holo-
cene marine and continental sediments, whose terraces dip west-
wards, dominate the plain whilst Cretaceous to Eocene flysch
formations occur in the central and eastern part of the study area
(Bartoletti et al., 1985; Costantini et al., 1993; Mazzanti and Senesi,
1996). Occasionally, Messinian gypsum-rich evaporitic rocks crop
out in the Neogene sediments, while ophiolite blocks made up of
serpentinites and basalts can be recognized within the flysch se-
quence. Finally, Mesozoic carbonate formations are present in the
southern part of the study area (Fig. 1).
The subsoil consists of a succession of units with medium to
high permeability (gravel, sand, sandy limestone; hydraulic con-
ductivity (k) ffi 102 m/s), interbedded with low permeablility or
impermeable units (silt and clay; hydraulic conductivity
(k) ffi 104–109 m/s) (Pranzini, 2004). These units form a multi-
layered aquifer system, which exhibits variable permeability.
According to Grassi et al. (2000), the aquifer is recharged by mete-
oric waters flowing from the surrounding hills (oriented NE–S) and
by infiltration through the plain and the riverbeds. The annual
rainfall pattern is typical of the Mediterranean area, being low in
July (mean monthly temperature ffi 24 °C) and with a peak of pre-
cipitation in November (mean monthly temperature ffi 13 °C). Over
30 a (from 1970 to 2001) the rainfall average measured at the Ceci-
na Plain weather station was 725 mm/a. Water level measure-
ments indicate that the water-table depth is affected by seasonal
fluctuations and over-exploitation, particularly strong in summer-
time. In the study area the water level variation is approximately
Please cite this article in press as: Nisi, B., et al. Dissolved nitrates in the groundwater of the Cecina Plain (Tuscany, central-western Italy): Clues from the
isotopic signature of NO 3 . Appl. Geochem. (2013), http://dx.doi.org/10.1016/j.apgeochem.2012.12.004
3
2.9 and +2.00 m in September and May 2002, respectively
(Cerrina Feroni et al., 2010). In general, water-coning depressions
are mainly due to the pumping systems located near urban centers
(i.e. Cecina, Rosignano Solvay, San Vincenzo), where the multi-
layered aquifer is undergoing an ever-rising water demand due
to anthropogenic activities.
2.2. Human activity
In the Cecina Valley the main anthropogenic contributions are
due to agriculture, industry/mining (halite extraction in the sur-
rounding areas of Volterra 30 km ENE from the city of Cecina),
tense along the coast of the Tyrrhenian Sea during the summer sea-
son. Land use in the whole study area is dominated by agriculture
(i.e. seeded, greens, corn, grapevine), which occupies 2354 ha and
requires 5,674,776 m3 of water annually for irrigation (ARSIA,
2000). According to the National Directive 217/06 (http://
www.parlamento.it/leggi/deleghe/06217dl.htm), inorganic and or-
ganic commercial fertilizers are used for most crops.
In the southern part of the Cecina River basin the anthropogenic
contribution is related to past industrial activities in the Larderello
geothermal field. Here, from 1817 until the first half of the 20th
century boric acid (H3BO3) was extracted from the geothermal flu-
ids. After the Second World War, boric acid extraction shifted from
the geothermal fluids to B minerals, mainly colemanite [CaB3O4-
(OH)3H2O], imported from Western Anatolia (Turkey). Subse-
quently, the exhausted geothermal fluids were re-injected into
the geothermal reservoir after 1980 (Pennisi et al., 2006). As a con-
sequence, the presence of B in the groundwater, often exceeding
1 mg/L, is likely related to both the past discharge of geothermal
waters in the surficial waters and the residual B-rich mud associ-
ated with the chemical industry (Grassi and Squarci, 2004; Pennisi
et al., 2006; Grassi et al., 2007). Currently, the main industries, lo-
cated between Rosignano Solvay and Cecina, have a water demand
of 6.8 million m3/a (Pranzini, 2004).
Finally, as the main urban centers are distributed along the Tyr-
rhenian Sea coast where most summer tourism is also concen-
trated, domestic sewage may contribute to spoil the quality of
the groundwater. Furthermore, sea water intrusion is caused dur-
ing summer by the over-exploitation of water resources for human
supply (up to 10 million m3/a; Pranzini, 2004).
3. Sampling and analytical procedures
In the Cecina Plain 92 groundwater samples were collected
from wells distributed throughout the valley in urban and agricul-
tural areas, 49 in June (beginning of the irrigation practice) and 43
in October (before the main manure application), 2006 (Fig. 1).
Moreover, during the October sampling, 19 samples with NO 3 con-
tent >20 mg/L were selected for the determination of N and O iso-
topes in dissolved NO 3 , in order to consider only those waters
where the anthropogenic input was present since, according to
Widory et al. (2005), natural NO 3 in groundwater occurs at moder-
ate concentrations, i.e. around 10 mg/L.
Furthermore, the sampling strategy was aimed at assessing the
usefulness of combined d15N and d18O in NO 3 as an indicator of
NO3 source when (i) fertilizers are not added to the cultivated
fields, and (ii) the effect of the denitrification rate is theoretically
not favorable due to low autumnal temperatures (Mariotti et al.,
1988; Søvik and Mørkved, 2008). Finally, to evaluate the actual
spatial variation of dissolved NO 3 in the groundwater, further spe-
cific sampling was aimed at the determination of the concentration
of NO3 . Thus, 155 and 126 water samples were analyzed in June
(phase I) and October (phase II) 2006, respectively.
4 B. Nisi et al. / Applied Geochemistry xxx (2013) xxx–xxx
Groundwater samples were collected from wells with depths in
the range of 3–65 m and collected at the wellheads, after purging.
Measurements of pH and temperature were conducted in the field.
For each sampling site three aliquots were collected using polyeth-
ylene bottles, as follows: (i) 250 mL for the determination of the
 
main anions, F, Br, and the N species (NHþ 4 , NO2 and NO3 ), (ii)
50 mL for the determination of the main cations, filtered in the
field through 0.45 lm membrane filters and acidified with 0.5 mL
of concentrated Suprapur HNO3 and (iii) 1 L for d18O–NO3 and
d15N–NO3 isotopes for the selected sites, filtered in the field with
0.2 lm polycarbonate membrane filters to avoid microbial reduc-
tion–oxidation reactions (Patton and Gilroy, 1999). The latter sam-
ples were stored and transported in ice-filled boxes to the
laboratory and kept refrigerated at approximately 4 °C prior to
the isotopic analysis.
Anions (SO2  
4 , Cl , NO3 , Br

and F) were determined by ion
chromatography (Methrom 761 Compact IC) and HCO 3 by titration
with 0.01 M HCl using methyl-orange as indicator. Major (Ca2+,
Mg2+, Na+ and K+) cations were determined by Atomic Absorption
Spectrophotometry (Perkin Elmer Aanalyst 100), while dissolved

NHþ 4 and NO2 were measured by molecular spectrophotometry
(Hach DR2001) within 24 h of sampling. Analytical errors are gen-
erally <3% for the main components and <5% for NO  
3 , Br , F and
NHþ 4 . The isotopic composition of d15
N–NO3 and d18
O–NO 3 was
determined by using a slightly modified version of the method pro-
posed by Silva et al. (2000). Nitrate was collected by passing the
water sample through pre-filled anion exchange resin columns in
a Cl form (Bio-Rad AGÒ 1-X8 resin, 100–200 mesh; 0.8  4 cm).
This analytical technique involved desorption of NO 3 by HCl flush-
ing, and producing AgNO3 by addition of purified Ag2O. The AgNO3
was then oven-dried. For O isotope analysis all O-bearing com-
pounds were removed by addition of (i) BaCl2 to precipitate SO2 4 with (Cl > HCO
and PO3 4 and (ii) activated C to eliminate organic matter. The
AgNO3 solid products were collected and stored in amber glass
vials in a desiccator prior to the isotopic analysis. Freeze-dried
AgNO3 was packed in Ag-foil cups and combusted. Isotope mea-
surements were carried out at the Stable Isotope Laboratory of
the Instituto Andaluz de Ciencias de la Tierra (CSIC, Granada,
Spain). During the programmed runs, individual samples for
d15N–NO3 were combusted at 1050 °C. Successively, samples were
positioned in the Elemental Analyzer (EA, Carlo Erba NA1500 NC 2)
where the analytes were combusted at 650 °C in a reduced envi-
ronment to form N2 from NOx. Samples for d18O–NO3 were com-
busted within the reactor TC pyrolysis (Finnigan) device at
1450 °C to obtain CO. Finally, the N and O isotopic ratios were
determined by using a Finnigan-Mat 251 mass spectrometer.
Stable isotope ratios re expressed using the delta ‰ notation
relative to an international reference standard, as follows: sample
(‰) = [(Rsample  Rstandard)/Rstandard] ⁄ 1000 where Rsample and
Rstandard are the 15N/14N or 18O/16O ratio of the sample and interna-
tional reference standard, respectively. The international reference
standards were atmospheric AIR for the 15N/14N isotopic ratio and
Vienna Standard Mean Ocean Water (V-SMOW) for that of 18O/16O.
Each sample was analyzed, at least, three times. The experimental
error was 0.2‰ for d15N–NO3 and d18O–NO3.
4. Results
4.1. Water chemistry and nitrogen compounds
The data collected during the different sampling periods are re-
ported in Table 1. Groundwaters from the Cecina Plain exhibited
pH values from 6.3 to 8.5, most samples being slightly alkaline.
Temperature values did not show significant seasonal variations
(June: from 14.5 to 23 °C; October: 15.5–20 °C). The highest
Please cite this article in press as: Nisi, B., et al. Dissolved nitrates in the groundwater of the Cecina Plain (Tuscany, central-western Italy): Clues from the
isotopic signature of NO 3 . Appl. Geochem. (2013), http://dx.doi.org/10.1016/j.apgeochem.2012.12.004
contents of TDSs (Total Dissolved Solids) were recorded in June
2006 with values varying between 320 and 4513 mg/L (mean va-
lue: 1173 mg/L) and from 270 to 2597 mg/L (mean value:
1019 mg/L) in October 2006, similarly to what was observed by
Grassi et al. (2007). Total cation concentrations (TZ+ = Ca2+ +
Mg2+ + Na+ + K+ + NHþ 4 ) ranged from 4.85 to 75.78 meq/L and from
3.92 to 44.90 in June and October, respectively. The cation chemis-
try indicated Ca2+ as the most abundant cation, constituting 84%
and 91% of the total cations (TZ+) in June and October, respectively,
whereas in the remaining samples, alkalis (Na+ + K+) dominated.
2 
Total anion concentrations ðTZ ¼ HCO 3 þ SO4 þ Cl þ NO2 þ


NO3 Þ varied from 4.85 to 75.78 meq/L in June and from 4.26 to
40.94 meq/L in October. In terms of anionic abundance, 80% and
84% of the samples (in June and October, respectively) had HCO 3
as the dominant anion, whereas Cl had the highest concentrations

in the 20% and 16% of the samples, respectively. Dissolved Br and
F were relatively variable, being comprised in June between 0.19
and 5.69 and 0.05–0.27 mg/L, respectively, and between 2.55 and
0.02 and 0.08–0.75 in October, respectively.
The chemical composition of the sampled water was classified
in terms of relative Ca2+, Mg2+, Na+, K+, HCO  
3 , Cl and SO4 concen-
trations by using the Langelier–Ludwig square diagram (Langelier
and Ludwig, 1942) (Fig. 2). Due to the close proximity to the coast
2 2
of most samples, HCO 3 ðþCO3 Þ and SO4 were grouped together,

whilst Cl was considered as a single variable in this diagram. Most
waters had Ca(Mg)–HCO3(SO4) and, subordinately, Na–Cl composi-
tions, although the water samples did not cluster into two clearly
separated groups (Fig 2), showing a continuous variation from
Ca–HCO3 to Ca–SO4(Cl) and subordinate Na(Ca)–Cl(SO4) composi-
tions. As a general observation, the salinity of the 92 groundwater
samples was below 50 meq/L, although the salinity of some waters

2
3 þ SO4 ) (#28, #29, #31, #48 and #97) ranged
from 50 up to 150 meq/L (Fig 3).
The contents of N species are reported in Table 1, whereas those
NO 3 (phase I and II) are summarized in Table 2. The range of NH4
þ
contents was similar in the two different periods, being comprised
between 0.01 and 4.13 mg/L and 0.01 and 4.77 mg/L in June and
October, respectively. In contrast, NO 2 contents were relatively
low in June (0.01–0.47 mg/L), whereas in October they ranged be-
tween 0.007 and 3.130 mg/L. Finally, a significant variability of
NO 3 concentrations was observed in the Cecina Plain groundwater
system, ranging between 1 and 354 mg/L, and 0.01–260 mg/L,
in June (phase I) and October (phase II), respectively. About 35%
and 19% of the sampled wells in June and October, respectively,
had levels of NO 3 higher that those recommended by the World
Health Organization (<50 mg/L).
4.2. Stable isotope composition of nitrate
The measured d18O–NO3 and d15N–NO3 values in groundwater
are listed in Table 3 and ranged between 7.5‰ and 22.6‰ and
2.8‰ and 14.9‰, respectively. In Fig. 4, the measured isotopic
compositions of NO 
3 are compared with the NO3 contents. Setting
aside samples #62, #400, #74, #36, #139 and #491 (d18O–NO3 val-
ues ranging from 10.2‰ to 16.4‰ with NO 3 < 70 mg=L), two
trends for the d18O–NO3 values are recognized (Fig. 4a): (1) sam-
ples #92, #134, #169, #109, #60 and #133 have d18O–NO3 values
of 21.0‰ and NO 3 contents between 56 and 252 mg/L; (2) sam-
ples #58, #77, #5 and #105 display d18O–NO3 values of 8‰ and
NO3 contents between 41 and 260 mg/L. Similarly, two trends are
also shown for the d15N–NO3 values (Fig. 4b): (3) samples #122,
#77, #5 and #105 have an isotopic composition that reflects a
correlation between increasing NO 3 concentrations (from 69 to
260 mg/L) and more positive d15N–NO3 values (from 7.5‰ to
14.3‰); (4) samples #74, #92, #36, #134, #169, #109, #60
and #133 highlight a correlation between increasing NO 3
 B. Nisi et al. / Applied Geochemistry xxx (2013) xxx–xxx 5

Table 1
Temperature, pH, and chemical data (mg/L) for the groundwaters of the Cecina Plain. Coordinates are in UTM (Gauss-Boaga). TDS = Total Dissolved Solids; n.d.: not determined;
<dl: detection limit. All values are in mg/L, TZ and TZ+ are the sum of anions and cations, respectively, in meq/L. Numbers refer to the sampling sites in Fig. 1.

ID Date GB_E GB_N Depth T (°C) pH Ca Mg Na K NH4 NO2 NO3 HCO3 Cl SO4 Br F TDS TZ TZ+
2 June ‘06 1620578 4800515 nd 18.3 7.07 148 22 76 2.4 0.100 0.033 63.0 464 99 96 0.28 0.14 970 13.42 12.56
24 June ‘06 1617386 4805549 6.60 19.5 7.46 114 50 69 3.0 0.040 0.200 35.0 422 116 103 0.32 0.25 912 12.90 12.89
28 June ‘06 1625838 4798287 11.30 15.0 7.10 190 96 162 3.3 4.130 0.180 13.0 811 421 65 1.18 0.18 1767 26.75 24.80
29 June ‘06 1618632 4798162 1.13 14.5 7.31 310 163 659 60.0 0.170 0.030 2.0 655 1043 753 2.35 0.26 3646 55.88 59.12
31 June ‘06 1619040 4797520 6.72 17.4 7.20 360 214 924 30.9 0.260 0.470 11.5 484 2145 343 5.69 nd 4513 75.78 76.58
36 June ‘06 1615820 4805331 5.10 17.9 7.14 156 35 116 2.4 0.050 0.036 77.0 411 158 165 0.37 0.20 1120 15.87 15.79
38 June ‘06 1620735 4796185 5.84 nd nd 127 76 225 3.2 0.060 0.033 47.0 620 343 166 0.86 0.24 1607 24.07 22.44
44 June ‘06 1621511 4795101 1.96 16.7 7.45 151 55 121 9.2 0.030 0.066 33.0 474 276 127 0.52 0.12 1245 18.71 17.58
46 June ‘06 1626612 4794397 nd 19.2 7.21 136 19 54 2.5 0.120 0.003 3.8 442 116 29 <dl 0.09 802 11.16 10.82
48 June ‘06 1622910 4794151 nd nd nd 140 37 103 3.2 0.120 0.002 53.0 398 183 97 <dl 0.11 1014 14.57 14.57
50 June ‘06 1626044 4793989 nd 18.7 7.28 173 32 96 3.1 0.080 0.002 22.0 393 308 54 <dl 0.11 1081 16.60 15.54
53 June ‘06 1626657 4792817 nd 19.2 7.20 168 33 85 3.7 0.060 0.003 27.0 433 219 103 0.29 0.10 1071 15.85 14.91
55 June ‘06 1624562 4792587 nd 23.0 7.29 138 37 101 5.0 0.060 0.002 45.0 316 176 137 <dl 0.19 955 13.73 14.47
56 June ‘06 1622952 4792466 18.70 18.4 9.48 5 15 72 5.0 0.250 0.002 0.3 110 113 1 <dl 0.06 320 5.00 4.73
58 June ‘06 1626544 4792205 nd 17.8 7.19 176 85 81 1.7 0.060 0.002 38.0 470 168 360 <dl 0.18 1380 20.56 19.36
60 June ‘06 1625321 4791535 1.80 16.4 7.07 134 49 81 9.9 0.050 0.002 88.0 515 95 141 <dl 0.22 1114 15.50 14.51
62 June ‘06 1629231 4790609 1.82 20.5 7.32 134 34 70 2.2 0.090 0.002 10.0 355 122 168 <dl 0.11 896 12.94 12.61
65 June ‘06 1616534 4804200 2.33 16.5 7.10 166 24 244 2.3 0.040 0.016 20.0 476 226 260 0.52 0.20 1418 19.92 20.95
68 June ‘06 1628880 4789087 nd 17.6 6.94 120 45 95 3.4 0.050 0.002 64.0 503 124 68 <dl 0.08 1023 14.18 13.99
72 June ‘06 1623828 4789282 11.42 18.8 7.2 146 22 77 4.3 0.060 0.020 72.0 421 108 99 0.34 0.12 950 13.17 12.58
73 June ‘06 1620590 4803916 5.51 20.1 7.05 152 18 115 1.2 0.050 0.033 90.0 437 158 95 0.40 0.27 1066 15.05 14.12
74 June ‘06 1626037 4789163 13.34 15.5 7.43 179 62 145 4.9 0.080 0.003 81.0 377 301 283 <dl 0.21 1433 21.87 20.49
77 June ‘06 1627407 4788265 nd 18.0 6.88 126 73 94 3.1 0.040 0.002 124.0 505 131 114 <dl 0.07 1171 16.36 16.47
84 June ‘06 1625282 4785894 nd 20.1 6.99 105 28 43 2.5 0.080 0.002 0.6 437 78 14 <dl 0.11 707 9.66 9.46
86 June ‘06 1630905 4785308 nd 16.8 6.72 152 25 46 2.6 0.050 0.002 34.0 387 93 68 <dl 0.05 807 10.93 11.73
91 June ‘06 1617460 4803187 2.95 16.8 7.67 91 40 75 9.6 0.030 0.023 11.0 498 86 60 0.27 0.24 871 12.02 11.35
92 June ‘06 1621426 4803444 2.14 17.8 7.12 170 49 130 1.4 0.050 0.013 107.0 404 328 90 0.62 0.25 1279 19.48 18.22
95 June ‘06 1626621 4783104 nd nd nd 92 26 33 1.2 0.290 0.060 6.0 369 52 55 0.29 0.07 635 8.76 8.23
97 June ‘06 1625188 4782906 1.50 18.1 7.09 110 95 240 12.0 2.090 0.049 2.4 498 578 70 1.09 0.18 1608 25.98 24.18
101 June ‘06 1629581 4782071 16.93 20.0 6.72 149 35 45 2.6 0.040 0.013 26.0 464 88 113 <dl <dl 923 12.87 12.38
104 June ‘06 1616570 4806386 8.20 17.0 6.80 178 24 66 1.0 0.010 0.010 26.0 516 100 140 0.37 0.20 1051 14.62 13.77
105 June ‘06 1622170 4802550 1.86 17.5 7.10 202 12 77 1.4 0.130 0.260 127.0 434 110 151 0.30 0.08 1115 15.42 14.50
109 June ‘06 1626516 4780801 nd 16.3 7.56 161 46 54 8.8 0.040 0.026 155.0 429 102 129 0.32 0.09 1084 15.10 14.37
112 June ‘06 1628644 4779533 15.88 17.7 6.63 93 26 59 3.9 0.040 0.020 118.0 268 84 62 <dl 0.08 714 9.97 9.42
116 June ‘06 1625747 4776130 15.97 nd nd 101 31 82 3.6 0.130 0.002 70.0 362 80 101 <dl 0.14 830 11.42 11.20
118 June ‘06 1617795 4802080 6.20 nd nd 197 50 149 26.0 0.060 0.023 14.0 697 224 212 0.47 0.18 1569 22.39 21.11
120 June ‘06 1620622 4801880 1.33 18.6 7.43 87 47 43 2.3 0.120 0.016 9.0 438 87 47 0.30 0.16 762 10.77 10.20
121 June ‘06 1618394 4801742 1.44 16.5 7.30 174 19 73 2.0 0.060 0.420 65.0 405 159 105 0.50 0.11 1002 14.35 13.45
124 June ‘06 1621450 4801590 3.21 17.5 7.08 155 45 69 1.8 0.060 0.007 68.0 449 163 111 0.36 0.12 1063 15.38 14.50
128 June ‘06 1618014 4805915 1.93 16.7 6.96 110 20 148 2.3 0.050 0.036 24.0 500 59 135 0.25 0.18 998 13.06 13.64
132 June ‘06 1627246 4799818 1.70 18.5 7.60 71 42 138 6.7 1.790 0.033 0.8 488 165 61 0.34 0.20 974 13.93 13.28
133 June ‘06 1627030 4778333 16.89 18.1 6.82 297 65 101 9.0 0.140 0.131 354.0 671 258 121 0.51 0.05 1876 26.50 24.83
134 June ‘06 1626628 4781146 nd 16 7.26 147 40 85 1.2 0.050 0.001 84.0 441 158 118 0.29 0.10 1074 15.49 14.36
137 June ‘06 1627011 4783890 nd 18.0 7.30 66 25 49 3.0 0.040 0.341 0.1 244 118 30 0.30 0.10 536 7.96 7.57
139 June ‘06 1629537 4784324 2.44 19.5 6.82 126 22 62 2.7 0.040 0.013 40.0 394 109 66 <dl 0.10 822 11.56 10.87
149 June ‘06 1626138 4778556 nd nd nd 218 36 81 2.9 0.130 0.318 192.0 411 240 97 0.43 0.09 1279 18.63 17.51
155 June ‘06 1621513 4799053 nd 16.9 7.35 60 10 15 3.7 0.180 0.023 4.2 250 19 8 <dl 0.24 369 4.85 4.55
156 June ‘06 1621515 4799063 nd 17.4 6.90 161 27 110 7.5 0.220 0.190 5.8 633 141 99 0.29 0.08 1185 16.51 15.26
157 June ‘06 1620181 4801918 nd 17.4 6.90 153 11 60 1.8 0.050 0.001 103.0 386 68 96 0.19 0.12 879 11.89 11.27
1 October ‘06 1620574 4800506 16.98 17.7 7.06 158 25 74 1.49 0.052 0.023 61.8 424 99 88 0.35 0.15 931 12.56 13.22
2 October ‘06 1620578 4800515 16.95 18.2 6.93 84 23 29 1.25 0.100 0.026 5.7 379 19 21 0.02 0.62 562 7.27 7.39
5 October ‘06 1620200 4801940 nd 18.8 7.00 171 12 61 1.10 0.050 0.013 160.0 378 67 81 0.30 0.17 932 12.35 12.22
24 October ‘06 1617386 4805549 7.45 17.7 6.46 112 46 65 2.93 0.052 0.013 26.5 409 121 88 0.05 0.24 870 12.38 12.29
28 October ‘06 1625838 4798287 2.80 18.9 6.98 180 90 160 2.70 4.773 3.126 1.2 743 450 37 1.56 0.26 1672 25.66 23.70
31 October ‘06 1619040 4797520 1.54 18.0 7.05 262 127 490 1.80 0.013 0.030 1.2 569 1044 102 2.55 0.08 2598 40.94 44.90
36 October ‘06 1615820 4805331 5.20 19.2 nd 165 34 111 2.94 0.010 0.013 69.7 404 164 142 0.27 0.26 1093 15.33 15.95
38 October ‘06 1620735 4796185 2.10 19.0 7.06 163 86 251 1.86 0.010 0.086 86.9 574 408 180 1.41 0.39 1751 26.07 26.19
44 October ‘06 1621511 4795101 2.27 19.4 6.74 168 59 94 7.44 1.006 0.112 0.1 505 268 65 0.63 0.31 1168 17.21 17.59
46 October ‘06 1626612 4794397 nd 18.4 6.86 138 18 54 2.14 0.013 0.033 4.0 445 108 26 0.32 0.12 795 10.94 10.78
48 October ‘06 1622910 4794151 nd 17.0 6.69 278 49 240 3.75 0.077 0.023 42.5 366 593 166 1.90 0.21 1738 26.87 28.47
50 October ‘06 1626044 4793989 20.70 18.0 6.98 142 28 64 2.62 0.010 0.010 15.1 406 179 30 0.41 0.31 867 12.58 12.25
53 October ‘06 1626657 4792817 12.20 17.3 7.2 171 30 86 3.13 0.010 0.010 30.8 438 180 93 0.39 0.75 1032 14.69 14.85
55 October ‘06 1624562 4792587 1.85 17.6 6.31 146 38 95 3.64 0.010 0.013 54.8 442 158 126 0.62 0.38 1064 15.21 14.65
56 October ‘06 1622952 4792466 nd nd 8.25 4 11 61 7.49 0.297 0.013 0.1 87 100 0.5 0.19 0.18 270 4.26 3.92
58 October ‘06 1626544 4792205 nd 16.8 6.52 189 72 76 1.16 0.065 0.023 41.2 550 160 170 0.30 0.21 1260 17.74 18.71
60 October ‘06 1625321 4791535 4.10 16.5 6.76 104 71 159 1.80 0.065 1.480 208.8 471 154 159 0.70 0.37 1330 18.73 18.01
62 October ‘06 1629231 4790609 nd 15.5 6.46 142 39 78 1.78 0.077 0.020 14.2 406 110 174 0.35 0.12 965 13.61 13.75
65 October ‘06 1616534 4804200 2.05 19.7 6.96 182 56 165 2.43 0.010 0.046 13.1 477 283 247 0.69 0.35 1425 21.15 20.95
68 October ‘06 1628880 4789087 nd 18.1 7.04 132 46 121 1.73 0.010 0.036 119.7 516 115 91 0.35 0.17 1142 15.54 15.67
74 October ‘06 1626037 4789163 2.30 17.8 6.28 110 22 76 7.41 0.013 0.033 38.5 218 124 148 0.28 0.24 744 10.78 10.78
77 October ‘06 1627407 4788265 nd 18.3 6.83 132 71 85 2.40 0.010 0.023 125.8 512 126 100 0.30 0.30 1153 16.04 16.18
86 October ‘06 1630905 4785308 14.65 20.0 7.82 164 32 56 2.79 0.013 0.026 3.8 535 110 63 0.34 0.14 966 13.23 13.34
91 October ‘06 1617460 4803187 2.95 18.0 7.24 75 29 59 9.65 0.100 3.043 0.1 384 53 35 0.20 0.34 648 8.52 8.94

(continued on next page)

Please cite this article in press as: Nisi, B., et al. Dissolved nitrates in the groundwater of the Cecina Plain (Tuscany, central-western Italy): Clues from the
isotopic signature of NO 3 . Appl. Geochem. (2013), http://dx.doi.org/10.1016/j.apgeochem.2012.12.004
6 B. Nisi et al. / Applied Geochemistry xxx (2013) xxx–xxx

Table 1 (continued)

ID Date GB_E GB_N Depth T (°C) pH Ca Mg Na K NH4 NO2 NO3 HCO3 Cl SO4 Br F TDS TZ TZ+
92 October ‘06 1621426 4803444 18.21 17.1 6.45 171 46 106 1.45 0.077 0.033 56.1 403 250 74 0.74 0.45 1108 16.11 16.99
95 October ‘06 1626621 4783104 nd 18.0 6.95 108 27 46 1.86 0.013 0.008 9.9 450 84 20 0.19 0.41 746 10.30 9.68
104 October ‘06 1616570 4806386 8.75 17.0 6.89 193 27 71 1.62 0.010 0.602 13.5 515 109 134 0.26 0.34 1065 14.53 14.98
105 October ‘06 1622170 4802550 16.20 18.2 6.72 209 17 91 1.14 0.026 0.026 260.5 406 131 117 0.07 0.13 1232 16.99 15.81
109 October ‘06 1626516 4780801 2.60 19.4 7.8 164 44 50 8.72 0.010 0.010 144.3 399 97 117 0.33 0.24 1022 14.02 14.17
112 October ‘06 1628644 4779533 15.83 18.4 7.28 76 24 51 2.12 0.010 0.007 75.6 217 81 47 0.23 0.19 573 8.03 8.03
118 October ‘06 1617795 4802080 1.80 18.3 7.28 92 20 62 1.66 0.039 0.016 6.6 372 51 71 0.09 0.46 676 9.12 8.99
120 October ‘06 1620622 4801880 13.50 19.8 7.27 89 47 43 1.47 0.026 0.046 7.5 419 90 38 0.28 0.28 735 10.33 10.16
121 October ‘06 1618394 4801742 1.73 18.8 6.67 159 18 80 1.25 0.065 0.023 61.7 378 115 85 0.36 0.28 898 12.20 12.95
122 October ‘06 1619830 4801690 nd 17.4 7.10 132 12 45 1.20 0.080 0.018 69.0 366 47 71 0.30 0.20 744 9.92 9.58
124 October ‘06 1621450 4801590 16.01 17.3 6.67 159 42 69 1.47 0.052 0.013 66.3 423 150 96 0.34 0.25 1007 14.24 14.45
133 October ‘06 1627030 4778333 12.54 20.0 6.4 280 53 85 8.06 0.039 0.013 252.1 659 181 101 0.53 0.17 1619 22.08 22.27
134 October ‘06 1626628 4781146 4.10 19.5 6.78 137 37 57 0.99 0.010 0.013 71.2 413 85 96 0.24 0.21 897 12.33 12.35
139 October ‘06 1629537 4784324 8.87 19.6 6.88 123 23 54 2.42 0.039 0.016 35.1 395 82 51 0.30 0.13 765 10.42 10.39
156 October ‘06 1621515 4799063 11.16 17.5 7.05 64 9 14 3.44 0.142 0.033 6.3 250 23 11 0.04 0.36 380 5.06 4.65
157 October ‘06 1620181 4801918 0.67 18.2 6.88 155 13 59 1.27 0.100 0.013 85.8 417 71 84 0.14 0.25 886 11.96 11.42
169 October ‘06 1620500 4806400 nd 18.0 7.10 115 28 51 2.06 0.013 0.010 102.8 286 89 61 0.22 0.14 734 10.13 10.28
400 October ‘06 1628460 4786540 nd 19.4 6.70 138 34 80 2.20 0.060 0.013 42.0 505 127 58 0.50 0.10 987 13.75 13.24
491 October ‘06 1630792 4783520 nd 18.1 6.70 132 12 40 2.50 0.260 0.027 18.0 466 46 36 0.30 0.19 753 9.98 9.41

Fig. 2. Square diagram of Langelier–Ludwig (1942) for the Cecina Plain groundwaters. S.W.: sea water.

concentrations (from 38 to 252 mg/L) and lighter d15N–NO3 values
(from 14.9‰ to 2.8‰).
5. Discussion
5.1. Seasonal and spatial variations of nitrate
A preliminary evaluation of the behavior of NO
3 dissolved in the
Cecina Plain groundwater can be derived by investigating the prob-
ability diagrams reported in Fig. 5, where the NO
3 distribution for
the different sampling periods (June and October 2006; phase I and
II, respectively) is reported. Statistical analysis indicates that the
NO 3 values are bimodal and log-normally distributed. Further-
more, this statistical approach allows distinguishing several popu-
lations, providing the mathematical tools needed to proceed to the
separation of different contributions. According to Sinclair (1974,
1991), the methods used to extract individual populations from a
bimodal distribution consisting of a combination of two or more
populations, is named partitioning. In Fig. 5 the partitioning was
applied to the bimodal distributions of the dataset for June and
October 2006, and an estimation of their proportions is given by
the inflection point or change in direction of curvature on the prob-
ability curve, respectively. Based on the position of the inflection

Please cite this article in press as: Nisi, B., et al. Dissolved nitrates in the groundwater of the Cecina Plain (Tuscany, central-western Italy): Clues from the
isotopic signature of NO 3 . Appl. Geochem. (2013), http://dx.doi.org/10.1016/j.apgeochem.2012.12.004
 B. Nisi et al. / Applied Geochemistry xxx (2013) xxx–xxx 7

Fig. 3. Binary diagrams of Cl vs. (HCO3 + SO4) for the Cecina Plain groundwaters for June and October 2006 sampling campaigns, where salinity lines corresponding to (A)
<150 meq/L and (B) <50 meq/L are also reported.

point of the overall curve, the percentage contribution of each pop-
ulation to the whole dataset [% (family A) + % (family B)] is derived.
The cumulative probability values lie on the straight lines drawn in
Fig. 5, defining for June (family A = 85.8%; family B = 14.2%) and
October (family A = 84.9%; family B = 15.1%) 2006 two populations
indicating that NO 3 may be considered as due to the result of mul-
tiple sources. The two curves can be referred to different NO
sources, with the coexistence of (i) middle-high NO 3 concentra-
tions and (ii) low NO 3 concentrations.
The geostatistical investigation has allowed reconstructing the
distribution of NO 3 in the Cecina Plain, highlighting those areas
were the most elevated concentrations (up to 354 mg/L) of dis-
solved NO 3 are located. The spatial variations of dissolved NO3
in the groundwater during the different sampling periods are illus-
trated in Fig. 6. The interpolation on the maps was performed by
using the kriging estimation method and the NO 3 concentrations
are reported as logarithmic values. The methodology is based on
mandatory preliminary steps: (i) realization of the experimental
variogram and (ii) selection of the best fitting mathematical model.
Finally, the fitted models were cross-validated with the experi-
mental data (Fig. 6) in order to check the performance of the model
for kriging (Devijer and Kittler, 1982). Geostatistical processing
indicates that the spherical model with a nugget effect is the best
model to describe the spatial variability of NO 3 for both the June
and October 2006 samplings. Variogram parameters for NO 3 in
June and October 2006 are: range of 3722 and 4364 m, Sill of
0.964 and 1.265 and Nugget of 0.57 and 0.58 [mg/L]2, respectively.
Experimental variograms, relative mathematical models and the
cross-validation results are shown in Fig. 6a and b.
The iso-concentrations [ln (NO3) mg/L] show that areas with
high NO 3 contents are located NW of Colle Mezzana and along
the peri-Tyrrhenian side of the Cecina Plain, which extends from
Vada to Donoratico. The decreasing trend from June to October
2006 is also noticeable in terms of spatial extension. This suggests
that seasonal variations have to be considered in an experimental
design plan so that the investigated NO 3 pollution phenomena
could be understood in all its aspects. Moreover, the complexity
of the Cecina Plain due to the presence of a multi-aquifer system
does not allow an accurate identification of the depth at which
the water samples were collected.
5.2. Water geochemistry: process signal
The interpretation of the geochemical facies sources is in good
3 agreement with Grassi et al. (2007). Most groundwater samples
collected in the Cecina Plain have a chemical composition from
Ca–HCO3 to Ca(Mg)–HCO3 and originate through interaction with
calcite and dolomite, whose dissolution rates are much higher than
those of silicate minerals (e.g. Marini et al., 2000). Calcium–SO4
waters are present locally and are derived from dissolution of gyp-

sum and/or anhydrite contained in both evaporitic rocks cropping
out in the nearby hills and clastic constituents in the alluvial
deposits. Moreover, the presence of seawater intrusion in coastal
aquifers locally generates Na–Cl waters, with high concentrations
(up to 2145 mg/L) of dissolved Cl. As a consequence, Na–Ca and
Na–Mg ion exchange may take place and water chemistry changes
from Na–Cl to either Ca–Cl or Ca(Mg)–Cl (Appelo and Postma,
1996).
According to Spruill et al. (2002), Min et al. (2002) and Koh et al.
(2010), changes of the groundwater type from a Ca–HCO3 chemical
facies to Na(–K)–Cl type are thought to be caused by agricultural
activities, local contamination by domestic sewage or manure.
These authors reported that the sources of Cl and K+ enrichment
was swine-manure and found positive correlations between NO 3,
Cl, and K+ in groundwater; moreover they determined the median
d15N–NO3 value 15.4‰ in groundwater for this type of
contamination.
According to Roy et al. (1999, and references therein), among
the possible anthropogenic components, inputs of NO 
3 , Cl , and
Na+ are mainly derived from fertilizers and communal effluent.
Chemical ratios of these elements can be calculated to estimate
the agricultural component (agricultural component: A.C.) and
communal effluent (communal effluent: C.E.) that are character-
ized by NO3/Na molar ratios close to ca. 10 and ca. 0.1 and Cl/
Na+ ratios of ca. 3–5 and 0.8 ± 0.2, respectively. Moreover, these ra-
tios can be considered independent of flow rates and dilution and

Please cite this article in press as: Nisi, B., et al. Dissolved nitrates in the groundwater of the Cecina Plain (Tuscany, central-western Italy): Clues from the
isotopic signature of NO 3 . Appl. Geochem. (2013), http://dx.doi.org/10.1016/j.apgeochem.2012.12.004
8 B. Nisi et al. / Applied Geochemistry xxx (2013) xxx–xxx

Table 2
Nitrate concentrations (mg/L) for the Cecina Plain groundwaters sampled in June (phase I) and October (phase II) 2006, respectively. Geographical coordinates are in UTM (Gauss-
Boaga).

GB_E GB_N NO3 (mg/L) GB_E GB_N NO3 (mg/L) GB_E GB_N NO3 (mg/L) GB_E GB_N NO3 (mg/L)
June 2006 June 2006 October 2006 October 2006
1615719 4806388 50.0 1626368 4793637 20.0 1626896 4788279 30.3 1620500 4806400 102.8
1616570 4806386 26.0 1622440 4793454 10.0 1627407 4788265 125.8 1616570 4806386 13.5
1617501 4805995 61.0 1626657 4792817 27.0 1629935 4788125 26.3 1617501 4805995 37.1
1618014 4805915 24.0 1624562 4792587 45.0 1624350 4787723 3.4 1620554 4805820 20.4
1620554 4805820 36.0 1625080 4792260 73.0 1629000 4787627 18.6 1617386 4805549 26.5
1617386 4805549 35.0 1626544 4792205 38.0 1625218 4787598 9.6 1618679 4805526 21.0
1618679 4805526 47.0 1628498 4792019 7.0 1626923 4787192 11.1 1616879 4805381 32.5
1616879 4805381 63.0 1625321 4791535 88.0 1627046 4787073 20.7 1615820 4805331 69.7
1615820 4805331 77.0 1627374 4791513 18.0 1624520 4786831 1.2 1619261 4805255 164.0
1619261 4805255 145.0 1629160 4791479 48.0 1628430 4786590 64.4 1616534 4804200 13.1
1617672 4804683 50.0 1626928 4791457 7.0 1630906 4786115 24.8 1620274 4803449 23.2
1616534 4804200 20.0 1629231 4790609 10.0 1625266 4785923 0.9 1621426 4803444 56.1
1620590 4803916 90.0 1628805 4790580 21.0 1624829 4785628 2.2 1618598 4803311 0.01
1620274 4803449 66.0 1626370 4790295 36.0 1626115 4785481 5.9 1617460 4803187 0.1
1621426 4803444 107.0 1624681 4790217 31.0 1630905 4785308 3.8 1619138 4802985 6.2
1618598 4803311 42.0 1623813 4790019 15.0 1631032 4785278 27.2 1618541 4802832 34.0
1617460 4803187 11.0 1627613 4789688 94.0 1631130 4784598 20.1 1622170 4802550 260.5
1619138 4802985 10.0 1629587 4789684 6.0 1629843 4784336 22.3 1617795 4802080 6.6
1618541 4802832 46.0 1625338 4789465 27.0 1629537 4784324 35.1 1619590 4802010 23.5
1622170 4802550 127.0 1623828 4789282 92.0 1627319 4784065 14.9 1623840 4801960 38.4
1621318 4802407 26.0 1626037 4789163 81.0 1630651 4783615 21.0 1620622 4801880 7.5
1617795 4802080 14.0 1628880 4789087 64.0 1626621 4783104 9.9 1618394 4801742 61.7
1623840 4801960 40.0 1628676 4788848 8.0 1629539 4783044 9.3 1621450 4801590 66.3
1620200 4801940 77.0 1625968 4788601 14.0 1628261 4782937 1.2 1617926 4801103 8.7
1620179 4801923 101.0 1627407 4788265 124.0 1626947 4782782 6.5 1623080 4800740 15.8
1620181 4801918 103.0 1629935 4788125 4.0 1628580 4782564 17.0 1621780 4800635 9.0
1620622 4801880 9.0 1624350 4787723 1.0 1630283 4782325 0.04 1620605 4800530 39.6
1618394 4801742 65.0 1625218 4787598 13.0 1630172 4782268 0.04 1620578 4800515 5.7
1619830 4801690 62.0 1626923 4787192 20.0 1627085 4782220 13.0 1620574 4800506 61.8
1621450 4801590 68.0 1627046 4787073 17.0 1631155 4782149 34.0 1618975 4800395 92.8
1623963 4801418 23.0 1630756 4786974 12.0 1625839 4782093 6.2 1623635 4799900 26.0
1617926 4801103 48.0 1624520 4786831 9.0 1625262 4781646 0.03 1621560 4799082 6.3
1623080 4800740 26.0 1629278 4786404 80.0 1629698 4781579 24.1 1619555 4798925 41.8
1621780 4800635 2.0 1630862 4786387 24.0 1627539 4781547 21.7 1620195 4798360 43.3
1620578 4800515 63.0 1630906 4786115 27.0 1630427 4781286 14.9 1625838 4798287 1.2
1620574 4800506 72.0 1625266 4785923 6.0 1626628 4781146 71.2 1621530 4797625 68.1
1618975 4800395 126.0 1625282 4785894 1.0 1628631 4780879 16.7 1624092 4797625 40.8
1623635 4799900 46.0 1624829 4785628 13.0 1626516 4780801 144.4 1619040 4797520 1.3
1627246 4799818 1.0 1626115 4785481 5.0 1627684 4780059 46.4 1620638 4797209 65.0
1621515 4799063 6.0 1630905 4785308 34.0 1630227 4779565 24.8 1618845 4797207 4.3
1621513 4799053 4.0 1631032 4785278 45.0 1629682 4779556 43.3 1623412 4797140 0.9
1624200 4798962 5.0 1627921 4785149 360.0 1628644 4779533 75.6 1619457 4796814 0.04
1619555 4798925 68.0 1630868 4784612 24.0 1626813 4779377 46.4 1625083 4796714 3.7
1621850 4798900 32.0 1631130 4784598 86.0 1627235 4779197 32.5 1624855 4796219 4.6
1622405 4798845 110.0 1629537 4784324 40.0 1625986 4778552 37.1 1620735 4796185 86.9
1624115 4798684 10.0 1627319 4784065 46.0 1627030 4778333 252.1 1625083 4796095 0.4
1626106 4798606 17.0 1630656 4783612 58.0 1626741 4777779 99.0 1621415 4796075 5.3
1620195 4798360 158.0 1626621 4783104 6.0 1625619 4774859 20.4 1624212 4795755 29.4
1625838 4798287 13.0 1629539 4783044 24.0 1620784 4795634 10.5
1618632 4798162 2.0 1628261 4782937 4.0 1623135 4795519 13.0
1622019 4797651 28.0 1625188 4782906 2.0 1626510 4795410 0.04
1621530 4797625 102.0 1626947 4782782 15.0 1621511 4795101 0.1
1619040 4797520 12.0 1628580 4782564 42.0 1621831 4794710 0.04
1620638 4797209 123.0 1630283 4782325 11.0 1626612 4794397 4.0
1618845 4797207 9.0 1630172 4782268 24.0 1624250 4794332 26.6
1623412 4797140 18.0 1627128 4782232 47.0 1625958 4794308 7.7
1619457 4796814 1.0 1631155 4782149 91.0 1622910 4794151 42.5
1625086 4796714 1.0 1629581 4782071 26.0 1627000 4794097 55.7
1623910 4796355 33.0 1629698 4781579 50.0 1626044 4793989 15.1
1624855 4796219 17.0 1627539 4781547 44.0 1624092 4793880 23.2
1620735 4796185 47.0 1630427 4781286 34.0 1627302 4793826 4.3
1625083 4796095 4.0 1626628 4781146 84.0 1622440 4793454 1.3
1621415 4796075 16.0 1625507 4780908 1.0 1626657 4792817 30.8
1624212 4795755 69.0 1628631 4780879 42.0 1624562 4792587 54.8
1620784 4795634 42.0 1626516 4780801 155.0 1622952 4792466 0.1
1623135 4795519 33.0 1627684 4780059 77.0 1625080 4792260 48.0
1626510 4795410 9.0 1629698 4779734 102.0 1626544 4792205 41.2
1621511 4795101 33.0 1630227 4779565 44.0 1628498 4792019 0.04
1621831 4794710 2.0 1628644 4779533 118.0 1625321 4791535 208.8
1628021 4794572 8.0 1626813 4779377 233.0 1626928 4791457 2.5
1626612 4794397 4.0 1627235 4779197 82.0 1629231 4790609 14.2
1624250 4794332 34.0 1626138 4778556 192.0 1628805 4790580 7.4

Please cite this article in press as: Nisi, B., et al. Dissolved nitrates in the groundwater of the Cecina Plain (Tuscany, central-western Italy): Clues from the
isotopic signature of NO 3 . Appl. Geochem. (2013), http://dx.doi.org/10.1016/j.apgeochem.2012.12.004
 B. Nisi et al. / Applied Geochemistry xxx (2013) xxx–xxx 9

Table 2 (continued)

GB_E GB_N NO3 (mg/L) GB_E GB_N NO3 (mg/L) GB_E GB_N NO3 (mg/L) GB_E GB_N NO3 (mg/L)
June 2006 June 2006 October 2006 October 2006
1625958 4794308 16.0 1625986 4778552 62.0 1624681 4790217 20.4
1622910 4794151 53.0 1627030 4778333 354.0 1623813 4790019 4.6
1627000 4794097 105.0 1626741 4777779 147.0 1625338 4789465 9.3
1626044 4793989 22.0 1625747 4776130 70.0 1623828 4789282 13.9
1624092 4793880 61.0 1625619 4774859 44.0 1626037 4789163 38.5
1627302 4793826 12.0 1628880 4789087 119.7

Table 3
Nitrogen and O isotopic composition for the Cecina Plain groundwaters. d15N(NO3)
(AIR) and d18O(NO3) (V-SMOW) values are in ‰. Numbers refer to the sampling sites
in Fig. 1.

ID Date d15N–NO3 d18O–NO3

5 October ‘06 9.7 8.5
24 October ‘06 8.6 10.2
36 October ‘06 11.3 15.5
58 October ‘06 9.0 8.7
60 October ‘06 2.8 19.2
62 October ‘06 7.1 14.8
74 October ‘06 14.9 15.4
77 October ‘06 9.7 7.5
92 October ‘06 12.2 21.0
105 October ‘06 14.3 7.7
109 October ‘06 5.4 19.3
121 October ‘06 8.4 11.2
122 October ‘06 7.5 10.2
133 October ‘06 2.2 22.6
134 October ‘06 10.2 21.2
139 October ‘06 11.0 12.3
169 October ‘06 7.3 22.2
400 October ‘06 7.9 16.4
491 October ‘06 13.7 13.3

evaporation effects. The NO þ  +

3 =Na vs. Cl /Na (as molar ratios) bin-
ary diagram is reported in Fig. 7 together with the potential
anthropogenic end-members as defined by Roy et al. (1999). The
Cecina groundwaters tend to be distributed along two main trends.
The first (solid line) is characterized by an increase in the Cl/Na+
molar ratio possibly due to ion exchange processes between clay
sediments and seawater-affected groundwaters (e.g. #95, #86,
#46, #31, #120, #48, #28 and #38) that favor the absorption of
Na+ and the release of Ca2+, as also supported by the Ca–Cl compo-
nent present in most waters. The second trend (dashed lines) is
likely related to mixing processes between the groundwater sys- Fig. 4. Binary diagrams of the variation of d15N–NO3 (A) and d18O–NO3 (B) vs. NO
3
(mg/L). d15N(NO3) (AIR) and d18O(NO3) (VSMOW) values are in ‰.
tem and communal and agricultural sources to different degrees.
In particular, water samples #5, #105, #109, #133, #169 and Br by anthropogenic sources (e.g. horticulture, Br concentration
#149 are characterized by high NO þ
3 =Na (from 0.88 to 1.30) ratios being from 5 to 17 mg/L, Flury and Papritz, 1993) or by diluted sea
and point towards the A.C. box suggesting a strong contribution of water (seawater Cl/Br ratio of 293; Br = 65 mg/L). In addition
NO 
3 and Cl . In contrast, samples #155, #91, #132, #156, #2, and Vengosh and Pankratov (1998, and references therein) showed that
#118 plot close to the C.E. end-member and are characterized by sewage effluents have a large range of Cl/Br ratios (average:
Cl/Na+ and NO þ
3 =Na molar ratios ranging from 0.41 to 0.83 and 732). According to Vengosh and Pankratov (1998), anthropogenic
from 0.001 to 0.64, respectively, indicating an input from commu- high Cl/Br ratios can be considered a universal tracer for the im-
nal effluent. Moreover, several water samples (#29, #38, #56, #62, pact of domestic wastewaters.
#65, #95 and #104; characterized by Cl/Na+ = 0.91–1.11 and The chemical reactions during fresh/salt or sewage water dis-
NO þ
3 =Na ¼ 0:0004—0:14) exhibit an enrichment in Cl

and Na+ placements can be deduced more specifically by calculating a com-
 +
which is responsible for a shift towards high Cl /Na ratios due position based on conservative mixing of salt (or Domestic Waste
to either mixing processes with seawater (S.W.: NO þ
3 =Na  Water: D.W.W.) water and fresh water, and comparing the conser-
6  +
9:9  10 and Cl /Na  1.16; Nordstrom et al., 1979) intrusion vative concentrations with those actually found. The concentration
in coastal aquifers or the influence of a C.E. component. of an ion i, by conservative mixing of seawater (or D.W.W.) and
In order to discriminate mixing processes between seawater fresh water can be written, as follows:
intrusion and a potential C.E. end-member, the Cl/Br ratio was
used to detect the origin of the contamination as Cl and Br are mi;mix ¼ fsea ðor D:W:W:Þ  mi;sea ðor D:W:W:Þ þ ð1  fsea ðor D:W:W:Þ Þ  mi;fresh
not affected by water–rock interaction processes (Davis et al., ð1Þ
1998). Conservative characteristics of Cl/Br ratios for tracing
 
the origin of mixing source in groundwater show that it is possible where mi is the concentration of Cl (or Br ) (mg/L), fsea (or D.W.W.) is
to modify the original Cl/Br ratio of groundwaters enriched in the fraction of seawater (or D.W.W.) in the mixed water, and

Please cite this article in press as: Nisi, B., et al. Dissolved nitrates in the groundwater of the Cecina Plain (Tuscany, central-western Italy): Clues from the
isotopic signature of NO 3 . Appl. Geochem. (2013), http://dx.doi.org/10.1016/j.apgeochem.2012.12.004
10 B. Nisi et al. / Applied Geochemistry xxx (2013) xxx–xxx

Fig. 5. Probability plots for the NO3 concentrations (mg/L) of the Cecina Plain groundwaters for the June (phase I) and October (phase II) 2006 sampling campaigns,
respectively. Circle indicates the cumulative distribution of the measured data. The separated populations (A and B) are obtained by partitioning (Sinclair, 1974) and plotted
with a different symbol (+). For further explanations see text.

Fig. 6. Maps and cross validation of the numerical model selected for ln(NO
3 ) (concentrations are in mg/L) for June (A) and October (B), respectively, of the Cecina Plain
groundwaters. Variogram data are in ln(NO 3 ).

subscripts mix, sea (or D.W.W.), and fresh indicate the conservative
mixture, and end-member seawater (or D.W.W.) and fresh water,
respectively.
In Fig. 8 the binary diagram of Cl (mg/L) vs. Cl/Br ratios is re-
ported with the computed theoretical lines representing the mixed
fresh water with seawater and D.W.W. end-members. In this study
the mixing process was calculated from a low TDS value and a
chemical composition typical of surficial or shallow waters, i.e.
Ca–HCO3, similar to sample #156, collected in October 2006:
TDS = 380 mg/L, Cl = 23, Br = 0.04 mg/L. Average S.W. composition

Please cite this article in press as: Nisi, B., et al. Dissolved nitrates in the groundwater of the Cecina Plain (Tuscany, central-western Italy): Clues from the
isotopic signature of NO 3 . Appl. Geochem. (2013), http://dx.doi.org/10.1016/j.apgeochem.2012.12.004
 B. Nisi et al. / Applied Geochemistry xxx (2013) xxx–xxx 11

Fig. 7. Binary diagram of NO þ  +

3 =Na vs. Cl /Na (as molar ratios) for the Cecina Plain groundwaters. Agricultural Component (A.C.) and Communal Effluent (C.E.) fields are from
Roy et al. (1999). Sea Water (S.W.) end-member from Nordstrom et al. (1979). Dashed and solid lines represent the mixed fresh water with the (A.C.) and (C.E.) end-members,
and the increase in the Cl/Na+ molar ratio, respectively.

was taken from Nordstrom et al. (1979) and that of the D.W.W.
end-member from Vengosh and Pankratov (1998). The geochemi-
cal modeling that best fits the observed Cl–Br composition of the
Cecina Plain waters suggests three possible scenarios: (1) contam-
ination of regional groundwater, with a Cl/Br ratio  290 by sea-
water, e.g. #48, #28, #38, #109 and #120; (2) contamination of
regional groundwater by sewage effluent, e.g. #36, #53, #105,
#24, #58, #65, #118, #104 and #56), generally enriched in Cl
(Cl/Br up to 2,330), and 3) contamination of regional groundwa-
ter enriched in Br (Cl/Br < 300); e.g. #95, 122, # 491, # 5, and #
400, possibly due to agricultural practices. According to Wagman
et al. (1981) and Flury and Papritz (1993) Br from fertilizers and
pesticides used in the agricultural practices or leaching farm-
animal or septic waste (Alcalà and Custodio, 2008) can also lower
the Cl/Br ratios with respect to that of seawater. Bromide-
containing components remaining in the soil degrade by methyla-
tion of organic matter and by hydrolysis, which releases Br to the
soil fluids and the underlying aquifers. Elevated Br concentrations
in drainage water can be associated with high contents of NO 3 and
pesticides. The occurrence in groundwater of high NO 3 contents
with high pesticide values is described in many regions around
the world (e.g. Hamilton and Helsel, 1995; Silva et al., 2006;
Hildebrandt et al., 2008).
Summarizing, the Cl and Cl/Br ratio allows a better charac-
terization of the Cecina groundwater system whose salinity derives
from mixing processes between seawater intrusion and a potential
C.E. end-member to which a contribution by D.W.W. is added.
Water samples #48, #28, #38, and #120 can be regarded as the re-
sult of mixing processes dominated by groundwaters interacting
with seawater rather than an interaction with the C.E. component
and/or ion exchange processes between clay sediments and seawa-
ter as observed in Fig. 7. In contrast Cl contents and Cl/Br ratios
of water samples #65, #56, #104 identify contamination due to
sewage effluent instead of mixing processes with seawater.
5.3. Sources of nitrate: constraints from d15N–NO3 and d18O–NO3
Nitrate in the environment rarely maintains its pristine isotopic
composition as various fractionation processes may alter the initial
composition (e.g. Kendall, 1998). Nevertheless, since different NO 3
sources have a distinctive isotopic composition mixing processes
may provide intermediate values. The correlation between the
d18O–NO3 and d15N–NO3 values and anionic and cationic concen-
trations provides valuable information for identifying NO 3 sources,
as chemical constituents from anthropogenic sources are prone to
dominate over those deriving from natural sources.
The d15N–NO3 and d18O–NO3 values for the Cecina Plain
groundwaters are shown in Fig. 9, where the fields for the most
probable sources of NO 3 are also shown (Clark and Fritz,1997;
Kendall, 1998; Mayer et al., 2002; Nisi et al., 2005; Xue et al.,
2009; Fenech et al., 2012). The location of the wells and the specific
point sources provide additional evidence of the influence of the

Please cite this article in press as: Nisi, B., et al. Dissolved nitrates in the groundwater of the Cecina Plain (Tuscany, central-western Italy): Clues from the
isotopic signature of NO 3 . Appl. Geochem. (2013), http://dx.doi.org/10.1016/j.apgeochem.2012.12.004
12 B. Nisi et al. / Applied Geochemistry xxx (2013) xxx–xxx

Fig. 8. Binary diagrams of Cl/Br ratio vs. Cl (mg/L) for the Cecina Plain groundwaters. Domestic Waste Water (D.W.W.) and Sea Water (S.W.) compositions are from
Vengosh and Pankratov (1998) and Nordstrom et al. (1979), respectively. The theoretically computed solid and dash lines represent the mixed fresh water with the seawater
and D.W.W. end-members, respectively.

two main inputs: sewage/manure and synthetic fertilizers. Manure
and sewage are generally enriched in 15N with respect to N-bearing
synthetic fertilizers. During storage, treatment and application of
sewage and animal waste, NH3 volatilization causes a large enrich-
ment of 15N in the residual NHþ 4 , which is subsequently converted
into 15N-rich NO 3 . The data clustering close to or in the sewage/
manure fields (#105, #58, #77, #121, #122, and #5; d15N–NO3
from +7.5 to +14.3‰ and d18O–NO3 from +7.5‰ to +11.2‰) are
in agreement with the suggestions of Min et al. (2002) and Choi
et al. (2007), who observed a correlation between increasing NO 3 1999; Fukada et al., 2003; Chen and MacQuarrie, 2005). Although
concentrations and more positive d15N–NO3 values (Fig. 4b) when
manure (or sewage?) is considered to be the main source. In con-
trast, Iqbal et al. (1997) found a correlation between increasing
NO 15
3 concentrations and more negative d N–NO3 values (Fig. 4b)
when fertilizer was the predominant source. The latter consider-
ation is consistent for those isotopic values that are typically close
to or in the synthetic fertilizer field (#92, #169, #109, #60, #134
and #133: d15N–NO3 from 2.8‰ to +12.2‰ and d18O–NO3 from
+19.2‰ to +22.6‰). The isotopic data that are not included in
any of the end-member boxes can likely be related to denitrifica-
tion processes and/or mixing of different NO 3 sources (e.g. syn-
thetic fertilizer and sewage). Most of the reduced N used for
agriculture is quickly oxidized to NO 3 , which is taken up by plants,
leached from the soil zone, or denitrified to N2. A portion of the N
from fertilizers can be lost via volatilization or immobilized in the
soil by uptake, storage, and recycling in the microbial biomass
within the soil zone (e.g. Kendall, 1998; Mengis et al., 1999).
Biologically mediated reactions such as denitrification induce the
fractionation of N and O isotopes, increasing the d15N–NO3 and
d18O–NO3 values of the remaining (undenitrified) NO 3 . The frac-
tionation factors for d15N–NO3 and d18O–NO3 vary according to
the local conditions and rates of reaction. Some studies have re-
ported that a linear relationship, indicating an enrichment of 15N
relative to 18O between 1.3:1 and 2.1:1, gives strong clues for deni-
trification processes, as shown by the two arrows in Fig. 9 (Bött-
cher et al., 1990; Aravena and Robertson, 1998; Mengis et al.,
samples #5, #77 and #105 could mainly be associated with
increasing pollution effects by sewage, the mean value (0.73) of
their d18O/d15N ratio suggests that their relatively heavier N isoto-
pic signature (+9.6‰, +9.7‰ and +14.3‰, Table 3) could be related
to denitrification processes. Finally, the anomalously high values of
d15N–NO3 and d18O–NO3 observed for samples #36, #62, #74, #
139, #400 and #491 (d15N–NO3 from +7.2‰ to +14.9‰ and
d18O–NO3 from +12.3 to +16.4‰) can be explained as being derived
by synthetic fertilizers in which sewage inputs and denitrification
processes may overlap. In this way, while denitrification decreases
NO 
3 concentrations, concomitant admixture of NO3 from synthetic
fertilizer and sewage/(manure?) sources tends to increase the NO 3
contents in the groundwaters.
Recognizing denitrification processes is very important in terms
of identification of NO 3 sources because this process can increase
the values of d15N–NO3 derived from synthetic fertilizer, which
originally has low d15N value, leading to the wrong identification

Please cite this article in press as: Nisi, B., et al. Dissolved nitrates in the groundwater of the Cecina Plain (Tuscany, central-western Italy): Clues from the
isotopic signature of NO 3 . Appl. Geochem. (2013), http://dx.doi.org/10.1016/j.apgeochem.2012.12.004
 B. Nisi et al. / Applied Geochemistry xxx (2013) xxx–xxx 13

Fig. 9. Oxygen and N isotopic compositions of NO 3 for the Cecina Plain groundwaters. Fields are from Clark and Fritz (1997), Kendall (1998), Mayer et al. (2002), Nisi et al.
(2005), Xue et al. (2009) and Fenech et al. (2012). The dashed lines represent the isotopic enrichment trend of d15N–NO3 and d18O–NO3 the during denitrification process
(Aravena and Robertson, 1998; Mengis et al., 1999; Fukada et al., 2003).

of NO
3 sources (e.g. sewage and/or manure). In the Cecina Plain
groundwaters more detailed investigations on the evolution of
the concentration and isotopic composition of dissolved NO 3 NO
would improve understanding of the role of denitrification
processes.
6. Conclusions
The complex hydrogeological situation of the Cecina Plain
groundwaters makes it difficult to understand the geochemical
and anthropogenic processes acting in this multi-aquifer system.
This may also pose problems for recognizing both the distribution
of the possible contaminants and pollutants and their sources.
Nevertheless, it is matter of fact that several anthropogenic factors
are affecting these groundwaters and contribute to their deteriora-
tion despite the fact that this water body is the most important re-
source for local agricultural, industrial and tourism activities.
Currently, water management has thus to take into account B con-
tamination, though decreasing substantially with time, salinization
and NO
3 pollution. In this respect, Grassi et al. (2007) suggested
that fertilizer addition and related agricultural practices (e.g. irri-
gation) were the main causes for the high concentrations of NO
3,
locally reaching >300 mg/L.
In the present work, the isotopic composition of N and O in
NO
3 has enabled obtaining important clues regarding the source
of the NO
3 . Synthetic fertilizers are undoubtedly playing an impor-
tant role in polluting the Cecina aquifer. However, the data indicate
the presence of a significant sewage/manure input that worsens
the quality of this groundwater system. It is likely that mixing pro-
cesses between synthetic fertilizer and sewage sources are able to
produce some of the observed isotopic composition. Furthermore,
water samples with d18O/d15N ratios clustering around 2:1 suggest
the occurrence of denitrification processes that partially lower the
NO 3 contents of the Cecina Plain multi-aquifer. The concomitant
effect of multiple pollution sources in the Cecina Plain aquifer is
also recognizable by considering both the probability plots of the
 
3 concentration and the Cl /Br ratios. This further corroborates

what has emerged from the NO3 isotopic data.
Despite the relatively low number of isotopic analyses per-
formed in the present study it is evident that the application of
coupled d18O and d15N in dissolved NO 3 is a valid and useful tool
to trace anthropogenic processes in groundwaters. This approach
can be used by the institutional agencies to properly act and inter-
vene for the remediation of NO 3 pollution.
As a consequence, it is possible to assess that countermeasures
to increase the quality of the Cecina Plain groundwaters are neces-
sary. However, monitoring activity in selected sites by using N and
O isotopes in NO 3 and an evaluation of the denitrification pro-
cesses are important pre-requisites to address a remediation
program.
Acknowledgments
This work was carried out in the framework of a research pro-
ject of national interest (PRIN-2006) funded by the Italian Ministry
of Education, University and Research (Responsible of the Working
Unit of Florence, G. Pranzini). The authors wish to thank R. Frullini
and F. Capecchiacci for their help and assistance during the field-
work and the analytical part related to the main components.
One of the Guest Editors (E. Sacchi) of this special issue and two
anonymous reviewers are gratefully acknowledged for signifi-
cantly improving an early version of the manuscript.
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Please cite this article in press as: Nisi, B., et al. Dissolved nitrates in the groundwater of the Cecina Plain (Tuscany, central-western Italy): Clues from the
isotopic signature of NO 3 . Appl. Geochem. (2013), http://dx.doi.org/10.1016/j.apgeochem.2012.12.004