Applied

Geochemistry
Applied Geochemistry 20 (2005) 20632081
www.elsevier.com/locate/apgeochem

Stable isotope (2H, 18O and 87Sr/86Sr) and hydrochemistry

monitoring for groundwater hydrodynamics analysis in a
karst aquifer (Gran Sasso, Central Italy)
a,b,*
Maurizio Barbieri , Tiziano Boschetti c, Marco Petitta a,b
, Marco Tallini d

a
Dipartimento Scienze della Terra, Universita` La Sapienza di Roma, Piazzale A. Moro 5, 00185 Roma, Italy
b
Istituto di Geologia Ambientale e Geoingegneria (IGAG-CNR), Via Bolognola 7, 00138 Roma, Italy
c
Dipartimento di Scienze della Terra, Universita` di Parma, Parco Area delle Scienze 157a, 43100 Parma, Italy
d
Dipartimento di Ingegneria delle Strutture, delle Acque e del Terreno, Universita` di LAquila, Monteluco di Roio 67040 LAquila, Italy

Received 14 October 2004; accepted 25 July 2005

Editorial handling by P. McMahon
Available online 5 October 2005

Abstract

This paper deals with chemical and isotope analyses of 21 springs, which were monitored 3 times in the course of 2001;
the monitoring program was focused on the groundwater of the Gran Sasso carbonate karst aquifer (Central Italy), typical
of the mountainous Mediterranean area.
Based on the hydrogeological setting of the study area, 6 groups of springs with dierent groundwater circulation patterns
were distinguished. The hydrogeochemistry of their main components provided additional information about groundwater
owpaths, conrming the proposed classication. The spatial distribution of their ion concentrations validated the assump-
tions underlying the hydrogeological conceptual model, showing diverging groundwater owpaths from the core to the
boundaries of the aquifer. Geochemical modelling and saturation index computation elucidated watercarbonate rock inter-
action, contribution by alluvial aquifers at the karst aquifer boundaries, as well as impacts of human activities.
The analysis of 18O/16O and 2H/H values and their spatial distribution in the aquifer substantiated the hydrogeology-
based classication of 6 groups of springs, making it possible to trace back groundwater recharge areas based on mean
isotope elevations; the latter were calculated by using two rain monitoring stations. 87Sr/86Sr analyses showed seasonal
changes in many springs: in winterspring, the changes are due to inow of new recharge water, inltrating into younger
rocks and thus increasing 87Sr/86Sr values; in summerautumn, when there is no recharge and spring discharge declines,
changes are due to base ow groundwater circulating in more ancient rocks, with a subsequent drop in 87Sr/86Sr values.
The results of this study stress the contribution that spatio-temporal isotope monitoring can give to the denition of
groundwater owpaths and hydrodynamics in ssured and karst aquifers, taking into account their hydrogeological
and hydrogeochemical setting.

2005 Elsevier Ltd. All rights reserved.

1. Introduction
*
Corresponding author. Tel.: +39 06 49914593; fax: +39 06
4454729. Optimum protection and management of ground-
E-mail address: maurizio.barbieri@uniroma1.it (M. Barbieri). water resources in karst areas is a priority objective

0883-2927/$ - see front matter
2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apgeochem.2005.07.008
2064 M. Barbieri et al. / Applied Geochemistry 20 (2005) 20632081
(European Commission, 1995) in both industria-
lised and developing countries. Fissured carbonate
aquifers host huge resources of high-quality ground-
water. They also feed springs that are often used as
sources of drinking water or that give rise to wet-
lands of high environmental value (Bradford and
Watt, 1998). These springs or wetlands may be part
of protected areas, as in this study.
Reconciling environmental protection with
human needs requires an accurate and up-to-date
assessment of available resources, based on hydro-
geological studies. The availability of resources
is inuenced, in part, by anthropogenic factors
(Custodio, 1997): water exploitation and construc-
tion work, such as the Gran Sasso motorway tunnel
in Central Italy (Monjoie, 1975; Massoli Novelli
and Petitta, 1997; Celico et al., 2004), may interfere
with the natural hydrogeological setting.
Often, hydrogeological studies are not sucient
to shed light on the groundwater hydrodynamics
of carbonate karst environments, since groundwater
also ows through fractures and karst conduits. As
described in this study, this knowledge gap can be
bridged using hydrogeochemical investigation meth-
ods, some of which are based on stable isotopes,
such as 18O, 2H and 87Sr/86Sr (Banner et al., 1994;
Han and Liu, 2004; Johnson et al., 2000; Jorgensen
and Banoeng-Yakubo, 2001; Kattan, 1993, 2001;
Katz and Bullen, 1996; Mara et al., 2004; Walrae-
vens and Cardenal, 1994; Thomas and Rose, 2003).
Isotope-based methodologies have become well
established in the hydrological community for water
resource assessment, development and manage-
ment, and are now an integral part of many water
quality and environmental studies (Clark and Fritz,
1997; Cook and Herczeg, 1999). These methodolo-
gies usually rely on tracing either isotope species
naturally occurring in water (environmental isoto-
pes) or on isotope tracers intentionally introduced
into them (UNESCO, 2000).
Unlike the stable isotopes of 18O and 2H in water
that have long been used in hydrology (Craig, 1961;
Bison et al., 1989; Gonantini, 1978), Sr isotopes do
not measurably fractionate in nature. Groundwater
acquires dissolved Sr: (i) in its recharge area,
through inltration and percolation processes; (ii)
along its owpath, through dissolution or ion
exchange with minerals. Hence, 87Sr/86Sr ratios give
insight into waterrock interaction processes (Naftz
et al., 1997). Various authors (Banner et al., 1989;
Dogramaci and Herczeg, 2002; Frost and Toner,
2004; Katz and Bullen, 1996; Petelet-Giraud et al.,
2003; Peterman and Stuckless, 1992; Barbieri and
Sappa, 1997; Barbieri and Morotti, 2003) demon-
strated the advantage of using Sr isotopes as tracers
in hydrogeological applications.
Hydrogeochemical and isotope analyses can test
and ne-tune a conceptual hydrogeological model.
Furthermore, monitoring changes in stable isotopes
over time and in space can give a better understand-
ing of aquifer recharge and spring discharge that are
essential for dening groundwater hydrodynamics.
In addition, monitoring of stable isotopes proves
to be a useful tool when urgent land planning
decisions are to be made, such as those concerning
conservation and management of water resources,
as well as assessment of the quality of water for hu-
man use (Miroladov and Marjanovic, 1998).
2. Hydrogeological setting
The study area is the Gran Sasso massif (about
800 km2 wide and with an elevation of 2702912 m
a.s.l.), a carbonate ridge consisting of MesoCeno-
zoic units belonging to slope-to-basin lithofacies.
The sequence has evidence of tectonic movements
due to the Apennine orogenesis, such as overthrusts
and successive extensional faults. The massif holds a
regional aquifer, with high values of recharge
(700 mm/a with respect to 1100 mm/a of precipita-
tion) due to joints, faults and karst features. The
aquifer supplies minor local springs of perched
aquifers and low-altitude large springs located at
the boundaries of Gran Sasso (total discharge:
19.5 m3/s). The location of the investigated springs
in the study area is shown in Fig. 1. The boundaries
of this regional aquifer are well dened by strati-
graphic and tectonic contacts with aquicludes
(Miocene terrigenous deposits, northern and eastern
boundaries) or aquitards (Quaternary clastic conti-
nental deposits, southwestern and southeastern
boundaries) with groundwater seepage. Karst mor-
phology, such as conduits and caves, is dominant
in recharge areas, vadose and epikarst zones (Ford
and Williams, 1989; Lore et al., 2002), while it is ab-
sent in discharge areas, owing to fast emplacement
of clastic deposits with dierent grain size and
mineralogical composition (e.g., sands and uvio-
lacustrine clays) in the Quaternary valley (Petitta
and Tallini, 2003).
In the study area, ssured carbonate rocks have a
hydraulic conductivity of 10
810
7 m/s. However,
in places where the fracturing is more widespread
owing to intense tectonic movements, hydraulic
 M. Barbieri et al. / Applied Geochemistry 20 (2005) 20632081 2065

Fig. 1. Hydrogeological map of Gran Sasso. 1 continental deposits of tectono-karst basins (Quaternary); 2 terrigenous deposits
pelites and sandstones (upper Miocene); 3 carbonate sequences of platform (including shelf), scarp to basin and ramp lithofacies
(Miocene upper Trias); 4 dolomites (upper Trias); 5 overthrust; 6 extensional fault; 7 spring group; 8 location of rainwater
sampling for isotope analyses; 9 motorway tunnel; 10 main directions of groundwater owpaths. Spring and rain sampling station
numbers refer to Table 2. Spring symbols refer to spring groups of Table 2.

conductivity is in the range of 10
610
5 m/s
(Monjoie, 1980). In karst environments, particularly
developed in specic morphoevolutionary settings
(e.g., present epikarst and deep karstied areas;
Monjoie, 1978; Lore et al., 2002), permeability
may reach 10
4 m/s (Monjoie, 1980). The major
tectono-karst depression (Campo Imperatore) of
the study area, located at high altitude, has signi-
cant rainfall values. The combination of intense
rainfall with endorheic morphology gives rise to
concentrated inltration phenomena (Scozzafava
and Tallini, 2001).
Some faults segment the karst aquifer, as they act
as low hydraulic conductivity walls (K = 10
8 m/s,
Monjoie, 1978) against groundwater discharge. At
its base, the fractured and karstied aquifer is sup-
ported by dolomites; fracturing-induced hydraulic
conductivity of these dolomites is lower than that
of the limestones (10
910
8 m/s, Monjoie, 1980).
Consequently, in places where they are exposed, the
dolomites may hinder groundwater discharge. The
main tectonic unconformities and structural highs
of the dolomites act as a groundwater divide between
the northern and southern sectors of the massif,
which have distinct hydrogeological characteristics.
On the regional scale, the hydrogeological system
of Gran Sasso (Petitta and Tallini, 2002) accommo-
dates a single basal aquifer. This aquifer of consid-
erable extent and potential has a hydraulic gradient
of about 520&. At its boundaries, the aquifer feeds
low-altitude, high-discharge basal springs, lying on
the southern side of the massif and, to a lesser
extent, high-altitude springs on its northern side
(Fig. 1). Moreover, some tens of minor springs
occur at mediumhigh altitude. These springs, with
a discharge of 0.0010.01 m3/s, are the expression of
perched aquifers of limited extent.
Recent hydrogeological investigations (Tallini
et al., 2000) classied the main springs of the study
area into 6 groups according to their hydrogeologi-
cal setting (Fig. 1). Along the main thrust fault on
the northern side of Gran Sasso, multiple springs
(1 m3/s) drain the regional aquifer (group A, springs
17, 18, 19, 20 and 21). On the southern side of
the massif, several springs with moderate discharge
(total amount 0.2 m3/s) are connected to perched
2066 M. Barbieri et al. / Applied Geochemistry 20 (2005) 20632081
aquifers (group B, spring 16). The springs with the
highest discharge values are located along the south-
ern boundary of the massif. The area of LAquila
hosts springs (group C, springs 4 and 5) with very
steady discharge (1 m3/s), and other springs (0.9
m3/s) that receive signicant contributions (Petitta
and Tallini, 2003) from a multi-layer clastic aquifer
(group D, springs 1, 2, 3, 12 and 13). In the south-
eastern part of the study area, the main springs
(group E, springs 6, 7, 8, 9, 10 and 11), at the lowest
elevations, are chiey supplied by the regional aqui-
fer (15 m3/s). The regional aquifer is also drained
by the Gran Sasso motorway tunnels (group F,
1.4 m3/s, springs 14 and 15): their construction in
the 1970s has interfered with the local ow patterns,
decreasing the discharge of many springs (mainly of
groups A and C, partially of group E). At present,
the groundwater drained by the tunnels and by the
springs of groups A, D and partially E is exploited
for drinking uses.
Springs draining the Gran Sasso aquifer initially
produced extremely high discharges, which then
decreased due to tunnel drainage (Petitta and Tallini,
2002; Celico et al., 2004). In the subsequent period,
the aquifer reached a new hydrodynamic equilib-
rium, which was not natural but forced by tunnel
drainage. In this new steady state of the aquifer,
the tunnels (and their drainage) may be regarded as
two new anthropogenic springs. Tunnel drainage
and the generalised decline in precipitation help
explain the observed downward trend of natural
spring discharge.
3. Methodology, sampling and analytical procedures
To obtain detailed information about groundwa-
ter owpaths and spring recharge areas and to bet-
ter understand the above-described hydrogeological
setting (see Fig. 1), 3 spring water sampling surveys
were conducted in 2001 (January, April and
November), collecting data on in situ physico-chem-
ical parameters and carrying out chemical analyses
of main components and stable isotopes. Samples
were collected directly from the spring outlets. Dur-
ing the January 2001 survey, all 21 identied springs
were sampled. The April survey was limited to 17
springs (excluding springs 5, 13, 14 and 15) and no
2
H/H and 18O/16O analyses were carried out. In
the November survey, it was not possible to sample
springs 12, 13, 14 and 21.
Water temperature, electrical conductivity and
pH values were determined in the eld. Bicarbonate
was determined by titration with 0.1 N HCl. Water
samples were ltered through cellulose lters
(0.45 lm) and their major and minor constituents
were determined with a Dionex DX-120 ion chro-
matograph (replicability 2%). A Dionex CS-12
column was used for determining cations (Na, K,
Mg, Ca), whereas a Dionex AS9-SC column was
used for anions (F, Cl, NO3, SO4). Silica was deter-
mined by a spectrophotometric method (b-silico-
molybdenum blue). Chemical analyses of Sr were
carried out via atomic absorption spectrophotome-
try. The analytical accuracy of these methods ran-
ged from 2% to 5%. The results are listed in Table 1.
Water stable isotope (2H/H and 18O/16O) analy-
ses were conducted on two rainfall water samples
collected from two pluviometers located on the
opposite sides of the massif: one near Pietracamela
(1024 m a.s.l.), on the northern slope of the massif
(R1, Fig. 1 and Table 2), and the other close to LA-
quila (685 m a.s.l.), on its southern slope (R2, Fig. 1
and Table 2). These samples express mean rainfall
from February to April 2001 (R1) and from Decem-
ber 2000 to April 2001 (R2). Ten-litre polyethylene
bottles containing 300 ml of vaseline oil (preventing
evaporation) were used to collect the 2 rainwater
samples (Barbieri et al., 2003).
Analyses of 2H/H isotopes used the method of
Kendall and Coplen (1985) (reaction with Zn at
450 C), while 18O/16O analyses relied on the CO2
water equilibration technique (Epstein and Mayeda,
1953). Mass spectrometry was performed with a
Finnigan Delta Plus mass spectrometer. The results
are reported in d& units vs. the international
V-SMOW standard (Craig, 1961). The standard devi-
ations of the measurements were equal to approxi-
mately 1& for 2H/H and to 0.2& for 18O/16O.
The results are summarised in Table 2.
87
Sr/86Sr values of water samples were determined
as follows: 50 ml of water was mixed with 50 mg
Sr-free Na2CO3 and the solution was heated to
70 C. The resulting residue was dissolved with
2.5 N HCl and the Sr in solution was separated by
means of an ion exchange resin (Dowex 50 W* 8,
200400 mesh, hydrogenionic form, Barbieri and
Morotti, 2003). Measured isotope ratios were com-
pared to the SrCO3 Standard 987 SRM NBS
(SrCO3). The mean 87Sr/86Sr ratio over the analysis
period was 0.71024. Analyses were performed with
a VG 54E mass spectrometer, and the resulting
values were normalised to 88Sr/86Sr = 0.1194 for
natural Sr. The analytical error (expressed as 2r)
was 0.00002. The values are listed in Table 2.
Table 1
Main characteristics and chemical composition of sampled waters
No. Spring Discharge Elevation Date T EC pH Na K Ca Mg Sr Cl HCO3 SO4 NO3 F SiO2 TDS
group (m3/s) (m a.s.l.) (mm/yy)
1 D 0.43 640 01/01 8.8 408 7.56 5.98 0.64 73.79 13.04 0.15 7.09 278.77 6.45 8.34 0.08 6.96 401.29
04/01 10.5 390 7.56 4.87 0.72 61.95 10.22 0.16 6.29 228.74 6.87 8.80 0.12 7.28 336.02
11/01 8.6 402 7.58 3.76 0.69 67.99 11.85 0.17 4.22 256.50 5.53 6.65 0.11 7.03 364.50

2 D 0.22 625 01/01 10.8 352 7.77 6.04 0.92 64.43 11.55 0.13 8.24 271.45 4.39 6.77 0.10 5.05 379.07
04/01 10.5 358 7.77 4.09 0.71 68.33 11.24 0.14 6.59 255.40 4.38 6.92 0.09 4.86 362.75
11/01 11.2 343 7.74 4.10 0.72 61.80 10.95 0.13 6.50 231.36 4.82 5.99 0.09 5.02 331.48

3 D 0.05 635 01/01 11.1 576 7.32 15.95 3.15 78.70 10.65 0.14 16.25 258.20 21.90 28.75 0.13 7.36 441.18

M. Barbieri et al. / Applied Geochemistry 20 (2005) 20632081

04/01 14.0 621 7.53 10.44 4.32 92.99 5.04 0.14 15.60 262.36 21.40 27.44 0.14 7.27 447.14
11/01 11.7 608 7.34 23.60 5.20 75.44 6.99 0.14 14.28 267.78 22.84 26.96 0.12 7.36 450.71

4 C 0.80 650 01/01 8 234 7.93 2.05 0.27 39.89 13.61 0.07 4.80 180.16 2.30 2.44 0.05 4.21 249.85
04/01 8.0 222 8.00 1.61 0.29 41.86 8.91 0.06 3.79 154.31 2.34 2.12 0.05 3.90 219.24
11/01 8.3 230 8.04 3.78 0.51 35.83 12.03 0.09 3.11 170.31 2.64 2.18 0.04 3.92 234.44

5 C 0.19 650 01/01 8.2 239 7.57 2.11 0.26 42.82 14.26 0.07 4.84 194.61 2.27 2.56 0.06 12.31 276.17
04/01 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
11/01 8.2 240 8.26 3.42 0.37 40.89 12.91 0.11 2.85 190.06 2.18 2.10 0.05 11.06 266.00

6 E 2.80 340 01/01 10.9 480 7.13 4.39 0.73 89.96 23.25 0.29 20.05 343.23 19.80 3.55 0.15 10.06 515.46
04/01 11.0 500 7.41 3.32 0.77 87.80 19.20 0.25 17.94 317.42 20.64 3.21 0.15 9.85 480.55
11/01 10.1 494 7.39 5.88 0.90 89.94 18.28 0.30 12.86 326.95 20.64 3.23 0.14 9.87 488.99

7 E 1.90 336 01/01 11.5 519 6.89 5.08 1.01 86.70 22.69 0.34 5.25 353.94 20.45 4.45 0.25 6.21 506.37
04/01 11.2 508 7.32 3.94 1.01 83.51 16.10 0.30 4.20 292.92 26.80 2.39 0.16 6.89 438.22
11/01 11.1 512 7.42 7.76 1.26 81.04 20.08 0.30 3.28 328.26 25.60 4.37 0.16 6.95 479.06

8 E 5.50 300 01/01 9.1 448 8.28 4.97 0.90 83.67 20.06 0.30 4.50 329.96 21.55 5.22 0.14 4.12 475.39
04/01 11.5 430 7.75 5.85 0.77 74.76 14.71 0.31 7.20 285.08 18.65 1.25 0.10 4.36 413.04
11/01 11.2 433 8.02 4.57 1.23 77.62 15.40 0.32 3.50 290.92 18.64 6.02 0.13 4.49 422.84

9 E 0.50 300 01/01 11.2 482 7.47 3.42 0.67 58.68 18.28 0.28 4.13 236.28 23.46 3.49 0.13 5.38 354.20
04/01 10.7 470 7.75 3.31 0.74 60.14 8.93 0.26 4.04 197.64 23.48 3.54 0.13 6.21 308.42
11/01 11.1 480 7.84 5.72 0.96 58.07 12.28 0.28 2.87 222.78 21.84 3.05 0.13 6.39 334.37

10 E 7.00 270 01/01 12.2 502 7.08 5.33 0.94 64.91 19.72 0.20 7.07 260.14 28.04 3.37 0.16 6.31 396.19
04/01 11.5 510 7.33 4.35 1.06 77.53 15.65 0.20 6.41 268.12 27.20 3.10 0.15 6.29 410.06
11/01 12.4 504 7.3 3.99 1.18 65.65 16.44 0.23 4.93 250.32 26.00 3.08 0.14 6.46 378.42

11 E 2.00 255 01/01 11.5 452 6.83 3.62 0.70 69.47 16.15 0.24 4.65 268.61 19.80 3.78 0.11 5.10 392.23
04/01 10.9 420 7.46 3.51 0.78 63.98 11.82 0.22 4.25 232.70 19.08 3.90 0.11 5.03 345.38
11/01 11.3 426 7.44 2.94 1.27 61.13 15.28 0.22 3.33 240.36 20.28 3.52 0.13 5.61 354.07

2067
(continued on next page)
Table 1 (continued)

2068
No. Spring Discharge Elevation Date T EC pH Na K Ca Mg Sr Cl HCO3 SO4 NO3 F SiO2 TDS
group (m3/s) (m a.s.l.) (mm/yy)
12 D 0.20 650 01/01 10.8 230 7.50 5.08 0.85 63.13 16.53 0.19 6.00 260.46 5.85 10.00 0.01 6.49 374.59
04/01 10.8 220 7.50 4.98 1.00 55.99 14.71 0.20 6.40 244.38 5.68 9.52 0.05 6.40 349.31
11/01 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

13 D 0.01 670 01/01 10.8 312 7.25 29.40 0.78 86.91 10.23 0.28 25.20 328.51 12.50 6.60 2.10 9.62 512.13
04/01 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
11/01 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

14 F 0.45 967 01/01 6.3 312 8.22 3.86 0.42 23.64 11.60 0.05 3.00 130.20 3.50 1.21 0.08 5.09 182.65

M. Barbieri et al. / Applied Geochemistry 20 (2005) 20632081

04/01 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.06 n.d. n.d. n.d. n.d. n.d. n.d. n.d.
11/01 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.07 n.d. n.d. n.d. n.d. n.d. n.d. n.d.

15 F 0.90 964 01/01 5.2 286 7.65 0.92 0.18 24.32 12.27 0.04 2.30 131.20 1.36 1.67 0.02 4.03 178.31
04/01 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.07 n.d. n.d. n.d. n.d. n.d. n.d. n.d.
11/01 5.1 265 7.63 0.78 0.23 20.90 11.57 0.09 1.87 120.96 1.42 1.56 0.03 4.21 163.62

16 B 0.01 1150 01/01 9.5 295 7.43 1.60 0.25 68.21 0.88 0.10 3.38 200.71 1.95 0.63 0.05 5.21 282.97
04/01 8.8 305 7.60 1.51 0.27 69.71 0.40 0.09 3.45 209.12 2.05 0.47 0.04 5.04 292.15
11/01 10.3 300 7.9 1.11 0.25 66.87 0.92 0.08 2.21 206.08 1.80 0.63 0.04 5.22 285.21

17 A 0.08 1315 01/01 5.7 306 7.41 2.82 0.77 62.26 12.20 0.21 3.59 235.83 12.47 0.44 0.05 6.24 336.88
04/01 6.0 301 7.80 2.96 0.87 58.77 10.46 0.20 3.72 214.21 13.21 0.39 0.05 6.19 311.03
11/01 6.4 295 8.36 2.30 1.29 51.91 11.71 0.18 1.71 205.62 12.70 0.63 0.05 6.30 294.40

18 A 0.10 1524 01/01 3.9 310 8.04 0.77 0.16 31.41 2.50 0.07 1.45 108.20 1.80 1.00 0.04 4.52 151.92
04/01 7.4 318 7.74 1.03 0.20 44.60 2.31 0.09 3.81 137.25 3.88 1.18 0.02 4.58 198.95
11/01 5 320 8.43 0.52 0.16 46.72 1.99 0.07 1.78 142.12 1.72 0.87 0.05 4.66 200.66

19 A 0.30 900 01/01 5.5 298 7.78 0.98 0.16 35.38 4.98 0.07 1.60 130.05 1.65 0.66 0.04 5.05 180.62
04/01 5.5 300 7.78 1.00 0.19 36.78 3.33 0.07 1.45 126.21 1.73 0.52 0.05 5.31 176.64
11/01 7.2 290 8.33 0.63 0.18 31.40 4.85 0.08 0.91 116.51 1.62 0.65 0.03 5.42 162.28

20 A 0.28 650 01/01 9.0 263 7.85 2.12 0.26 46.24 13.38 0.10 3.07 202.86 3.45 1.10 0.06 6.31 278.95
04/01 9.0 260 7.85 2.53 0.35 45.66 8.99 0.10 3.69 175.60 5.06 1.08 0.06 6.24 249.36
11/01 9.2 266 7.98 1.61 0.26 45.32 11.89 0.12 2.23 192.34 3.36 1.01 0.05 6.32 264.51

21 A 0.38 690 01/01 6.5 216 8.10 2.44 0.31 55.39 8.37 0.49 2.84 186.91 20.47 1.23 0.06 7.26 285.77
04/01 6.5 208 8.10 2.13 0.30 52.35 4.77 0.46 3.08 181.31 19.12 0.91 0.07 7.11 271.61
11/01 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

The results of the 3 surveys (January, April and November 2001) are expressed in mg/L (accuracy ranges from 2% to 5%); elevation is expressed in m above sea level; temperature in C
(accuracy 0.1 C); pH in pH units (accuracy 0.01); EC, electrical conductivity in lS/cm at 25 C (accuracy 0.05 lS/cm); n.d., not determined. Spring numbers and groups refer to
Fig. 1.
 M. Barbieri et al. / Applied Geochemistry 20 (2005) 20632081 2069

Table 2
Isotope composition of sampled waters (chemical values of Sr are expressed in mg/L)
Spring Spring group January 2001 April 2001 November 2001
87
Sr/86Sr Sr d18O d2H 87
Sr/86Sr Sr 87
Sr/86Sr Sr d18O d2H
1 D 0.70840 0.15
9.12
59.83 0.70838 0.16 0.70824 0.17
9.22
61.67
2 D 0.70813 0.13
8.95
60.71 0.70815 0.14 0.70805 0.13
9.43
63.25
3 D 0.70866 0.14
9.45
63.54 0.70869 0.14 0.70862 0.14
9.44
63.34
4 C 0.70810 0.07
10.20
69.27 0.70815 0.06 0.70807 0.09
10.61
72.32
5 C 0.70803 0.07
10.35
69.28 0.70800 0.08 0.70792 0.11
10.62
72.39
6 E 0.70794 0.29
9.70
64.69 0.70796 0.25 0.70790 0.30
10.01
67.72
7 E 0.70801 0.34
9.35
63.49 0.70803 0.30 0.70785 0.30
9.79
66.04
8 E 0.70792 0.30
9.99
65.93 0.70791 0.31 0.70792 0.32
9.99
67.59
9 E 0.70802 0.28
9.80
64.56 0.70806 0.26 0.70819 0.28
9.82
66.25
10 E 0.70787 0.20
9.60
65.53 0.70788 0.20 0.70781 0.23
9.99
67.55
11 E 0.70779 0.24
9.29
63.57 0.70781 0.22 0.70821 0.22
9.73
65.56
12 D 0.70864 0.19
8.68
57.81 0.70862 0.20 n.d. n.d. n.d. n.d.
13 D 0.70933 0.28
8.13
51.90 n.d. n.d. n.d. n.d. n.d. n.d.
14 F 0.70799 0.05
10.11
69.05 0.70780 0.06 0.70781 0.07
10.24
69.52
15 F 0.70783 0.04
10.45
72.91 0.70785 0.07 0.70795 0.09
11.05
75.70
16 B 0.70835 0.09
9.89
65.35 0.70832 0.09 0.70823 0.08 n.d. n.d.
17 A 0.70924 0.21
9.12
60.40 0.70926 0.20 0.70913 0.18
10.36
70.44
18 A 0.70787 0.07
10.05
67.31 0.70785 0.09 0.70775 0.07
10.67
72.81
19 A 0.70782 0.07
9.68
65.80 0.70785 0.07 0.70762 0.08
10.72
73.14
20 A 0.70804 0.10
9.66
66.61 0.70802 0.09 0.70780 0.11
10.76
73.49
21 A 0.70881 0.50
9.68
64.28 0.70883 0.45 n.d. n.d. n.d. n.d.
R1 (1024 m asl) n.d. n.d.
8.90
59.85 n.d. n.d. n.d. n.d. n.d. n.d.
R2 (685 m asl) n.d. n.d.
8.10
51.41 n.d. n.d. n.d. n.d. n.d. n.d.
The 87Sr/86Sr isotope ratio is aected by an error expressed as 2r (0.00002). The isotope composition of O and H is reported in d units
per mil vs. the V-SMOW standard accuracy: 1& for 2H/H and 0.2& for 18O/16O. R1 and R2, rainwater samples. n.d., not determined.
Spring numbers and groups refer to Fig. 1.

The PHREEQCI software, version 2.10.0.0 (Park-
hurst and Appelo, 1999), was used to compute aque-
ous speciation and uid-mineral equilibria, relying
on the thermo.com.V8.R6 thermodynamic data-
base (full LLNL database). Computed saturation
indexes (SI) are approximate due to analytical and
activity concentration uncertainties and are assumed
to be 0.5 accurate.
4. Results
4.1. Major ions
As shown in Fig. 2, groundwater samples were
classied by analysing their main groups of cations
and anions and by determining their reaction values
(relative percentages). All sampled waters were clas-
sied as of Ca++
Mg++ HCO
3 type (Chebotarev,
1955; Appelo and Postma, 1993), in line with the
interpretation of a common origin from the Gran
Sasso carbonate aquifer. Nonetheless, some of
the waters had more pronounced Ca++ + Mg++
HCO
3 characteristics (groups B, C, D, F and, par-
tially, A), while others had an increase in their


SO 4 Cl values (mainly groups E and, partially,
A). Furthermore, springs 3 and 13 were enriched in
Na+ and K+.
The spatial distribution of major ion concentra-
tions is consistent with the hydrogeological setting
of the massif described earlier (Fig. 3). Maps were
constructed using the January 2001 data set, the
only one that encompassed all the springs. The
trends of TDS, HCO
3 and Ca
++
ions are virtually
identical and indicate increased concentrations from
the core of the massif (area extending between
Campo Imperatore and the motorway tunnel) to
its boundaries, with peak values for spring groups
D and E. The trend of Mg++ shows a more marked
enrichment in group C and, partially, in group F.
Also the distribution of SO 4 is quite similar, with
local increases of its concentration in specic springs
of groups A (spring 21), D (spring 3) and in all the
springs of group E. Finally, the concentration of
Sr++, albeit very low, conrms enrichment in the
peripheral sectors of the massif. The other incom-
plete sampling surveys (April and November 2001)
suggest a stable spatial distribution of major ele-
ments (see Table 1).
2070 M. Barbieri et al. / Applied Geochemistry 20 (2005) 20632081
SO4-- + Cl-
SO4- - + Cl-
25 50
Ca++ +M g++
Na+ + K+
A B C the recharge area (group E) have higher ratios and
D E F increased HCO

Na+ + K+
0 5
HCO3-+ CO3--
25
HCO3- + CO3--
Fig. 2. Reaction values as percentage of signicant groups of
cations and anions. All collected samples grouped by spring type
are shown. Spring groups refer to Table 1.


Most of the waters had low NO
3 and Cl con-
centrations, which were considered as indicators of
human activities (urban and agricultural settle-
ments), except for springs 3, 6 and 13 (Table 1).
4.2. Geochemical modelling
The chemical evolution of the Gran Sasso spring
water is characterised by interaction with carbonate
rocks. Carbon dioxide, absorbed by the soil upon
recharge, reacts with the carbonate rocks in the
aquifer, dissolving calcite and dolomite according
to the following reactions:
2CaCO3 2CO2 2H2 O 2Ca2 4HCO

3
CaMgCO3 2 2CO2 2H2 O Ca2 Mg2 4HCO

3
The results of geochemical modelling show that al-
most all springs are undersaturated in dolomite
and saturated in calcite (Fig. 4). From the January
to the November survey, a positive trend in satura-
tion indexes is observed (Table 3).
The fact that the waters are undersaturated in
dolomite indicates that dolomite can dissolve in this
system. Dolomite dissolution is likely to add Ca++,
Mg++, and HCO
3 to the solution, while calcite
precipitation is necessary to keep the observed cal-
cite saturation. Thus, the combination of dolomite
dissolution and calcite precipitation is thought to
increase Mg/Ca ratios along owpaths.
0 25 Indeed, high-elevation springs near the recharge
area (group A) have the lowest Mg2+/Ca2+ ratios
(<0.1), while low-elevation springs farther from
3 concentrations (Fig. 5).
Ca++ + Mg++
Gypsum and halite may participate in waterrock
0
interactions, probably as natural salts (interbedded
minerals and/or continental deposits) or anthropo-
genic salts (road salts). Groups D and E show higher
concentration of Na+ and Cl
(Fig. 6), testifying
possibly to longer waterrock interactions. The high
Cl
concentration of sample 6 is likely to be of
anthropogenic origin.
Venturelli et al. (2003) proposed that the Na+
50 excess of some springs (3 and 13) compared to halite
dissolution (Na/Cl = 1) might be due to progressive
interaction of water with albite under conditions of
saturation with respect to other silicate phases
(quartz, kaolinite). The upward trend of Na excess
in spring 3 from April to November was simulated
with the PHREEQCI software, using the concentra-
tions and SI values measured in April for the initial
solution, assuming equilibrium in kaolinite satura-
tion and logPCO2 =
2.10, and then incrementally
adding 0.0006 moles of albite (Fig. 6 and Table 4).
A similar approach was adopted to explain Na
excess in spring 13 (Fig. 6). Final calculated compo-
sitions compared well with measured concentra-
tions. This process of albite dissolution probably
occurs in the Quaternary continental deposits (LA-
quila Plain, Petitta and Tallini, 2003), near the
terminal part of the owpaths. For similar reasons,
spring group E (samples 8, 9, 10, 11) also shows
Na/Cl > 1 (Fig. 6).
4.3. Stable isotope analysis
Isotope analyses revealed dierences in space and
time in the sampled spring waters and provided de-
tails on local groundwater owpaths. The results
are summarised in Table 2, where the O and 2H iso-
tope values recorded in November are more negative
than those of January. This nding suggests a rela-
tionship between mean local temperature and mean
isotope composition of atmospheric precipitation.
This relationship was rst demonstrated by Dansg-
aard (1964) and then, in Italy, by Longinelli and
Selmo (2003). As expected, measured seasonal
changes in the isotope composition of precipitation
(Longinelli and Selmo, 2003) are more signicant
 M. Barbieri et al. / Applied Geochemistry 20 (2005) 20632081 2071

337 152 236 108

183 130
283 181 130
201 187
178 286 131
375 500 260 203 300
279
379 250 279 180
512 276 329 195
401 400 271 258 250
441 LAquila
LAquila

300 343 200

515 354
At 506

Tir
er At
TDS HCO3- er

Ti r
no

ino
R no

ino
. 200 R . 150

R.
R.
475 330
354 236
392 100 269 100
396 260

62 31 12 2
24
35 1 12 5
68 8
55
24 12 13
63 46 80 17 20
74 40 10 13 14
87 64 43 12 14
LAquila 79
65 11 15
LAquila

90 50 23 10

Tir in
Tir ino

87 23
Ca ++ At
er Mg ++ At
er

o R
no no
R R
. 35
R.

.
.
84 18 20
59 16
69 20 20 0
65

12 2 0.21 0.07
3 0.05
2 2 0.10 0.07
1 20 0.49
3 0.04 0.10
6 25 0.19 0.4
12 6 2 0.28 0.15 0.07
4 2 0.13 0.07
22 19 0.14 0.3
LAquila LAquila

20 0.29
20
13 0.2
At At 0.34 Tir
ino
Ti r

er er
= no ++ no
SO
ino

R
Sr R
R.
4
. 7 . 0.1
0.30
R.

22 0.28
23
20 0.24
1 0
28 0.20

B F A
D
C
20 km
N
E

Fig. 3. Isopleths (January 2001 survey) of TDS, HCO
3 , Ca
++
, Mg++, SO4 and Sr concentrations in mg/L. Data refer to Table 1. The
lower-left sketch shows the locations of the spring groups: A, B, C, D, E and F refer to the spring groups (see Fig. 1 and Table 1).

than those observed in the Gran Sasso spring waters. sent recharge areas located at dierent mean eleva-
Taking into account the lack of data for the two tions, as shown by the location of the precipita-
rainwater samples (R1 and R2, Table 2), which were tion data on the local meteoric water line (Fig. 7).
collected only during the rst survey, no specic The equation for the local line (dD = 7.76d18O +
conclusions can be drawn with regard to changes 9.95) is very close to that for northern Italy cal-
in the isotope content of the spring waters over time. culated by Longinelli and Selmo (2003) (d =
However, it should be pointed out that the nding of 7.61d18O + 9.21) and is consistent with other equa-
systematically lower values in the November survey tions previously identied for central Italy (Celico
is consistent with the seasonal trend of the composi- et al., 1984; Barbieri et al., 2003). As the deviations
tion of precipitation observed for Central Italy by of the individual samples from the nIML line fall
Longinelli and Selmo (2003). within the analytical error range and the correlation
Considering the January survey alone (including coecient is high (R2 = 0.94), evaporation is unli-
precipitation data), the observed values may repre- kely. This assumption is supported by the alignment
2072 M. Barbieri et al. / Applied Geochemistry 20 (2005) 20632081

1.5 1.0 dolomite dissolution

S.I. calcite
1.0 0.9 A B C
S.I. dolomite
0.5 0.8 D E F
Saturation Index (S.I.)

0.7
0.0
0.6

++
-0.5

Mg /Ca
0.5 calcite + dolomite

++
-1.0 dissolution
0.4
-1.5
0.3
-2.0
0.2 3j
13j
-2.5 3n
0.1
3a
-3.0 calcite dissolution
0.0
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
- -
HCO 3 (mmol/L) HCO3 (mmol/L)

Fig. 4. Saturation Index (S.I.) of calcite and of dolomite versus Fig. 5. Mg/Ca vs. HCO3
in mEq/L. Spring groups refer to
HCO
3 of all collected samples (see Table 3). Table 1.

Table 3 1.4
Mean values of SI for calcite and dolomite for the dierent spring A B C
13j
groups, calculated by the PHREEQCI software, version 2.10.0.0 1.2 D E F
(Parkhurst and Appelo, 1999)
3n 0.0006
Survey Group SI calcite SI dolomite 1.0
0.0005 albite
January A 0.01
1.17
Na (mmol/L)

dissolution
0.0004
April A 0.06
1.22 0.8
0.0003
3j
November A 0.43
0.37 n
utio
January B
0.08
2.38 0.6 0.0002
sol
dis
+

ite
April B 0.11
2.38 0.0001
hal
November B 0.40
1.38 0.4 3a
January C
0.03
0.88
Cl addition?
April C 0.15
0.73 0.2 6n
6j
November C 0.32
0.20
6a
January D 0.12
0.86
0.0
April D 0.18
0.81 0.0 0.2 0.4 0.6 0.8
November D 0.13
0.92 -
Cl (mmol/L)
January E
0.05
0.98
April E 0.14
0.77 Fig. 6. Cl
vs. Na+ in mEq/L. Spring groups refer to Table 1.
November E 0.20
0.56 Groups ABCF are distinguished from groups DE. Vertical
January F
0.25
1.19 arrows show albite dissolution trend.
November F
0.64
1.95
Errors in computed saturation indexes (SI) are estimated at 0.5.
Note that, for groups A, B and C and E, the SI for calcite in
one of
0.2&/100 m, reported by Longinelli and
November is always more positive. Selmo (2003) for Italy, and to other gradients pro-
posed for central Italy:
0.27&/100 m (Zuppi
et al., 1974) and
0.24&/100 m (Conversini and
of the isotope values of the two sampled meteoric Tazioli, 1993). Taking into account these gradients,
waters with those of groundwater and is in agree- the mean recharge elevation of each spring of Gran
ment with the high inltration capability of terrains Sasso was determined (Fig. 8).
and rocks in the study area (Boni et al., 1986; As mentioned above, the lack of precipitation
Scozzafava and Tallini, 2001). data made it impossible to establish a direct corre-
Based on isotope and elevation values obtained lation for the November samples. Nevertheless,
from the two sampling pluviometers, a vertical iso- assuming the same gradient as the one calculated
tope gradient of
0.24&/100 m was computed for for January, the recharge elevations computed for
the January survey; this gradient is close to the the November survey are always higher than the
 M. Barbieri et al. / Applied Geochemistry 20 (2005) 20632081 2073

Table 4
Inputoutput data for geochemical model based on two dierent approaches for simulating albite dissolution, starting from calculated
saturation indexes and Na/Cl = 1 (see Fig. 4 and text for details)
Real sample Calculated sample
Sample 13
Imposed (start)
T 10.8
SI calcite 0.0
SI dolomite-dis
1.20
SI gypsum
2.50
SI quartz 0.54
log PCO2(g)
1.80
Cl 7.11 10
4
Na 7.11 10
4
Ad hoc values
SI kaolinite 0.0
SI albite
2.10
Calculated (nal)
pH 7.25 7.22
t-Alk 5.3 10
3 5.5 10
3
Ca 2.2 10
3 2.1 10
3
Mg 4.2 10
3 4.6 10
3
Na 1.3 10
3 1.3 10
3
S 1.3 10
4 1.2 10
4
Si 1.6 10
4 1.6 10
4
Al 5.4 10
10

Sample 3
Imposed (sample 3a)
T 14.0
SI calcite 0.20
SI dolomite-dis
1.20
SI gypsum
2.20
SI quartz 0.40
log PCO2(g)
2.10
CI 4.20 10
4
Na 4.20 10
4
Ad hoc values
SI kaolinite 0
Calculated sample (3n) after addition of 0.0006 mol of albite
pH 7.34 7.46
t-Alk 4.4 10
3 4.5 10
3
Ca 1.9 10
3 2.0 10
3
Mg 2.9 10
4 1.6 10
4
Na 1.0 10
3 1.0 10
3
S 2.4 10
4 2.3 10
4
Si 1.2 10
4 1.4 10
4
Al 1.5 10
9
In sample 13 simulation, saturation indexes of Al-silicates were imposed up to a specic value of Na excess (SIkaolinite = 0.0, corre-
sponding to a precipitation of 2.8 10
4 mol; SIalbite =
2.1, corresponding to a dissolution of 5.7 10
4 mol). In sample 3 simulation,
Na excess was obtained with an incrementally calculated reaction path (i.e., albite titration up to 6.0 10
4 mol) and SIkaolinite = 0.0
(corresponding to precipitation of 2.9 10
4 mol). Computations made with the PHREEQCI software (Parkhurst and Appelo, 1999).
Element concentration in mol/L.

January ones (Fig. 9). Single groups of springs show side of the massif; groups C and F show similar
dierences in computed isotope recharge elevations dierences, evidencing a seasonal eect; groups B,
between January and November: major dierences E and D show less signicant seasonal dierences
are observed in group A, located on the northern (Fig. 9).
2074 M. Barbieri et al. / Applied Geochemistry 20 (2005) 20632081

-46
y = 7,76x + 9,95 fit to January data

MML Rws2
13J
-52
nIML
cIML
D/H vs V-SMOW

-58 12J
1J Rws1
17J 2J
3J GML
9J 21J 7J, 11J
-64 16J 6J
8J 10J
19J
18J 20J
4J 14J
5J A B C
-70
D E F
15J *R

-76
-11,00 -10,40 -9,80 -9,20 -8,60 -8,00
18 16
O/ O vsV-SMOW
Fig. 7. Isotope values for January samples plotted together with the Mediterranean Meteoric Line (MML), the World Meteoric Line
(WML) (Rozanski et al., 1993) and the northern and the central Italy meteoric lines (nIML, cIML) (Longinelli and Selmo, 2003). A, B, C,
D, E and F refer to spring groups. R1 and R2 refer to rainwater samples (Table 2 and Fig. 1). The line tted to the January data is very
close to the nIML.

1800
Group A B C Group D Group E Group F
1700 15
5
1600
4
18 14
8
1500
Isotope elevation (m asl)

16
9
1400
19 20 21 6
10
1300
3
7 11
1200
17 1
1100
2
1000
12
900
800
13
700
600
Spring

Fig. 8. Isotope elevation (m a.s.l.) of the springs, calculated from the January d18O values (Fig. 7) and an isotope gradient of
0.24%/
100 m. Numbers refer to Table 2.

The results of the rst and third surveys (Janu- In most cases, signicant changes (more than twice
ary and November 2001) for the monitoring of Sr the analytical accuracy) were observed in 87Sr/86Sr
isotopes are shown in Fig. 10 for spring groups A, ratios (Table 2) between January and November
B and C and in Fig. 11 for D, E and F. The results samplings. However, these changes were often
of the second survey (April 2001) are not plotted, not accompanied by similar changes in Sr concen-
because their isotope ratios and Sr concentrations trations (Table 1), as evidenced by the analysis of
are very similar to those of the previous survey. major constituents. In particular, many samples
 M. Barbieri et al. / Applied Geochemistry 20 (2005) 20632081 2075

2000 ised by clayey minerals, with carbonate and silici-

Computed isotope recharge elevation (m a.s.l.)

1800 clastic sand and gravel beds (Magaldi and Tallini,

2000). The values closest to the continental 87Sr/86Sr
1600
values are those pertaining to springs located in or
1400 near the deposits, at the boundaries of the aquifer
1200 (Fig. 12).
1000
5. Discussion
800

600 The results of hydrogeochemical and isotope

A B C
November Janua ry analyses are consistent with the assumed conceptual
400 D E +F

A+B C model of groundwater owpaths in the massif

200
0 adopted in this study, oers clues for a more
0 500
Real spring elevation (m a.s.l.)
Fig. 9. Real elevation vs. isotope elevation (m a.s.l.) of springs,
calculated from the January and November d18O values, starting
from precipitation values of Fig. 7. Spring groups refer to Table 2.
had lower 87Sr/86Sr values in November than in
January (Figs. 10 and 11). Only springs 9, 11 and
15 had an opposite behaviour, with higher
87
Sr/86Sr isotope ratios in January (Fig. 11). The
87
Sr/86Sr values of springs 2, 3, 4, 6, 7, 8, 10, 12
and 13, showed changes that are assumed to be
negligible or to fall within the instrumental error
range.
Most of the data plot between the values expec-
ted for Sr coming from deep Mesozoic carbonates
and Quaternary continental deposits (Figs. 10 and
11). Quaternary continental deposits are character-
D E F (Fig. 1). The integrated monitoring technique,
1000 1500 2000
in-depth understanding of the regional hydrody-
namics, based on observed changes of the moni-
tored isotopes over time and in space.
The Gran Sasso aquifer contains an active
groundwater ow system that is supported by high
recharge rates (about 700 mm/a) (Boni et al., 1986;
Scozzafava and Tallini, 2001). Recharge rates have
peaks in the central and northern areas of the
massif, where the dolomite bedrock outcrops. Con-
sequently, groundwater generally ows from the
core to the boundaries of the massif (Fig. 1) (Petitta
and Tallini, 2002).
Hydrogeochemical monitoring of the main com-
ponents of the sampled water shows that they are
generally fairly homogeneous over time (Fig. 2).
The principal nding from the main components
analysis is that the samples from higher-discharge
springs (group E and, to a lesser extent, group D,

0.70940
17J A B C
0.70920 17N
0.70900 dissolution of continental deposits*
0.70880 21J

0.70860
Sr/ Sr
86

0.70840 16J
16N
87

0.70820 4J
4N
20J 5J
0.70800
5N 18J
0.70780 upper Trias 20N 19J
18N
0.70760 19N
0.70740
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0
1/Sr

Fig. 10. Plot of 87Sr/86Sr vs. 1/Sr of samples of spring groups A, B and C for the January (J) and November (N) surveys. Note, in many
samples (5, 7, 16, 17, 18, 19, 20), the signicant seasonal variations of 87Sr/86Sr (more than 0,00010 units). Numbers refer to Table 2.
* from Bierman et al., 1998.
2076 M. Barbieri et al. / Applied Geochemistry 20 (2005) 20632081

0.70960
0.70940 13J
D E F
0.70920
0.70900 dissolution of continental deposits*
Sr/ Sr 0.70880
3J
86

12J
0.70860 3N
87

0.70840 1J
11N
9N 1N
0.70820 2J
7J 9J 2N
0.70800 6J, 10J 15N 14J
8N, 8J 15J
0.70780 10N, 6N 14N upper Trias
7N, 11J
0.70760
0.0 5.0 10.0 15.0 20.0 25.0 30.0
1/Sr

Fig. 11. Plot of 87Sr/86Sr vs. 1/Sr of samples of spring group D, E and F for the January (J) and November (N) surveys. Note, in some
samples (1, 14), the signicant seasonal variation of 87Sr/86Sr (more than 0,00010 units). Numbers refer to Table 2. * from Bierman et al.,
1998.

1
0.70924 0.70787
0.70799
0.70835 0.70782
0.70783 0.70881
0.708640.7081 0.70804 0.7096
0
0.709330.70840
0.70813 0.7080
3
LAq uila 0.70866
0.70895

0.7079
4 0.7083
At 0.70801
Ti r i

er
no
R
no

. 0.70765
0.70792
R.

0.70802
0.70779 0.707
0.70787
2
0.7091307. 0775
0.70781
0.70823 0.70762
0.70795 N.D.
N.D. 0.70807 0.70780 0.7096
N.D. 0.7082 4
0.7079
2
0.70805 0.70895
LAq uila 0.7086
2
0.70790
0.7083
At
er
0.70785
Ti r i

no
R
no

. 0.70765
0.70792
R .

0.70819
0.70821 0.707
B F A 0.70781
D
C
E 20 km
N

Fig. 12. Isopleths of 87Sr/86Sr ratio: 1 January 2001 survey, 2 November 2001 survey. Numbers refer to Table 2. The lower-left sketch
shows the locations of the spring groups: A, B, C, D, E and F refer to the spring groups (see Fig. 1 and Table 2). N.D., not determined.
 M. Barbieri et al. / Applied Geochemistry 20 (2005) 20632081
Table 1), located at the boundaries of the aquifer,
have a higher content in dissolved solids, especially
in Ca++ and HCO
3 ; in addition, they are richer in
SO4 and Sr (Fig. 3) and often have higher Mg/Ca
ratios (Fig. 5). This nding is to be ascribed to a
more intense waterrock interaction, reecting
longer residence times and/or deeper owpaths; in
fact, the above springs are more distant from the
main recharge area corresponding to the core of
the regional aquifer (Fig. 1, Campo Imperatore
endorheic depression). Isotope elevations indicate
that water from these springs was recharged at
much higher elevations (Figs. 8 and 9), which is con-
sistent with a mountain-core recharge area. The low
mineralisation of the samples of groups A, B, C, F
can be attributed to shorter and/or faster ground-
water owpaths.
At the aquifer boundaries, groundwater interacts
with terrigenous (Miocene) and alluvial deposits
(Quaternary); anthropogenic activities concentrated
in these sectors are likely to aect groundwater
chemistry. This interaction is shown by the enrich-
ment in Na+, Cl
and NO
3 (Fig. 2) recorded in
spring groups D and, partially, A and E. Geochem-
ical modelling oers an explanation of the process,
which may occur through albite dissolution in an
open system (Fig. 6 and Table 4) for samples 3 and
13 (group D). Similar processes may aect group
E, showing Na/Cl > 1; for spring 6, an anthropo-
genic addition of Cl
is supposed. The assumed
interaction with human activities is substantiated
by the shallow depth of the water table and by the
number of total and faecal coliforms found in several
wells of the study area (Petitta and Tallini, 2003).
The analysis of stable isotopes shows signicant
spatial variability of 2H and O isotopes, corroborat-
ing the assumptions underlying the hydrogeological
conceptual model.
Calculated mean isotope recharge elevations are
largely variable within and between the individual
groups of springs. For example, sample 13 (eleva-
tion 660 m a.s.l.) has a calculated isotope recharge
elevation (700 m a.s.l.) which is consistent with the
one of the nearby rainwater sample 2 (685 m
a.s.l.). The hydrogeological setting of the spring
(low and variable discharge) suggests that it is al-
most exclusively recharged by the local aquifer. In
contrast, spring 3, with a mean isotope recharge ele-
vation of 10001100 m a.s.l., indicates that it is pre-
sumably recharged in more elevated areas of the
aquifer. It also has relatively high and abundant
ows (Table 1).
2077
Isotope elevations of samples from group F are
similar to those determined for spring group C
(Fig. 8); this nding supports the hydrogeological
assumption (Petitta and Tallini, 2002) that both
these groups are directly recharged by the core of
the massif (Campo Imperatore, mean elevation
1700 m a.s.l.). Group E includes springs with iso-
tope recharge elevations ranging from about
1200 m a.s.l. (springs 7 and 11) to about 1450 m
a.s.l. (springs 8 and 9) and has the highest discharge
among all spring groups.
With regard to group A, springs 19, 20 and 21
have the same isotope elevation, whereas springs 17
and 18 tend to be dierent. Their fairly high
calculated isotope recharge elevation values are com-
patible with a hydrogeological scenario where this
group of springs is recharged by the higher-elevation
aquifer zones, lying north of the groundwater divide
in the area of the dolomite outcrop.
Temporal variability in the spatial pattern of
Mg/Ca ratios provides additional insight into the
seasonal variation in owpaths (Fig. 13). During
periods of high recharge (April survey), new inl-
trating waters, which only circulate in the shallow
system (unsaturated and epikarst areas), introduce
Ca++ enriched waters in groundwater with high
Mg++/Ca++ ratio (group F), diluting it and lower-
ing its Mg++/Ca++ ratio. Conversely, during no-
recharge periods (November survey), the core of
the massif has higher Mg/Ca ratios, due to a more
substantial contribution of base ow groundwater,
not aected by recently inltrated freshwater.
The seasonal change of 87Sr/86Sr ratios is evident
in several springs fed by the regional karst aquifer (1,
2, 3, 5, 14, 18, 19 and 20, belonging to groups A, C,
D and F) (Figs. 10 and 11). As illustrated in Fig. 14,
this nding infers that, in low-discharge periods
(summerautumn, represented by the November
survey), spring waters with lower 87Sr/86Sr ratios
are fed by water circulating in more ancient geo-
logical units (Dogramaci et al., 1998), considering
the low position of the groundwater table. During
the recharge period (winterspring, represented by
the January survey), newly inltrated waters raise the
aquifer water, which thus comes into contact with
more recent stratigraphic units, including carbon-
ates. This situation is evident at the core and in the
northern portion of the massif (Fig. 14(b)), where
seasonal uctuations of the water table are fairly
wide (tens of meters) and the contribution of waters
circulating in more recent units (higher 87Sr/86Sr
ratio) is signicant and capable of changing the
2078 M. Barbieri et al. / Applied Geochemistry 20 (2005) 20632081

1 b
.
0.18 0.05 aquifer

.fromJ urassic to Paleogene

N.D. maximum
0.01 0.09 water level
0.09
N.D. 0.20
0.26 Spring
LAq uila H
N.D. 0.16 0.21 0.3 group A
0.16 N.D. minimum
0.05 water level

0.22
0.2
At
0.19 aquiclude
Ti r i
er
no
no 0.1
R .
R.
0.15 0.20
0.18 a
0.20 0 2000 H>>Z
2
H
0.23 0.04 1000
N.D. Z
0.01 0.15
N.D.
0.55 0.26 0m 1 2 3 4 5 6 0m
N.D. 0.4
N.D. 0.17 0.33 NW SE
0.18 0.31
LAq uila 0.09
0.3 c .maximum
water level Spring group E
0.20 0.2
At
0.25
Ti r i

er
no
no

R . 0.1 Z
minimum
R.

0.21 0.20 water level

0.25
0.25
B F A
D .
C
E 20 km
Fig. 13. Isopleths of Mg/Ca ratio: 1 April 2001 survey, 2
November 2001 survey. Numbers refer to the Table 1. The lower-
left sketch shows the locations of the spring groups: A, B, C, D, E
and F refer to the spring groups (see Fig. 1 and Table 1).
Isopleths take into account data from springs of nearby carbon-
ate aquifers. ND, not determined.
mean isotope values of low-discharge periods. In ef-
fect, the springs of group F (motorway tunnel) are
more aected by seasonal recharge, just as the
nearby springs on the northern side of the massif
(group A). Also the characteristics of the waters of
group C (whose fast circulation is due to the likely
presence of karst features, Tallini et al., 2000) are
similar to the tunnel waters and have a signicant
seasonal variability of their 87Sr/86Sr ratio.
The absence of seasonal signals in the 87Sr/86Sr
values of groups D and E is consistent with the pro-
posed hydrogeological conceptual model in which
the waters of these groups are fed by groundwater
coming from the aquifer core. Moreover, minor
uctuations of the water table (of few meters) reduce
the interaction between groundwater and rocks of
dierent ages (Fig. 14(c)).
aquifer aquiclude
0
aquifer aquiclude
Fig. 14. Sketch (not in scale) of the dierent contributions of
N waterrock interaction in the Gran Sasso carbonate aquifer,
along a NWSE direction, in relation to the seasonal movement
(vertically exaggerated) of the water table; in the proposed model,
water table variations can inuence the seasonal values of
measured isotope ratios 87Sr/86Sr: (a) Hydrostructural section:
(1) aquiclude, (2) aquifer, (3) water table line, (4) thrust (no-ow
boundary), (5) spring, (6) main recharge contribution; (b)
hydrostructural zoom of spring group A: H water table seasonal
movement; (c) hydrostructural zoom of spring group E: Z water
table seasonal movement. H is higher than Z.
The highest 87Sr/86Sr ratios, recorded in springs
3, 12, 13, 17 and 21, support this interpretation of
hydrogeochemical data: at the boundaries of the re-
gional aquifer, water interacts with more recently
deposited units, such as clastic continental deposits
(3, 12, 13, group D) or terrigenous deposits (17
and 21, group A).
The proposed hydrodynamic model requires a
signicant contribution of deep regional groundwa-
ter to spring discharge during the dry season, i.e.,
prior to the new recharge cycle (Rademacher
et al., 2002). The contribution of recently inltrated
waters to spring discharge becomes signicant only
in high-elevation areas where the recharge rate is
high and there are large water table uctuations.
 M. Barbieri et al. / Applied Geochemistry 20 (2005) 20632081
In these areas, recharging shallow groundwater is
likely to increase the Sr isotope ratios as a result
of waterrock interactions with younger carbonate
rocks. Springs located at lower elevations, with
higher and more stable discharge and lower water
table uctuations, have low seasonal variability
resulting from the contribution of dierent and
wider recharge areas. Moreover, these springs show
a higher content in dissolved solids, which is in turn
due to a longer travel distance; in these cases, the
87
Sr/86Sr ratio does not signicantly change.
6. Conclusions
Qualitative groundwater circulation models based
on water budgets can be enhanced through the use of
chemical and isotopic tracers, particularly in karst
aquifers. In the studied fractured karst aquifer,
groundwater hydrogeochemistry of the main compo-
nents was consistent with the proposed division of
the springs into 6 groups, showing an increase in dis-
solved solids, mainly Ca++ and HCO
3 , along
groundwater owpaths from the aquifer core to its
boundaries. Groundwater chemistry also was altered
by water/rock interactions in hydraulically connec-
ted alluvial aquifers and by anthropogenic activity
at the aquifer boundaries.
The main ndings from this study were obtained
by isotope monitoring over time, which oered in-
depth clues into groundwater circulation:
(a) in several groups of springs, 87Sr/86Sr changes
over time were non-negligible, especially in
higher-elevation springs which have large
seasonal water table variations and shorter
groundwater owpaths (groups A, C, F);
(b) d18O values showed seasonal variations, evi-
dencing a general increase in November, before
the new recharge period;
(c) the seasonal reversal of the Mg/Ca ratio con-
rms a sharp dierence between periods of
recharge and periods of exhaustion of ground-
water circulation, due to the contribution of
new recharge waters.
From the above observations, two types of
groundwater contribution to spring discharge can
be inferred: (i) a contribution by deeper groundwater
(interacting with more ancient rocks, giving a lower
87
Sr/86Sr ratio), which takes place during the dry
periods (summer/autumn) and (ii) a contribution
by new recharge waters (interacting with younger
2079
rocks, inltrating from the surface to the water
table), which increase the 87Sr/86Sr ratio during
recharge periods (winter/spring).
The latter point implies the need for building
a more comprehensive model, to be validated by
future time-monitoring surveys. The renement of
knowledge might contribute to policies of conserva-
tion and management of water resources, relying on
the identication also with time-based criteria of
sensitive areas to be protected.
Acknowledgements
The Authors thank the Ministry of Universities
and Scientic Research MIUR (Ambiente terres-
tre project Cluster C11b subproject Law
Decree no. 720/99) for its nancial support, Con-
sorzio di Ricerca Gran Sasso for its useful assis-
tance, GEOKARST (Trieste, Italy) for d2H and
d18O analyses, Dr. Giuseppina Benedetti for major
element chemical analyses and E. Di Biasio for the
chemical preparation of samples analysed by mass
spectrometer (VG-54E).
The authors are indebted to Z.E. Peterman, who
generously oered helpful comments and sugges-
tions on earlier versions of this manuscript. Com-
ments made by anonymous reviewers and by P.B.
McMahon were highly appreciated.
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