The groundwaters of Fontevivo (Parma Province, Italy): redox processes

and mixing with brine waters

Lorenzo Toscani1, Tiziano Boschetti1, Monica Mani2, Maurizio Barbieri3 &
Claudio Mucchino2
1
Department of Earth Sciences, University of Parma, Parco Area delle Scienze 157/A, 43100 Parma, Italy
(e-mail: tosco@unipr.it; tiziano.boschetti@unipr.it)
2
Department of Inorganic Chemistry, Analytical Chemistry and Physical-Chemistry, University of Parma,
Parco Area delle Scienze, 43100 Parma, Italy
3
Department of Earth Sciences, University of Rome
La Sapienza
, P.le A. Moro, 00185 Rome, Italy

ABSTRACT: This paper describes the chemical and isotopic characterization of

H2S-bearing groundwaters of the Fontevivo area, northern Italy. Groundwaters from
Fontevivo (Parma Province) contain dissolved H2S and minor hydrocarbons, which
are released from the truncated front of a buried geological structure (Calabrian
Miocene terrains) and through abandoned unsealed oil wells. H2S concentration is up
to 5.54 mg/l in groundwaters from the topographical high of the village and its
distribution in the investigated area is inversely related with those of NH4+ and
SO42
. Groundwaters are dominantly Ca-HCO3 type with lesser Ca-SO4 and Na-Cl
types and display two compositional trends: group A, waters from Ca-HCO3 to
Ca-SO4; group B, waters from Ca-HCO3 to Na-Cl. Group A water compositions are
influenced by redox processes including the oxidation of H2S to SO42
. Primary
sulphate from dissolution of Messinian evaporite is rare. Group B waters represent
mixing of meteoric water with small amounts of brine. The most Cl (Br, I)-rich
groundwaters are located in the NE of the investigated area, where a ClBrI-rich
brine was encountered by an exploration well in the Calabrian stratum. Berner has
provided a classification of redox environments starting from the observation of the
sequence of reduction/oxidation processes as shown by groundwater composition.
At Fontevivo the Berner redox zones show an areal distribution where the anoxic
zones occur in the topographical high.
The
2H and
18O values of groundwaters plot close to the Global Meteoric
Water Line. They indicate that local precipitation recharges the shallow aquifer
(<30 m deep), whereas rainwater from the higher elevated Apennine ridge recharges
the deeper aquifer (X30 m deep) via the Taro river and its alluvial fan.
Dissolved H2S is depleted in 34S consistent with biogenic sulphate reduction.
Secondary origin from oxidation of H2S in shallow groundwater is invoked for
depleted
34S (SO42
). The studied saline sample (27.8 g/l TDS) show a
34S (H2S)
value of +24.9, suggesting a nearly complete reduction of Messinian sulphate
within a system closed to H2S.
A hydrogeological model is presented based on a chemical-thermodynamic, trace
element statistical, and multi-isotope approach.
KEYWORDS: groundwater, dissolved gases, H2S, methane, redox processes, mixing, Berner zones,
isotopes, Po Plain, Italy

INTRODUCTION Ca-carbonate type is the most abundant, but locally, where

Venturelli et al. (2000), Toscani et al. (2001) and Boschetti (2003)
discuss the origin of several spring water systems in the
northern Apennines of Parma and Reggio Emilia provinces,
Italy. Basically, the chemical composition of these waters
appears to be controlled by the lithologies. Because of the wide
distribution of limestones and calcite-rich sandstones, water of
Geochemistry: Exploration, Environment, Analysis, Vol. 7 2007, pp. 2340
ophiolitic basalts and evaporites (mainly gypsum/anhydrite)
crop out, Mg-carbonate and Ca-sulphate waters commonly
occur (Boschetti 2003).
Sulphide waters are represented by Ca-carbonate, Na-
carbonate, Na-hydroxide and Na-chloride types. In comparison,
groundwaters of the Po plain, which are used for the drinking
water supply, show a rather monotonous chemical composition
1467-7873/07/$15.00  2007 AAG/ Geological Society of London
24 L. Toscani et al.
(Martinelli et al. 1998); they are invariably Ca-carbonate and
typically oxidized (Di Dio et al. 1997). Within this general
picture, the occurrence of reducing groundwaters in the middle
Po plain constitutes a relevant anomaly, which is suggestive of
deeper fluids that are possibly released due to underlying
structures. They may also be related to brine contamination
from abandoned oil and gas wells in the area.
In this paper, we studied the H2S-bearing groundwater of the
Fontevivo area (Parma Province, northern Italy), which is called
acqua pussa (smelly water) in the local slang, in order to
characterize the system both chemically and isotopically and
investigate the origin of the waters and the role of redox
processes.
GEOLOGICAL SETTING
Fontevivo village and its neighbouring area (Bellena and
Bianconese villages) were investigated for hydrocarbon research
from the 1920s to the 1950s. Natural emanations of H2S,
methane and other hydrocarbons triggered exploration by the
national company AGIP, which used both gravimetric (1929)
and seismic (1954) methods. Some of the c. 50 exploration wells
produced methane and oil (at a depth of 190 to 200 m). Brine
waters (salinity as NaCl=164 to 167 g/l; S. Rogledi pers. comm.
2003) issued after depletion of oil or from unproductive wells;
since the 1950s most of the wells have silted up. With the
exception of Sborgi et al. (1936), there has been no additional
chemical data on the Fontevivo brine waters.
In the Fontevivo territory, Upper MioceneLower Pliocene
terrains occur within 300 m of the surface. They form a thrust
with the front of the structure trending NWSE (Bernini &
Papani 1987; S. Rogledi pers. comm. 2003). Upper Pliocene
and Quaternary sediments cover the Miocene terrains of the
thrust structure and reach relevant thickness to the SW and
especially to the NE of the village. Pliocene sediments cover the
Miocene of the SW part of the structure, whereas Quaternary
sediments (both marine and continental) cover the front of the
thrust to the NE (Di Dio et al. 1997). The thrust of Fontevivo
is the southeastern termination of a long-buried structure
(Cortemaggiore Unit), approximatively oriented NWSE,
which underlies the towns of Cortemaggiore (Piacenza
Province), Busseto, Soragna and Fontevivo (Parma Province)
and is the result of the compressive tectonic phase of the
Apennine orogen toward the Po Plain. Geomorphology and the
shallow water hydrogeochemical evidence presented below
reveal the buried structure of Fontevivo: the central part of the
village forms a topographical high (53 m a.s.l., i.e. 4 m higher
than the surrounding plain), which is bordered to the east and
north by the Canale Vecchio stream (Fig. 1).
The shallow aquifer below Fontevivo belongs to the
Quaternary Upper Emilian System (Di Dio et al. 1997), which is
composed of sands, gravels and clays showing the typical
lens-shaped distribution of river sediments. Fontevivo village is
located on the large alluvial fan of the Taro River, which
extends northeastward for at least 30 km from the town of
Fornovo (Fig. 1), and the aquifer contains all the lithotypes
cropping out in the Taro valley. The lithotypes are described
below.
Ophiolitic basalts and ultramafic rocks
These rocks have undergone oceanic metamorphism. Basaltic
rocks consist of albitized plagioclase, augite, chlorite (after
olivine), sphene, FeTi-oxides, ilmenite, epidote,  pumpelly-
ite,  prehnite (Venturelli et al. 1981). Peridotites consist of
relics of olivine, othopyroxene, clinopyroxene, Al-rich spinel,
lizardite, chrisotile, magnetite, calcite and clay minerals
(Venturelli et al. 1997).
Quartz-feldspathic turbidites
The quartz-feldspathic turbidites of the Apennine ridge, known
as the Macigno Formation, are composed of quartz, plagioclase
and K-feldspar with minor muscovite, biotite, chlorite, calcite,
lithic fragments and clays in the matrix. The interbedded strata
of siltites and pelites are composed of illite, illite/smectite,
smectite and chlorite (Bonazzi et al. 1982).
Marly to pelitic formations
These are invariably composed of limestone and clayey
materials. The most important formations are the Canetolo
Clays and Limestones (calcite-rich rocks and black pelites with
illite, illite/smectite mixed layer, smectite and chlorite; Bonazzi
et al. 1982) and the micritic-marly turbidites (Helmintoid flysch
of Mt. Caio, Mt. Cassio and Solignano) grading to minor
arenitic-silicoclastic turbidites with interbedded pelites (illite,
illite/smectite, chlorite: Venturelli & Frey 1977).
Sandstones
Quartz-feldspathic, carbonate to quartz-feldspathic sandstones
and tuffitic sandstones mostly crop out far from the Apennine
ridge. This group of lithotypes belongs to several formations of
different age including the Ostia Sandstones Formation (quartz-
feldspathic sandstones with interbedded pelites; Mezzadri
1964), the Petrignacola Sandstone Formation (tuffitic sand-
stones with subordinate conglomerates and siltites; Mezzadri
1970), the Ranzano Sandstone Formation (conglomerate to
pelitic sediments containing quartz, feldspars, calcite, mica,
chlorite, metamorphic and volcanic clasts, clays minerals) and
the Bismantova Formation (calcareous to quartz-feldspathic
sandstones with marls and pelites; Zuffa 1969).
ANALYTICAL METHODS
Field methods
All water samples were filtered through 0.45 m cellulose
acetate filters and the portion for cation analysis was acidified
with 65% HNO3 Suprapur Merck (1 ml HNO3 to 100 ml
water). Parameters including temperature, conductivity, pH, Eh,
total alkalinity, NH4+ and reduced sulphur species as S(-II) were
determined in the field. Temperature, pH and Eh were deter-
mined using an Orion 250A instrument equipped with a Ross
glass electrode for pH and a platinumsilver/silver chloride
combined electrode for Eh determination. The
electrode for Eh was calibrated at different temperatures with a
ZoBells solution (Nordstrom 1977). Specific conductance (at
20C) was measured using a Yellow Spring 85 conductivity
meter. Total alkalinity was determined in the field by acidimetric
titration (HCl 0.01N) using bromocresol green as indicator and
in the laboratory by the Gran titration (Gran 1952) not later
than 12 hours after sampling. Reduced dissolved species were
determined by spectrophotometry using a portable photometer
(Merck SQ300) with Merck Spectroquant kits by adding
indophenol blue in basic solution (pH ] 13) for N(-III), and
methylene blue in acidic solution for S(-II).
Major and trace element analyses
Cl
, NO3
and SO42
were determined by ion chromato-
graphy (Dionex DX100 with autoregenerated anionic suppres-
sion; Department of Chemistry, University of Parma), silica and
 Groundwaters of Fontevivo 25

Fig. 1. (A) Location of the investigated waters in the area of Fontevivo (Parma Province): shaded area, topographical high; AA line, seismic
line. (B) Seismic profile (S. Rogledi pers. commun. 2003; Argnani et al. 2003) of the Fontevivo structure: 1, Quaternary (continental); 2,
Quaternary (marine); 3, Pliocene; 4, Upper Messinian, chaotic (olistostromes) post-evaporitic unit; 5, Upper Messinian, resedimented evaporites;
6, Upper- Middle Miocene (turbidites).

Cl
by spectrophotometry (photometer Merck SQ300), Na, K, Jobin-Ivon; Department of Chemistry, University of Parma),
Ca, Mg, S, Li, B, Mn, Fe, Sr, Ba, Zn, As by ICP-OES Co, Ni, Cu, Se, Rb and again Li, As, Ba and Mn by ICP-MS
(inductively coupled plasma mass spectrometry; Ultima 2 (inductively coupled plasma mass spectrometry; X7 Thermo
26 L. Toscani et al.
Elemental, Department of Chemistry, University of Parma).
Total I and Br were determined by flow injection ICP-MS
(ICP-MS was coupled with a gradient pump Dionex GP-40 and
an automatic injection valve ERC iVALVE) using 15 l of
sample and rinsing the system with a solution of 0.5% NH3
solution (Carlo Erba RPE). Quantification limits and precision
are 0.050.03 g/l for I and 7.00.6 g/l for Br (Boschetti
2003).
Isotopes
The
2H and
18O analyses were performed on a Finnigan GLF
1086 automatic equilibration device and a Delta Plus Finnigan
mass-spectrometer (Department of Earth Sciences, University
of Parma). Hydrogen for
2H determination was obtained by
equilibration of hydrogen gas with water using a Pt-rich catalyst;

18O determination was carried out on CO2 after equilibration
with water at 18C (Epstein & Mayeda 1953). Data are referred
to V-SMOW and standard errors are c. 1.0 and better than
0.1 for
2H and
18O, respectively.
34S (versus V-CDT)
and
18O(SO42
) (versus V-SMOW) were determined,
respectively on SO2 (Glesemann et al. 1994) and CO (Kornexl
et al. 1999), by CF-IRMS (continuous flow isotope ratio mass
spectrometry) technique (Department of Geological Sciences
and Engineering, University of Nevada, Reno); H2S was pre-
cipitated in the field as CdS, whereas dissolved SO42
was
precipitated as BaSO4. 87Sr/86Sr ratio was determined on a VG
54E mass spectrometer (IGAG CNR at the Department of
Earth Sciences, la Sapienza University of Rome) and the
measured ratios normalized to a 88Sr/86Sr ratio of 0.1194 for
natural Sr. Pure Sr for analysis was obtained by treating 50 ml of
water with 50 mg of Sr-free Na2CO3 and the solution heated to
70C. The residue was washed with bidistilled water until the
removal of SO42
and then resulting Ca(Sr)CO3 was dissolved
by 2.5N HCl acid and the Sr in solution separated by ion
exchange resin (Dowex 50W 8200400 mesh, hydrogenionic
form).
Thermodynamic calculations
PHREEQCI software, version 2.8.0.0 (Parkhurst & Appelo
1999), was adopted for calculations of speciation in water and
evaluation of the equilibrium/disequilibrium between dis-
solved ionic species and the pure mineral phases (using the
llnl.dat-thermo.com.V8.R6. thermodynamic database). The
saturation indexes (SI=log Q/K, where K is the equilibrium
constant for the pure solid phase dissolution reaction and Q
the ion activity product of the dissolved species) are approxi-
mate due to the analytical and thermodynamic uncertainties.
For this reason, saturation is assumed in the range SI=00.2.
Data of Gf0 for dissolved species, minerals and gases at the
temperature of the water samples and P=1 bar were calculated
(and averaged) using the SUPCRT92-SLOP98.DAT (Johnson
et al. 1992; http://geopig.asu.edu/supcrt_data.html) and
FACTASAGE (Bale et al. 2002) databases. Data of Gr of
the reactions reported in the discussion are calculated as
logQlogK.
Statistical approach
We applied principal component analysis (PCA) to the water
analyses. The combination of classical graphic-chemical and
statistical techniques provides a consistent and objective tool
to classify large numbers of samples (Gler et al. 2002). The
full data set of Fontevivo consists of 30 samples and 30
physical/chemical/isotopic variables. Mutually related variables
(e.g. TDS related to total ions and conductance; hardness
related to the concentration of Ca2+ and Mg2+) were not
considered as they could cause undesirable statistical redun-
dancy. Unfortunately, the concentrations of some dissolved
species are lower than the detection limit (DL). In that case, if
the undetected data are more than 30% of the total samples, we
omitted the variable from the statistical treatment (i.e. NO3
,
NH4+, Zn); in some cases (e.g. for Fe) the DL/2 parameter was
used (Farnham et al. 2002). We performed two sets of calcula-
tions, which differ by the presence or absence of the salt water
FV04 in the matrix. Both calculations check the Bartlett
sphericity test, whereas the Keyser Meyer Olkin test of sampling
adequacy is <0.6. This result is probably due to the small
number of samples treated or, alternatively, to the large number
of variables. In this case, the extracted principal components
could not be considered as totally representative of the data
matrix. So the results of the two PCA calculations are taken
only as representative of possible clusters of samples or
variables. In the PCA calculation including water FV04, most
of variables show good internal correlation and with the salt
water FV04 itself, with the exception of Eh, Ba, Fe and
Mn. The PCA calculation without FV04 shows that (i) Br, I, Cl,
Na, As and Se are clustered for waters FV28, 14, 01 of group B
(see below) and (ii) waters of group A (see below) define
two clusters, which are related to high values of Eh, Mn, Fe, Ba
(e.g. FV07) and Ca-SO4 composition (e.g. FV12), respectively.
Good positive correlations are also shown by Co, Ni and Cu
(Table 2).
RESULTS
The investigated groundwaters were sampled from wells drilled
during the 1960s. All but two waters are from shallow wells
(c.10 m below the ground level); water FV06 is from a 30 m
deep well and salt water FV04 is from an AGIP exploration well
(c.900 m below the ground level). The chemical composition set
is reported in Table 1.
Using the Piper plot (Fig. 2) we classify the waters of
Fontevivo as:
1. Ca-HCO3 waters. Most studied waters are of this type.
According to the TDS table of Drever (1997), they are fresh
waters (TDS 492 to 888 mg/l; EC 399 to 1341 S/cm), very
hard (276 to 607 mg/l CaCO3), supersaturated with respect
to chalcedony, saturated relative to calcite and their PCO2 is
high (0.031 to 0.139 bar). Most water samples with the
highest Ca and total-alkalinity (t-alk) contents and with the
most positive
2H and
18O values come from wells drilled
in the topographical high (Fig.1).
2. Ca-SO4 waters. This type of water is represented by sample
FV12. FV12 is a brackish water (TDS 1311 mg/l; Drever
1997), shows elevated hardness (956 mg/l CaCO3), EC (1
488 S/cm), relatively high SO42 (510 mg/l), NH4+
(0.59 mg/l), Sr (2635 g/l) concentrations and is slightly
undersaturated with respect to gypsum (S.I.=
1.18).
3. Na-Cl waters. They are represented by the fresh-brackish
sample FV28 (hardness 388 mg/l CaCO3, TDS 928 mg/l,
EC 1 505 S/cm) and the saline FV04 (hardness 8 067 mg/l
CaCO3, TDS 27 768 mg/l, EC 34 441 S/cm), which also
contains dissolved hydrocarbons and gases (CH4 and H2S).
For comparison brine sample SB34 from Sborgi et al. (1936)
showed elevated hardness (29 600 mg/l CaCO3) and TDS
(> 150 000 mg/l).
4. Na-HCO3 waters. This type of water is represented by sample
FV26, which is moderately hard (186 mg/l CaCO3) and
exhibits salinity and conductivity of 604 mg/l and
786 S/cm, respectively.
Table 1. Chemical data of the Fontevivo groundwaters

Sample Sampling Latitude/longitude Altitude T water T air HRD TDS Cond. (20C) Eh pH Alkalinity (as HCO3) Cl- Stot H2S SO42-(as Stot-H2S) SO42- NO3- NH4 SiO2
date (s.l.m.) (C) (C) (mg/l) (mg/l) (S/cm) (mV) (Twater) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l)
FV01 06.02.03 445153/101048 47.9 13.6 5 441 819 1341 42 6.98 562 225 1.22 0.98 0.89 <5 <3 0.28 22.7
FV02 06.02.03 445129/101029 52.8 16.1 5 459 613 930 71 6.79 662 41.0 0.95 0.85 0.45 <5 <3 0.17 28.3
FV03 06.02.03 445138/101035 52.3 14.9 8 479 628 949 3 6.84 658 40.0 5.84 4.49 4.84 <5 <3 0.16 28.4
FV04 06.02.03 445155/101154 47.3 10.6 4 8067 27768 34441 -139 7.61 4575 13000 987 <5 <3
FV05 18.02.03 445136/101039 50.6 16.3 4 607 777 1007 126 6.59 632 42.0 45.3 0.05 136 144 <3 0.22 28.6
FV06 18.02.03 445138/101037 52.3 14.4 6 351 543 794 -3 6.89 532 57.0 0.86 1.93 <5 <3 <0.06 21.7
FV07 18.02.03 445139/101038 51.0 10.5 6 512 641 852 158 6.77 556 39.0 30.4 0.09 90.9 69.6 <3 0.09 20.1
FV08 18.02.03 445138/101025 52.3 13.4 10 499 659 904 47 6.88 648 51.0 7.58 1.61 18.5 <5 <3 <0.06 30.0
FV09 18.02.03 445134/101033 50.0 14.9 10 431 599 822 216 6.86 639 40.5 1.50 0.03 4.42 <5 <3 <0.06 27.7

Groundwaters of Fontevivo
FV10 08.05.03 445146/101030 47.8 17.1 25 371 629 943 16 6.95 528 110 3.41 2.38 3.51 <5 <3 <0.06 26.7
FV11 08.05.03 445142/101037 48.3 14.6 27 499 841 1190 113 6.99 623 101 36.8 0.44 109 107 <3 <0.06 29.3
FV12 08.05.03 445155/101057 47.2 15.6 29 956 1312 1488 40 6.72 592 84.0 171 0.68 510 458 <3 0.59 27.6
FV13 08.05.03 445137/101028 52.3 16.3 29 439 585 849 131 6.82 622 35.0 0.99 0.05 2.83 <5 <3 0.10 30.4
FV14 08.05.03 445201/101045 46.8 14.3 29 414 763 1146 64 7.04 427 239 1.24 0.52 2.25 <5 <3 <0.06 23.6
FV15 26.05.03 445143/101028 51.5 16.0 29 431 640 399 63 6.88 695 43.1 2.04 1.19 2.76 <5 <3 0.22 31.4
FV16 26.05.03 445140/101032 51.7 15.5 29 566 888 1300 -1 6.89 667 183 14.1 5.54 26.7 36.0 <3 <0.06 31.0
FV17 26.05.03 445113/101025 54.0 15.0 29 276 528 698 164 7.02 465 81.5 0.71 0.04 2.02 <5 <3 0.52 23.8
FV18 26.05.03 445137/101028 52.5 16.1 29 454 608 406 238 6.93 654 35.0 1.16 0.07 3.28 <5 <3 0.14 30.8
FV19 26.05.03 445133/101033 52.0 16.1 29 450 612 889 107 6.96 657 33.0 1.83 0.27 4.73 <5 <3 0.21 29.1
FV20 09.09.03 445138/101046 49.6 15.7 23 426 591 798 206 6.75 500 43.5 26.8 0.01 80.4 71.9 <3 0.48 24.3
FV21 09.09.03 445135/101043 50.3 17.6 23 579 792 1025 256 6.60 592 47.1 58.7 0.04 176 240 <3 0.38 26.0
FV22 09.09.03 445116/101055 52.7 16.1 23 352 506 717 217 6.80 487 29.0 14.2 0.05 42.4 38.4 <3 <0.06 22.0
FV23 09.09.03 445121/101025 52.8 15.2 23 332 492 746 134 6.79 446 71.7 0.88 0.14 2.24 <5 <3 0.21 20.9
FV24 17.09.03 445143/101125 48.2 15.6 27 467 655 885 453 6.58 460 41.0 43.9 <0.02 132 128 30.7 <0.06 18.8
FV25 17.09.03 445154/101138 46.4 14.8 27 552 763 1005 405 6.52 531 43.5 60.2 <0.02 181 191 17.9 <0.06 18.7
FV26 17.09.03 445203/101117 46.5 13.8 27 186 604 786 160 7.14 531 19.6 29.4 0.02 88.1 82.2 <3 0.44 24.4
FV27 17.09.03 445124/101039 53.6 15.8 27 465 617 865 199 6.54 586 23.6 25.6 0.08 76.6 70.2 <3 0.13 27.2
FV28 17.09.03 445201/101055 46.8 17.4 27 388 926 1505 56 6.94 493 316 4.25 1.49 8.54 <5 <3 <0.06 24.0
FV29 15.10.03 445122/101034 52.2 14.7 15 329 529 862 235 6.85 434 100 0.40 <0.02 1.20 <5 <3 0.20 22.4
FV30 15.10.03 445134/101028 52.8 15.9 15 407 571 860 255 6.68 620 36.0 0.65 <0.02 1.95 <5 <3 <0.06 28.0

SB34 02.02.34 445153/101047 47.9 7.5(?) 154600 7.7 435 95450 63 22.8 167

27
 28
Table 1. Continued

Sample Ca Mg Na K Li B Mn Fe Co Ni Cu Zn As Se Rb Sr Ba I Br
(mg/l) (mg/l) (mg/l) (mg/l) (g/l) (g/l) (g/l) (g/l) (g/l) (g/l) (g/l) (g/l) (g/l) (g/l) (g/l) (g/l) (g/l) (g/l) (g/l)
FV01 111 39.9 128 6.82 16 137 104 118 0.27 2.1 0.28 <3 0.33 3.90 0.69 1643 501 240 1233
FV02 102 49.5 51.7 4.64 18 178 67 45 0.32 2.3 0.41 <3 0.15 0.44 0.24 1156 543 57 117
FV03 101 55.2 51.4 4.40 22 230 113 5 0.31 2.7 0.31 <3 0.13 0.46 0.22 1175 414 52 116
FV04 1829 850 6735 106 517 37350 7 <3 5 33 17 211 19 419 29 36218 34 53520 99855
FV05 155 53.7 38.3 7.07 20 203 224 850 0.44 3.7 0.48 35 0.14 0.30 0.18 1495 484 20 71
FV06 97.3 26.1 67.4 3.98 15 109 117 398 0.27 2.6 0.27 <3 0.13 1.10 0.38 868 349 104 328
FV07 133 43.8 29.9 5.17 16 175 223 7429 0.41 3.4 0.42 109 0.13 0.40 0.16 1375 464 20 83
FV08 123 46.3 57.3 4.15 24 188 130 70 0.34 2.8 0.34 <3 0.12 0.82 0.33 993 348 64 232
FV09 107 39.9 54.2 4.91 23 189 139 856 0.10 2.1 0.43 974 0.07 0.26 0.62 1116 360 103 106
FV10 89.9 35.5 87.4 4.24 16 184 94 278 0.27 2.1 0.24 <3 0.13 1.60 0.07 1084 247 113 462
FV11 120 48.3 112 6.38 19 538 131 229 0.36 3.2 0.35 <3 0.15 1.30 0.21 1513 273 84 360
FV12 238 87.7 56.1 8.18 20 171 137 73 0.61 5.0 0.71 <3 0.12 0.62 0.62 2635 46 18 143

L. Toscani et al.
FV13 108 41.3 51.7 4.36 20 161 96 21 0.34 2.8 0.42 3 0.07 0.51 0.23 1022 373 68 138
FV14 110 34.2 133 6.13 15 119 12 102 0.29 2.2 0.37 <3 0.20 3.80 0.31 846 248 223 1130
FV15 103 42.0 59.9 4.89 19 191 89 4 0.32 3.4 0.71 <3 0.10 0.64 0.31 968 376 219 1105
FV16 118 66.2 108 6.01 22 216 61 <3 0.33 2.8 0.36 <3 0.17 2.60 0.17 1349 485 174 682
FV17 68.8 25.4 85.8 5.39 14 123 102 64 0.22 2.3 0.71 9 0.09 1.40 0.64 768 323 101 372
FV18 111 43.1 52.4 4.67 19 164 126 214 0.37 2.8 0.43 13 0.08 0.51 0.33 1032 317 60 127
FV19 104 46.2 50.8 13.2 31 201 69 51 0.10 1.0 0.44 <3 0.09 0.26 1.10 1163 474 55 119
FV20 107 38.6 40.7 4.51 20 161 230 2180 0.27 1.7 0.46 24 0.12 0.22 0.62 1363 422 16 101
FV21 159 44.3 33.9 7.90 26 191 395 1527 0.41 5.0 0.84 489 0.08 0.30 0.69 1586 535 12 86
FV22 99.7 25.1 40.7 3.34 20 92 120 4400 0.25 1.3 0.45 777 0.11 0.31 0.77 1100 364 18 70
FV23 88.3 27.1 54.1 3.60 16 101 119 133 0.22 0.93 0.49 <3 0.14 0.69 0.88 1067 310 127 340
FV24 131 34.2 33.4 4.02 19 136 44 <3 0.47 4.2 2.3 9 0.22 4.70 0.54 792 126 7.1 60
FV25 153 41.6 35.9 6.56 22 172 492 <3 1.20 8.7 3.3 16 0.13 1.40 0.62 851 68 6.6 56
FV26 41.8 19.9 138 4.80 17 306 17 207 0.10 0.81 0.25 <3 0.06 0.36 0.68 1089 280 8.7 48
FV27 111 45.3 35.2 3.67 25 136 110 1034 0.29 2.4 0.71 143 0.11 0.43 0.50 1175 435 25 71
FV28 97.9 34.8 188 5.41 22 142 54 29 0.24 0.96 0.26 <3 0.32 2.35 0.43 1061 338 221 1335
FV29 83.2 29.5 70.4 4.28 18 107 161 443 0.25 0.95 0.18 85 0.12 0.77 0.98 1045 325 146 544
FV30 106 34.6 49.4 4.22 24 149 178 527 0.31 1.4 0.26 62 0.04 0.20 0.41 953 340 60 121

SB34 7140 2859 48220 2750 70 470 216530 27220 246570

H2S refers to H2S, HS , S ; NH4 refers to NH4 and NH3; Cond (20C)=KT/(0.02*(T
20)+1), where KT is the conductivity at the temperature T of interest; TDS (calculated total dissolved solids)=0.5 * alkalinity
2
+

(as HCO3)+Ca+Mg+Na+K+Cl+3*S+NO3+1.02 SiO2+3.44 NH4 (mg/l) (modified after Eaton et al. 1996); HRD (hardness)=2.497 Ca+4.118 Mg (mg/l). SB34 after Sborgi et al. (1936); -=not analysed.
Table 2. Correlation matrix of the chemical and isotopic parameters of the H2S-bearing waters of Fontevivo.

TC 1
pH
0.222 1
Eh 0.065
0.555 1
tAlk 0.120
0.056
0.299 1
Cl 0.050 0.402
0.404
0.311 1
SO4 0.031
0.434 0.171 0.005
0.137 1
H2S 0.028 0.230
0.624 0.325 0.329
0.180 1
SiO2 0.346 0.188
0.445 0.826
0.116
0.093 0.324 1
Ca 0.075
0.575 0.085 0.236
0.036 0.830
0.048 0.074 1

Groundwaters of Fontevivo
Mg 0.086
0.278
0.303 0.585 0.024 0.614 0.373 0.506 0.780 1
Na
0.016 0.711
0.447
0.237 0.826
0.217 0.273
0.003
0.356
0.179 1
K 0.114 0.069
0.108 0.268 0.117 0.323
0.060 0.190 0.387 0.417 0.055 1
Li 0.369
0.362 0.175 0.506
0.226 0.109 0.031 0.410 0.263 0.344
0.289 0.478 1
B
0.108 0.258
0.138 0.416
0.077 0.158 0.118 0.394 0.028 0.254 0.224 0.231 0.119 1
Mn 0.010
0.629 0.479 0.024
0.298 0.364
0.264
0.248 0.453 0.113
0.486 0.153 0.250
0.007 1
Fe
0.438
0.197 0.163
0.141
0.229 0.073
0.231
0.340 0.089
0.101
0.335
0.133
0.091
0.118 0.262 1
Co
0.036
0.592 0.403 0.007
0.101 0.548
0.071
0.257 0.626 0.347
0.308 0.098 0.046 0.010 0.697
0.015 1
Ni
0.026
0.572 0.358 0.165
0.191 0.594
0.037
0.130 0.692 0.428
0.373 0.197 0.100 0.116 0.693
0.020 0.918 1
Cu 0.036
0.576 0.690
0.175
0.205 0.373
0.224
0.449 0.353 0.026
0.338 0.078 0.113
0.091 0.534
0.097 0.809 0.788 1
As
0.060 0.123
0.223
0.302 0.802
0.057 0.247
0.337 0.068 0.035 0.571 0.048
0.247
0.108
0.230
0.120 0.056
0.030 0.056 1
Se
0.092 0.158 0.026
0.398 0.662
0.067 0.211
0.361 0.012
0.083 0.484 0.002
0.327
0.121
0.311
0.275 0.112 0.098 0.280 0.768 1
Rb 0.060
0.020 0.371
0.394
0.102 0.096
0.450
0.390
0.103
0.291
0.086 0.323 0.249
0.296 0.120
0.046
0.140
0.197 0.145
0.079
0.096 1
Sr 0.011
0.150
0.277 0.254 0.077 0.753 0.049 0.209 0.709 0.747
0.033 0.417 0.121 0.253 0.151 0.127 0.139 0.208
0.177 0.098
0.148 0.032 1
Ba 0.004 0.077
0.332 0.384 0.023
0.474 0.178 0.303
0.257
0.008
0.032 0.118 0.197
0.032
0.058 0.246
0.483
0.383
0.523 0.076
0.209
0.067 0.043 1
I 0.003 0.538
0.502
0.110 0.781
0.471 0.342 0.084
0.298
0.136 0.675
0.022
0.303
0.141
0.427
0.333
0.311
0.340
0.342 0.556 0.497
0.083
0.163 0.168 1
Br 0.024 0.472
0.455
0.184 0.861
0.307 0.290
0.007
0.183
0.099 0.743 0.037
0.293
0.117
0.360
0.267
0.186
0.231
0.238 0.689 0.579
0.096
0.069 0.106 0.945 1

18O 0.019
0.676 0.440 0.520
0.627 0.443
0.120 0.212 0.514 0.471
0.667 0.075 0.433 0.302 0.485 0.224 0.490 0.587 0.458
0.376
0.330
0.249 0.231
0.028
0.710
0.664 1

2H 0.011
0.681 0.478 0.422
0.565 0.477
0.198 0.087 0.523 0.433
0.627 0.150 0.422 0.261 0.551 0.264 0.505 0.603 0.504
0.266
0.319
0.134 0.262 0.002
0.724
0.646 0.953 1
TC pH Eh tAlk Cl SO4 H2S SiO2 Ca Mg Na K Li B Mn Fe Co Ni Cu As Se Rb Sr Ba I Br
18O
2H

Pearson values (r) of correlation matrix exctracted from Fontevivo samples (N=29, excluding FV04 salt sample).
Bold entries indicate significant correlation at 0.05 (two-tailed t-test)
Bold and italic entries indicate significant correlation at 0.01 (two-tailed t-test)

29
30 L. Toscani et al.

Fig. 2. Piper diagram of the Fontevivo waters. Open circle, Ca-HCO3 s.s. (sensu strictu); open square, Ca-HCO3 to Ca-SO4 waters of group
A; open triangle, Ca-HCO3 to Na-Cl waters of group B; dashed triangle, salt water FV04; closed triangle, brine water SB34 (Sborgi et al. 1936);
diamond, Na-HCO3 water FV26. Dashed lines, compositional evolution of group A and group B waters.

Distribution of reduced S(-II) and N(-III)
The highest H2S concentrations were found in waters from the
topographical high (H2S >1 mg/l; 5.54 and 4.49 mg/l in waters
FV16 and FV03, respectively; Fig. 3a). The amount of H2S
decreases southward (FV02, 19, 23, 27 with 0.85, 0.27, 0.14 and
0.08 mg/l, respectively) and displays relatively high values to the
north (FV10, H2S = 2.38 mg/l) and NE (FV01, 12, 14, 28 with
0.98, 0.68, 0.52, 1.49 mg/l, respectively) of the topographical
high. It is noteworthy that H2S is quite low or absent in all the
waters sampled to the east of the village. Samples FV24 and
FV25 (Fig. 1) are H2S-free. Saline water FV04 was not fully
analysed because the water level of the well decreased and water
flow ceased. Later the well was buried during agricultural
ploughing, preventing, de facto, any further possibility of sam-
pling. However, speciation of total sulphur at the sampling
conditions (Eh =
139 mV, pH = 7.61) by PHREEQCI gives
a virtually null concentration of S(-II) (1.49  10
17 mol/kg).
NH4+ shows a rough inverse trend with H2S (Figs 3b and
4a). Highest NH4+ contents have been found in waters sampled
to the east (FV20, 21 with 0.48 and 0.38 mg/l, respectively) and
to the south (FV17, 23, 27, 29 with 0.52, 0.21, 0.13, 0.20 mg/l,
 Groundwaters of Fontevivo 31

Fig. 3. Distribution of dissolved H2S (A), NH4+ (B), Cl
(C) and SO42
(D) in the groundwaters of Fontevivo. The reported value (mg/l) is
the highest detected content: circle areas are directly proportional to contents.
32 L. Toscani et al.
respectively) of the topographical high, as well as in sample
FV12 (0.59 mg/l) to the NE. The low NH4+ concentration in
H2S-rich waters FV16 and FV03 suggests that the ammonium
is not released from the buried geological thrust.
Distribution of total alkalinity, sulphate, nitrate and
halogens
Total alkalinity (as HCO3
427 to 695 mg/l) is high in the
H2S-rich waters (FV03, 13, 15, 16) from the topographical high,
whereas HCO3
is lowest in the Na-chloride waters. Chloride
concentrations are highest in groundwaters sampled to the
south and NNE of the topographical high (FV28, 14, 01 with
316, 239 and 225 mg/l respectively; Fig. 3c), whereas salty
FV04 has 13 000 mg/l Cl
. Similar distribution is shown by Br
and I, which show the highest contents in sample FV28 (Br = 1
335 g/l) and FV01 (I =2 40 g/l). NO3
was detected only in
samples FV24 (30.7 mg/l) and FV25 (17.9 mg/l). The abun-
dance of sulphate increases in the H2S-poor waters and its field
distribution roughly overlaps that of ammonia (Fig. 3b, d). As
reported above, sample FV12 has the highest SO42
content,
but all the waters sampled to the east of the village (FV20, 21)
and particularly on the east end of the topographical high
(FV05, 07) show significant concentrations of sulphate
(80186 mg/l).
Distribution of major and trace components
Calcium, Mg and Sr correlate positively (Table 2) and show high
concentrations in all the investigated waters, as expected for
dissolution of calcite and dolomite, which reach saturation or
supersaturation in all the waters. The best correlation is shown
by waters with the highest element concentrations. Sodium is
relatively low in Ca-HCO3 waters and high in Cl-rich waters.
Iron and Mn are locally elevated. Fe2+ and H2S do not coexist
in groundwaters (Fe-rich waters FV07 and FV22, 7429 and
4400 g/l, respectively, are H2S-poor), which supports the
controlling influence of pyrite solubility and/or redox processes
(Fig. 4c). PCA (Fig. 5A1 and Table 2) shows that Fe and Mn are
clustered with Eh and Ba in all waters of group A (Fig. 2),
except in water FV12. In addition, PCA (Fig. 5A2) shows the
Fig. 4. Variation diagrams of the
Fontevivo waters. Symbols as in
Figure 2.
good correlation of Co, Ni, Cu and Mg, probably due to
dissolution of basic and ultrabasic rock clasts occurring in the
Taro alluvial fan. Saline water FV04 shows high contents of all
major elements, as well as of Li, B and Sr; Fe, Mn and Ba
concentrations are low.
Isotopic compositions
Excluding water FV04, the
2H and
18O values of the waters
are in the range
48.4 to
59.1 and
7.3 to
8.7
(V-SMOW), respectively (Table 3). The data define a linear
distribution (Fig. 6a) between the Northern Italy Meteoric
Water Line (y = 7.7094x + 9.4034; Longinelli & Selmo 2003)
and the Global Meteoric Water Line of Rozanski et al. (1993),
thus supporting the meteoric origin of the studied ground-
waters.
The isotope composition of sulphur is reported in Table 4.
At this stage of preliminary investigation of the
34S distri-
bution, the composition of coexisting sulphide and sulphate was
not measured due to the low concentration of the paired
species. The
34S value of dissolved sulphide is
11.9 in the
groundwater FV16 and +24.9 in the salt water FV04,
whereas sulphate FV12 has
34S =
12.4.
18O of sulphate
FV12 is +2.2, which is in the range of terrestrial evaporites
(Clark & Fritz 1997).
The 87Sr/86Sr ratios obtained for the analysed waters
(Table 4) vary between 0.70860 and 0.70878. These isotopic
signatures may have been inherited from sedimentary rocks of
15.3 to 17.9 Ma (Early LanghianBurdigalian from McArthur
et al. 2001), which exist in the stratigraphic sequence of
Fontevivo.
DISCUSSION
In the Piper diagram (Fig. 2), the waters of Fontevivo form two
main trends that diverge from the Ca-HCO3 field. Trend A is
composed by waters evolving towards Ca-SO4 composition,
whereas trend B evolves towards Na-Cl waters.
Group A: waters from Ca-HCO3 to Ca-SO4 composition
Despite the linear distribution in the Piper diagram these waters
do not have a common origin. The PCA distinguishes two
 Groundwaters of Fontevivo 33

Fig. 5. Results of statistical treatment of the data matrix. (A) Plot of the factor loadings obtained from PCA (principal component analysis) data
elaboration. Number 1 and 2 on the apex refer to the treatment with or without the FV04 salt sample, respectively. Principal components were
calculated with SPSS 12 software (Norusis 2002) using covariance extraction method and Varimax rotation. (B) PC1 versus PC2 factor scores
for groundwaters of Fontevivo. In graph B1, sample FV04 appears to be an outlier in the plot. In the rescaled insert, this sample was removed
and the grouping of the samples FV01, 14, 28 is manifest as in B2 graph.

clusters, related to high values of Eh, Mn, Fe, Ba (e.g. FV07)
and of Ca and SO42
composition (e.g. FV12), respectively.
Water FV12 with Ca/SO4 = 1.12 and Na/Cl = 1.07 molar
ratios, high SO42
(510 mg/l) and Sr (2635 g/l), and high
Ca/alk ratio have resulted from dissolution of evaporites.
However, the
34S of FV12 sulphate is
12.4 which
disagrees with that of Messinian sulphates (+22; Dinelli et al.
1999; Palmer et al. 2004). This suggests that SO42
derived
from oxidation of H2S, which, in turn, originated by bacterial
reduction of the Messinian SO42
precursor. The high N(-III)
content in the water supports the oxidation of H2S by the
involvement of nitrate, along with oxygen:
H2S + 2O2 2SO24
+ 2H+ (1)
H2S + NO3
+ H2O SO24
+ NH4+ (2)
For the investigated waters, reactions 1 and 2 are spontaneous,
being characterized by negative Gr values (Gr = logQ

logK; Gr0 values were calculated as described previously).
Reaction 2 is not spontaneous (Gr > 0) only in Fe-rich water
FV07.
Waters FV05, 07, 20, 21, 27 show a good negative correlation
between H2S and NH4+ (Fig. 4b) and rough positive trends of
SO42
with NH4+ and of Mn with Fe (Fig. 4d). These features
34 L. Toscani et al.

Table 3. Oxygen and hydrogen isotopes of the Fontevivo groundwaters ( vs. V-SMOW).

2 2
Sample
18O()
2H() H ex () Sample
18O()
2H() H ex ()

FV01
8.6
56.8 11.8 FV16
7.8
53.4 8.8

FV02
7.6
50.3 10.1 FV17
8.5
55.5 12.3
FV03
7.8
51.7 10.3 FV18
7.7
51.0 10.5
FV04 4.68
14.6
52.0 FV19
8.0
52.7 10.9
FV05
7.5
49.1 10.6 FV20
7.5
50.4 9.7
FV06
8.4
56.9 10.0 FV21
7.5
48.6 11.0
FV07
7.4
48.4 10.6 FV22
8.2
54.9 10.4
FV08
7.8
52.2 10.0 FV23
8.3
54.3 11.9
FV09
7.7
51.6 10.2 FV24
7.3
48.8 9.8
FV10
8.3
56.4 10.0 FV25
7.3
47.9 10.3
FV11
7.7
51.7 9.5 FV26
8.0
53.7 10.5
FV12
7.6
51.0 9.9 FV27
7.6
50.7 9.9
FV13
7.8
53.3 8.8 FV28
8.6
55.5 13.0
FV14
8.7
59.1 10.5 FV29
8.6
57.6 11.0
FV15
7.8
53.2 9.0 FV30
7.6
53.1 7.8

The deuterium excess is calculated as 2H ex ()=
2H
8
18O.

can be explained with the oxidation of H2S by species
with higher redox potential (oxygen, nitrate, Mn-Fe
oxides/hydroxides). In addition to reactions 1 and 2, other
redox reactions can be deduced:
H2S + 4MnO2Pyr + 6H + 4Mn2 + + SO24
+ 4H2O (3)
H2S + 8FeO(OH)Goe + 14H + 8Fe2 + + SO24
+ 12H2O (4)
where Pyr = pyrolusite and Goe = goethite.
Reaction 3 is spontaneous (Gr < 0) in all the samples,
confirming that sedimentary Mn-oxides can be dissolved by
H2S-bearing waters. On the contrary, reaction 4 is spontaneous
only in H2S-rich and Fe-poor waters, such as FV16. This feature
agrees with the mutual exclusion of Fe and H2S in waters
(Fig. 4c) and supports the control of sulphide (pyrite) solubility.
Because an apparently positive correlation exists between
NH4+ with pH in waters FV05, 20, 21, 27, redox reactions 2, 3
and 4 may be dominant. Moreover, these waters show substan-
tial concentrations of SO42
, Fe2+ and Mn2+ and then can be
related to the post-oxic ferrous zone of Berner (1981; Fig. 7).
Waters FV24 and 25 are the most oxidized (Eh 405 to
453 mV), contain substantial nitrate concentrations (NO3

17.9 to 30.7 mg/l), have a Ca/SO4 ratio higher than unity and
the lowest concentration of Sr (792 to 851 g/l). These features
argue against a natural source of SO42
from dissolution of
evaporite and/or oxidation of H2S, and point to a human
source from the intensive local farming and the related use of
fertilizers. Waters FV24 and 25 belong to the post-oxic nitric
zone of Berner (1981; Fig. 7).
Group B: waters from Ca-HCO3 to Na-Cl composition
In the Fontevivo area, the abundance of halogens in ground-
water can be related to meteoric contribution (rain waters), rock
dissolution (evaporite) and mixing with deep formation waters.
The 1.57 mg/l content of Cl
in local precipitation (Venturelli
2003, and references therein) precludes precipitation as a
primary contributor. Group B waters plot along a mixing trend
from the Ca-HCO3 member to the brine SB34 (similar trends
can be obtained by evaporation of seawater and dilution of
brine water; Figs. 2 and 8). This mixing process is supported by
the distribution of the Cl-rich groundwaters in the field: i.e. the
brine SB34 well was drilled close to groundwaters FV01, 14 and
28 (Figs. 1 and 3c). Dissolution of halite is excluded by Figure
8 and by the molar Na/Cl ratio, which is far from unity, with
values of 0.900.86 in the most Cl-rich waters FV28, 14 and 01,
and trends to the value of 0.78 shown by brine SB34 (Fig. 9).
Also the PCA indicates that this group of samples is composi-
tionally related to brine water. PCA put together typical
elements of brine waters (Br, I, Cl, Na, As, Se; Conti et al. 2000)
for samples FV28, 14 and 01. Figure 8 also shows that brine
waters of Fontevivo, Salsomaggiore and Monticelli have similar
composition and are evaporated seawater. By contrast, salt
water FV04 has a more complex origin as it plots outside of the
seawater evaporation trend at higher Br and I values (Fig. 8).
The bromine and iodine excess in formation waters has been
related to several processes, including mixing with brine,
dissolution of K-rich salts (e.g. sylvite), membrane filtration
(Worden 1996), and organic matter decomposition in an anoxic
environment during diagenesis (Fontes & Matray 1993; Mller
1999). According to Muramatsu et al. (2001), the latter process
deals particularly with iodine, which is abundant in algal and
planktonic matter. In Figure 8b, FV04 and other salt waters
from the Po Plain in the Parma, Reggio Emilia and Modena
Provinces plot close to the maximum I-Br content of the pore
fluids from oceanic sediments field (Martin et al. 1993). This
suggests that the enrichment of iodine in the brine waters of the
Po Plain (FV04 included) could imply the recycling of the
element during the emplacement of the turbidite front
(Kennedy & Elderfield 1987) of the Cortemaggiore Unit and
subsequent diagenesis and organic matter decomposition.
Tentatively we calculated the addition of SB34 brine into
Cl-rich groundwaters FV28, 14 and 01 using FV22 as the other
end-member (cf. Appelo & Postma 1996). From this calcula-
tion, waters FV28, 14 and 01 contain c.0.2 to 0.3% of brine. The
recalculated contents of Na (Table 5) are close to the mixing
percentages. Similar calculations from the chemical data show
that salt water FV04 could contain 13.6% of brine SB34.
Nonetheless,
2H and
18O values for water and iodine content
preclude, as an origin for FV04, the mixing of present day
meteoric water and brine. The abundance of H2S and the near
absence of SO42
and Fe relate group B waters to the sulphidic
zone of Berner (1981; Fig. 7).
Fe-rich waters
Fe-rich waters may derive from pyrite oxidation due to oxidized
species in solution (e.g. O2, NO3
) (Nordstrom 1982) and
reductive dissolution of Fe-oxides/hydroxides by dissolved
H2S, methane and organic matter. In Fe-rich groundwaters,
siderite (FeCO3) can control the iron concentration: these
 Groundwaters of Fontevivo 35

Fig. 6. (A, B)
2H(H2O) versus

18O(H2O) diagrams. Open circle,
waters sampled outside the
topographical high; open triangle,
waters sampled on the topographical
high; filled diamond, local rain water
(Longinelli & Selmo 2003); filled square,
Taro river water mean value (our
unpublished data); solid line, Northern
Italy Meteoric Line (NIML) (Longinelli
& Selmo 2003); dashed line, Global
Meteoric Water Line (GMWL)
(Rozanski et al. 1993). S, Salsomaggiore
brines; M, Monticelli brines (Iacumin
et al. 2004).

Table 4. Sulphur, oxygen and strontium isotope data of the Fontevivo groundwaters and
waters are typically saturated to supersaturated with respect to other brine and salt waters of the Parma Province.
siderite (Nesbitt 1980; Magaritz & Luzier 1985; Morin & Cherry
1986). Siderite typically is found in reducing fresh waters Sample (species)
34S
18O (SO4) Sample 87
Sr/86Sr Sr
(swamp, bog; Postma 1977, 1982), and its precipitation takes () () (mg/l)
place from SO42
and H2S-free waters (Postma 1982). Pyrite
precipitates rather than siderite when reduced S-species occur in FV12 (SO4)
12.4 2.2 FV01 0.70877 1643
FV16 (H2S)
11.9 FV03 0.70860 1175
solution. Waters FV07 and FV22 (Fe-rich, SO42
and H2S- FV04 (H2S) 24.9 FV04 0.70867 36218
poor) are saturated relative to siderite (SI=
0.10 and
0.19, FV06 0.70867 868
respectively). These features support a controlling role for FV07 0.70868 1375
methane and organic matter. Goethite is possibly dissolved by FV12 0.70870 2635
aqueous CH4:
Salsomaggiore (Marzano well 13/05/02) 0.70875 407450
Monticelli well 10 (24/07/2002) 0.70901 298310
CH4 + 8FeO(OH)Goe + 16H + CO2 + 8Fe2 + + 14H2O (5) well 13 (24/07/2002) 0.70901 334800
Sant Andrea Bagni (Rio Fabbro well 19/04/02) 0.70911 24988
The Gr of the reaction cannot be calculated as the PCH4
values of our waters are unknown. However, given the activities Standard errors (1) for
18O and
34S are 0.3 and 0.2, respectively.
of the other solutes from the speciation calculation, the PCH4 of Standard error (1) for the 87Sr/86Sr ratio is 0.00002.
36 L. Toscani et al.
waters FV07 and FV22 was calculated, obtaining very low
values of 0.03 bar. Reaction 5 may also be driven to the right at
lower PCH4, especially in Fe-poor waters. The origin of Fe-rich
waters from dissolution of sedimentary Fe-oxides/hydroxides is
a realistic interpretation, since methane is currently released
from the buried structure of Fontevivo. Reaction 5 should
increase the pH and produce CO2 but this is not obvious in data
for FV07 and FV22 waters. This suggests that pH and PCO2
buffering reactions occur during Fe-oxide reduction. Fe-rich
and siderite-saturated waters belong to the methanic zone of
Berner (1981; Fig. 7).
Isotopic features
Local precipitation cannot explain the rather large range of the

2H and
18O values of groundwaters from Fontevivo. Rain
water at Parma has a weighted mean composition of

2H =
49.4 and
18O =
7.7 (Longinelli & Selmo 2003)
and can explain only the heaviest groundwaters sampled on the
topographical high. By contrast, the most negative composi-
tions are similar to precipitation of a lower temperature and/or
higher altitude environment, that can be found only on the
Apennines mountain ridge. As stated above, Fontevivo is built
on the Taro alluvial fan, which has its apex and recharge zone
in the Fornovo area (Fig. 1). The most negative isotopic
composition of the Taro River at Fornovo, related to the winter
precipitation, is
2H =
58.0 and
18O =
8.8 (February
2004; unpublished data), that is quite similar to the most
depleted groundwaters at Fontevivo. Therefore, it may be
inferred that the depleted water of the Apennines is collected by
the Taro River catchment, enters and flows in the alluvial fan as
far away as the middle Po plain. Thus, the data distribution in
Figure 6a can be interpreted as being due to mixing of middle
Po plain precipitation with infiltrating Taro River water.
Unlike the other samples from the topographical high, water
FV06 has a clear Taro River imprint. This anomalous com-
position can be related to the greater depth of its well (c. 30 m
compared to the typical 10 m). Valloni (2004) studied the
sub-soil hydrology of the Fontevivo area and found two water
tables separated by an aquitard at a depth of c.20 m, suggesting
that well FV06 taps a different aquifer.
Fig. 7. Distribution of the Berner
zones (Berner 1981) in the investigated
area.
Summarizing, hydrologic and isotopic data reveal: (i) an
isolated surface water layer fed by local precipitation in the
topographical high; and (ii) water flow in the alluvial fan around
and under Fontevivo recharged by the Taro River.
Saline water FV04 has
2H=
14.6 and
18O=4.7,
plots far on the right of the GMWL (Fig. 6b) and its origin
cannot be related to present-day precipitation. From an isotopic
point of view, the composition of water FV04 may be inter-
preted as a mixture between brine waters such as those found
at Salsomaggiore and Monticelli Terme. However, the relatively
low salinity of water FV04 suggests that other processes (e.g.
dilution) besides mixing determined its composition.
Hydrogen sulphide in the studied waters derives from
reduction of aqueous sulphate, which at Fontevivo comes from
dissolution of Messinian evaporites trapped in buried structure.
The isotopic composition of the evaporite under question is
unknown, but its
34S value should be within the range +21.5
to +22.2 (Claypool et al. 1980; Fritz et al. 1988; Pierre &
Fontes 1978; Ricchiuto & Mckenzie 1978). Messinian evapor-
ites from Tuscany (Italy) and Turkey yield
34S =+20.0
(Dinelli et al. 1999) and +20.9 to +25.3 (Palmer et al. 2004),
respectively.
The
34S (H2S) of sample FV16 can be explained with
bacterial reduction of sulphate. According to Thode (1981, and
references therein) bacterial dissimilatory sulphate reduction, in
the presence of the bacterial culture Desulphovibrio desulphuricans,
can produce H2S with
34S in the interval +3 to
46
depending on environmental conditions, whereas the
34S
(H2S) of sample FV04 suggests a nearly complete reduction of
sulphate in a closed system. The reduction may have occurred
either biologically at a temperature lower than 100C (possibly
involving water poor in SO42
) or chemically at T > 100C. In
both cases, the H2S produced is isotopically similar to the
parent SO42
. The thermochemical reduction of sulphates has
been invoked to explain the origin of H2S associated with many
crude oils of variable provenance and age (Nielsen et al. 1988,
and references therein), and this may be the case with H2S from
the oil reservoir at Cortemaggiore, as supported by the
13C of
methane and the occurrence of light hydrocarbons (Pieri &
Mattavelli 1986). The oil is trapped in a buried structure similar
to that beneath Fontevivo. However, any further discussion on
 Groundwaters of Fontevivo
the origin of H2S is purely speculative, as the few available data
do not allow to discrimination between biogenic and abiogenic
sources.
The
34S and
18O values of sulphate (
12.4 and +2.2
respectively; Table 4) refer only to the FV12 water, which is by
far the richest in SO42
. These values are incompatible with
those of marine evaporites, and clearly point to a terrestrial
origin of the sulphate (Clark & Fritz 1997), probably from
oxidation of H2S in a sedimentary environment. The latter
process does not involve significant sulphur isotope fraction-
ation under anaerobic conditions (Thode 1991). This interpreta-
tion is supported by the absence of terrestrial evaporites in the
sedimentary terrains of Fontevivo, and the normal pH and the
low metal contents in water FV12. The latter two features
are the opposite of the expected result from oxidation of
Fe-sulphides (Smith & Melville 2004). The SO42
of FV12
probably derives from an H2S precursor with a negative
37
Fig. 8. Chlorine versus bromine
(A) and iodine (B) concentrations.
Open symbols, Fontevivo groundwaters
(classification as in Fig. 2). Solid line,
static evaporation of marine water
(pointed numbers refer to mineral
precipitation as in Matray 1988; Fontes
& Matray 1993; 0.0=seawater). Black
symbols, brine waters of Salsomaggiore
(S), Monticelli (M) and Fontevivo
(SB34) (Artusi et al. 1977; Artusi &
Marenghi 1983; Bazzicalupo 1958;
Sborgi et al. 1936; our unpublished
data). Grey triangle, FV04 salt water.
Grey pentagons, salt waters from
Parma, Reggio Emilia and Modena
Provinces (Artusi et al. 1977;
Bazzicalupo 1958; Canuti 1973; Coppini
& Bertolani 1961; Pedroni 1953). Grey
stars, waters dissolving salts from
Triassic and Messinian evaporitic
formations of Northern Appennine
(Coradossi & Martini 1965; Bencini
et al. 1977; Boschetti et al. 2004; our
unpublished data). Black stars,
approximate composition of
halite-saturated solution (Br and I of
the solution were calculated by partition
coefficients of Siemann (2003) and
using the mean natural halite
composition of Braitsch & Hermann
1963; Niino et al. 2003; Rozsa 1924).
White drop, rain water average
composition (Yuita 1994). Dotted line,
rain water-halite-saturated solution
mixing line. Dashed line, rain
water-brine/salt waters mixing line.
Dashed area, pore and interstitial waters
of oceanic sediments (Martin et al.
1993).
isotopic signature. The low
18O value of sulphate suggests that
oxygen from groundwater (
18O
8.7 to
7.3) and atmos-
pheric oxygen (
18O ] +23) entered into the sulphugenic
molecule of sulphate (Clark & Fritz 1997, and reference
therein). Data of Van Stempvoort & Krouse (1994) show
experimentally that
18O of sulphate from abioticbiotic oxi-
dation of sulphide ranges from
18O(SO42
)=
18O(H2O) to

18O(SO42
) = 0.62[
18O(H2O)]+9. In sample FV12, the
value of
18O(SO42
) is within the limits (
7.7 to +4.2)
calculated by the equation of Van Stempvoort & Krouse (1994),
thus giving further support to the sulphugenic nature of SO42
.
Finally, it is noteworthy that the difference
18O(SO42
)


18O(H2O) = +9.9 is within the range +8+12, which is
expected from sulphide anaerobic oxidation by biotic culture in
the presence of Mn-oxides (Bttcher & Thamdrup 2001).
In contrast to the light elements, Sr isotopes do not
fractionate during coprecipitation with major minerals from
38 L. Toscani et al.

Table 5. Element mass-balance during mixing (elements as mmol/l)

Cl f*100 Na* Na Ca* Ca Mg* Mg

FV01 6.35 0.21 6.05 5.57 2.81 2.76 1.26 1.64
FV14 6.74 0.22 6.36 5.79 2.84 2.74 1.28 1.40
FV28 8.91 0.30 8.05 8.17 2.98 2.44 1.37 1.43
FV04 367 13.6 287 293 26.3 45.6 16.9 35.0
RW 0.04 0.05 0.04 0.01
FV22 0.82 1.77 2.49 1.03
SB34 2693 2097 178 118

f, Fraction of brine water SB34 (Sborgi et al. 1936); * calculated; RW, rainwater
f=(Cl sample
ClRW)/(ClSB34
ClRW)
X*=f*X(SB34
RW)+(1
f)*X(FV22
RW), where X is the generic ele-
ment

Messinian evaporites (Matano et al. 2005) matches that of

Fig. 9. Na/Cl versus Cl diagram for waters of Group B of
Fontevivo. Symbols as in Figure 2.
solutions. Selected shallow groundwaters from Fontevivo show
an average 87Sr/86Sr ratio value of 0.708700.00007, which is
similar to that of salt water FV04 (0.70867; Fig. 10). According
to the Sr isotope timescale of McArthur et al. (2001), this value
corresponds to the range 17.62 to 15.37 Ma and to Burdigallian
Langhian age (Middle Miocene). This age is considered as
indicative since the McArthur et al. (2001) timescale (quite
accurate in the last 30 Ma) refers to a global scale. Local
variations of the 87Sr/86Sr ratio of our samples may reflect
the tectonic and palaeogeographic controls during sediments
deposition of the Messinian evaporites from southern Apennine
foredeep. Effectively, isotopic composition of Sr of the
Fontevivo waters. The Sr concentrations in the studied waters
indicate that some dilution by fresh water (FV01, FV06) and/or
variable degrees of watergypsum interaction (FV12) occurred.
From a general point of view, our salt water FV04 and other
saline waters of the Po Plain originate from OligoceneMiocene
marine sediments. They show some variation of the isotopic
composition of Sr (Fig. 10; Conti et al. 2000), which can be
explained by prolonged waterrock interaction during the
deformation and the reactivation of the complex tectonic
structures of the northern Apennine.
CONCLUSIONS
Groundwaters of Fontevivo contain dissolved H2S. This gas is
released from the Calabrian level of the buried thrust, which
also includes Middle and Late Miocene terrains (Messinian

Fig. 10. 87Sr/86Sr versus 1/Sr diagram.

Open symbols, ground waters of
Fontevivo; grey triangle, FV04 salt
water; grey pentagons, salt waters of the
Po Plain (SA=S. Andrea Bagni; this
work, Conti et al. 2000), closed
symbols=brine waters of Monticelli
Terme (M) and Salsomaggiore
Terme (S).
 Groundwaters of Fontevivo
evaporites). Most of the groundwaters are fresh Ca-HCO3
because of the interaction with calcite and dolomite of the
aquifer rocks. Rarely, groundwaters assume Na-Cl and Ca-SO4
brackish compositions. On the whole, the waters form two
trends connecting a Ca-HCO3 end-member with Ca-SO4 and
Na-Cl end-members. SO42
in the groundwaters on the east
side of Fontevivo derives from oxidation of H2S by oxidized
constituents in shallow groundwater derived from the Taro
River. In turn, H2S is provided by bacterial reduction of
Messinian evaporite at depth. Oxidation is promoted by mol-
ecular oxygen and nitrate, as well as Mn(IV) and Fe(III) oxides
in the shallow aquifer sediments. Groundwater composition
agrees with the sequence of redox processes that characterize
the redox environments of Berner (1981). At Fontevivo we find
an areal distribution of the redox environments where the most
reduced groundwaters occur in the wells of the topographical
high. Iodinebromine-rich saline to brine waters occur in the
subsurface. These are probably fossil waters similar to those
occurring at Salsomaggiore and Monticelli Terme, which occur
today at depths of 150 to 200 m, where they are released from
the Calabrian and Upper Miocene terrains. Where the brine
mixes with Ca-HCO3 waters, the latter changes its composition
to a Na-Cl character. More specific hydrological and geochemi-
cal studies are necessary to understand the role of both natural
and anthropogenic-induced mixing of deep brine waters with
groundwaters.
The
2H and
18O values support a meteoric origin of the
Fontevivo groundwaters. Most of them have isotopic com-
positions similar to those of the Taro river waters, which
effectively flow in the Quaternary sediments of the alluvial fan
upon which Fontevivo is built. The shallow aquifer under the
topographical high in the central part of the village shows the
isotopic composition of the local precipitation, whereas that of
the deeper aquifer suggests a Taro River supply, which flows
northward under the topographical high.
We are grateful to Professor Giampiero Venturelli (Parma University,
Italy) and Professor Mario Barbieri (La Sapienza University, Roma,
Italy) for the useful suggestions and for the critical reading of the
manuscript. We are indebted to Professor Gianni Cortecci (CNR,
Pisa, Italy) for improving the English and for the constructive review
of an earlier version of the manuscript. We want to thank Dr G.
Phipps, Dr S.M. Hamilton and an other anonymous referee of
GEEA. We are grateful to Dr Sergio Rogledi (ENI SpA) for the
interpretation of the seismic profiles. We thank Dr Enrico Selmo for
assistance with hydrogen and oxygen isotope analyses and Mrs E.
Masini for drawing Figures 1, 3 and 7. Financial support was from
University of Parma (Local Grant) and from Comune di Fontevivo
(gift). In particular we want to thank Mayor Massimiliano Grassi and
Alderman Franco Ballarini of the Comune di Fontevivo for their
sensitivity for scientific research and for popularizing the results of
this work.
REFERENCES
APPELO, C.A.J. & POSTMA, D. 1996. Geochemistry, Groundwater and Pollution.
Balkema, Rotterdam.
ARGNANI, A., RIZZINO, F., ROGLEDI, S. et al. 2003. Tectonic structures in the
subsurface of the Northern Pede-Apennines: implications for Messinian
reconstructions. In: FIST Geoitalia 2003: 4 Forum Italiano di Scienze della Terra
Bellaria (RN), 1618 settembre. 2003, 698700.
ARTUSI, G.C. & MARENGHI, I. 1983. Recenti analisi di acque salsobromoiod-
iche della zona pedemontana del Parmense. Acta Naturalia de lAteneo
Parmense, 19, 3948.
ARTUSI, G.C., DE MARCHI, A., MARENGHI, I., TAGLIAVINI, S. & ZANZUCCHI, G.
1977. The mineral waters of the Parma province. Origin, composition and classification.
Universit degli Studi di Parma, Italy.
BALE, C.W., CHARTRAND, P., DEGTEROV, S.A., ERIKSSON, G., HACK, K.,
MAHFOUD, R.B., MELANO, J., PELTON, A.D. & PETERSEN, S. 2002.
FACTSAGE Thermochemical Software and Databases. Calphad, 28 (2),
189228.
39
BAZZICALUPO, L. 1958. Sulle acque minerali della Provincia di Parma. Ateneo
Parmense, 29 (6), 94130.
BENCINI, A., DUCHI, V. & MARTINI, M. 1977. Geochemistry of thermal springs
of Tuscany (Italy). Chemical Geology, 19, 229252.
BERNER, R.A. 1981. A new geochemical classification of sedimentary
environments. Journal of Sedimentary Petrology, 51, 359365.
BERNINI, M. & PAPANI, G. 1987. Alcune considerazioni sulla struttura del
margine appenninico emiliano fra lo Stirone e lEnza (e sue relazioni con il
Sistema del F. Taro). Acta Naturalia de l Ateneo Parmense, 23, 219240.
BONAZZI, A., CHIERICI, R., SALVIOLI-MARIANI, E. & VERNIA, L. 1982. Meta-
morfismo e diagenesi in formazioni dellAppennino Settentrionale (Val
Dolo, province di Modena e Reggio Emilia). Dati di cristallinit dellillite.
Mineralogica et Petrografica Acta, 26, 121141.
BOSCHETTI, T. 2003. Studio geochimico e geochimico-isotopico di acque a composizione
estrema e termali dellAppennino Settentrionale. PhD thesis. Parma University,
Italy.
BOSCHETTI, T., VENTURELLI, G., TOSCANI, L., BARBIERI, R. & MUCCHINO, C.
2005. The Bagni di Lucca thermal waters (Tuscany, Italy): an example of
Ca-SO4 waters with high Na/Cl and low Ca/SO4 ratios. Journal of Hydrology,
307, 270293.
BRAITSCH, O. & HERMANN, A.G. 1963. Zur geochemie des broms in salinaren
sedimenten, Teil I: experimentelle bestimmung der Br-verteilung in ver-
schiedenen natrlichen salzsystemen. Geochimica et Cosmochimica Acta, 27,
361391.
BTTCHER, M.E. & THAMDRUP, B. 2001. Anaerobic sulphide oxidation and
stable isotope fractionation associated with bacterial sulphur dispropor-
tionation in the presence of MnO2. Geochimica et Cosmochimica Acta, 65,
15731581.
CANUTI, A. 1973. Analisi delle acque minerali di Lesignano (Parma). Industrie
delle Bevande, 3.
CLARK, I. & FRITZ, P. 1997. Environmental Isotopes in Hydrogeology. Lewis
Publishers, Boca Raton.
CLAYPOOL, G.E., HOLSER, W.T., KAPLAN, L.R., SAKAI, H. & ZAK, I. 1980. The
age curves of sulphur and oxygen isotopes in marine sulphate and their
mutual interpretation. Chemical Geology, 28, 199260.
CONTI, A., SACCHI, E., CHIARLE, M., MARTINELLI, G. & ZUPPI, G.M. 2000.
Geochemistry of the formation waters in the Po plain (Northern Italy): an
overview. Applied Geochemistry, 15, 5165.
COPPINI, D. & BERTOLANI, G. 1961. Le acque salso-bromo-iodiche di
Castelvetro (Modena). Bollettino Laboratorio Chimico Provinciale (Bologna), 12,
332335.
CORADOSSI, N. & MARTINI, M. 1965. Contributo allo studio geochmico delle
acque di Montecatini Terme. Rendiconti della Societa Mineralogica Italiana, 21,
6790.
DI DIO, G., LASAGNA, S., PRETI, D. & SAGNE, M. 1997. Stratigrafia dei depositi
quaternari della Provincia di Parma. Bollettino della Societ Paleontologica
Italiana, 36, 179187.
DINELLI, E., TESTA, G., CORTECCI, G. & BARBIERI, M. 1999. Stratigraphic and
petrographic constraints to trace element and isotope geochemistry of
Messinian sulphates of Tuscany. Memorie della Societ Geologica Italiana, 54,
6174.
DREVER, J.I. 1997. The Geochemistry of Natural Waters: Surface and Groundwater
Environments 3rd edn. Prentice Hall.
EATON, A.D., CLERSCERI, L.S. & GREENBERG, A.E. 1996. Standard methods for
examination of water and wastewater. American Public Health Association,
American Water Works Association, Water Environment Federation.
EPSTEIN, S. & MAYEDA, T. 1953. Variations of 18O/16O ratio in natural waters.
Geochimica et Cosmochimica Acta, 4, 213224.
FARNHAM, I.M., SINGH, A.K., STETZENBACH, K.J. & JOHANNESSON, K.H. 2002.
Treatment of nondetects in multivariate analysis of groundwater geochem-
istry data. Chemometrics and Intelligent Laboratory Systems, 60 (1-2), 265281.
FONTES, J. C. & MATRAY, J. M. 1993. Geochemistry and origin of formation
brines from the Paris Basin, France. 1. Brines associated with Triassic salts.
Chemical Geology, 109, 149175.
FRITZ, P., LAPCEVIC, A., MILES, M., FRAPE, S.K., LAWSON, D.E. & OSHEA, K.J.
1988. Stable isotopes in in sulphate minerals from the Salina formation in
southwestern Ontario. Canadian Journal of Earth Sciences, 25, 195205.
GLESEMANN, A., JAGER, H.J., NORMAN, A.L., KROUSE, H.R. & BRAND, W.A.
1994. On-line sulphur-isotope determination using an elemental analyzer
coupled to a mass spectrometer. Analytical Chemistry, 66, 28162819.
GRAN, G. 1952. Determination of the equivalence point in in the potentio-
metric titrations. Analyst, 77, 661671.
GLER, C., THYNE, G.D., MCCRAY, J.E. & TURNER, A.K. 2002. Evaluation of
graphical and multivariate statistical methods for classification of water
chemistry data. Hydrogeology Journal, 10 (4), 455474.
IACUMIN, P., VENTURELLI, G., BURRONI, B., TOSCANI, L. & SELMO, E. 2004. The
San Andrea Bagni waters, and on microclimatic variations. In: Developments
in Aquifer Sedimentology and Ground Water Flow Studies in Italy, Parma, 25 June
2004, 25.
JOHNSON, J.W., OELKERS, E.H. & HELGESON, H.C. 1992. SUPCRT92: a
software package for calculating the standard molal thermodynamic
40 L. Toscani et al.
properties of minerals, gases, aqueous species, and reactions from 1 to 5000
bar and 0 to 1000C. Laboratory of Theoretical Geochemistry, University
of California, Berkeley. Computer & Geosciences, 18, 899947.
KENNEDY, H.A. & ELDERFIELD, H. 1987. Iodine diagenesis in non-pelagic
deep-sea sediments. Geochimica et Cosmochimica Acta, 51, 25052514.
KORNEXL, B.E., GEHRE, M., HOFLING, R. & WERNER, R.A. 1999. On-line
18O
measurement of organic and inorganic substances. Rapid Communications in
Mass Spectrometry, 13, 16851693.
LONGINELLI, A. & SELMO, E. 2003. Isotopic composition of precipitation in
Italy: a first overall map. Journal of Hydrology, 270, 7588.
MAGARITZ, M. & LUZIER, J.E. 1985. Water-rock interactions and seawater-
freshwater mixing effects in the coastal dunes aquifer, Coos Bay, Oregon.
Geochimica et Cosmochimica Acta, 49, 25152525.
MARTIN, J.B., GIESKES, J.M., TORRES, M. & KASTNER, M. 1993. Bromine and
iodine in Peru margin sediments and pore fluids implications for fluids
origins. Geochimica et Cosmochimica Acta, 57, 43774389.
MARTINELLI, G., MINISSALE, A. & VERRUCCHI, C. 1998. Geochemistry of
heavely exploited aquifers in the Emilia Romagna region (Po valley,
Northern Italy). Environmental Geology, 36, 195206.
MATANO, F., BARBIERI, M., DI NOCERA, S. & TORRE, M. 2005. Stratigraphy and
strontium geochemistry of Messinian evaporite-bearing successions of the
southern Apennines foredeep, Italy: implications for the Mediterranean
salinity crisis and regional palaeogeography. Palaeogeography, Palaeoclimatol-
ogy, Palaeoecology, 217, 87114.
MATRAY, J.M. 1988. Hydrochimie et gochimie isotopique des eaux de rservoir ptrolier
du Trias et du Dogger dans le Bassin de Paris. Thse de 3me. Universit de
Paris-Sud, Orsay, France.
MCARTHUR, J.M., HOWART, R.J. & BAYLEY, T.R. 2001. Strontium isotope
stratigraphy: LOWESS version 3: best fit to the marine Sr-isotope curve for
0-509 Ma and accompanying look-up table for deriving numerical age.
Journal of Geology, 109, 155170.
MEZZADRI, G. 1964. Petrografia delle arenarie di Ostia. Rendiconti Societ
Mineralogica Italiana, 20, 192228.
MEZZADRI, G. 1970. Osservazioni preliminari sui conglomerati ed arenarie di
Petrignacola (Val Parma). Acta Naturalia de lAteneo Parmense, 6, 160169.
MORIN, K.A. & CHERRY, J.A. 1986. Trace amounts of siderite near uranium-
tailings impoundment, Elliot Lake, Ontario, Canada, and its implication in
controlling contaminant migration in a sand aquifer. Chemical Geology, 56,
117134.
MURAMATSU, Y., FEHN, U. & YOSHIDA, S. 2001. Recycling of iodine in fore-arc
areas: evidence from the iodine brines in Chiba, Japan. Earth and Planetary
Science Letters, 192, 583593.
MLLER, G. 1999. Natural organochlorines in sediments. In: The Natural
Chemistry of Chlorine in the Environment A series of overviews by a panel of
independent scientists 2nd. World Chlorine Council, 1314.
NESBITT, H.W. 1980. Characterization of mineral-formation water interactions
in carboniferous sandstones and shales of the Illinois sedimentary basin.
American Journal of Science, 280, 607630.
NIELSEN, H., PILOT, J., GRINENKO, L.N., GRINENKO, V.A., LEIN, A.Y., SMITH,
J. W. & PANKINA, R. G. 1988. Lithospheric sources of sulphur. In: KROUSE,
H.R. & GRINENKO, V.A. (eds) SCOPE 43, 43. Wiley, New York, 65132.
NIINO, Y., NISHIMURA, H. & KOGA, A. 2003. Amount of iodine in commercial
edible salt. (in Japanese)Kaisui Sogo Kenkyusho Kenkyu Hokoku, 5, 3437.
NORDSTROM, D.K. 1977. Thermochemical redox equilibria of ZoBells
solution. Geochimica et Cosmochimica Acta, 41, 18351841.
NORDSTROM, D.K. 1982. Aqueous pyrite oxidation and the consequent
formation of secondary iron minerals. In: NORDSTROM, D.K. (ed.) Acidic
Sulphate Weathering. Special Publication, 10. Soil Science Society of America,
3756.
NORUSIS, M.J. 2002. SPSS 11.0: Guide to Data Analysis. Prentice Hall.
PALMER, M.R., HELVACI, C. & FALLICK, A.E. 2004. Sulphur, sulphate oxygen
and strontium isotope composition of Cenozoic Turkish evaporites.
Chemical Geology, 209, 341356.
PARKHURST, D.L. & APPELO, C.A.J. 1999. Users guide to PHREEQC (version 2)-
A computer program for speciation, batch reaction, one-dimensional transport and inverse
geochemical calculations. Water Resources Investigations Report, 95-4259. US
Geological Survey.
PEDRONI, I. 1953. Contributo alla conoscenza delle acque salse
dellAppennino Modenese. Bollettino Societ Medico-Chirurgica di Modena, 53,
199206.
PIERI, M. & MATTAVELLI, L. 1986. Geologic framework of Italian petroleum
resources. American Association of Petroleum Geologists Bulletin, 70, 103130.
PIERRE, C. & FONTES, J.C. 1978. Isotope composition of Messinian sediments
from the Mediterranean sea as indicators of paleoenvironments and
diagenesis. Initial Report of the Deep Sea Drilling Project, 42.1, 635650.
POSTMA, D. 1977. The occurrence and chemical composition of recent Fe-rich
carbonates in a river bog. Journal of Sedimentary Petrology, 47, 10891098.
POSTMA, D. 1982. Pyrite and siderite formation in brackish and freshwater
swamp sediments. American Journal of Science, 282, 11511183.
RICCHIUTO, T.E. & MCKENZIE, J.A. 1978. Stable isotopic investigation of the
Messinian sulphate samples from DSP Leg 42A, Eastern Mediterranean
sea. Initial Report of the Deep Sea Drilling Project, 42.1, 657660.
ROZANSKI, K., ARAGUAS-ARAGUAS, L. & GONFIANTINI, R. 1993. Isotopic
patterns in modern global precipitation. In: SWART, P.K., LOHMAN, K.L.,
MCKENZIE, J.A. & SAVIN, S. (eds) Climate Change in Continental Isotopic Record.
Geophysical Monograph, 78, 137.
ROZSA, M. 1924. The iodine content of german salts. Kali, 18, 249252.
SBORGI, V., GALANTI, A. & CONTINI, Z. 1936. Chemical and physicochemical
analyses of the mineral waters of Fontevivo (Parma). Annali di Chimica
Applicata, 26, 502515.
SIEMANN, M.G. 2003. Extensive and rapid changes in seawater chemistry
during the Phanerozoic: evidence from Br contents in basal halite. Terra
Nova, 15, 243248.
SMITH, J. & MELVILLE, M.D. 2004. Iron monosulphide formation and
oxidation in drain-bottom sediments of an acid sulphate soil environment.
Applied Geochemistry, 19, 18371853.
THODE, H.G. 1981. Sulphur isotope ratios in petroleum research and
exploration; the Williston Basin. American Association of Petroleum Geologists
Bulletin, 65, 15271535.
THODE, H.G. 1991. Sulphur isotope in nature and the environment: an
overview. In: KROUSE, H.R. & GRINENKO, V.A. (eds) SCOPE 43. Wiley,
New York, 126.
TOSCANI, L., VENTURELLI, G. & BOSCHETTI, T. 2001. Sulphide-bearing waters
in the Northern Apennines, Italy: general features and water-rock
interaction. Aquatic Geochemistry, 7, 195216.
VALLONI, R. 2004. Pleistocene alluvial fans, Holocene fluvial channels and
aquifer recharge in the southern margin of the Po river plain. In:
Developments in Aquifer Sedimentology and Ground Water Flow Studies in Italy,
Parma, 25 June 2004, 25.
VAN STEMPVOORT, D. R. & KROUSE, H. R. 1994. Controls of
18O in sulphate:
review of experimental data and application to specific environments. In:
ALPERS, C.N. & BLOWES, D.W. (eds) Environmental Geochemistry of Sulfide
Oxidation. ACS Symposium Series, 550, 466480.
VENTURELLI, G. & FREY, M. 1977. Anchizone metamorphism in sedimentary
sequences of the Northern Apennines. Rendiconti Societ Mineralogica Italiana,
33, 109123.
VENTURELLI, G., THORPE, R.S. & POTTS, P.J. 1981. Rare earth and trace
element characteristics of ophiolitic metabasalts from the Alpine-Apennine
belt. Earth and Planetary Science Letters, 53, 109123.
VENTURELLI, G., CONTINI, S., BONAZZI, A. & MANGIA, A. 1997. Weathering
of ultramafic rocks and element mobility at Mt. Prinzera, Northern
Apennines, Italy. Mineralogical Magazine, 61, 765778.
VENTURELLI, G., TOSCANI, L., MUCCHINO, C. & VOLTOLINI, C. 2000. Study of
the water-rock interactions of spring waters in the northern Apennines.
Annali di Chimica, 90, 359368.
VENTURELLI, G. 2003. Acque, minerali e ambiente. Pitagora Editrice, Bologna.
WORDEN, R.H. 1996. Controls on halogen concentrations in sedimentary
formation waters. Mineralogical Magazine, 60, 259274.
YUITA, K. 1994. Overview and dynamics of iodine and bromine in the
environment 1. Dynamics of iodine and bromine in soil-plant system. Japan
Agricultural Research Quarterly, 28, 9099.
ZUFFA, G.G. 1969. Arenarie e calcari arenacei miocenici di Vetto-Carpineti
(formazione di Bismantova, Appennino settentrionale). Mineralogica et
Petrografica Acta, 15, 191229.