Boschetti T.

(2005) Geochemical and isotope-geochemical study of compositionally extreme and thermal waters from
Northern Apennines (Italy). L'Ateneo Parmense - Acta Naturalia 40, 71-75.

Geochemical and isotope-geochemical study of compositionally extreme and thermal

waters from Northern Apennines (Italy)

Titolo Abbreviato: Geochemical study of waters from Northern Appennines

TIZIANO BOSCHETTI

XV CIclo Dottorato di Ricerca in Scienze della Terra

Consorzio Universit di Ferrara e Parma
Universit di Parma Dipartimento di Scienze della Terra
Parco Area delle Scienze 157/A 43100 Parma
e-mail: tiziano.boschetti@unipr.it

INTRODUCTION
This thesis was aimed to the geochemical characterization of some selected extreme water samples
issued out from different lithologies of the Emilian and Tuscan Northern Apennines.
One hundred forty water samples from Taro-Secchia and Magra-Serchio-Nievole hydrologic basins
were examined. The survey dealt with: (i) major and minor/trace chemical in water samples and
rocks; (ii) O, H, S and Sr isotopes (2H, 18O, 3H in H2O; 34S in H2S; 34S and 18O in aqueous
SO42- and gypsum/anhydrite minerals; 87
Sr/86Sr in water, rocks and minerals); (iii) definition of
water origin and water-rock interaction processes coupling chemical and isotopic data.

ANALYTICAL PROCEDURES
The experimental work was carried out as follows:
(i) Sampling and field analyses of the labile chemical-physical parameters (T, pH, Eh, total
alkalinity, conducibility, total H2S, total NH3);
(ii) Analysis in laboratory of the major and minor/trace chemical parameters by ICP-AES, ICP-MS,
AAS, ion chromatography, ion-selective electrode, spectrophotometry. The measurements were
performed at the Departments of Chemistry and Earth Sciences of the University of Parma.
A specific strategy for the simultaneous determination of 17 trace elements by ICP-MS was
validated. By this method it was possible to analyze 60 water samples (10 ml each) automatically in
10 hours (Boschetti et al., 2001; 2004).
The quantification of I and Br in water samples by ICP-MS required a further analytical effort. In
particular for iodine, the traditional analytical methods provide the determination of one species or

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Boschetti T. (2005) Geochemical and isotope-geochemical study of compositionally extreme and thermal waters from
Northern Apennines (Italy). L'Ateneo Parmense - Acta Naturalia 40, 71-75.

the total content following long and tedious reduction/oxidation reactions (e.g. APHA-AWWA-
WEF, 1995). In this study, total iodine content (I- + IO3- + I2) was determined by means of an
innovative FI-ICP-MS method (flow injection inductively coupled plasma - mass spectrometry).
Worthy of note, this new method requires small water amounts (15 l) and it is lacking of memory
and matrix effects even analysing brines.
(iii) Isotope analysis 2H(H2O) and 18O(H2O) were carried out in the Isotope Laboratory of the
87
Department of Earth Sciences of the University of Parma; Sr/86Sr ratios were determined at the
Department of Earth Sciences of the La Sapienza, University of Rome. Other analyses (3H in
H2O; 34S and 18O in H2S and SO42-) were performed to the Rafter Stable Isotope Laboratory,
Geological and Nuclear Sciences, Lower Hutt, New Zealand.

DISCUSSION OF THE RESULTS

From a lithological point of view, we could distinguish four water groups:
1) Ipothermal waters issuing from spilitized basalts and associated soils;
2) ipothermal waters issuing from serpentinized ultramafic and associated soils;
3) ipothermal waters issuing from pelitic-marly and pelitic-arenaceous sedimentary rocks;
4) thermal and ipothermal waters from solfatic-carbonatic Triassic rocks and from Mesozoic
limestone.
Extreme definition refers to the major chemical composition of the waters; in fact, representative
samples occupy all the area of the classification diagrams. In details, it is possible to distinguish a
variety of water types: calcium-bicarbonate, magnesium-bicarbonate, sodium-bicarbonate, calcium-
sulfate, sodium-chloride, sodium-chloride brines, sulphide-bearing calcium-bicarbonate, sulfide-
bearing sodium-bicarbonate, sulfide-bearing sodium-chloride, sulfide-bearing sodium-(calcium)-
hydroxylate.
Due to the compositional heterogeneity, different approaches were adopted for the data
interpretation like: (i) classic classification ternary diagram; (ii) statistical methodologies
(descriptive, non-parametric, factor analysis); (iii) thermodynamic calculations using specific
software (PHREEQCI, SUPCRT92, JCHESS) and databases.
The isotopic composition of water molecule allowed us to confirm the meteoric origin of all the
studied samples, while the sulfur and strontium isotope compositions were useful to put in evidence
bacterial reduction processes and water-rock interaction trends, respectively.

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 Boschetti T. (2005) Geochemical and isotope-geochemical study of compositionally extreme and thermal waters from
Northern Apennines (Italy). L'Ateneo Parmense - Acta Naturalia 40, 71-75.

Waters from Ophiolites of the Taro Valley

As far as the springs from Taro Valley are concerned, their chemical composition confirms the
progressive interaction between ultramafic rocks (variably affected by serpentinization) and
meteoric water as responsible of the production of Ca-Mg-HCO3 waters in shallow aquifers open to
CO2 exchange, that is followed by the development of sulfide-bearing Na-Ca-OH type waters under
closed-system conditions with respect to CO2. Forward reaction path modelling implies an initial
water saturation relative to Fe-Mg-montmorillonite and goethite, a final water saturation relative to
Fe-Mg-saponite, goethite, Fe-Mg-chlorite, brucite and oversaturation in calcite, and intermediate
stages with saturation of the water with respect to amourphous silica and lizardite (Fig. 1). Cr
concentration up to 20 g/l in the Ca-Mg-HCO3 waters is mainly related to the dissolution of
picotitric spinel, as well as to the high mobility of Cr(VI) ion (98 100 % of the total Cr). In Na-
Ca-OH type waters, Cr is below the quantification limit (< 0.8 g/l), due to reduction/adsorption
processes promoted by clays and mixed layer clays (e.g. Brigatti et al., 2000).

C
0
100

10
90
UM15
20
80
PR10
30
70

40
60

50
50
PR10/98
60
40
magnesian
non silicatic 70 UM1
minerals 30

80 clinochlore serpentine diopside

enstatite 20 silica
C/M minerals
g =4
90 Mg-saponite talc
forsterite 10
C/Mg
=2
100
0
MgX5
0 10 20 30 40 50 60 70 80 90 100 Six5

hydroxylated-Ca-(Na)
hydroxylated-Na-(Ca) waters from
bicarbonatic-Ca ultramafic rocks
bicarbonatic-Mg
waters from basalts
stream waters
waters from sedimentary formations

Fig. 1 Mg-Si-C ternary diagram in mol/kg for waters from the Taro Valley. Other high pH hydroxylated-
Ca-(Na) waters (small black diamonds) are from Gruppo di Voltri area (data from Marini e Ottonello, 2002).
White crosses represent the water composition resulting from the dissolution of specific minerals.

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 Boschetti T. (2005) Geochemical and isotope-geochemical study of compositionally extreme and thermal waters from
Northern Apennines (Italy). L'Ateneo Parmense - Acta Naturalia 40, 71-75.

Thermal waters from Bagni di Lucca

Thermal springs of Bagni di Lucca (Lucca province, Tuscany) are of calcium-sulfate type and are
characterised by high Na/Cl ( 2) and low Ca/SO4 ( 0.7) mole ratios. Assuming equilibrium of the
waters with anhydrite and chalcedony, the evaluated temperature and pressure are about 70-75C
and 200-300 bar, respectively; considering the pressure as hydrostatic, the evaluated depth of
equilibration approaches that of the metamorphic basement (about 3.0-3.8 km) underlying the
carbonate-evaporite formations occurring in the area. Backward reaction path modelling indicates
that the high Na/Cl ratio and the low Ca/SO4 ratio in the waters may be due to progressive
dissolution of albite, anhydrite, dolomite and carbon dioxide accompanied by calcite precipitation
(Boschetti et al., 2005). The isotopic composition of dissolved sulfate confirms the interaction with
Upper Triassic gypsum/anhydrite of the Calcare Cavernoso Formation in these and other
34
ipothermal calcium-sulfate waters from the upper reaches of the Secchia Valley (Fig. 2). The S-
enrichment shown by sulfate in the Bagni di Lucca and Monsummano thermal waters with respect
to the Triassic source may be ascribed to bacterial reduction effects during subsoil circulation.

20.0

18.0

gypsum-anhydrite
16.0 Upper Trias
O(SO4) ()

14.0 ction Bagni di Lucca p1

ic redu p2
tio
n batter p3
olu
18

12.0 di ss Poiano p4
te
lfa POIg Gallicano
su
ion Monsummano
10.0 uit cinque
dil PAN3
cerri Rossendola

Rosg1 Rosg2
8.0
13.0 14.0 15.0 16.0 17.0 18.0 19.0
34
S(SO4) ()

calcium-sulfatic waters
sodium-chloride waters
gypsum and anhydrite
(this study)
Upper Triassic evaporite
(mean values and ranges)

Fig. 2 Plot of 34S vs. 18O in SO42-. Grey and white symbols depict ipothermal (Poiano, Rossendola,
Cinque Cerri = Secchia Valley springs) and thermal waters (Gallicano, Bagni di Lucca = Serchio Valley
springs; Monsummano = Nievole Valley), respectively. Sketched area marks the boundary isotopic
composition of Italian Upper Triassic evaporites analyzed to date (this study and literature). For the isotopic
effects on sulfur and oxygen isotopes of sulfate due to bacterial reduction (p lines) see Seal et al. (2000).

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 Boschetti T. (2005) Geochemical and isotope-geochemical study of compositionally extreme and thermal waters from
Northern Apennines (Italy). L'Ateneo Parmense - Acta Naturalia 40, 71-75.

ACKNOWLEDGMENTS
I would like to express my gratitude to Prof. Giampiero Venturelli, supervisor of this thesis, and to
the co-tutor Dott. Claudio Mucchino (Dipartimento di Chimica Generale ed Inorganica, Chimica
Analitica, Chimica Fisica Universit di Parma) for introducing me in ICP analysis. Special thanks
to Prof. Lorenzo Toscani for support and stimulating discussions. I am grateful also to Dott. Mario
Barbieri (Dipartimento di Scienze della Terra, Universit La Sapienza Roma) for 87
Sr/86Sr
analyses, and to Prof. G. Cortecci (Istituto di Geoscienze e Georisorse, Area della Ricerca CNR,
Pisa) for inedit data and useful suggestions.

REFERENCES

APHA-AWWA-WEF (1995). Standard Methods for the Examination of Water and Wastewater,
19th edition. American Public Health Association, American Water Works Association, Water
Environment Federation.

Boschetti T., Mangia A., Mucchino M., Toscani L. (2001). Determinazione simultanea di 17
elementi mediante ICP-MS in campioni di acque interagenti con rocce ultramafiche e basaltiche
dellAppennino Settentrionale. Societ Chimica Italiana - Atti del XVI Congresso Nazionale di
Chimica Analitica Portonovo (Ancona), Settembre 2001 Chimica Analitica e Scienze del Mare.
390 - 391.

Boschetti T., Mucchino C., Bianchi F. (2004). Simultaneous determination of 17 trace elements in
groundwaters by ICP-MS. Annali di Chimica (in revision).

Boschetti T., Venturelli G., Toscani L., Barbieri M., 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 (in publication).

Brigatti M.F., Franchini G., Lugli C., Medici L., Poppi L., Turci E. (2000). Interactions between
aqueous chromium solutions and layer silicates. Applied Geochemistry, 15, 1307-1316.

Marini L., Ottonello G. (2002). Atlante degli acquiferi della Liguria, Volume 3. Pacini Editore,
Pisa. 102 pp.

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Boschetti T. (2005) Geochemical and isotope-geochemical study of compositionally extreme and thermal waters from
Northern Apennines (Italy). L'Ateneo Parmense - Acta Naturalia 40, 71-75.

Seal R.R. II, Alpers C.N., Rye R.O. (2000). Stable isotope systematic of sulfate minerals. In:
Reviews in Mineralogy & Geochemistry 40, Sulfate Minerals Crystallography, Geochemistry and
Environmental Significance. MSA, Washington DC. 541 602.