HYDROLOGICAL PROCESSES

Hydrol. Process. 21, 120 (2007)

Published online 23 August 2006 in Wiley InterScience
(www.interscience.wiley.com) DOI: 10.1002/hyp.6270

The River Arno catchment, northern Tuscany: chemistry of

waters and sediments from the River Elsa and River Era
sub-basins, and sulphur and oxygen isotopes of aqueous
sulphate
Gianni Cortecci,1 * Enrico Dinelli2 and Tiziano Boschetti3
1 Istituto di Geoscienze e Georisorse, CNR, Area della Ricerca, Via Moruzzi 1, I-56124 Pisa, Italy
2 Centro Interdipartimentale di Ricerca per le Scienze Ambientali, Alma Mater Studiorum-University of Bologna, Sede di Ravenna, Via SantAlberto
163, I-48100 Ravenna, Italy
3 Dipartimento di Scienze della Terra, University of Parma, Parco Area delle Scienze 157a, I-43100 Parma, Italy

Abstract:
Within the hydrologic balance of the River Arno catchment (northern Tuscany), the Rivers Elsa and Era are important tributaries
entering the main river from the left bank in the lower part of the watershed. Waters and bed sediments were sampled in June
2000 during low discharges in the Rivers Elsa and Era, as well as in major tributary streams. Water samples were analysed
for major chemistry and sulphur isotope composition of sulphate, and sediment samples were analysed for major composition
and selected trace elements of environmental concern (Zn, Cu, Pb, Cr and Ni).
The main results for the waters are: (1) Na and Cl in solution show consistent downstream positive trends in the main rivers,
thus supporting progressive contributions of anthropogenic salts; the highest concentration values are observed in tributaries;
(2) as shown by sulphur isotopes, sulphate in solution is mainly controlled by dissolution of evaporites (Elsa basin) or oxidation
of reduced organic/biogenic sulphur (Era basin), with anthropogenic contributions in most streams not higher than 10% in
both the basins. A 34 S signature in the range
2 to C3 is estimated for pollutant sulphate in the basins studied. The main
results for the sediments are: (1) major chemistry is essentially controlled by the lithotypes drained by the waters; (2) pollution
by heavy metals does not reach high levels; (3) compared with local fine-grained rocks, copper is more frequently anomalous,
whereas lead and zinc show only occasional anomalies; (4) local high concentrations of chromium and nickel can be attributed
to upstream occurrences of ophiolites. Copyright 2006 John Wiley & Sons, Ltd.
KEY WORDS River Elsa catchment; River Era catchment; northern Tuscany; waters and sediments; trace elements; sulphur
isotopes; oxygen isotopes

Received 17 March 2005; Accepted 29 November 2005

INTRODUCTION These catchments were chosen because they are dis-

Within the River Arno catchment, the Elsa and Era tinguished from others in the Arno hydrographic basin
tributaries receive waters draining Plio-Quaternary fine- by the presence of evaporites along with siliciclastic
grained marine and lacustrine clayey and sandy deposits, rocks. In addition, the human load in the study catch-
ments is relatively high compared with the land extents,
and minor Triassic and Messinian evaporites in the upper
and the related influence on waters was expected to
reaches of the sub-catchments studied.
be traceable. We also want to check the consistency
Following the acquisition of the chemical and sulphur
between the data from the present study and the inter-
isotopic data published in Cortecci et al. (2002)errata
pretative model drawn out by Cortecci et al. (2002).
corrige: some mistakes need to be pointed out in Cortecci
Using this model, the relative proportions of aqueous
et al. (2002: table III) concerning the River Elsa; the
sulphate contributed to the main River Arno and trib-
corrections are: Ugriano D Ugliano, and River Elsa at
utaries by natural (evaporite dissolution and oxidation
Castellina in Chianti D Staggia tributary at Castellina
of sedimentary sulphide) and human (domestic, indus-
Scaloa more detailed sampling of the Elsa and Era
trial, agricultural) sources were tentatively approximated
hydrologic networks was carried out in June 2000, includ-
by combining major hydrochemistry and sulphur isotopic
ing major and minor streams. Water samples were anal-
composition of sulphate ions. The model is undoubtedly
ysed for the principal chemistry and the sulphur isotope
questionable, as it assumes that: (1) sulphate derives from
composition of sulphate in solution. Some sulphates were
technogenic sources, like dissolution of sodium sulphate
also analysed for the oxygen isotope composition.
or oxidation of sodium sulphite and sulphide in treatment
plants, these compounds being used in abundance in the
* Correspondence to: Gianni Cortecci, Istituto di Geoscienze several dyeing works and tanneries of the middlelower
e Georisorse, CNR, Area della Ricerca, Via Moruzzi 1, I-56124 Pisa,
Italy. part of the catchment, as well as from natural sources
E-mail: g.cortecci@igg.cnr.it like dissolution of evaporites and oxidation of sulphides;

Copyright 2006 John Wiley & Sons, Ltd.

2 G. CORTECCI, E. DINELLI AND T. BOSCHETTI
(2) chloride in solution basically derives from dissolu-
tion of sodium chloride (natural and/or anthropogenic);
(3) sodium derives from sulphide, sulphite and sulphate
(anthropogenic) and from chloride (natural and anthro-
pogenic) salts. Incongruent dissolution of albite and pla-
gioclase was considered to be a very minor to negligible
source of sodium in the waters. On the other hand, a
number of additional sulphur- and sodium-bearing sub-
stances from human sources can be listed depending on
the industrial or agricultural applications. However, it
is a matter of fact that, in the Cortecci et al. (2002)
paper on the River Arno drainage basin, the concentration
ratio R D [SO4 C Cl
Na/SO4 ] (on equivalent basis)
approaches unity in pristine or relatively unpolluted trib-
utaries and is zero in the more polluted ones. No values
of this ratio outside this zero to one range were observed
for any of the waters analysed from the main river and
tributaries, thus providing a good level of reliability for
the assumptions adopted in the model. Negative R val-
ues should be obtained if additional sources of sodium
are involved, whereas R values greater than unity are
expected for chloride sources other than NaCl.
Along with waters, bed sediments were also sampled
and analysed for major and selected trace elements of
environmental concern. The evaluation of the metal con-
tent in sediments is important because the largest part
of metals is transported by rivers in particulate forms
(e.g. Gibbs, 1977), and bed sediments represent sinks
and possible secondary sources for metals in the aquatic
environment (Cooper and Thornton, 1994).
Published data on waters and sediments from previ-
ous samplings in 1996 and 1997 (Cortecci et al., 2002;
Dinelli et al., 2005) will be recalled for comparison.
During the present and older sampling campaigns, the
discharges of the main river and its tributaries were low.
HYDROGRAPHY AND LITHOLOGY
The River Arno is the main river of Tuscany and one of
the longest in Italy; it is 241 km long and its catchment
extends from the Apennine ridge to the Tyrrhenian Sea,
over an area of 8228 km2 . The Rivers Elsa and Era are
both left-hand tributaries of Arno (Figure 1a) and join the
main river in the lower part of its catchment. Their stream
networks are dendritic, with high density in correspon-
dence of the clayeysandy terrains. Permeability is low
and erosion is high in the middle and lower parts of the
catchments, due to the predominantly clayey composition
of rocks.
The River Elsa is 72 km long and its catchment cov-
ers a surface of 876 km2 , with a mean elevation of
236 m a.s.l. (16 m at the confluence with the Arno to
671 m at Monte Maggio). Major tributaries are Staggia,
Foci and Agliena (Figure 1a). Apart from recent alluvia,
the main lithotypes (Figure 1b) areally in the catchment
are Pliocene clay and sand, lacustrine, fluvio-lacustrine
and marine deposits, followed in the upper reaches by
Upper Triassic dolomitic limestone (Calcare Cavernoso
Copyright 2006 John Wiley & Sons, Ltd.
Fm.) containing anhydrite breccias (Burano Fm.), and by
Holocene tabular travertines. Other minor to very minor
outcrops are calcareous rocks of the Tuscan Nappe, cal-
careous allochthonous units, Cretaceous pelites and scat-
tered occurrences of Jurassic ophiolite.
The main river cuts basically sandy and clayey terrains
and Holocene travertines, and drains ophiolites and evap-
orites in the uppermost part of the catchment upstream
of Collalto. The Staggia stream flows mainly through
sandy terrains and collects waters draining the Calcare
Cavernoso and travertine deposits. The Foci stream sub-
basin includes sandy and dolomite/anhydrite rocks. The
Agliena stream drains exclusively clays and sands. Rel-
evant to the present study is the occurrence of several
thermal springs, like the CaSO4 springs in the upper
part of the basin near Gracciano (Onci/Le Vene and
San Marziale springs) and in the Gambassi area. Halite
deposits are unknown through the valley; however, saline
cold NaClHCO3 springs occur in the Gambassi area
(Bencini et al., 1977; Peruzzi and Mantelli, 2003), like
the Acqua salsa di Pillo with 16 g l
1 total dissolved
solids (TDS), 5980 mg l
1 Na, 5400 mg l
1 Cl and
5780 mg l
1 HCO3 (Peruzzi and Mantelli, 2003), and in
the Acqua di Luiano with 155 g l
1 TDS, 2989 mg l
1
Na, 2163 mg l
1 Cl and 7991 mg l
1 HCO3 (Bencini
et al., 1977). The Na/Cl ratios (on equivalent basis) in
these waters are 17 and 21 respectively.
The River Era is 57 km long, with a catchment of
595 km2 ; mean elevation is 225 m a.s.l., with a range
of 6 to 675 m. Major tributaries are Sterza, Roglio and
Cascina (Figure 1a). The main lithology (Figure 1b) is
very similar to that of the Elsa catchment. With respect
to the latter, relevant differences are the distribution of
the Pliocene clays in the lower part instead of in the upper
part (and vice versa for the sandy deposits), the occur-
rence in the upper reaches of notable Messinian clays
with gypsum and halite lenses, and small outcrops of
Upper Triassic dolomite/anhydrite rocks. Some Jurassic
ophiolite occurs uppermost in the basin, and Holocene
travertines can be found near Casciana Terme, where
thermal springs of calciumsulphate type are nowadays
flowing out with a temperature of about 36 C.
The Sterza stream and its tributary network drain
basically clayeymarly sediments. In the Roglio and
Cascina basins, clayey and sandy terrains are prevailing,
without any evaporite. Also in the Era basin, thermal
CaSO4 with low Na and Cl (Acqua dei Bagni) and cold
NaHCO3 with high SO4 and Cl (Acqua San Leopoldo)
springs are known at Casciana Terme (Bencini et al.,
1977; Rosetti and Valenti, 1997). In addition, halite
deposits occur in the uppermost part of the basin in the
Volterra area.
For more details, the reader should consult the Carta
Geologica dItalia (Geological Map of Italy, scale
1 : 100 000, sheets 105 (1969), 112 (1965) and 113
(1967)) of the Istituto Geografico Militare of Italy, or the
Interactive Geological Map of Italy (SGN, SSN, ANAS;
Rome).
Hydrol. Process. 21, 120 (2007)
DOI: 10.1002/hyp
 RIVER ARNO CATCHMENT WATER AND SEDIMENT GEOCHEMISTRY 3

Figure 1. Schematic geological map and locations of the sampling stations in the Elsa and Era valleys. The boundaries of the watershed are also
shown. Legend: (1) alluvial deposits; (2) clays, sands and conglomerates of lacustrine and marine environments (Pliocene-Pleistocene); (3) shales;
(4) limestone and sandstone of the Ligurian units; (5) sandstones; (6) limestone and clays of the Ligurian units; (7) dolomite and evaporite rocks;
(8) travertine

ANTHROPOGENIC LOADS Industries mainly deal with wood and furniture

In the Elsa catchment, the major towns are Castelfioren-
tino, Certaldo, Poggibonsi and Colle Val dElsa, with a
total of about 70 000 inhabitants. In the Era catchment,
the major towns are Pontedera, Ponsacco and Volterra,
with a total of about 52 000 inhabitants. In both catch-
ments, several minor urban settlements also occur, each
with 1000 to 5000 inhabitants.
workings, boot and clothing manufactories, glass/crystal
works, metalworking, hide works, textiles, and building
materials. The types and degrees of pollution of these
activities are difficult to assess.
Urban wastewaters from major towns undergo treat-
ment before entering local streams, whereas wastes from
small settlements are not treated. Industrial effluents are
untreated or only partially treated. The soils are mainly

Copyright 2006 John Wiley & Sons, Ltd. Hydrol. Process. 21, 120 (2007)
DOI: 10.1002/hyp
4 G. CORTECCI, E. DINELLI AND T. BOSCHETTI
used for extensive and intensive agricultural activities,
both in the plain and the hills, and for breeding.
ANALYTICAL METHODS
Temperature, pH and electrical conductivity of waters
were measured in the field. Calcium, magnesium, sodium
and potassium were analysed by atomic absorption spec-
trometry, chloride by argentometry and sulphate by tur-
bidimetry, following the methods of Bencini (1977).
Bicarbonate was determined by acidimetric titration. The
reproducibility of these methods is in the range 2 to
5% for cations and 1 to 10% for anions. All but
one of the errors due to imbalance in the ionic budgets
range between 09 and 25%.
Aliquots of waters were sampled for the analysis of the
sulphur isotopic composition of sulphate ions. Sulphate
was separated as barium sulphate, and then thermally
decomposed to yield SO2 for the mass-spectrometric
measurement, basically following the procedure of Holt
and Engelkemeir (1970), i.e. BaSO4 is mixed with
V2 O5 powder in a quartz tube, the mixture is heated to
about 1000 C, and the SO3 from sulphate decomposition
reduced to SO2 by reaction with hot copper turnings.
The oxygen isotope composition of some barium sul-
phate samples was measured by catalytic carbothermic
reduction using a TC/EA device (reactor at 1420 C and
GC column at 70 C) coupled in continuous-flow mode
with a Delta Plus XP mass spectrometer (Boschetti and
Iacumin, 2005). The measured isotopic compositions 34 S
and 18 O are given in per mille, relative to the Canyon
Diablo troilite (CDT) standard and the Vienna Standard
Mean Ocean Water (V-SMOW) respectively. The over-
all precision of the methods, including preparation and
analysis, is about 03 for both sulphur and oxygen.
Separation and concentration of sulphate from relatively
diluted water samples (<70 mg l
1 SO4 2
) was carried
out by ion exchange, using a Dowex 1-X8 (Cl-form,
50100 mesh), followed by elution with 1 M NaCl solu-
tion (see Nehering et al., 1977).
The <80 mesh fraction (siltclay fraction) of active
bed sediments was sampled and analysed for major and
trace elements by X-ray fluorescence spectrometry on
pressed powder pellets, following the matrix correction
methods of Franzini et al. (1972, 1975), Leoni and Saitta
(1976), and Leoni et al. (1982). The estimated precision
and the accuracy for trace-element determinations are
better than 5%, except for those elements at 10 ppm or
lower (when they are 1015%). Loss on ignition (LOI)
was evaluated after overnight heating at 950 C.
PHREEQCI software, version 21000 (Parkhurst and
Appelo, 1999), was adopted to compute aqueous specia-
tion and fluidmineral equilibria, using the thermo.com.
V8.R6 thermodynamic database (full LLNL database).
Computed saturation indexes (SI) are approximate due
to analytical and activity concentration uncertainties, and
then saturation is assumed when SI D 00 02.
Copyright 2006 John Wiley & Sons, Ltd.
RESULTS AND DISCUSSION
The analytical results on waters and sediments are
reported in Tables I and II. They refer to samples col-
lected in July 2000, and will be compared here with
those obtained for samples of June 1996 and June 1997
(Cortecci et al., 2002). The corrections of the major ions
concentration values for the rainwater inputs, follow-
ing the methodology of Grosbois et al. (2000), cannot
be applied here owing to the inadequacy of the avail-
able data. However, these corrections are not influential
here, due to the high concentration values observed in
the waters studied, when compared with the low val-
ues of no-systematic precipitation collected near to Ponte
a Elsa in 1991 and 20012002 (Peruzzi and Mantelli,
2003), i.e. 198 to 552 S cm
1 , 12 to 5 mg l
1 Na,
13 to 62 mg l
1 Ca, 18 to 22 Cl mg l
1 and 23 to
3 mg l
1 SO4 .
Major hydrogeochemistry
This will be discussed separately for the Elsa and Era
basins, and then combined in an isotopic-chemical model
in order to semi-quantify the natural and anthropogenic
contributions of sulphate in the waters. The classification
of the waters is shown in Figure 2. The concentrations
of the major ions along the rivers and in their tributaries
are shown in Figure 3, where the data from the above-
mentioned previous studies are also reported. The spatial
distributions of the 34 SSO4 2
 values in the basins are
shown in Figure 4. All the waters studied are oversatu-
rated with respect to calcite and dolomite, and are under-
saturated with respect to gypsum (Figure 5). The thermal
springs in the Elsa catchment are nearly saturated relative
to calcite, dolomite and gypsum.
Sulphate content and sulphur and oxygen isotope com-
positions. River Elsa catchment: The main river is fairly
diluted in the spring area near to the Collalto locality
(EC D 900 S cm
1 ), with calcium (972 mg l
1 ) and
bicarbonate (4386 mg l
1 ) being by far the prevail-
ing ions in solution. Sulphate is a minor constituent
(331 mg l
1 ), the molar ratio of Ca/SO4 > 7, and the
34 S value is C29, all these features concurring to
exclude dissolution of Upper Triassic evaporite (C146;
Dinelli et al., 1999) as an important source for the
ion. In 1997, a nearly identical sulphate concentra-
tion (294 mg l
1 ) and a sulphur isotopic composition
(C30) were obtained. Downstream, the river water
changes to calciumsulphate type; this is due to the
Botro degli Strulli tributary, which provides high cal-
cium (291 mg l
1 ) and sulphate (737 mg l
1 ) water near
Gracciano. The 34 SSO4 2
 value of C142 in this
stream matches with an almost exclusive evaporitic ori-
gin of the sulphate; this sulphate can be related to rocks
outcropping in the uppermost part of the sub-basin and/or
to mineral springs (like Onci/Le Vene) that discharge
directly in the stream. These springs can provide up to
95% of the water to the River Elsa during low water
conditions (Peruzzi and Mantelli, 2003). Downstream
Hydrol. Process. 21, 120 (2007)
DOI: 10.1002/hyp
 Table I. Major chemistry and sulphur isotope composition of aqueous sulphate in the Rivers Elsa and Era and their tributariesa

Samplea Locality Dist.b T pH Cond. Ions (meq l
1 ) COD 34 SSO4 2
 18 OSO4 2

(km) ( C) (mS cm
1 ) (mg l
1 ) ( vs CDT) ( vs V-SMOW)
Ca2C Mg2C NaC KC tAlk SO4 2
Cl
NHC
4

III Era (r) Pontedera 0 280 80 17 1036 581 341 016 653 1034 320 <0013 4 64 113
III-5 Cascina (t) Ponsacco 7 285 79 24 1880 728 267 014 432 2296 210 0026 3 145
III-4 Roglio (t) Peccioli 21 242 79 12 569 454 252 018 631 419 208 0013 7
62
III-1 Era (r) Peccioli 22 269 81 11 573 385 237 014 449 637 167 <0013 3
113 69
III-3 Sterza (t) La Sterza 28 290 81 06 291 194 144 007 355 138 122 <0013 2
84
III-2 Era (r) Vicarello 40 285 81 13 675 405 309 020 459 651 237 0026 4
63 72

Copyright 2006 John Wiley & Sons, Ltd.

IV Elsa (r) Ponte a Elsa 0 247 79 16 1051 507 311 015 539 1031 256 0013 4 125
IV-4 Agliena (t) Certaldo 24 204 81 18 750 698 430 012 535 1057 395 0013 4
138
IV-3 Elsa (r) Ulignano 29 231 82 17 1166 492 234 012 565 1174 195 0077 2 132
IV-5 Foci (t) Poggibonsi 36 197 80 12 784 196 288 014 655 256 305 0039 2 07 76
IV-1 Staggia (t) Castellina Scalo 50 228 83 13 564 162 563 025 521 153 501 0039 4 60 74
IV-6 Botro degli Strulli (t) Gracciano 62 211 75 19 1452 63 142 006 562 1536 120 <0013 1 142
IV-2 Elsa (r) Collalto 69 177 81 09 486 339 130 003 719 069 128 0051 2 29

a (r): main river; (t): tributary.

b Distance is from the confluence of the Rivers Elsa and Era into the River Arno.

Table II. Major and trace elements abundances in bed sediments from the main Rivers Elsa and Era and their tributaries

Samplea Locality Dist.b SiO2 TiO2 Al2 O3 Fe2 O3 MnO MgO CaO Na2 O K2 O P2 O5 LOI Cr Ni Cu Zn Pb
(km) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (ppm) (ppm) (ppm) (ppm) (ppm)

III Era (r) Pontedera 0 4693 063 1435 559 024 343 1045 064 202 017 1556 167 109 45 97 21
III-4 Roglio (t) Peccioli 21 4770 078 1853 712 011 333 530 034 261 015 1401 214 115 52 118 23
III-1 Era (r) Peccioli 22 3236 042 1168 428 013 568 1952 027 139 009 2418 169 156 41 78 15
III-3 Sterza (t) Sterza 28 4644 061 1293 499 010 312 1337 053 180 011 1599 121 82 25 80 22
III-2 Era (r) Vicarello 40 3385 043 911 349 011 264 2720 050 125 013 2128 99 60 30 61 10
RIVER ARNO CATCHMENT WATER AND SEDIMENT GEOCHEMISTRY

IV Elsa (r) Ponte a Elsa 0 4797 064 1429 553 011 297 1117 050 187 020 1475 148 91 65 111 28
IV-4 Agliena (t) Certaldo 24 4939 061 1307 502 012 271 1181 055 160 015 1496 130 81 59 90 52
IV-3 Elsa (r) Ulignano 29 3868 055 1280 512 014 252 1727 023 157 024 2088 139 87 64 112 23
IV-5 Foci (t) Poggibonsi 36 4146 055 1183 438 013 237 1671 037 143 033 2044 173 102 67 109 40
IV-1 Staggia (t) Castellina Scalo 50 4517 062 1420 589 011 278 1201 032 178 017 1693 143 87 64 109 25
IV-6 Botro degli Strulli (t) Gracciano 62 3932 057 1251 491 009 291 1888 025 141 015 1900 217 137 37 143 95
IV-2 Elsa (r) Collalto 69 4119 051 1226 477 015 434 1307 026 109 020 2217 300 237 34 70 24

a (r): main river; (t): tributary.

b Distance is from the confluence of the Rivers Elsa and Era into the River Arno.

DOI: 10.1002/hyp
Hydrol. Process. 21, 120 (2007)
5
6 G. CORTECCI, E. DINELLI AND T. BOSCHETTI

Figure 2. Triangular diagrams showing the relative proportions of major cations and anions in the Rivers Elsa and Era and their tributaries. The
grey RDB path describes the chemical evolution of the thermal springs San Marziale (sm) and Onci/Le Vene (oc) from the Elsa drainage basin
(data from Bencini et al. (1977) and Peruzzi and Mantelli (2003)) in a carbonate-evaporite aquifer, involving dedolomitization (R to D) and halite
dissolution (D to B) as in Hanshaw and Back (1979). Arrows depict possible mixings and compositional evolutions of the stream samples. Stream
samples are identified according to Table I

of Gracciano, the Staggia and Foci streams enter the
main river. The first, near to Castellina Scalo, is water
of sodium (129 mg l
1 )bicarbonate (318 mg l
1 ) type,
with notable amounts of calcium and chloride. Sulphate
is subordinate (73 mg l
1 ), with a relatively low 34 S
value of C60, in spite of the fact that the stream
flows in the upper reaches through a passage cut in the
Calcare Cavernoso. Likely, the 34 S value identifies a
mixture of evaporite sulphur and biogenic reduced sul-
phur (pyrite, mineralization of organic matter), the latter
from clayey terrains, including lignite tails from mining
workings on the right hydrographic side. The second is
a calciumbicarbonate stream on the left bank, and was
sampled at its confluence in the Elsa below Poggibonsi.
Also in this stream, the observed 34 S value of C07 of
the dissolved sulphate (123 mg l
1 ) may be interpreted as
representing a mixture of biogenic sulphur trapped in the
sandy terrains drained out and evaporite sulphate from the
Calcare Cavernoso outcropping in the uppermost part of
the basin. Running down to Ulignano, the main river pre-
serves the calciumsulphate composition, with sulphate
concentration (564 mg l
1 ) and sulphur isotopic compo-
sition (C132) manifestly controlled by inputs from the
Botro degli Strulli; highly consistent data were found in
1997 for both sulphate concentration (5203 mg l
1 ) and
sulphur isotopes (C135). Flowing down to Certaldo,

Copyright 2006 John Wiley & Sons, Ltd. Hydrol. Process. 21, 120 (2007)
DOI: 10.1002/hyp
 RIVER ARNO CATCHMENT WATER AND SEDIMENT GEOCHEMISTRY 7

Figure 3. Spatial distributions of major dissolved substances in stream waters from the Elsa and Era catchments. Bold type circle: main river; normal
circle: tributaries

Elsa receives the Agliena tributary, which is rich in
sulphate (507 mg l
1 ) and distinguishes itself by the
quite low sulphur isotope composition (34 S D
138).
The high concentration and the low isotopic composi-
tion apparently contradict each other, as sulphate-rich
water is expected from dissolution of evaporite, which
is absent in the drainage basin of the Agliena stream.
Therefore, one should admit that abundant isotopically
light sulphide material is present in the clayeysandy
terrains drained by the stream or that sulphate in solu-
tion is anthropogenic. Going downstream towards Ponte
a Elsa, sulphate in the main river undergoes some dilu-
tion, while decreasing a little its 34 S value, due to the
influence of some tributaries, like the Casciani stream,
which conveys spring water from the Gambassi Terme
area and enters the River Elsa on the left bank after
the Agliena tributary confluence below Certaldo. In the
Casciani stream, Ca and SO4 may derive largely from

Copyright 2006 John Wiley & Sons, Ltd. Hydrol. Process. 21, 120 (2007)
DOI: 10.1002/hyp
8 G. CORTECCI, E. DINELLI AND T. BOSCHETTI
Figure 4. Sulphur isotope composition 34 S of aqueous sulphate in the studied stream waters from the Elsa and Era catchments, and spatial distribution
of the data. Bold type circle: main river; normal circle: tributaries
evaporitic sediments (Peruzzi and Mantelli, 2003), pos-
sibly somewhat enriched in 34 S. At Ponte a Elsa, the
[SO4 2
] and the 34 SSO4 2
 values remain rather con-
stant in 1996, 1997 and 2000, with ranges of 433 to
495 mg l
1 and C116 to C129 respectively.
Apparently, the nearly identical 18 OSO4 2
 values
of C75 01 in the Staggia and Foci streams conflict
with the interpretation given above on the origin of the
sulphate in solution, if one admits a uniform 18 O sig-
nature for the evaporitic fraction, which may be close to
C11 in northern Tuscany (Boschetti et al., 2005). This
discrepancy with the 34 SSO4 2
 values can be solved
by assuming that the average 34 S content of reduced sul-
phur in the Staggia basin terrains is higher than in the
Foci basin. The alternative, by which the supergene sul-
phate fraction in the Staggia can be considerably richer
in 18 O than in the Foci stream, appears to be unlikely, as
similar ambient water 18 O and sulphide oxidation mech-
anisms are expected in both sub-basins. A review on the
roles of the ambient water 18 O and sulphide oxidation
mechanism to control the 18 O of product sulphate can
be found in Van Stempvoort and Krouse (1994).
River Era catchment: In the upper part close to
Vicarello di Volterra, the River Era water is of cal-
cium (135 mg l
1 )sulphate (3125 mg l
1 ) type, with
a molar ratio of Ca/SO4 D 104 and sulphate 34 S and
18 O values of
63 and C72 respectively. As
the drained waters can interact with marine Messinian
clays that possibly contain gypsum lenses, a mixture of
isotopically light supergene sulphate and gypsum sul-
phate may be concluded from the low values. In fact,
34 S values of C19 to C20 (selenitic gypsum from
Copyright 2006 John Wiley & Sons, Ltd.
the Era Viva locality in the upper part of the catch-
ment; Dinelli et al., 1999) and 18 O of C12 to C16
(gypsum from a clayey deposit from central Tuscany;
Cortecci, 1973) can be assigned to the evaporite frac-
tion. If correct, Ca from an additional source other than
gypsum should be admitted for the river water, thus jus-
tifying the observed calcium to sulphate ratio close to
unity.
Downstream of Vicarello, the main river receives
the calciumbicarbonate contribution of the Sterza
stream, which is relatively low in sulphate (662 mg l
1 )
and shows a 34 SSO4 2
 value of
84. The
drainage area of the stream consists mainly of
MiocenePliocene lacustrine (lignitiferous) and marine
clays and conglomerates. The 34 S depletion points to a
supergene origin of the sulphate via oxidation of biogenic
reduced sulphur. At Peccioli, calcium (1146 mg l
1 )
and sulphate (3058 mg l
1 ) are unchanged in the Era
water, as substantially shown also by the sulphate 34 S
(
113) and 18 O (C69) values, thus emphasizing
the minor role of the Staggia and other middle-
way tributaries. Downstream, the main tributaries are
Roglio and Cascina. The Roglio drainage system,
though once again involving Pliocene marine to brackish
clayey and sandy sediments, is much wider than
that of the Sterza. The water is rich in calcium
(1138 mg l
1 ) and bicarbonate (3849 mg l
1 ), with
notable sulphate (2011 mg l
1 ). The 34 SSO4 2
 value
of
62 is compatible with the signature expected for
waters draining the sediments mentioned. The Cascina
tributary behaves quite differently. It is a high calcium
(377 mg l
1 )sulphate (1104 mg l
1 ) stream, with a
molar ratio of Ca/SO4 D 086. In keeping with the
high sulphate concentration, the 34 SSO4 2
 value of
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 RIVER ARNO CATCHMENT WATER AND SEDIMENT GEOCHEMISTRY
Figure 5. Saturation indexes (SI) of stream waters studied with respect
to calcite, dolomite and gypsum, and comparison with SI values of ther-
mal springs San Marziale (sm) and Onci/Le Vene (oc) from the Elsa
valley (filled circles; Bencini et al., 1977; Rosetti and Valenti, 1997).
The grey field shows equilibrium between the mineral and the solu-
tion (SI D 00 02). The arrow depicts CO2 degassing from the ther-
mal springs in the interval between log PCO2 D
12 and the average
log PCO2 D
26 value in the Rivers Elsa and Era. The evolution of the
SI upon mixing between degassed thermal water and sample III-3 is
described by . The correspondence between the model and the samples
is quite up to the mark, probably due to re-equilibration of the mix-
ture with carbonate minerals. Model calculations are based on PHREE-
QCI 21000 software (Parkhurst and Appelo, 1999). For symbols, see
Figure 2
C145 clearly denotes an Upper Triassic origin of
the sulphate. The Calcare Cavernoso formation does not
outcrop in the drainage basin of the Cascina stream;
however, the sulphate in the Cascina stream very likely
derives from the Calcare Cavernoso via the calcium
(671 mg l
1 )sulphate (1680 mg l
1 ) thermal spring
system (35 C) exploited in the Casciana Terme spa, and
for which a 34 SSO4 2
 value of C154 was measured
(Grassi and Cortecci, 2005). This water likely feeds
the small Rio Caldana stream, which borders Casciana
Copyright 2006 John Wiley & Sons, Ltd.
9
Terme and enters the Cascina stream just below the
country town. The Era joins the River Arno at Pontedera,
its water being of calcium (208 mg l
1 )sulphate
(496 mg l
1 ) type and displaying a 34 SSO4 2
 of
C64. Both the chemical and isotopic figures are
intermediate with respect to the various upstream
contributions. The 34 SSO4 2
 value in the River Era
at Pontedera varied in time, changing from
85 in
1996 (2238 mg l
1 SO4 2
; 690 mg l
1 TDS) to C59
in 1997 (4165 mg l
1 SO4 2
; 970 mg l
1 TDS), to
C64 in 2000 (497 mg l
1 SO4 2
; 1097 mg l
1
TDS). The variations relate positively with sulphate
concentration and total dissolved salts, thus suggesting
that the contribution of the Cascina tributary plays a
major role in determining the Eras chemical and isotopic
features at the mouth. The contribution was low in 1996
and notable in 1997 and 2000, as supported also by the
18 OSO4 2
 value of C113 in the water from the last
sampling.
Variations of calcium, sulphate, sodium and chloride
along the Rivers Elsa and Era. Calcium and sulphate
vary in a nearly synchronous way along both rivers.
Near to the confluence at Ponte a Elsa, the River Elsa
shows Ca/SO4 molar ratios very close to unit, i.e. 087
in 1996, 100 in 1997 and 100 in 2000; these ratios
and the 34 SSO4 2
 values strongly support dissolution
of anhydrite and/or gypsum as the principal source
of these ions in the Elsa catchment. The downstream
concentration trends are mainly controlled by the Botro
degli Strulli in the upper part of the course, and by
the Agliena in the lower part. In the River Era at
Pontedera, the Ca/SO4 molar ratio is also close to unit
(084 in 1996, 090 in 1997 and 102 in 2000), but the
34 SSO4 2
 values exclude a dissolution of evaporite
as the major source of sulphate in the catchment. The
observed concentration trends along the main river match
the composition of the tributaries.
Sodium and chloride also vary synchronously along
the rivers. Their concentrations increase progressively
downstream in the Elsa from 299 to 715 mg l
1 Na
and 448 to 896 mg l
1 Cl. These variations are clearly
controlled by the lateral streams. In the Era, sodium and
chloride vary irregularly, and no relation exists between
the main river and the Cascina stream; the former pos-
sibly receives NaCl from an additional source near to
the confluence point. The contribution from albite and
plagioclases should be very minor to negligible in the
catchments studied.
Calciumsulphate and sodiumchloride relationships:
The relationships are shown in Figures 6 and 7, where
previous samples are also plotted. In the CaSO4 plot,
waters from the Elsa catchment with calcium contents
higher than 200 mg l
1 (Botro degli Strulli stream and
River Elsa at Ulignano and Ponte a Elsa) approach well
the equality line, in keeping with an almost exclusive
evaporite source of both ions. In the Ca/SO4 > 1 sector,
calcium in the bicarbonate waters from the River Elsa
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10 G. CORTECCI, E. DINELLI AND T. BOSCHETTI

Figure 6. Ca versus SO4 plot for the rivers and tributaries studied. The data are compared with those of San Marziale (sm) and Onci/Le Vene (oc)
thermal springs (filled circles; Bencini et al., 1977; Rosetti and Valenti, 1997) and precipitation (Peruzzi and Mantelli, 2003) in the Elsa catchment,
and water samples from the River Arno drainage basin (Cortecci et al., 2002)

at Collalto and the Staggia and Foci streams can have
been provided by additional sources that include disso-
lution of carbonate (omnipresent), as well as probably
hydrolysis of igneous plagioclase in the Collalto area.
Anthropogenic carbonate sewages cannot be excluded.
The Ca/SO4 in the calciumsulphate Agliena stream is
lower than unity, possibly due to a mostly supergene
origin of sulphate or to the addition of anthropogenic
sulphate other than CaSO4 . The samples of 1996 and
1997 gave nearly the same results as those of 2000.
Waters from the Era catchment fit a straight line between
diluted water (Sterza stream) and salty water (Cascina

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 RIVER ARNO CATCHMENT WATER AND SEDIMENT GEOCHEMISTRY 11

Figure 7. Na versus Cl plot for the rivers and tributaries studied. The data are compared with those of San Marziale (sm) and Onci/Le Vene (oc)
thermal springs (filled circles; Bencini et al., 1977; Rosetti and Valenti, 1997) and precipitation (Peruzzi and Mantelli, 2003) in the Elsa catchment,
and water samples from the River Arno drainage basin (Cortecci et al., 2002)

stream). The relation is likely misleading for the Roglio
stream, as evaporite and thermal springs are unknown in
its basin. The Ca/SO4 ratio in the Cascina stream is sig-
nificantly lower than unity, this figure possibly indicating
that the feeding spring water dissolved evaporite MgSO4
salt along with CaSO4 during its circulation at depth.
Magnesium in this water is high and it is not balanced
by bicarbonate.
The data points in the NaCl plot fall close to
the equality line, thus suggesting that both ions derive

Copyright 2006 John Wiley & Sons, Ltd. Hydrol. Process. 21, 120 (2007)
DOI: 10.1002/hyp
12 G. CORTECCI, E. DINELLI AND T. BOSCHETTI
basically from the dissolution of NaCl (natural and
anthropogenic), or in the Na/Cl > 1 sector, which is as
to be expected if additional sources are involved with
sodium prevailing on chloride. In addition, Na and Cl
in the Elsa and Era drainage network have concentra-
tions higher to much higher than expected for mixtures
between rainwater and thermal spring water, this support-
ing that dissolution of halite (in the Era drainage basin)
and cold NaCl springs (in the Elsa and Era catchments)
should play a substantial role in determining the chemical
composition of the waters.
Calcium and total alkalinity relationships: The waters
studied appear to be characterized by high alkalinity
(mostly bicarbonate), with values ranging from 318 to
439 mg l
1 (mean 357 mg l
1 ) in the Elsa basin and
217 to 398 mg l
1 (mean 303 mg l
1 ) in the Era basin.
The highest alkalinity value is found in the River Elsa
at Collalto, where water interacts with ophiolites. Waters
from both basins are oversaturated with respect to cal-
cite and dolomite (Figure 5), and their computed log PCO2
values range between
28 and
21. It may be con-
cluded that the waters investigated are influenced by
geothermal(?) CO2 , indirectly due to mixing with ground-
water (i.e. Acqua salsa di Pillo spring at Gambassi
Terme in the Elsa valley: 138 C, 5780 mg l
1 HCO3
,
1800 mg l
1 SO4 2
, <50 g H2 S; Peruzzi and Mantelli,
2003) or directly by gas emanations. The latter are
widespread in the Gambassi area, a spectacular exam-
ple being represented by the so-called Bollori at about
4 km to the south of the village. The gas efflux is con-
stituted by CO2 and some H2 S, and irregularly gas and
water are emitted together, giving rise to warm springs
(2022 C, 29 g l
1 TDS; Rosetti and Valenti, 1997).
The Bollori springs affect the Casciani stream (Rosetti
and Valenti, 1997), thus influencing its chemical and iso-
topic compositions somewhat (and possibly the River Era
downstream of Certaldo). Establishing the importance
of the H2 S emissions for the sulphur isotope budget is
problematic, but it should be minor to negligible. CO2
and H2 S emissions are also known in the Era valley at
Chiecinella (Commune of Palaia); they bubble from the
bed of the homonymous stream, which, however, does
not affect the River Era drainage basin.
In Figure 8, a manifest relation can be observed
between thermal springs (Onci/Le Vene and San
Marziale) and streams of the Elsa valley, thus supporting
the important role of the former in feeding the surface
water network. In particular, it is supported that the Botro
degli Strulli stream (sample IV-6) is mainly fed by the
nearby Onci springs. The same can be concluded for the
Cascina stream (sample III-5) in the Era valley, relating
Ca and SO4 to the thermal spring system of Casciana
Terme. Many samples show a Ca excess with respect
to calcite dissolution, possibly related to the mixing
with thermal spring water. Mixing of different water
types induces reactions that lead to a water composition
that is different from the conservative mixing. In detail,
owing to the common ion effect, mixing of water in
Copyright 2006 John Wiley & Sons, Ltd.
equilibrium with gypsum (thermal springs) with water in
equilibrium with calcite (streams) causes oversaturation
(and precipitation) of carbonate (Figure 5). This process
may be enhanced by CO2 degassing of thermal springs
and by the high atmospheric temperature of the sampling
season (on average 24 C).
Modelling of the natural and anthropogenic contribu-
tions of aqueous sulphate: As shown in Figure 9, positive
34 SSO4 2
 versus SO4 2
curved trends are obtained
for the main rivers and tributaries in the Elsa and Era
catchments, assuming a binary mixing between natural
components represented by supergene sulphate from sul-
phide oxidation with 34 S of
15 and Triassic (Elsa
catchment) or mixed TriassicMiocene (Era catchment)
sulphate with 34 S between C15 and C22. Sulphate
from the Agliena tributary (Elsa catchment) is excluded
from the mixing model, as its 34 S[SO4 2
] coupling
looks anomalous, suggesting interaction of the water with
sediments particularly rich in biogenic sulphide. This sub-
basin is distinguished from the others by its dominance of
marine to brackish clayey sediments instead of dominant
sandy sediments.
The 34 S[SO4 2
] relations do not allow one to eval-
uate the role of anthropogenic contributions, as the mea-
sured 34 S values of aqueous sulphate fall in the range
found for pollutant sulphur-bearing compounds like urban
detergents (Vit`oria et al., 2004), fertilizers (Mizota and
Sasaki, 1996; Robinson and Bottrell, 1997; Moncaster
et al., 2000; Vit`oria et al., 2004) and industrial sludges
(Longinelli and Cortecci, 1970; Cortecci et al., 2002).
Instead, the human influence may be approximated by
applying the Cortecci et al. (2002) 34 SSO4 2
 versus
R (with R D [SO4 2
C Cl

NaC ]/SO4 2
 model, by
which sulphate is anthropogenic when R D 0, and natural
when R D 1. The results are shown in Figure 10, which
also includes older data. The main features are:
1. All data points are included with a mixing triangle,
with end members represented by anthropogenic sul-
phate having a 34 S value close to 0, and natural
sulphate constituted by evaporite (34 S C15) and
reduced sulphur (34 S as low as
15) or their mix-
tures. The isotopic signature of the anthropogenic sul-
phate corresponds to the lower limit of the range of
values inferred by Cortecci et al. (2002) for sulphate
pollutants through the whole River Arno catchment.
2. In all but one of the tributary streams the proportion
of natural sulphate should be between 85% (Sterza
stream) and 100% (Foci stream). The only exception is
with the Staggia stream (IV-1 samples), which shows
natural sulphate proportions of 52% in 1997 and 59%
in 2000; these high proportions of anthropogenic sul-
phate are supported by the high Na and Cl concentra-
tion values.
3. Natural sulphate proportions in the range 89 to 100%
are calculated for all but one water sample from the
Rivers Elsa and Era, sometimes depending on the
sampling point along the course.
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 RIVER ARNO CATCHMENT WATER AND SEDIMENT GEOCHEMISTRY 13

Figure 8. Ca versus tAlk (total alkalinity) relationship for the waters studied, compared to the Onci/Le Vene (oc) and San Marziale (sm) thermal
springs in the Elsa valley (Bencini et al., 1977; Rosetti and Valenti, 1997), and waters from the River Arno drainage basin (Cortecci et al., 2002).
Data are compared with stoichiometry of calcite and dolomite dissolution reactions. Solid lines identify mixing phenomena between stream water
and thermal water

4. The results are quite different for the River Elsa in the
Collalto locality (IV-2 samples), where largely incon-
sistent proportions are obtained in 1997 (34% natural
sulphate; 34 S C30) and 2000 (97% natural sul-
phate; 34 S C29). Possibly, natural and pollutant
sulphates have close isotopic compositions in the area
of interest.
5. From the model used, the sulphate sources should have
the following isotopic signature: dissolution of evapor-
ite (34 S C145 or higher), oxidation of sedimen-
tary sulphide (34 S as low as
15), and pollutant sul-
phate (34 S
2 to C3, at the single basin scale).
6. The ternary mixing plot relies heavily on a few data
points from the Elsa catchment to estimate the anthro-
pogenic end-member, i.e. the contribution of this kind
of sulphate in the surface waters from both catchments
is minor, and then the observed full range of sulphur
isotope data can be related basically to the heterogene-
ity of the natural sources.
Chemical composition of bed sediments
The chemical composition of the sediments is pre-
sented in Table II, and refers to major elements and
selected trace metals distribution in the active bed load
sediments of the main two rivers and tributaries sampled
in July 2000. In the discussion, data from an older sur-
vey in the area will also be considered (Dinelli et al.,
2005). Given the geology of the two catchments, the
composition of the stream sediments will be compared
with data on local fine-grained clayey Pliocene sedi-
ments (Dinelli E., unpublished) that were sampled from
a borehole near Volterra. This type of rock covers about
30% of the surface of the two catchments. For the same
reason, reference will also be made to the average lime-
stone composition from Turekian and Wedephol (1961),
to account for another important lithotype in the areas
studied.
Major element composition. From the major element
data it appears that the bulk chemistry is strongly con-
trolled by the mixing between carbonate and clayey sed-
iments, as confirmed by the negative correlation between
CaO and Al2 O3 in Figure 11a. Almost all the samples
fit the mixing line connecting the limestone end-member
to the field of Pliocene clays. Only sample III-4 has a
higher Al2 O3 concentration, and is separated in all the

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14 G. CORTECCI, E. DINELLI AND T. BOSCHETTI

Figure 9. 34 S versus SO4 2
mixing curves between sulphate from sulphide oxidation and dissolution of Triassic evaporite (Elsa catchment) or
combined Triassic and Miocene evaporite (Era catchment). The models are compared with those involving dissolution of evaporite by rainwater
(dashed curves). Crosses and dotted lines depict mixing proportions. Data on rainwater (shown by a drop) are from Cortecci and Longinelli (1970),
Cortecci (1976) and Panettiere et al. (2000)

diagrams; it comes from the Roglio stream, which drains
nearly exclusively clayeysandy rocks. Compared with
previous samples, those from the present survey seem
to be richer in Al2 O3 , reflecting a higher concentra-
tion of the fine-grained fraction in the sediments due to
lower flow conditions. On the contrary, the older sed-
iments tend to be richer in CaO, which is associated
with the coarse-grained fraction. In the Elsa sub-basin,
the highest concentrations are observed in two tributaries
(Botro degli Strulli, IV-6, 189% CaO; Foci, IV-5, 167%
CaO), in keeping with the presence of Calcare Caver-
noso, organogenic breccia and travertine in their drainage
system. These high concentrations influence the River
Elsa in the downstream station Ulignano (IV-3, 173%),
whereas CaO is relatively low (between 11 and 13%)
in the other stations of the main river and in the other
tributaries. In the Era sub-basin, the highest CaO concen-
tration is observed at Vicarello (III-2, 272%), followed
by a progressive decrease downstream to the confluence.
The lowest CaO concentration of all the data set is shown
by the Roglio tributary (III-4, 53%).
Elements that are generally enriched in the fine-grained
sediment fraction, such as Fe2 O3 and K2 O (Figure 11b
and c), display a positive correlation with Al2 O3 , and

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 RIVER ARNO CATCHMENT WATER AND SEDIMENT GEOCHEMISTRY
Figure 10. 34 S versus R (fraction of natural sulphate) from the present studys water samples and previous studies on the Rivers Elsa and Era from
Cortecci et al. (2002). See text for details on the model
their ratios are comparable to older samples, testifying
for a common linking. Among them, Fe2 O3 shows a
narrow scatter of values, with the only ones from the
Roglio (III-4, 71% Fe2 O3 ) and from the Era at Vicarello
(III-2, 35% Fe2 O3 ) resulting as outliers. K2 O is slightly
more scattered, with maximum and minimum in the same
two stations. MgO displays a rather different distribution:
the majority of the samples are positively correlated to
Al2 O3 , pointing to a MgO-poor carbonate end-member
that contrasts with the high value in the Turekian and
Wedephol (1961) compilation. The deviation of some
points (River Elsa at Collalto, IV-2, 43% MgO; River
Era at Peccioli, III-1, 57% MgO) towards high MgO
and their negative correlation with Al2 O3 can be related
to the presence of ophiolites upstream of these two sites,
rather than to the occurrence of magnesium-limestone or
dolomite. Sediments from these two sites also displayed
the same MgO signal in the previous surveys, although
with slightly different concentration values.
Trace element composition. The trace elements dis-
cussed in this section (Zn, Cu, Pb, Cr, Ni) are those of
possible environmental concern, because they are widely
used in many human activities, and then their natural
distribution could be substantially altered (Cooper and
Thornton, 1994). As previously discussed, we will use
the local Pliocene clays to evaluate possible alterations
of natural concentrations, given that all elements under
Copyright 2006 John Wiley & Sons, Ltd.
15
question tend to be concentrated in the fine-grained frac-
tion of sediments (Horowitz, 1991), and mixing with
limestone leads to dilution.
Zinc displays some scattering (Figure 12a), with
concentrations significantly different from those of the
Pliocene clays only in the Botro degli Strulli (IV-6,
143 ppm Zn), but deviating points are also shown in
other stations within the Elsa catchment. Previous data
recorded a significant anomaly in the River Era at
Pontedera, which has disappeared in this survey, whereas
in the Elsa catchment the concentrations were nearly
preserved.
Copper concentrations are distinctly higher than for
the reference rocks in many stations of the River Elsa
(Figure 12b), and in particular values near or higher than
60 ppm are observed in the Staggia (IV-1), Foci (IV-5)
and Agliena (IV-4) tributaries and along the River Elsa
at Ulignano (IV-3) and at Ponte a Elsa (IV). This testifies
for a large and widespread anthropogenic contribution of
this element in the Elsa sub-basin, which does not occur
in the Era sub-basin, where concentrations are lower and
more similar to the reference values or to the expected
values after dilution with carbonate. As for zinc, the
copper concentration in the River Era at Pontedera was
high in the past, but it has decreased markedly in this
survey.
Lead shows a more strict correlation with Al2 O3 ,
with only three Elsa tributaries clearly deviating from
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16 G. CORTECCI, E. DINELLI AND T. BOSCHETTI

Figure 11. Relations between Al2 O3 and CaO (a), Fe2 O3 (b), K2 O (c), and MgO (d), compared with a mixing model involving local clayey sediments
(Dinelli E., unpublished) and average limestone from worldwide occurrences (Turekian and Wedephol, 1961)

a generally positive correlation (Figure 12c). These are
the Botro degli Strulli (IV-6), where Pb concentration
reaches 95 ppm, a value at least four times higher than
expected for an uncontaminated sediment, and Agliena
(IV-4, 52 ppm Pb) and Foci (IV-5, 40 ppm Pb). High
values like these were not observed with the old data,
although it is to be noted that these creeks were not
investigated in the past.
Chromium and nickel concentrations are less scattered
than the reference values (Figure 12d and e); only sta-
tion IV-2 for Cr and IV-2 and IV-6 and III-1 for Ni
are separated from the rest of the samples. The devi-
ating samples are also enriched in MgO; therefore, a
common origin of these elements from the weathering of
ophiolitic rocks is likely, rather than from anthropogenic
activities.
Multivariate analysis and relations between sediment
and water. Principal component analysis (PCA) is
applied to sediment (20 samples and 13 variables) and
water (20 samples and eight variables) matrix datasets,
which also include 1996 and 1997 samples both for
sediments (Dinelli et al., 2005) and waters (Cortecci
et al., 2002). Owing to the low number of samples, the
KeiserMeyerOlkin sampling adequacy test is 05 (i.e.
the variance is distributed on too many components), but
the Bartlett sphericity test does not preclude the analysis,
as it provides a good correlation between variables. The
component extraction was performed by the covariance
matrix method; therefore, a high percentage of variance
(92% for sediments and 72% for waters) was allocated
on only two components. In the iterative multivariate
treatment of the data on waters, the best results (high

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 RIVER ARNO CATCHMENT WATER AND SEDIMENT GEOCHEMISTRY 17

Figure 12. Relations between Al2 O3 and Zn (a), Cu (b), Pb (c), Cr (d) and Ni (e), compared with a mixing model involving local clayey sediments
(Dinelli E., unpublished) and average limestone from worldwide occurrences (Turekian and Wedephol, 1961)

sampling adequacy plus high percentage of variance on
two components) are obtained by excluding the distance
as a variable from the data matrix. The PC1 and PC2
factor loadings on variables and the factor scores on
samples are shown in Figure 13 for sediments and
Figure 14 for waters.
In the sediment plot, many samples show a restricted
distribution of variables, which corresponds to a compo-
sition made up by substantial FeAloxidehydroxide
colloids; therefore, trends due to hidden variables could
be obliterated. Moreover, some clusters are manifest:
(1) positive correlation between distance from mouth,
MgO, Cr and Ni due to dismantling of ophiolites in the
upper reaches of the catchments; (2) negative correla-
tion of CaO with siliciclastic rocks (SiO2 , K2 O, Na2 O)
and ophiolites (MgO, Cr, Ni, distance from mouth) in
the River Era from Vicarello to Peccioli (III-2, III-1),
as expected due to the downstream transition from car-
bonate/sulphate to clayey sediments. Sr (not reported in
Table II) was not introduced in the data matrix in order
to decrease the redundancy; however, it shows a very
good positive correlation with CaO. The grouping of
analysed variables from PCA was confirmed by the hier-
archical cluster analysis (HCA, not shown) carried out
using Wards method for linkage and the Euclidean dis-
tance for similarity/dissimilarity measurements. It should

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18 G. CORTECCI, E. DINELLI AND T. BOSCHETTI

Figure 13. PCA plots of the sediment data matrix: (a) factor loadings on variables; (b) factor scores on samples. Calculation performed using SPSS
13 software (Norusis, 2005). Italic text indicates key data distributions. Symbols as in Figure 2

be mentioned that, in the HCA treatment, the Pb, Cu, Zn
clustering was found to be better.
In the water PCA plot, variables appear to be well
separated, i.e. PC1 corresponds to carbonate/sulphate dis-
solution and PC2 to chloride (natural and anthropogenic)
dissolution. For the sake of brevity, manifest features
are not discussed. Instead, the sample grouping on the
negative side of the PC1 axis deserves some comments.
It denotes an inverse correlation between sulphate (and
calcium) and the 34 S variable, probably because an
appreciable fraction of sulphate in solution derives from
sulphide oxidation. The group includes the IV2/97 sam-
ple, which in Figure 10 appears to contain a substantial
proportion of anthropogenic sulphate, and waters IV-2,
III-3 and III-1, for which the natural sulphate proportion
should be by far prevailing. Therefore, the PCA statistics
cannot distinguish the human contribution from the nat-
ural background, as the total number of variables (data
matrix plus hidden variables) plays a role in determin-
ing the distribution of the samples in the plot. In fact,
the observed allocation of the above samples in the PCA
plot is controlled by their low salinity (plus distance as
hidden variable) values.
Satisfactory chemical relations between sediments and
waters are restricted to Cr and Ni, which show positive
trends (not shown) with total alkalinity, thus suggesting
that the alteration of ophiolite fragments by carbonic acid
is a factor controlling the carbonate load in the stream
waters.

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DOI: 10.1002/hyp
 RIVER ARNO CATCHMENT WATER AND SEDIMENT GEOCHEMISTRY 19

Figure 14. PCA plots of the water data matrix: (a) factor loadings on variables; (b) factor scores on samples. Calculation performed using SPSS 13
software (Norusis, 2005). Italic text indicates key data distributions. Symbols as in Figure 2

CONCLUSIONS 4. Combining the 34 SSO4  parameter with the

The main conclusions from the hydrochemical results are:
1. Na and Cl increase nearly progressively from spring
to mouth along the main Rivers Elsa and Era, this
supporting an increasing anthropogenic contribution
following the human load.
2. In the tributary streams with prevailing Ca and SO4 ,
both species derive from dissolution of Upper Triassic
(Elsa basin) or Upper Triassic and Messinian (Era
basin) evaporites.
3. In CaHCO3 waters, substantial SO4 in solution orig-
inates from oxidation of reduced sulphur disseminated
in the leached rocks.
SO4 ClNa chemical composition, the contribution of
pollutant sulphate is estimated to be not higher than
10% in most waters in the basins studied considering
the samples from 2000 and the previous ones of 1996
and 1997. The Staggia stream (Elsa basin) shows the
highest proportion of pollutant sulphate (41%) and the
highest Na (129 mg l
1 ) and Cl (175 mg l
1 ) concen-
tration values.
5. As from the isotopic-chemical model, the isotopic
signature of the sulphate sources should be 34 S
C145 or higher (Triassic and Miocene evaporites),
34 S as low as
15 (oxidation of reduced sulphur in
the country rocks), and 34 S in the range
2 to C3
(pollutant sulphate).

Copyright 2006 John Wiley & Sons, Ltd. Hydrol. Process. 21, 120 (2007)
DOI: 10.1002/hyp
20 G. CORTECCI, E. DINELLI AND T. BOSCHETTI
Pollution by heavy metals in the fluvial sediments
studied does not reach high levels. However, some
considerations can be inferred: (1) the sediments
throughout the Elsa drainage basin would seem to be
more contaminated than those of the Era drainage basin;
(2) compared with local fine-grained rocks, copper is
more frequently anomalous, whereas lead and zinc show
only occasional anomalies; (3) chromium and nickel
locally display high concentrations, but these can be
attributed to the occurrence of ophiolitic rocks upstream;
(4) comparison with older data indicates similar trends
in concentration, reveals a significant improvement of the
sediment quality in the River Era at Pontedera, and points
to a more widespread lead and copper contamination in
the Elsa basin.
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DOI: 10.1002/hyp