Eur. J. Mineral. Fast Track ArticleFast Track DOI: 10.1127/0935-1221/2007/0019-1754
Coexisting calc-alkaline and ultrapotassic magmatism at Monti Ernici, MidLatina Valley (Latium, central Italy)
M L FREZZOTTI1,2, G DE ASTIS3, L DALLAI4 and C GHEZZO1
1 Dipartimento di Scienze Della Terra, Università di Siena, Via Laterina 8, 53100 Siena, Italy*Corresponding author, e-mail: [email protected] IGAG – C.N.R., P.le A. Moro 5, 00185 Roma, Italy
3 Istituto Nazionale di Geofisica e Vulcanologia, Osservatorio Vesuviano, Via Diocleziano, 328 - 80124 Napoli, Italy4 Istituto di Geoscienze e Georisorse – C.N.R, Via G. Moruzzi, 1 - 56124 Pisa, Italy
Abstract: New major and trace element data, and Sr–Nd–Pb-O isotopic ratios for volcanic mafic rocks outcropping at MontiErnici in the Mid Latina Valley (southern Latium) are reported, with the aim of investigating the nature and evolution of Plio-Quaternary K-rich volcanism in Central Italy. Petrographical and geochemical studies allow us to identify mafic rocks rangingfrom ultrapotassic (HKS) to shoshonitic (SHO), and calc-alkaline (CA), these last ones being identified for the first time. The CArocks exhibit the most primitive signatures for Sr, Nd, and Pb isotopes (87Sr/86Sr = 0.706326-0.706654; 143Nd/144Nd = 0.512388–0.512361; 206Pb/204Pb = 18.944-18.940). The δ18O values are variable (δ18Ocpx from +5.75 to +7.08 ‰; and δ18Ool from +5.50 to+6.23 ‰), suggesting interaction with carbonate wall rocks. Radiogenic isotope ratios and incompatible elements distribution haveseveral characteristic in common with equivalent rocks from Pontine Islands (Ventotene), Campania and Aeolian arc volcanoes.Conversely, the HKS rocks closely resemble the ultrapotassic rocks from the Roman Province (87Sr/86Sr = 0.709679–0.711102;δ18Ocpx from +6.27 to +7.08 ‰). The high ratios of LILE (Large Ion Lithophile Elements: Rb, Cs, Th, U, K, LREE) and HFSE(High Field Strength Elements: Ta, Nb, Zr, Hf, Ti), and radiogenic isotope compositions of CA to HKS rocks indicate that allsuites contain subduction-related components, and suggest a N-MORB-type mantle source variably contaminated by hydrous fluidsand/or melts released by undergoing slabs, possibly during two distinct stages of metasomatism. The coexistence of ultra-alkalineand sub-alkaline orogenic magmatism, combined with tectonic, geophysical and geological evidence, support the possibility thatthe mantle beneath central-southern Italy (Ernici-Roccamonfina Province) was vertically zoned and produced different magmasuites during time.
Key-words: Monti Ernici, Latium magmatic Province, calcalkaline rocks, Ultrapotassic Rocks, geochemistry, igneous petrology.
1. Introduction1
The origin and geodynamic significance of Plio-2
Quaternary potassic alkaline volcanism in central-southern3
Italy has been extensively debated (see Peccerillo 2005,4
for a review). Most authors agree that K-rich mafic5
magmas originate in an upper mantle previously modified6
for both incompatible trace elements and radiogenic7
isotopes by metasomatic processes (e.g., Cox et al.,8
1976; Hawkesworth & Vollmer, 1979; Peccerillo, 1985;9
Conticelli & Peccerillo, 1992, Conticelli et al., 2002;10
Peccerillo 2005). There is, however, debate on the nature11
and timing of the processes that generated these mantle12
anomalies, as well as on the geodynamic setting: some13
authors suggest an origin by intracontinental rift environ-14
ment, whereas others propose a subduction-related setting15
(e.g., Vollmer, 1989; Ayuso et al., 1998; Peccerillo, 1985,16
1999).17
One of the most remarkable characteristics of K-rich 18
rocks in central-southern Italy – ranging from high-K calc- 19
alkaline (HKCA) and shoshonitic (SHO), to potassic (KS) 20
and ultrapotassic (HKS) – is their typical arc-type trace el- 21
ement signature (i.e., high LILE/HFSE ratios, low TiO2), 22
which has led to the suggestion of subduction-related man- 23
tle metasomatism and melting (e.g., Di Girolamo, 1978; 24
Peccerillo, 1985; 2003; Rogers et al., 1985). On the other 25
hand, these rocks have radiogenic isotope ratios and, in 26
most cases, a degree of enrichment in LILE, that are dis- 27
tinct from those of typical arc rocks. Moreover, although 28
magmatism in central Italy show variable potassium con- 29
tents, calc-alkaline rocks, which are typical of subduction 30
environments (e.g., Gill, 1981), are extraordinarily rare. 31
The Monti Ernici volcanoes (hereafter Ernici) in the Mid 32
Latina Valley (Central Italy), represent a key locality to 33
study these issues, since the erupted mafic magmas con- 34
tain variable potassium and incompatible element contents, 35
bridging the gap between typical arc-related volcanics 36
0935-1221/07/0019-1754 $ 7.20DOI: 10.1127/0935-1221/2007/0019-1754 © 2007 E. Schweizerbart’sche Verlagsbuchhandlung, D-70176 Stuttgart
2 M.L. Frezzotti, G. De Astis, L. Dallai, C. Ghezzo Fast Track Article
and ultrapotassic rocks. Radiogenic isotope compositions1
previously measured in the different rocks are also vari-2
able, with 87Sr/86Sr ∼ 0.7062–0.7112, and 143Nd/144Nd ∼3
0.51237–0.51173 (Civetta et al., 1981; D’Antonio et al.,4
1996; Conticelli et al., 2002; Gasperini et al., 2002). Fur-5
ther, the Ernici volcanoes consists of several small mono-6
genetic centres that erupted basaltic products, suggest-7
ing that evolutionary processes in shallow-level magma8
chambers might have been moderate, or negligible. There-9
fore, Ernici volcanic rocks may represent rather primitive10
mantle-derived melts, that have the potential to provide11
maximum information on mantle processes and geological12
setting of the volcanism.13
In this paper, we report major, trace element, and Sr-Nd-14
Pb-O isotopic data on selected representative rock-samples15
from Ernici to discuss their petrogenesis within the geo-16
dynamic setting responsible for the potassic magmatism17
in central-southern Italy. The investigated samples include18
ultrapotassic, potassic and low-potassium rocks, these last19
ones showing major element chemistry falling in the field20
of calc-alkaline (CA) suites. Present study allows us to rec-21
ognize for the first time a calc-alkaline series in spatial and22
temporal association with the HKS rocks, making the Er-23
nici volcanoes the most compositionally variable district in24
central Italy.25
2. Geological setting and sampling26
Both the geological and geophysical evidence, together27
with the compositional features of the magmas erupted28
in central-southern Italy (e.g., Selvaggi & Amato, 1992;29
Lucente et al., 1999; Savelli, 1988; Peccerillo, 2005, and30
references therein) suggest that Mio-Pliocene subduction31
processes affected the Italian peninsula (e.g., Doglioni32
et al., 1999, and references therein). The convergence33
of Africa with the European plate generated a west-34
ward subducting slab, probably made of both oceanic or35
thinned continental lithosphere (Ionian Sea), and continen-36
tal lithosphere (Adriatic plate). A sub-vertical body iden-37
tified through seismic studies and located beneath central-38
southern Italy (Panza, 1984; Wortel & Spakman, 2000), has39
been interpreted as the relict detached slab, whereas un-40
der the Calabria tear migration and Ionian slab roll-back41
continue (e.g., Gvirtzman & Nur, 2001). From about 7 Ma,42
persistent magmatism developed along the Tyrrhenian mar-43
gin of the Italian Peninsula, through a progressive migra-44
tion from Tuscany and Latium to Campania, which gave45
rise to the volcanoes of the Tuscan, Roman and Campanian46
Magmatic Provinces (Fig. 1a). Starting from the Pliocene,47
the compressional front responsible for the formation of48
the Apenninic chain migrated eastward and co-existed with49
extensional tectonic and rifting processes within the in-50
active thrust belt (i.e., Meletti et al., 2000). The Marsili51
basin opening (from ∼ 1.8 Ma) and the anticlockwise ro-52
tation of the Apennines, together with the SE migration of53
the Calabrian arc, addressed and supported this change to-54
ward the present extensional regime in southern Italy (from55
∼ 0.7 Ma; De Astis et al., 2006, and references therein).56
ADRIAPLATE MARGIN
AEOLIAN Arc
0 200 400 Km
N
EW
S
RomanProvince
Mt.Vulture
Vesuvius
Mt. Etna
Roman Province
Phleg. Fields - Vesuvius
ODP (Site Numbers)
Ernici - Roccamonfina
Ionian Plate subduction
Adria Plate margin
RMERN
ODP655 ODP
651
TYRRHENIAN SEA
SICILY
MARSILIStromboli
CALABRIA
IONIANSEA
LEGEND
CampanianProvince
HybleanPlateau
ODP 650
Sabatini
Albani
Vulsini
Adriatic Sea
& Seamounts
a
b
POFI
Villa Santo Stefano
Tecchiena
Ceccano
Giulianodi Roma
Patrica
Volcanic Centres
HKS Rocks
SHO-KS rocks
Frosinone
Tuscany
Mt.ERNICI
O-RLine
Main Faults
Colle Castellone
Is.-Pro.APULIA
A-ALine
Fig. 1. a) Map of the central-southern Italy and Tyrrhenian Sea,showing the main magmatic provinces, and the investigated area.The ODP sites are indicated by numbers. b) geological sketch mapof the Monti Ernici volcanic area (modified from Civetta et al.,1981), showing the main eruptive centres and the most importanttectonic lines. ERN =Monti Ernici volcanoes; RM = Roccamonfinavolcano; O-R = Ortona – Roccamonfina lithospheric discontinuity;A-A = Ancona-Anzio lithospheric discontinuity; Phleg. Fields =Phlegraean Fields; Is. – Pro. = Ischia and Procida Islands.
The volcanoes of Monti Ernici occur close to the Tyrrhe- 57
nian margin in an area affected by Lower Pliocene NW- 58
SE faulting, which generated graben-horst structures paral- 59
lel to the Apennine chain (Fig. 1b). As observed for the 60
surrounding regions of Campania and northern Latium, 61
NE-SW transverse faults – having a normal to strike-slip 62
component of motion – were associated with the main 63
“Apenninic” fault system. In particular, the Ernici vol- 64
canoes formed within the so-called Ancona-Anzio and 65
Ortona-Roccamonfina lines, that represent two important 66
NE-SW trending tectonic lineaments. The former cuts the 67
Apennine chain and divides the northern Apennines from 68
Fast Track Article Calc-alkaline and ultrapotassic magmatism at monti ernici 3
the Lazio and Abruzzi geological domains (Castellarin1
et al., 1982), whereas the latter separates the southern2
Apennines block from the central-northern sectors. Ac-3
cording to Locardi (1988) these lineaments were formed4
during the anticlockwise rotation of the Apennine chain.5
Paleomagnetic data support this hypothesis, and highlight6
different degrees of block rotation for the various Apennine7
sectors (Meloni et al., 1997),8
Most of the Ernici volcanoes consist of small mono-9
genic cones made of pyroclastic deposits, or, subordinately,10
lava flows (e.g., Colle Castellone, Giuliano di Roma, Colle11
Spinazzeta, Villa S. Stefano, Fig. 1b). Some cones (e.g.,12
Pofi volcano, and Patrica, Fig. 1b) have larger dimensions,13
resulting from a more intensive and alternating effusive and14
explosive activity. The bedrocks of the volcanic sequences15
consist of a wide variety of early Mesozoic to Quaternary16
rocks (e.g., Accordi et al., 1986), including Upper Triassic17
to Miocene neritic and pelagic carbonates, Upper-Middle18
Miocene calcareous and arenaceous sediments, and thin19
deposits of Pliocene to Lower Pleistocene terrigenous sed-20
iments. The crustal thickness in the Ernici area is estimated21
about 25–30 km (Piromallo & Morelli, 2003). The pyro-22
clastic deposits often contain sedimentary xenoliths, espe-23
cially carbonate rocks.24
Previous work on Ernici volcanics by Civetta et al. (1981)25
indicated the occurrence of two distinct series of alka-26
line rocks, characterised by different enrichments in potas-27
sium, incompatible elements, and radiogenic Sr: i) potas-28
sic (KS) rocks characterised by moderately potassic basalts29
and trachybasalts with shoshonitic affinity, and ii) ultra-30
potassic (HKS) rocks consisting mostly of leucite phono-31
litic tephrites. A different timing in the eruption of the32
two series was reported, based on K/Ar dating: HKS rocks33
range in age from 0.7 to 0.2 Ma, whereas the KS rocks34
are younger (0.2 and 0.1 Ma) (Basilone & Civetta, 1975;35
Civetta et al., 1981).36
The rock sampling was carried out in an extensively ur-37
banised and poorly exposed area, characterised by a limited38
number outcrops of modest area. However, every sector of39
the volcanic region was sampled, resulting in a collection40
of about 50 representative rock-samples. Only at Pofi vol-41
cano (Fig. 1b), it was possible to collect a continuous se-42
quences of volcanic products. Geochemical data coming43
from Pofi rocks (crossed symbols in some figures) indicate44
that low-potassium rocks (i.e., CA-SHO series, see below)45
alternate with HKS only during the final stages of the vol-46
canic successions, in agreement with Civetta et al. (1981).47
3. Analytical techniques48
More than 40 selected samples were analysed for major49
and trace elements by X-ray fluorescence analysis on fused50
glass disks, with a Philips MagixPro at the Dipartimento di51
Scienze della Terra dell’Università di Siena. Samples were52
prepared by mixing 1 g of homogenised powder and 8 g of53
lithium tetraborate (Merck Spectromelt A 10, Li2B4O7), as54
flux material, and by melting into glass beads. The back-55
ground and mass absorption intensities were calculated56
against the calibrations constructed from 24 international 57
geological reference materials. Loss on ignition was deter- 58
mined by heating samples to 1050 ◦C for 2 h. A selection of 59
representative samples, was further analysed for REE, Ta, 60
Hf, Cs, Pb, Th, and U by ICP-MS, (Table 1), at the Cen- 61
tre Petrographiques et Geochimiques (Vandouvre, France). 62
Precision of trace element data is better than 10 % for all 63
trace elements. 64
WDS analyses of mineral phases were performed with a 65
Cameca SX 50 (IGAG-CNR, Roma), using 15 kV accel- 66
erating voltage, 15 nA beam current, and a beam diameter 67
of 5 µm. Natural and synthetic silicates were used as stan- 68
dards for mineral analyses. 69
Sr, Nd and Pb isotopic ratios were determined on selected 70
whole rocks with TIMS 262 Thermo-Finnigan mass spec- 71
trometer at the Instituut voor Aard- and Levenschappen of 72
the Vrije Universiteit in Amsterdam. Sr and Nd isotope ra- 73
tios were normalized to NBS 987: 87Sr/86Sr = 0.710238 ± 8 74
on > 100 samples, and La Jolla: 143Nd/144Nd = 0.511834 ± 75
9 on > 100 samples, respectively. Total blanks were less 76
than 1.1 ng, which represents < 0.05 % of the element mass 77
in the measured fraction. For Sr-Nd, precision was better 78
than one unit on the fifth decimal place. 79
Pb was separated using 0.15 ml quartz ion-exchange 80
columns filled with AG1X8 200–400 mesh. Pb isotopes 81
were measured on solutions of 100 ppb Pb (or less) in 82
1 % HNO3. The method of standard–sample bracketing 83
was chosen since Pb does not have a pair of invariant iso- 84
topes that can be used to correct for mass bias during analy- 85
ses (cf. Elburg et al., 2005). Machine blanks were analyzed 86
before each standard and sample, and the average of these 87
two measurements was subtracted from each cycle before 88
calculation of the Pb isotopic ratios. The blank levels varied 89
between sessions with intensities of 1.5–3.0 mV on 208Pb. 90
A 100 ppb solution of NIST SRM-981 was used as the stan- 91
dard, and normalization was performed using the values of 92
Baker et al. (2004). Precision of Pb isotope ratios is better 93
than one unit on third decimal place. 94
Sr isotope ratios for some samples (see Table 1) were 95
measured at the Southampton Oceanography Centre on 96
a seven-collector VG sector 54 mass spectrometer with 97
a separable-filament source. Rock powder for Sr analy- 98
sis were leached with 2 N HCl for 1h at 140 ◦C prior to 99
dissolution and isolation of Sr using Sr resin. Isotope ra- 100
tios were normalized to 87Sr/86Sr = 0.710252 ± 15 (2s.d., 101
n = 169). Total blanks were less than 1.1 ng, which repre- 102
sents < 0.05 % of the element mass in the measured frac- 103
tion. 104
Oxygen isotope compositions of clinopyroxene and 105
olivine mineral separates were performed at the CNR- Is- 106
tituto di Geoscienze and Georisorse in Pisa by conven- 107
tional laser fluorination (Sharp, 1990), reacting the sam- 108
ples under an F2 gas atmosphere. Purified oxygen gas was 109
directly transferred into a Finnigan Delta XP Mass Spec- 110
trometer via a 13A zeolite molecular sieve for isotopic ra- 111
tio determinations (Sharp, 1995). All the data are given 112
following the standard δS MOW notation. During the course 113
of analysis, an in-house laboratory QMS quartz standard 114
was used (δ18OSMOW = ±14.05 ‰ yielding an average 115
(1σ) δ18O = +14.08 ‰, σ = 0.12 ‰. NBS28 standard 116
4 M.L. Frezzotti, G. De Astis, L. Dallai, C. Ghezzo Fast Track ArticleTa
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--
0.70
6446
0.70
6851
87Sr/8
6Sr
--
0.70
6599
-0.
7066
540.
7065
76*
0.70
6326
*-
143N
d/14
4Nd
0.51
2136
--
0.51
2086
--
0.51
2370
-14
3N
d/14
4Nd
--
0.51
2388
-0.
5123
61-
--
206P
b/20
4Pb
18.8
245
--
18.7
349
--
18.9
063
-20
6Pb/2
04Pb
--
18.9
444
-18
.939
9-
--
207P
b/20
4Pb
15.6
876
--
15.6
798
--
15.6
861
-20
7Pb/2
04Pb
--
15.6
860
-15
.684
9-
--
208P
b/20
4Pb
39.0
507
--
39.0
087
--
39.0
667
-20
8Pb/2
04Pb
--
39.0
710
-39
.062
7-
--
d18O
cpx
6.27
--
--
-6.
276.
09d1
8Ocp
x-
-6.
02-
6.40
5.75
6.07
6.50
d18O
ol-
--
--
-5.
84-
d18O
ol-
-5.
50-
-5.
505.
72-
Ast
eris
ksin
dica
teda
taob
tain
edat
Scho
olof
Oce
anan
dE
arth
Scie
nce,
Nat
iona
lOce
anog
raph
yC
entr
e,So
utha
mpt
on,U
K.
Fast Track Article Calc-alkaline and ultrapotassic magmatism at monti ernici 5
(δ18O = +9.60 ‰ gave an average values of δ18O =1
9.52 ‰ (σ = 0.14 ‰).2
4. Classification and petrography3
Figures 2a and b show alkalies and K2O vs. SiO2 plots for4
the Ernici rocks: our rock-samples straddle the boundary5
between sub-alkaline and alkaline fields, and range from6
CA up to HKS compositions. A variable degree of sil-7
ica saturation is also observed in the diagram K2O/Na2O8
vs. degrees of silica saturation indicated by ∆Q notation9
(Fig. 2c; Peccerillo, 2003). Compared to previous studies10
(Civetta et al., 1979; 1981), our samples show a consider-11
ably wider range of potassium content, with the occurrence12
of rocks that fall in the CA field; besides, the number of13
samples falling in the SHO field (the KS of Civetta et al.,14
1981) is much lower. All the samples containing low K2O15
abundances are unaffected by secondary alteration, as in-16
dicated by microscopic observations, and low LOI values17
(Table 1): their depletion in potassium likely reflects pris-18
tine magmatic compositions. We conclude that these mag-19
mas can be considered as belonging to the calcalkaline se-20
ries, on the basis of major element chemistry.21
The HKS rocks plot in the alkaline field of Irvine &22
Baragar (1971), and are variably undersaturated in silica,23
whereas the CA-SHO rocks are subalkaline, from mod-24
erately undersaturated to slightly oversaturated in silica25
(Fig. 2a, b, c). Overall, the HKS rocks fall in the field26
of the Roman magmatic Province, whereas SHO and CA27
rocks plot in the same field of Procida, and Ventotene vol-28
canoes, belonging to the Campanian Province (Peccerillo,29
2005). Ernici CA rocks further show similar K2O contents,30
and K2O/Na2O ratios, but slightly higher degrees of sil-31
ica undersaturation (i.e., slightly lower ∆Q) than CA rocks32
from the Aeolian arc with similar SiO2 and MgO contents33
(Fig. 2c).34
Based on the TAS diagram (not shown), the composition35
of the analysed rocks ranges from basalt to K-trachybasalt36
and leucite tephrite, to basaltic andesite; only one sample37
has andesitic composition. Notably, the rocks from Pofi38
volcano (crossed symbols in Fig. 2a, b), replicate, at a39
smaller scale, the same compositional trend outlined by the40
whole Ernici products.41
CA basalts are hypocrystalline and moderately por-42
phyritic rocks, with phenocryst contents varying between43
20 and 30 % in volume. Clinopyroxene is the dominant44
phenocryst phase together with minor olivine, and has a45
diopsidic-salitic composition (i.e., zoned; mg# 0.92–78;46
mg# =Mg/(Mg + Fe); Table 2). Olivine microphenocrysts47
have high MgO contents (mg# = 0.92–0.84), and are of-48
ten partially transformed to iddingsite. The groundmass49
consists of salitic clinopyroxene (mg# = 0.81–0.78), by-50
townitic plagioclase (An = 87–79), and rare olivine (mg#51
= 0.83–0.69), with minor glass, Fe–Ti oxides, and Fe-52
sulphides (Table 2). Orthopyroxene and K-bearing phases53
were not observed.54
SHO basalts are texturally similar to CA basalts, but by-55
townitic plagioclase may occur as a phenocryst phase (Ta-56
ble 2), whereas olivine phenocrysts are hardly ever ob-57
SubalkalineAlkalies
SiO2
a
48 52 56 60 64 68 72 760
2
4
6
8
10
Legend Low/Medium-K rocks (CA)
Medium-K rocks (HKCA-SHO) High-K rocks (HKS)HKS from C.Castellone
Pofi rocks with overprint
b
Arc Tholeiitic
Calc-alkaline
High-K calcalkaline
Shoshonitic
KS rocks(Literature)
HKS rocks(Literature) Ultra-Potassic
SiO2
K2O
Alkaline
40 50 60 700
5
10HKS rocks(Literature)
KS rocks(Literature)
-60 -40 -20 0 200.01
0.1
1
10
K2O/Na2O
∆Q = Q- (lc+ne+kal+ol)
HKS
SHO-KS
CATH
SilicaUndersaturated
SilicaOversaturated
Tuscany & RomanProvinces
AeolianAeolianCA & HKCACA & HKCAbasaltsbasalts
Procida &VentoteneIslands
c
HKS rocks(Literature)
ErniciKS rocks
(Literature)
Phleg.FieldsVesuvius
Fig. 2. Classification diagrams for Ernici volcanic rocks: a) SiO2vs.Alkalies (K2O + Na2O) diagram (Irvine & Baragar, 1971); b) SiO2
vs. K2O diagram (Peccerillo & Taylor, 1976); c) ∆Q vs. K2O/Na2Odiagram; ∆Q is the algebraic sum of normative quartz minus nor-mative undersaturated minerals (lc+ne+kal+ol) (Peccerillo, 2003).Rocks from Pofi volcano have been highlighted with an overprintedblack cross in Fig. 2a and 2b. In Fig. 2c the Colle Castellone HKSrocks are not distinguished. Oxides are normalised on a water-freebasis.
served. Clinopyroxene is zoned and has a diopside-salite 58
composition (mg# = 0.91–0.82; Table 2). The ground- 59
mass consists of salitic clinopyroxene (mg# 0.77–0.74; Ta- 60
ble 2), labradoritic plagioclase, and minor olivine (mg# 61
0.69–0.50) and K-feldspar (with rare glass, Fe–Ti oxides 62
and Fe-sulphides). 63
6 M.L. Frezzotti, G. De Astis, L. Dallai, C. Ghezzo Fast Track ArticleTa
ble
2.se
lect
edan
alys
esof
min
eral
phas
es.
Seri
eC
AC
AC
AC
AC
AC
AC
AC
AC
AC
AC
ASH
OSH
OSH
OSH
OSH
OSH
OL
ocal
ity
C.F
onta
naPo
fiPo
fiC
.Fon
tana
Pofi
C.F
onta
naPo
fiPo
fiPo
fiPo
fiC
.Fon
tana
Pofi
Pofi
Pofi
Pofi
Pofi
Pofi
Sam
ple
ER
0419
ER
0306
ER
0306
ER
0419
ER
0306
ER
0419
ER
0306
ER
0306
ER
0306
ER
0306
ER
0419
ER
0416
-cE
R04
16-c
ER
0416
-cE
R04
16-c
ER
0416
-cE
R04
16-c
Phas
eO
lO
lO
lO
lO
lC
pxC
pxC
pxri
mC
pxC
pxC
pxO
lO
lC
pxC
pxco
reC
pxri
mC
pxph
enoc
r.ph
enoc
r.ph
enoc
r.g.
mas
sg.
mas
sph
enoc
r.ph
enoc
r.ph
enoc
r.ph
enoc
r.ph
enoc
r.g.
mas
sg.
mas
sg.
mas
sph
enoc
r.ph
enoc
r.ph
enoc
r.g.
mas
s
SiO
239
.53
41.3
240
.65
39.6
937
.75
51.8
753
.48
52.1
852
.92
53.3
150
.50
37.3
235
.39
52.8
851
.16
50.5
745
.56
TiO
2n.
d.n.
d.n.
d.n.
d.n.
d.0.
400.
220.
290.
360.
200.
45n.
d.n.
d.0.
180.
350.
521.
41A
l2O
30.
060.
040.
06n.
d.0.
252.
381.
802.
082.
091.
634.
460.
032.
051.
893.
354.
058.
23C
r2O
3n.
d.0.
050.
05n.
d.n.
d.0.
180.
710.
250.
230.
63n.
d.n.
d.n.
d.0.
590.
190.
09n.
d.M
gO44
.53
51.0
151
.07
43.1
833
.70
16.3
117
.31
16.9
517
.13
17.5
014
.92
34.5
821
.64
17.7
016
.16
15.4
612
.77
CaO
0.23
0.33
0.44
0.34
1.12
22.8
623
.70
23.8
823
.15
23.5
522
.72
0.35
1.19
23.6
723
.55
23.3
123
.19
MnO
0.27
0.17
0.20
0.36
0.72
0.15
n.d.
0.06
0.13
0.06
0.14
0.75
1.33
0.06
0.05
0.20
0.14
FeO
14.8
18.
298.
5216
.12
27.0
34.
712.
823.
584.
202.
636.
1227
.82
38.4
62.
964.
455.
717.
72N
iO0.
060.
120.
200.
060.
08n.
d.0.
10n.
d.n.
d.n.
d.n.
d.n.
d.0.
050.
06n.
d.n.
d.0.
08N
a2O
n.d.
n.d.
n.d.
n.d.
n.d.
0.17
0.17
0.19
0.14
0.16
0.28
n.d.
n.d.
0.17
0.18
0.25
0.20
Tota
l:99
.49
101.
3910
1.28
99.7
810
0.77
99.0
510
0.32
99.4
710
0.40
99.6
799
.65
100.
9010
0.27
100.
1499
.44
100.
1699
.32
Wo%
46.3
247
.41
47.4
645
.96
47.1
146
.97
46.7
147
.55
47.1
649
.24
En%
45.9
848
.18
46.8
747
.33
48.7
042
.92
48.6
045
.37
43.5
237
.72
Fs%
7.70
4.41
5.67
6.72
4.19
10.1
14.
707.
089.
3313
.04
mg#
0.84
0.92
0.91
0.83
0.69
0.86
0.92
0.89
0.88
0.92
0.81
0.69
0.50
0.91
0.87
0.83
0.75
Seri
eH
KS
HK
SH
KS
HK
SH
KS
HK
SH
KS
HK
SH
KS
CA
SHO
SHO
HK
SH
KS
HK
SH
KS
Loc
alit
yPo
fiPo
fiPo
fiPo
fiPo
fiC
aste
llon
eC
aste
llon
eC
aste
llon
eC
aste
llon
ePo
fiPo
fiPo
fiPo
fiC
aste
llon
eC
aste
llon
ePo
fiSa
mpl
eE
R03
07E
R03
07E
R03
07E
R03
07E
R03
07E
R03
12-2
ER
0312
-2E
R03
12-2
ER
0307
ER
0306
ER
0416
-cE
R04
16-c
ER
0307
ER
0312
-2E
R03
12-2
ER
0307
Phas
eO
lO
lO
lC
pxC
pxC
pxC
pxC
pxC
pxPl
PlPl
PlL
euL
euL
euph
enoc
r.ph
enoc
r.g.
mas
sph
enoc
r.ph
enoc
r.ph
enoc
r.ph
enoc
r.ph
enoc
r.g.
mas
sg.
mas
sph
enoc
r.g.
mas
sg.
mas
sph
enoc
r.ph
enoc
r.g.
mas
s
SiO
240
.03
39.6
834
.91
50.7
450
.74
51.8
551
.15
51.8
849
.15
47.7
646
.59
54.2
649
.09
54.2
954
.10
54.6
0T
iO2
n.d.
n.d.
n.d.
0.58
0.58
0.56
0.64
0.50
0.84
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
Al2
O3
n.d.
n.d.
n.d.
3.58
3.58
2.89
2.46
2.25
4.40
31.3
932
.03
27.5
231
.27
22.3
622
.44
22.0
2C
r2O
3n.
d.n.
d.n.
d.0.
100.
10n.
d.n.
d.n.
d.n.
d.n.
d.n.
d.n.
d.n.
d.n.
d.n.
d.n.
d.M
gO47
.04
47.1
921
.17
15.5
515
.55
15.8
015
.51
16.2
315
.64
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
CaO
0.50
0.46
0.88
23.9
423
.94
24.7
824
.47
24.7
223
.09
15.7
816
.86
10.9
415
.32
n.d.
n.d.
0.05
MnO
0.32
0.32
1.37
0.11
0.11
0.07
0.16
0.11
0.19
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
FeO
11.5
511
.80
41.3
14.
494.
494.
014.
644.
465.
701.
010.
880.
600.
740.
530.
480.
47N
iO0.
100.
16n.
d.0.
030.
030.
04n.
d.n.
d.0.
06n.
d.n.
d.n.
d.n.
d.n.
d.n.
d.n.
d.N
a2O
n.d.
n.d.
n.d.
0.12
0.12
0.14
0.12
0.13
0.19
2.21
1.91
4.88
2.21
n.d.
n.d.
0.33
K2O
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
0.16
0.13
0.31
0.31
21.0
721
.06
20.4
5To
tal:
99.5
399
.60
99.6
399
.23
99.2
310
0.12
99.1
410
0.27
99.2
598
.41
98.4
898
.67
99.0
998
.33
98.1
598
.09
Wo%
48.6
948
.69
49.6
249
.14
48.6
047
.50
An%
78.9
782
.33
54.3
077
.84
En%
44.0
044
.00
44.0
243
.34
44.3
843
.05
Ab%
20.0
616
.89
43.8
820
.27
Fs%
7.31
7.31
6.36
7.52
7.02
9.46
Or%
0.97
0.78
1.82
1.89
mg#
0.88
0.88
0.48
0.86
0.86
0.88
0.86
0.87
0.82
mg#=
Mg/
(Mg+
Fe);
n.d.=
notd
etec
ted;
phen
ocr.=
phen
ocry
st;g
.mas
s=
grou
ndm
ass.
Fast Track Article Calc-alkaline and ultrapotassic magmatism at monti ernici 7
0
2
4
6
8
K2O
3 5 7 9 110
100
200
300
400
500
600
MgO
0
100
200
300
400
500
600
700
Cr
0
100
200
300
400
500
Ce
3 5 7 9 110
100
200
300
400
500
600
Zr
MgO
Rb
107
9
11
13
15
CaOKS rocks(Literature)
HKS rocks(Literature)
KS rocks(Literature)
HKS rocks(Literature)
HKS rocks(Literature)
KS rocks(Literature)
KS rocks(Literature)
HKS rocks(Literature)
HKS rocks(Literature)
KS rocks(Literature)
HKS rocks(Literature)
KS rocks(Literature)
a
c
e
b
d
f
Fig. 3. Harker variation diagrams for selected major (wt.%) andtrace (ppm) elements vs. MgO of Ernici rocks. Symbols as inFig. 2c. Fields of data from literature (Civetta et al., 1981) are alsoreported.
HKS leucite-tephrites are holocrystalline variably por-1
phyritic rocks. Phenocrysts (20–40 % in vol.) consist of2
clinopyroxene and leucite ± olivine, set in a groundmass3
of leucite clinopyroxene ± minor olivine, plagioclase, and4
ilmenite (Table 2). In a few samples, minor brown mica5
and K-feldspar are also present. Diopsidic-salitic clinopy-6
roxene (mg# 0.90–0.83) is the dominant phenocryst, with7
subordinate olivine (mg# 0.88–0.86) and leucite, set in a8
groundmass of salitic clinopyroxene (mg# 0.82–0.77), and9
leucite, with minor bytownitic-labradoritic plagioclase and10
Fe-rich olivine (mg# 0.52–0.48). At Colle Castellone, phe-11
nocrysts consist of leucite and salitic clinopyroxene (mg#12
0.88–0.86), while olivine is absent. The groundmass con-13
sists of salitic clinopyroxene (mg# 0.82–0.77), and leucite,14
with subordinate bytownitic-labradoritic plagioclase, and15
Fe-Ti oxides.16
5. Geochemistry17
5.1. Major and trace element data18
Variation diagrams of selected major and trace elements vs.19
MgO and K2O are reported in Fig. 3, and 4. The analysed20
samples show intermediate to high MgO contents, with21
HKS rocks displaying lower MgO, than CA and SHO sam-22
ples. Cr and Ni show a wide range of values, HKS rocks23
having lower contents, than SHO and CA rocks, in accor-24
dance with their lower MgO (Fig. 3).25
Large Ion Lithophile Elements (LILE: Rb, Ba, Th, U,26
Light Rare Earth Elements), and High Field Strength El-27
ements (HFSE: Zr, Hf, Nb, Ta, etc.) show an increase from28
calcalkaline to ultrapotassic rocks. A group of samples29
0
1000
2000
3000
4000
5000
Ba
0
100
200
300
La
0 2 4 6 8 100
20
40
60
80
100
Th
K2O
0
10
20
30
40
Nb
8
12
16
20
24
28
Zr/Nb
0 2 4 6 8 100,706
0,707
0,708
0,709
0,710
0,711
0,712
87Sr/86Sr
K2O
KS rocks(Literature)
HKS rocks(Literature)
HKS rocks(Literature)
HKS rocks(Literature)
KS rocks(Literature)
HKS rocks(Literature)
HKS rocks(Literature)KS rocks
(Literature)
KS rocks(Literature)
KS rocks(Literature)
HKS rocks (Literature)
KS rocks(Literature)
a
c
e
b
d
f
Fig. 4. Variation diagrams of selected Incompatible Trace Elements(ITE) contents (ppm), ITE ratios and 87Sr/86Sr vs. K2O for Ernicirocks. Symbols as in Fig. 2a.
from the HKS centre of Colle Castellone displays consid- 30
erably higher concentrations for all incompatible trace ele- 31
ments (ITE), with respect to other HKS rocks with similar 32
MgO contents (grey dots in Fig. 4). A wide range of Rb 33
concentration is observed in the poorly potassic CA rocks 34
(Fig. 3). Notably, this variation is not related to any other 35
geochemical parameters. 36
REE plots for representative samples (Fig. 5a) dis- 37
play variably fractionated patterns and degrees of LREE 38
enrichments for the different series, with a nega- 39
tive Eu anomaly (slight, but stronger for the HKS 40
rocks). Mantle-normalised incompatible element diagrams 41
(spider-diagrams; Fig. 5b, 6) show Ta-Nb troughs, positive 42
spikes for Rb, Cs, Th,U, LREE and Pb, and negative spikes 43
for Hf, Zr and Ba. All these characteristics are typical of 44
arc rocks, with exception of the negative Ba anomaly. The 45
CA rocks display a pattern very similar to the associated 46
shoshonites, but a much lower abundance in potassium, and 47
a relative enrichment in Cs, Th, U, La and Sr. A negative 48
Sr anomaly is present in Colle Castellone HKS rocks. 49
Figure 6 shows incompatible element patterns for rep- 50
resentative Ernici mafic rocks compared with analogous 51
volcanic rocks from other Italian magmatic provinces. 52
Compared with shoshonites from Procida and Ventotene 53
(Eastern Pontine islands, Campanian Province, Fig. 1a) 54
and with calc-alkaline basalt from Alicudi (Aeolian Arc, 55
Fig. 1a), the CA and SHO samples from Ernici have higher 56
enrichments in LILE (especially Cs, Rb, Ba, Th, U), and 57
stronger negative anomalies of HFSE (Fig. 6a). The HKS 58
magmas from Ernici (Fig. 6b) have incompatible element 59
abundances similar, or often higher (e.g., REE, Zr, Hf) 60
than the HKS rocks from Roccamonfina and Mt. Somma- 61
Vesuvius, and resemble leucite-tephrites from the Roman 62
Province (Peccerillo, 2005). The Colle Castellone sample 63
exhibits the highest enrichment in several elements (Cs, Ba, 64
8 M.L. Frezzotti, G. De Astis, L. Dallai, C. Ghezzo Fast Track Article
1
10
100
1000
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Roc
k/C
hond
rites
2
10
100
1000
Cs Rb Ba Th U K Ta Nb La Ce Sr Nd P Hf Zr Sm Ti Tb Y
Roc
k/P
rimor
dial
Man
tle
a
b
Fig. 5. REE and ITE patterns of Ernici mafic rocks (MgO > 4 wt.%)normalised to chondrites (Sun & McDonough, 1989) and to primor-dial mantle (Wood et al., 1979).
Th, Pb, LREE) with respect to any other ultrapotassic rocks1
in central-southern Italy (grey dots in Fig. 5a, and 6b). This2
suggests a bimodality among the Ernici HKS members, and3
that the Colle Castellone rocks represent an extremely en-4
riched HKS melt.5
5.2. Oxygen isotope composition6
Since clinopyroxene and olivine are the early crystalliz-7
ing phases in the CA and SHO basalts, their δ18O val-8
ues should represent the O-isotope composition of primi-9
tive magma, if the O-isotope equilibrium between miner-10
als and melt is maintained. The δ18Ocpx and δ18Ool data11
measured on Ernici clinopyroxenes and olivines are pre-12
sented in Fig. 7, and Table 1. They vary from +5.75 and13
+7.08 ‰, and from +5.50 and +6.23 ‰, respectively, and14
are positively correlated (Fig. 7c); they are significantly15
lower than δ18Owr values reported in previous studies (e.g.,16
Turi et al., 1991), but slightly higher than values reported17
for unaltered mantle rocks (e.g., MORB = δ18O ≈ +5.218
to +6.1 ‰). These results are also higher than ratios mea-19
sured in Alicudi CA basalts and andesites (δ18Ool = +5.1020
to +5.29 ‰; Peccerillo et al., 2004), the latter related to21
recent subduction.22
Roc
k/P
rimor
dial
Man
tle
10
100
1000
Cs Rb Ba Th U K Ta Nb La Ce Sr Nd P Hf Zr Sm Ti Tb Y2
HKS mafic rocks (MgO > 4 %)
Legend Ernici (C.C.) HKS
Ernici HKSRoccamonfina HKS
Som-Ves HKSRP HKS
CA - SHO mafic rocks (MgO > 6 %)
Legend Ernici CAErnici SHO
Procida SHOAlicudi CA
Roc
k/P
rimor
dial
Man
tle
5000
1
10
100
1000
Cs Rb Ba Th U K Ta Nb La Ce Sr Nd P Hf Zr Sm Ti Tb YPb
Pb
a
b
Fig. 6. Incompatible elements patterns of Ernici CA - SHO rocks(5a - MgO > 6 wt.%) and Ernici HKS rocks (5b, MgO > 4 wt.%)normalised to primordial mantle (Wood et al., 1979, except Pb fromSun & McDonough, 1989) and compared with rocks from sur-rounding regions and similar petro-chemical affinity. Legend: C.C. =Colle Castellone volcanic centre, Som-Ves = Mt.Somma.Vesuviusvolcano, RP = Roman Province.
Clinopyroxenes from three ultrapotassic samples were 23
also measured, and yielded δ18O values from +6.27 to 24
+6.45 ‰ (Fig. 7a, and d), in the range of typical Roman- 25
type magmas which are proposed to be affected by mod- 26
erate degrees of contamination by sedimentary carbonate 27
(e.g., Dallai et al., 2004). 28
The ∆18Ocpx−ol of CA rocks is close to the 0.4 ‰ expected 29
for oxygen isotope equilibrium at magmatic temperatures 30
(e.g., Mattey et al., 1994). This is different from what ob- 31
served for Roman-type volcanic rocks, where O-isotope 32
equilibrium between olivine and cpx is rarely achieved, 33
likely due to their crystallization conditions, occurring un- 34
der high Ca, CO2 and O2 activities (carbonate host-rock 35
contribution during pre-eruptive stage; Gaeta et al., 2006). 36
5.3. Sr-Nd-Pb isotopes 37
Radiogenic isotope compositions of the investigated sam- 38
ples are variable (Fig. 8, and Table 1). Measured Sr isotopic 39
Fast Track Article Calc-alkaline and ultrapotassic magmatism at monti ernici 9∂
∂
∂
∂∂
Fig. 7. Variation diagram of δ18O of mineral phases of Ernici rocks.Symbols as in Fig. 2a.
ratios range from 0.70633 to 0.71110. There is an overall1
increase of 87Sr/86Sr ratios with potassium; however, CA-2
SHO rocks have similar 87Sr/86Sr ratios ranging between3
0.706326 and 0.706654 (Fig. 8a). HKS rocks have much4
more radiogenic compositions (87Sr/86Sr = 0.709679–5
0.709840) with a large gap between these rocks and CA-6
SHO volcanics; another major variation is observed be-7
tween the HKS and Colle Castellone rocks (87Sr/86Sr =8
0.711102; also characterised by the highest incompati-9
ble element abundances). Nd isotopic ratios show an in-10
verse trend, decreasing from CA-SHO to HKS volcanics11
(143Nd/144Nd = –0.512086–0.512388; Fig. 8a). Compared12
with previous studies, our data show similar ranges of Sr-13
Nd isotopic ratios, although our CA-SHO rock-samples14
show narrower 87Sr/86Sr range than those observed by15
Civetta et al. (0.70622–0.70697; 1981). They match those16
reported by D’Antonio et al. (1996), Conticelli et al.17
(2002), and Gasperini et al. (2002), except for a significant18
difference in the 143Nd/144Nd value for the Colle Castellone19
lava (143Nd/144Nd = 0.51173, in Conticelli et al., 2002).20
Note, however, that our value falls within the array defined21
by central Italy volcanic rocks.22
Considering both present and literature data, the Sr-Nd23
isotope compositions of Ernici rocks cover a very wide24
compositional range, similar to those of Roccamonfina,25
and overlap with the Roman and Campanian provinces26
(Fig. 8a). Notably, the Sr isotopic ratios of the Ernici CA-27
SHO rocks are close to those from Ventotene, and Cam-28
panian volcanoes, having similar K2O contents, whereas29143Nd/144Nd values are slightly lower than Campanian30
rocks (Fig. 8a). Sr- and Nd-isotopic compositions of the31
HKS series fall in the field of the Roman Province.32
Pb isotopic ratios measured on our samples display mod-33
erate variations (Fig. 8b and 9a, and Table 1), with the HKS34
rocks displaying less radiogenic compositions than CA and35
SHO rocks. 206Pb/204Pb ratios range from 18.735 to 18.944,36207Pb/204Pb from 15.680 to 15.686, and 208Pb/204Pb from37
39.009 to 39.071 (Fig. 9a). Such variations are in agree-38
CA - HKCA Aeolian Basalts(central-western AVD sectors and Stromboli)
0.703 0.706 0.709 0.712 0.715 0.7180.5116
0.5120
0.5124
0.5128
143Nd/144Nd
87Sr/ 86 Sr
Vesuvius &Phlegr. Fields
Tuscany &Roman Provinces
Roccamonfina &Ventotene Island
Ernici CA-HKCAErnici SHO-KS
Ernici HKSErnici HKS (C.C.)
Ernici KS (Ref.)Ernici HKS (Ref.)
18.4
18.8
19.2
19.6
20.0
206Pb/ 204 Pb
0.703 0.706 0.709 0.712 0.715 0.71887Sr/ 86Sr
CA - HKCA Aeolian Basalts(central-western AVD sectors)
Tuscany &Roman Provinces
Roccamonfina &Ventotene Island
Procida
Procida
b
a
Vesuvius &Phlegraean Fields
CA - HKCAStromboli
Fig. 8. Sr-Nd-Pb isotopic composition of Ernici mafic rocks. Liter-ature data (Ref.) are from Civetta et al. (1981), D’Antonio et al.(1996) and Conticelli et al. (2002). Compositions of other CA-HKCA Italian volcanoes and Roman Province are also shown (Datafrom Peccerillo, 2005 and references therein).
ment with the few data available from previous studies 39
(D’Antonio et al., 1996; Gasperini et al., 2002). 40
The δ18O vs. 87Sr/86Sr diagram (Fig. 9b) shows that 41
Ernici CA-SHO rocks plot along a sub-vertical trend, a fea- 42
ture observed in many Italian volcanoes. 43
6. Discussion 44
The present study allows us to recognize for the first time 45
low-K2O rocks of CA composition at Ernici, and high- 46
lights an important case, where a close association of calc- 47
alkaline and ultrapotassic magmas occurs in central Italy. 48
The CA rocks have ITE abundances similar to the associ- 49
ated shoshonites, and resemble the equivalent rocks from 50
the Aeolian arc, Procida and Pontine Islands (Ventotene, 51
Fig. 6), although some minor but significant differences 52
in ITE abundances and ratios, and radiogenic isotopic sig- 53
natures are present. On the other hand, Ernici HKS rocks 54
closely resemble the HKS rocks from the Roman volcanoes 55
(i.e., Vulsini to Alban Hills), for trace element enrichment 56
and ratios, and for radiogenic isotope signatures (Fig. 6, 57
and 8). Therefore, the Ernici mafic rocks appear to encom- 58
pass the whole range of geochemical and isotopic features 59
shown by the central-southern Italy magmatism. 60
10 M.L. Frezzotti, G. De Astis, L. Dallai, C. Ghezzo Fast Track Article
∂
Fig. 9. a) 208Pb/204Pb vs. 206Pb/204Pb, and b) δ18O vs. 87Sr/86Sr dia-grams for Ernici mafic rocks (MgO > 4 wt.%). Literature data (Ref.)are from Civetta et al. (1981), D’Antonio et al. (1996) and Conticelliet al (2002). Fields of central-southern Italy magmatic provincesarea also shown Data source as in Fig. 8.
The variation diagrams of both incompatible and com-1
patible elements reveal an overall decrease in MgO, Ni2
and Cr, with increasing LILE and HFSE contents (Fig. 3).3
These variations are accompanied by an increase of Sr-4
isotope ratios, and a decrease of Nd and Pb-isotope com-5
positions. Whereas the variations in MgO and ferromagne-6
sian trace elements likely reflect magma evolutionary pro-7
cesses, the isotopic variations could be due to open system8
evolutionary processes (e.g., AFC), or could reflect pris-9
tine magma compositional characteristics, as seen in most10
of Roman Province magmas (e.g., Conticelli & Peccerillo,11
1992; Peccerillo, 2002, and references therein).12
Therefore, the following discussion will focus on: i) the13
roles of shallow level evolution vs. source nature and/or14
processes, in determining the observed rock compositions;15
ii) the genetic relationships between CA, SHO and HKS16
magmatism in the area; iii) the genetic relationships with17
other subalkaline to ultrapotassic rocks in Italy; iv) the geo-18
dynamic implications of the compositional characteristics19
observed at Ernici. These themes apply to other volcanoes20
in Italy, and may help in understanding the genesis and geo-21
dynamic significance of magmatism in the Italian peninsula22
and in the southern Tyrrhenian Sea.23
6.1. Shallow level evolution 24
The broadly negative correlations between MgO and in- 25
compatible trace element (ITE) abundances (Fig. 3) could 26
suggest derivation of HKS magmas from less potas- 27
sic magmas by shallow level evolution processes, dom- 28
inated by fractional crystallisation of dominant clinopy- 29
roxene, plus assimilation of crustal rocks. Clinopyroxene- 30
dominated fractional crystallisation can drive liquid com- 31
positions from CA to SHO and HKS, without changing 32
significantly their silica contents, as suggested by Trig- 33
ila & De Benedetti (1993) for Somma-Vesuvius rocks. 34
Such a process, however, requires substantial assimilation 35
of crustal rocks to explain the observed radiogenic isotope 36
variations. Assuming a CA or SHO starting composition, 37
more than 70% crustal material with a composition as the 38
Hercynian Calabrian basement (Rottura et al., 1991) is nec- 39
essary to obtain HKS magmas. This severely contrasts with 40
the strongly silica undersaturated character of HKS rocks 41
(see also discussion in Peccerillo, 2005). Moreover, oxy- 42
gen isotopic data obtained in this study indicate that HKS 43
values fall within the range of CA-SHO rocks, excluding 44
significant assimilation processes by CA magmas to pro- 45
duce HKS. Derivation of Colle Castellone rocks from HKS 46
parental magmas is similarly problematic. 47
Variation diagrams of some major and trace elements 48
against MgO (Fig. 3) show distinct trends for CA, SHO 49
and HKS, suggesting that individual suites represent dis- 50
crete evolutionary series. In CA rocks, the positive trends 51
of MgO vs. Ni and Cr clearly indicate fractional crystallisa- 52
tion of olivine and clinopyroxene as a first order evolution- 53
ary process. However, the variable oxygen isotopic compo- 54
sitions within this series require an open system evolution. 55
The lack of a significant correlation of δ18Ocpx vs. any in- 56
compatible element concentration and radiogenic isotope 57
ratio (Fig. 7b, d), suggests that heavy oxygen was episod- 58
ically added to CA magmas, without significant addition 59
of any other trace element. This suggests an interaction 60
with a material depleted in ITE, but having high-δ18O, such 61
as sedimentary carbonate country rocks (Peccerillo, 1998). 62
The high δ18Ocpx values of the HKS samples also argues 63
for the interaction of ultrapotassic melts with sedimentary 64
carbonate (cf. Dallai et al., 2004). 65
A further interesting aspect of CA rocks is their wide 66
range in Rb content, which spans over more than one order 67
of magnitude, at nearly constant composition of all other 68
geochemical parameters (Fig. 3). Such a spreading cannot 69
be attributed to secondary processes, because of the lack 70
of petrographic, and chemical evidence for deuteric trans- 71
formations in the studied rocks (i.e., low LOI, relatively 72
invariant concentration of other mobile elements such as 73
alkalies). Therefore, these variations are likely to represent 74
pristine geochemical signatures of CA magmas. It is worth 75
of note that similar or higher Rb variations were also de- 76
tected in potassic rocks at the nearby volcano of Rocca- 77
monfina (Giannetti & Ellam, 1994). 78
The HKS rocks have lower ferromagnesian element con- 79
tents than the bulk of CA-SHO rocks, which might repro- 80
duce a higher degree of evolution, and/or a less enriched 81
nature in compatible elements for the parent magmas (see 82
Fast Track Article Calc-alkaline and ultrapotassic magmatism at monti ernici 11
Zr/Th
4
6
8
10
12
14
KSLiterature
0.705
0.706
0.707
0.708
0.709
0.710
0.711
0.71287Sr/86Sr
Ni
0 2 4 6 8 100.705
0.706
0.707
0.708
0,709
0.710
0.711
0.712
K2O
87Sr/86Sr
FCAFCMixing
5
10
15
20
25Zr/Nb
0 20 40 60 80 100 120
ThKS Literature
Mixing
0 20 40 60 80 100 120
KSLiterature
HKSLiterature
HKSLiterature
Pofi volcano
Pofi volcano
HKS Literature
ThHKS Literature
KSLiterature
a b
c dODP655
Roman Province
Ventotene Is. & Roccamonfina
Fig. 10. Inter-element and isotopic variation diagrams for Ernicimafic rocks (MgO > 4 wt%). Symbols as in Fig. 2.
Rogers et al., 1985). Variation of Ni, Cr, and MgO in the1
HKS rocks (Fig. 3, and 10a) is explained by fractional crys-2
tallisation of mafic phases internal to this series.3
SHO rocks have intermediate potassium contents be-4
tween CA and HKS compositions. Some incompatible el-5
ement vs. incompatible element ratios (e.g., Zr/Th vs. Th,6
Fig. 10b) define hyperbolic trends between CA, and Colle7
Castellone HKS compositions, with SHO and HKS plot-8
ting along this trend. This may suggest mixing between9
magmas of extreme compositions to give intermediate-K10
magmas as hybrid products. Interaction between magmas11
with different enrichments in potassium was previously12
suggested by Civetta et al. (1981). However, such a pos-13
sibility is not supported by other geochemical parameters,14
such as Th vs. Zr/Nb, and poorly variable 87Sr/86Sr of CA-15
SHO rocks (Fig. 10c, and d).16
In conclusion, fractional crystallisation, assimilation of17
carbonate rocks, and probably mixing played important18
roles during magma evolution at Ernici. These processes,19
however, did not change significantly the first order trace-20
element compositional characteristics of magmas. Thus,21
we propose that at Ernici, at least three distinct magma se-22
ries – CA-SHO, HKS, and HKS-Colle Castellone – with23
distinct degree of silica saturation, enrichment in incom-24
patible elements, and radiogenic isotope signatures were25
generated and erupted.26
6.2. Petrogenesis of CA-SHO and HKS magmas27
Central Italy magmas originated from an anomalous upper28
mantle, which was contaminated by crustal material (e.g.,29
Hawkesworth & Vollmer, 1979; Peccerillo, 1985; Rogers30
et al., 1985). Several authors (e.g., Peccerillo, 2005 and ref-31
erences therein) identify sedimentary rocks, such as pelites32
and marly sediments, as the crustal component introduced33
in variable amounts into a lherzolitic upper mantle, to gen-34
erate a metasomatised source able to produce the vari-35
able but anomalous compositions of Roman magmas. The36
different degrees of silica saturation have been attributed, 37
based on the experimental evidence, to the depth of partial 38
melting, which generates potassic alkaline magmas with 39
increasing degree of silica undersaturation at increasing 40
pressure (e.g., Wendlandt & Eggler 1980a, and b; Melzer & 41
Foley, 2000). Since magmas with various degrees of silica 42
saturation also have distinct trace element and isotopic sig- 43
natures, it has been concluded that magmas were generated 44
at different depths in an upper mantle that was vertically 45
zoned for ITE and isotopes (Peccerillo, 1999). 46
Alternatively, some authors (e.g., Foley, 1992; Perini 47
et al., 2004) suggest that magmas with different enrich- 48
ments in incompatible elements could derive from partial 49
melting of a mantle crossed by phlogopite veins, involv- 50
ing variable contributions of vein material and host rocks 51
during melting processes: low degrees of partial melting 52
of a veined mantle would allow almost pure vein material 53
to melt, generating highly potassic magmas. At higher de- 54
grees of melting, the same mantle-source would allow in- 55
creasing amounts of lherzolite wall-rock to go into the melt, 56
generating magmas with lower enrichments in incompati- 57
ble elements. In this view, CA and SHO magmas would 58
represent “diluted” HKS melts. 59
This last hypothesis could explain some of the petrologi- 60
cal features of the Ernici rocks. As an example, the overall 61
higher ferromagnesian element contents in the CA rocks 62
could well derive from a higher participation of lherzolite 63
into the melt, whereas the lower Ni and Cr of HKS could 64
reflect the higher proportion of metasomatic veins partic- 65
ipating into the melt. Also the variable enrichments in in- 66
compatible elements could support such a theory. However, 67
this hypothesis fails to account quantitatively for some of 68
the major geochemical variations observed, notably Sr-Nd 69
isotopic signatures. If the Colle Castellone lava is assumed 70
as representative of a pure vein melt, dilution by a melt 71
derived from a normal OIB- or MORB-type mantle would 72
require high amounts of these depleted melts (>70–80 %) 73
to drive Sr isotopic compositions to those of CA rocks 74
(Fig. 8). Therefore, the strong compositional variability of 75
the Ernici rocks likely results from a heterogeneous mantle 76
source. If this conclusion is correct, the isotopic variations 77
observed through the eruptive sequence in the Pofi centre 78
(i.e., 87Sr/86Sr from 0.706446 to 0.709679, Fig. 10c) could 79
testify for a vertically heterogeneous upper mantle. 80
Two temporally distinct mantle metasomatic episodes 81
have been suggested by Peccerillo & Panza in the man- 82
tle beneath Ernici (1999): an earlier event, analogous to 83
that affecting the Roman region, and a later one, similar 84
to that affecting the Campanian region (Peccerillo, 2001, 85
2003). The first metasomatic event could account for the 86
HKS magma compositions, which are close to the equiv- 87
alent rocks of the Roman Province, whereas the latter 88
event could have generated the CA and SHO magmas, 89
which share several elemental and isotopic characteristics 90
with Campanian rocks. However, we note that, while ra- 91
diogenic isotope compositions span the values observed 92
for Campania and Roman provinces – thus supporting a 93
two-stage metasomatic modification for mantle sources – 94
trace element abundances and ratios depict a more complex 95
evolution. 96
12 M.L. Frezzotti, G. De Astis, L. Dallai, C. Ghezzo Fast Track Article
ODP655
0
50
100
150
200
250
Ba/Th
0
2
4
6
8
10
La/Nb
0
20
40
60
80
100
Th/Ta
0 2 4 6 8 100100
200
300
400
500
600
700
Zr/Ta
K2O
ODP655
ProcidaVentotene
Somma-Vesuvius
ProcidaVentotene
Somma-Vesuvius
ProcidaSomma-Vesuvius
Aeolian IslandsCA - HKCA
Suites
Aeolian IslandsCA - HKCA
Suites
ODP655
Roman Province
Roman Province
Roman Province
ProcidaSomma-Vesuvius
Roman Province
ODP655
Ventotene Is.Roccamonfina
Aeolian Is.CA - HKCASuites
a b
c d
0 2 4 6 8 10K
2O
Fig. 11. ITE ratios vs. K2O for Ernici mafic rocks (MgO � 4 wt.%)compared with fields of other southern Italy volcanoes. Symbols asin Fig. 5, 6. Data source as in Fig. 8.
Figure 11 shows the comparison of selected key ITE ra-1
tios of Ernici vs. Roman, Campanian, and western-central2
Aeolian arc mafic volcanics. The CA-SHO rocks fall away3
from Campania, and cluster in the field of western-central4
Aeolian arc. In particular, Ernici CA-SHO rocks have5
higher LILE/HFSE (e.g., La/Nb), and distinct LILE/LILE6
(e.g., lower Ba/Th) and HFSE/HFSE ratios (e.g., Zr/Ta)7
than Campanian rocks having similar K2O. Therefore,8
these data suggest a mantle source different from that be-9
neath the Campanian Province, and comparable to that of10
Aeolian volcanoes: the pre-metasomatic mantle composi-11
tion and/or the metasomatic events appear to be different12
for the Campania Province and for the Ernici CA-SHO13
source.14
The relatively low LILE/HFSE ratios at Vesuvius and the15
eastern Aeolian arc has been interpreted to indicate an OIB-16
type source prior to metasomatism (Ellam et al., 1989;17
Serri, 1990; Peccerillo, 2001; De Astis et al., 2003, and18
2004, and references therein). The higher values of these19
ratios and the lower abundance of HFSE at Ernici may re-20
veal a MORB-type pre metasomatic source. This issue will21
be further discussed below.22
As for the metasomatic event affecting source mantle23
rocks, the similar isotopic composition of the Ernici CA-24
SHO rocks, and of the Campanian volcanoes support a25
similar metasomatic agent. The observed difference in26
LILE/LILE ratios between Ernici and Campanian volca-27
noes may in fact either depend on the nature of metaso-28
matic agents or be a consequence of source mineralogy29
(e.g., occurrence of different proportions of phlogopite and30
amphibole), that have profound effects on ITE partition co-31
efficients, and abundance in magmas, (see, De Astis et al.,32
2006). Conversely, Ernici HKS rocks consistently plot in33
the field of the Roman Province, suggesting a similar man-34
tle source (i.e., similar pre-metasomatic composition), and35
nature of metasomatism.36
The issue of a genetic relationship among the different37
Ernici magma series requires a characterisation of the pre-38
metasomatic source composition. Since HFSE are poorly39
mobile during fuid-related metasomatism, the observed 40
HFSE abundances and ratios in the Ernici rocks could iden- 41
tify the pre-metasomatic mantle features. Low HFSE con- 42
centrations in the Ernici rocks suggest a MORB-type man- 43
tle source. The Zr/Nb vs. Th diagram (Fig. 10d) shows 44
that CA-HKCA rocks and “extreme” HKS rocks (i.e., 45
Colle Castellone) have comparable Zr/Nb ranges (CA- 46
HKCA = 13.6–18.4). The bulk of HKS has quite differ- 47
ent and higher Zr/Nb ratios (19.4–22.8). This range closely 48
overlaps the average values of MORB (≈ 22.1), and is sim- 49
ilar to Zr/Nb ratio of MORB-type rocks from the Tyrrhe- 50
nian Sea floor (ODP 655, Fig. 9d). Most of the Ernici 51
CA-HKCA rocks are in the field of Ventotene and Roc- 52
camonfina rocks, and not much different from Aeolian CA 53
rocks (Zr/Nb ≈ 11–12), which have been related to a E- 54
MORB-type pre-metasomatic mantle composition (Ellam 55
et al., 1989: Francalanci et al., 1993). 56
6.3. Relations between CA and SHO magmas 57
Whereas the generation of CA-SHO and HKS magmas in 58
distinct mantle sources is strongly supported by our data, 59
the processes that generated CA and SHO magmas are con- 60
troversial. These two rock groups have very comparable 61
incompatible element patterns (Fig. 5b), suggesting they 62
come from a single mantle source, affected by similar com- 63
positional modifications. However, CA rocks have lower 64
K2O than SHO, yet display higher Cs and very variable Rb. 65
At issue is the nature of the process that generated magmas 66
showing similar compositions for radiogenic isotopes and 67
for all ITE contents, except for K, Rb and Cs. The lack of 68
correlation between K and Rb, and between these and other 69
incompatible elements implies distinct processes for the 70
variation of these two elements. Similar features have been 71
observed also at Roccamonfina, and have been explained 72
in terms of the mineralogy of mantle sources by Giannetti 73
& Ellam (1994). The similar ITE (except for Rb) and ra- 74
diogenic isotopes suggest a homogeneous source rock and 75
similar degrees of partial melting. 76
Potassium is a major element, and its abundance depends 77
on the nature of the mineral phases contributing to the melt. 78
Accordingly, magmas with comparable trace element and 79
radiogenic isotope composition and distinct potassium con- 80
tent could derive from geochemically homogeneous mantle 81
sources, but having a different mineralogy. A phlogopite- 82
bearing source – with this mineral going into the melt – 83
could be responsible for the generation of SHO magmas, 84
whereas comparable degrees of partial melting of a geo- 85
chemically similar source containing amphibole could gen- 86
erate CA magmas. The variable mineralogy in the man- 87
tle might result from variation in the metasomatic fluids, 88
and/or of different pressure of partial melting. Such a very 89
general conclusion, does not explain the variation in Rb, 90
whose abundance can be tentatively ascribed to other pro- 91
cesses, including syn-eruptive transfer from altered HKS 92
rocks. 93
Fast Track Article Calc-alkaline and ultrapotassic magmatism at monti ernici 13
6.4. Nature of mantle metasomatic processes1
Geochemical data suggest that the mantle sources of Ernici2
magmas might have been variably modified by LILE-rich,3
and HFSE-poor metasomatic agents, such as a subduction-4
related hydrous fluid and/or melt. The high Sr- and low5
Nd-isotope ratios of Ernici rocks require that mantle con-6
tamination was provided by upper crustal material, such7
as pelitic to marly material (Peccerillo et al., 1999). This8
is supported by Sr-Nd-Pb isotopic ratios of Ernici rocks,9
which plot along a curved (mixing) trend between a HIMU-10
or FOZO-like mantle composition and metapelites (e.g.,11
Gasperini et al., 2002). Further, also incompatible ele-12
ment compositions show many characteristics in com-13
mon with metapelites and marl. However, both CA-SHO14
and HKS rocks have much higher LILE/HFSE ratios than15
both metapelites and marls. Also La/Yb ratios are higher,16
whereas HFSE contents are close to MORB values. More-17
over, the lack of a negative Sr anomaly in the mantle-18
normalised diagrams (except for Colle Castellone), which19
is common in pelites, agrees with marls rather than pelites20
as contaminants for the bulk of Ernici magma sources.21
The high LILE/HFSE ratios and REE fractionation re-22
quire that some element fractionation occurred during man-23
tle contamination. Subduction fluids may well fractionate24
incompatible trace elements. The liquid/mineral partition25
coefficients of trace elements, in fact, vary considerably26
depending on the nature of the agent of metasomatism,27
which has been theoretically and experimentally identi-28
fied in these environments either as aqueous solutions,29
or as hydrous-silicate melts, or as supercritical interme-30
diate aqueo-silicic liquids, mainly depending on temper-31
ature and pressure conditions (e.g., Stalder et al., 2000).32
Recently, experiments by Kessel et al. (2005) have out-33
lined the dichotomy of low-temperature dehydration versus34
high-temperature melting processes of subducting slabs,35
based on the contrasting solubilities of many trace elements36
in metasomatic aqueous fluids or hydrous melts at 4 GPa37
(120 km) (e.g., higher Sr, Ba, Th/U, and LREE in meta-38
somatic melts). At higher pressures (> 6 GPa; 180 km),39
melt-like solubilities are observed for trace elements in su-40
percritical liquids, yet at low temperatures.41
Although a precise reconstruction of the metasomatic42
events is not possible at this stage and requires further43
specific investigations, we propose that the metasomatic44
agents responsible for the modification of the mantle be-45
neath the Ernici region were hydrous fluids, and/or melts46
generated by subducted rocks at different depths. Dehydra-47
tion and/or melting at different P-T conditions generated48
the element fractionation reproduced by the magmas erupt-49
ing at the surface.50
6.5. Geodynamic implications and conclusions51
One of the key problems of a subduction-related ori-52
gin for potassic alkaline volcanism in central Italy is the53
scarcity or absence of calc-alkaline rocks, in comparison54
with the large volume of potassic magmas. However, rocks55
with CA to HKCA affinity occur at Procida and eastern56
Pontine islands (De Astis et al., 2004): Similar rocks are 57
also observed in the late stage of Roccamonfina activ- 58
ity (0.2–0.1 Ma; Peccerillo, 2005 and references therein), 59
whereas CA basalts and andesites with an age � 2 Ma have 60
been found by deep borehole drillings beneath the Campi 61
Flegrei caldera, in the Campanian region (Barbieri et al., 62
1979; De Astis et al., 2006; De Astis, unpublished data). 63
The subalkaline rocks from Ernici analysed in this 64
work also show CA compositions, closely resembling the 65
CA-HKCA rocks from the central-western Aeolian arc 66
(Fig. 11), which are subduction-related, for a number of 67
structural, geophysical and petrological data (see De Astis 68
et al., 2003, and references therein). Therefore, based 69
on the compositional affinities reported above, it can be 70
concluded that a subduction-related volcanism developed 71
along the Italian peninsula (peri-Tyrrhenian margin), erupt- 72
ing CA-HKCA magmas at Ernici, Roccamonfina, Ven- 73
totene, and some Campanian volcanoes, over a time span of 74
about 2 Ma (Metrich et al., 1988; Piochi et al., 2004). From 75
that time, the bulk of calc-alkaline magmatism shifted to- 76
ward the southernmost sector of the Tyrrhenian Sea, giv- 77
ing rise to the Aeolian Volcanic District, as a result of 78
the subduction of the thinned continental or oceanic-type 79
Ionian lithosphere beneath Calabria. However, the Ernici, 80
Roccamonfina and Campanian volcanoes testify for persis- 81
tency of CA-HKCA activity in central Italy. Isotopic sig- 82
natures of these latter rocks suggest introduction of upper 83
crustal material into their mantle source. This likely derived 84
from subduction of the Adriatic plate, which has a conti- 85
nental type composition distinct from the Ionian plate (e.g. 86
Panza & Pontevivo, 2004). The diversity of the subducting 87
foreland may thus provide an explanation for the scarcity 88
of CA-HCKA magmatism in Central Italy compared with 89
the Aeolian Volcanic District. 90
In terms of geodynamic evolution during the Plio- 91
Quaternary, there are several and slightly different geo- 92
physical/petrological models of subduction processes in 93
Central-Southern Italy (e.g. Keller, 1982; Serri et al., 1993; 94
Doglioni et al., 1999; Gvirtzman & Nur, 1999; Lucente 95
et al., 1999; Wortel & Spakman, 2000; Peccerillo, 2005 96
and references therein). Basically, these models differ for 97
the slab geometry beneath the Apennines, for the age and 98
nature of the mantle metasomatism, and/or for the pro- 99
cesses that were responsible the opening of the Tyrrhenian 100
back-arc basin. However, most of these models agree that 101
two different mantle-crust settings developed beneath the 102
northern Apennine chain and beneath the Calabrian Arc 103
– Southern Tyrrhenian Sea, and that the active subduc- 104
tion zones and related volcanism progressively migrated 105
south-eastward to its present position beneath the Aeo- 106
lian arc (Anderson & Jackson, 1987; Selvaggi & Am- 107
ato, 1992; De Astis et al., 2003) due to differential con- 108
tinental collision, and to south-eastward roll-back of the 109
NW dipping Ionian slab. Moreover, both the kinematic 110
model and seismotectonic framework by Meletti et al. 111
(2000) for the Southern Apennines, and the geodynamic 112
setting depicted by De Astis et al. (2006) for the Cam- 113
panian Province and Monte Vulture magmatism, indicate 114
that central-southern Italy recorded a dramatic change in 115
the geodynamic regime at about 0.8–0.7 Ma, because of the 116
14 M.L. Frezzotti, G. De Astis, L. Dallai, C. Ghezzo Fast Track Article
end of active subduction, slab detachment (break off) of the1
Adriatic slab (Wortel & Spakman, 2000), and a generalised2
uplift of the chain (Hippolyte et al., 1994), up to the fast3
development of rifting both within the inactive thrust belt4
and along the Tyrrhenian slope. Subsequently, the Campa-5
nian Province experienced an increase in the alkalinity of6
magmatism.7
On the basis of the framework depicted above, the late8
(< 0.2 Ma) occurrence of CA magmatism at Ernici, post-9
dating active subduction and mantle modification processes10
by the westward dipping Adriatic plate, poses the prob-11
lem of the relationships between subduction processes and12
CA magmatism in this area. The late onset of the CA-13
HKCA mafic magmatism at Ernici could reflect an in-14
creased degree of partial melting within the upper mantle,15
generated by back-arc extension and associated isotherms16
uprising following slab detachment, which may have in-17
duced melting in the uppermost levels of a vertically18
zoned, and/or isotopically heterogeneous mantle beneath19
the central-southern Italy. In this case, the transition from20
potassic alkaline to CA magmatism at Ernici would testify21
for isotherms upraise and progressively shallower melting22
events in a vertically zoned mantle sector, variably contam-23
inated by slab derived fluids during active subduction of the24
Adriatic plate.25
Finally, it should be noted that some authors (e.g., Lu-26
cente et al., 1999) suggest the presence of a slab window27
beneath Campania and Ernici-Roccamonfina sectors based28
on tomographic studies. However, slab window formation29
is often associated with OIB-type alkali-mafic volcanism30
(Hole et al., 1991). The opening of such a window be-31
low the central Italy would provide an efficient mecha-32
nism for allowing sub-slab asthenospheric mantle to rise33
and melt in a mantle region previously affected by subduc-34
tion (Thorkelson, 1996), likely interacting with subduction-35
related components. This may explain the mixed OIB- and36
arc-type trace element signatures of Campanian and Vul-37
ture volcanoes, which have much lower LILE/HFSE ratios38
than other central Italy magmas (Peccerillo, 2001, 2005;39
De Astis et al., 2006). However, it is unable to explain the40
high LILE/HFSE ratios of Ernici, which seem to exclude41
an OIB-type component. This does not represent a piece42
of evidence against the slab window model, but militates43
against the involvement of deep mantle components in the44
Ernici magma genesis. The same conclusion also applies45
to Roccamonfina, supporting the idea that OIB-type com-46
ponents in central-southern Italy region likely reflects hori-47
zontal mantle inflow from either the Adriatic plate or from48
the Tyrrhenian Sea area, rather than deep mantle compo-49
nents (Peccerillo, 2001; Peccerillo & Lustrino, 2005; De50
Astis et al., 2006).51
Acknowledgements: Authors are indebted to R.W. Nes-52
bitt and R. Taylor of the School of Ocean and Earth Sci-53
ence, National Oceanography Centre, Southampton for Sr54
isotope analyses, and to G. Davies and W. Lustenhouwer of55
the Instituut voor Aardwetenschappen of the Vrije Univer-56
sitieit in Amsterdam for Sr-Nd-Pb isotope analyses. Sug-57
gestions by Rob Ellam and an anonymous referee greatly58
contribute to improve the manuscript. Research is finan- 59
cially supported by MIUR-PRIN 2004 to M.L.F., and by 60
University of Siena (PAR 2004) to C.G. 61
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Received 23 October 2006 105
Modified version received 26 March 2007 106
Accepted 18 June 2007 107