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Contrib Mineral Petrol (2009) 157:122 DOI 10.

1007/s00410-008-0317-x

ORIGINAL PAPER

Petrology and SrNdHf isotope geochemistry of gabbro xenoliths from the Hyblean Plateau: a MARID reservoir beneath SE Sicily?
Giovanna T. Sapienza William L. Grifn Suzanne Y. OReilly Lauro Morten

Received: 20 February 2008 / Accepted: 28 May 2008 / Published online: 17 June 2008 Springer-Verlag 2008

Abstract In situ trace-element and isotopic (87Sr/86Sr) data and whole-rock SrNdHf data on 12 gabbro xenoliths from the Hyblean Plateau (south-eastern Sicily) illustrate the complex petrogenetic evolution of this lithospheric segment. The gabbros formed by precipitation of plagioclase + clinopyroxene from a HIMU-type alkaline melt, then were cryptically metasomatized by a low-Rb, high-87Sr/86Sr uid, and nally inltrated by an exotic, late FeTi-rich melt with 87Sr/86Sr * 0.7055, carrying high concentrations of Sr, Rb and HFSE. The geochemical and isotopic features of both the metasomatizing uid and the FeTi-rich melt are compatible with their common derivation by the progressive melting of an amphibole phlogopiteilmenite metasomatic domain (MARID-type?) that probably resided within the subcontinental lithospheric mantle. Therefore, both the astenosphere and the lithosphere underneath the Hyblean Plateau contributed to the petrogenesis of the gabbros. SmNd dating yields an age of 253 60 Ma for the cumulitic pile, roughly coinciding with a hydrothermal event recorded by crustal zircons in the area. We suggest that the Hyblean Plateau suffered a

thermal eventprobably related to lithospheric thinning and upwelling and melting of the asthenospherein Permo-Triassic time (the opening of the Ionian Basin?). The induced perturbation in the lithosphere caused consequent melting of some previously metasomatised portions. Keywords Gabbro xenoliths In situ Sr isotopes SrNdHf isotope data MARID Hyblean Plateau

Introduction The geochemical and mineralogical features of the lower crust vary widely in different areas of the Earth, reecting episodes of crustal extraction and tectonic modication. Much of our knowledge of the processes through which this inaccessible portion of the lithosphere evolves comes from the study of lower-crustal xenoliths brought to the surface by ascending magmas. Their rapid ascent after entrainment helps to preserve the geochemical and mineralogical features of the deep crust. In the last decades the discovery of a large number of lower crustal xenoliths in Miocene tuff-breccia pipes in the Hyblean Plateau (south-eastern Sicily) has yielded information on the petrological nature of the lithosphere in that area (Scribano 1986, 1988; Tonarini et al. 1996; Sapienza and Scribano 2000; Scribano et al. 2006; Sapienza et al. 2007). The Hyblean Plateau is located in the Central Mediterranean, a geodynamically complex area affected by the collision between the European and African Plates (Dewey et al. 1989). Within this geological framework, the Plateau has generally been considered to represent the northernmost portion of the Pelagian Block (African Plate). However, doubts have been expressed about the continental nature of this lithospheric micro-block (Vai 1994;

Lauro Morten deceased, November 18, 2006. Communicated by J. Hoefs. G. T. Sapienza (&) L. Morten Dipartimento di Scienze della Terra e Geologico-Ambientali, ` di Bologna, Piazza Porta San Donato 1, Universita 40126 Bologna, Italy e-mail: giovanna.sapienza@unibo.it W. L. Grifn S. Y. OReilly ARC National Key Centre for Geochemical Evolution and Metallogeny of Continents, Department of Earth and Planetary Sciences, Macquarie University, Macquarie, NSW 2109, Australia

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Scribano et al. 2006), and suggestions of a possible oceanic or transitional ocean-continent nature have been put forward. Recently, in situ techniques have provided evidence to substantiate the Archean origin of the Hyblean lower crust and upper mantle (Sapienza et al. 2007), but many aspects of the evolution of the Hyblean crust remain unconstrained: e.g., the reservoir(s) contributing to crustal accretion and the processes through which this lithospheric portion evolved. These observations highlight the need for a better knowledge of the Hyblean lower crust, and of its role within the geological framework of the Central Mediterranean setting. Among the Hyblean lower crustal lithotypes (e.g., basic granulites, gabbroic rocks; Sapienza and Scribano 2000; Scribano et al. 2006), the cumulitic gabbros in particular can provide useful clues. To this purpose, a geochemical and isotopic study of Hyblean gabbroic xenoliths has been carried out. Here we present isotopic and trace-element data for 12 gabbro xenoliths collected from the Valle Guffari diatreme (Hyblean Plateau). We discuss (1) the geochemical and isotopic characters of the magma source(s) and possible contaminant(s), and those of the parental magmas of the Hyblean gabbros (via whole-rock analysis and in situ LAM-MCICPMS data), (2) a petrogenetic model for the formation and evolution of these rocks and (3) the signicance of these geochemical results within the geological framework of the Central Mediterranean.

Fig. 1 Simplied geological sketch map of the Hyblean Plateau after Lentini (1984) and Sapienza and Scribano (2000), showing location of Valle Guffari (the sampling site)

Geological setting The Hyblean Plateau makes up the south-eastern corner of Sicily (Fig. 1). It is bordered by the ApennineMaghrebide Chain to the north and west, and by the oceanic Ionian Basin to the east through the HyblaMalta Escarpment. The exposed crust consists of a *10 kmthick MesozoicCenozoic carbonate sequence, overlain by Neogene-Quaternary clastics. Several volcanic layers of different ages interrupt the sedimentary cover (Bianchi et al. 1987) and show variable geochemical, mineralogical and volcanological characteristics: Cretaceous alkalibasaltic lavas (Amore et al. 1988; Sapienza et al. 2008), Miocene alkali-basaltic and nephelinitic lavas and tuff-breccia pipes (Bianchini et al. 1998, 1999), and Plio-Pleistocene lava ows (basalts, basanites and rare nephelinites, with both tholeiitic and alkaline afnities; Beccaluva et al. 1998; Trua et al. 1998). The oldest outcropping volcanics are Cretaceous, but Triassic alkalibasaltic layers are found in the subsurface (Cristofolini 1966). The Plateau has traditionally been considered the northernmost portion of the Pelagian Block (African Plate)

that extends through the thinned Sicily Channel and was subducted under the European Plate (Burollet et al. 1978; Ben-Avraham and Grasso 1990). Although the continental nature of the block is widely accepted, the poor constraints on the lithospheric structure have allowed alternative suggestions, such as oceanic or ocean-continent transitional afnities. On the basis of the distribution of pelagic deposits within the Mediterranean area, Vai (1994) proposed that the Hyblean Plateau represented the western part of the Ionian Permo-Triassic fossil oceanic domain (the socalled Neo-Tethys). Indeed, even the nature (oceanic vs. continental) and the age of the Ionian Basin is still matter of debate (Farrugia and Panza 1981; Catalano et al. 2001; Argnani 2005 and references therein). Petrographic similarities between the Hyblean gabbro xenoliths and oxide gabbros from oceanic settingse.g., the late intrusion of FeTi-rich melts into early gabbroic cumulates and the sheared microstructure along which these melts were injected (documented in gabbros from the South West Indian Ridge; Niu et al. 2002)led Scribano et al. (2006) to suggest an oceanic or ocean-continent transitional origin for this lithospheric sector. However, recent dating of zircons in crustal xenoliths attests to the presence of relic Archean crust beneath the Hyblean Plateau, and Re-Os data on suldes hosted in mantle-derived peridotite xenoliths

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testify to the presence of Archean lithospheric mantle roots (Sapienza et al. 2007). These results reinforce the continental nature of this lithospheric sector.

Analytical techniques The 12 samples studied here were selected among those studied by Scribano et al. (2006). The mineral major element compositions of Hyblean gabbros were determined on C-coated polished thin section using a Cameca SX50electron microprobe installed at the CNRIstituto di Geoscienze e Georisorse (Padova) and tted with four wavelength-dispersive spectrometers. The operating conditions were: accelerating voltage of 15 kV, beam current of 15 nA and a nominal spot size of *1 lm. Raw data collected with the probe were corrected for matrix effects using the ZAF procedure. Whole-rock and in situ isotopic data and mineral traceelement data were acquired in the Geochemical Analysis Unit at GEMOC, Macquarie University, Australia. Wholerock samples were nely powdered in an agate mortar, dissolved in HClO4 and nally loaded into resin columns. Strontium was separated from the bulk REE using 2.5 N HCl as elutant. The separation of Sm and Nd was performed using 6 N HCl as elutant. Hafnium was separated using rstly 6 N HCl (to collect Ti, Zr and Hf), and secondly 2.5 N HCl and 0.5 N HF. SrNdHf isotope data were performed by solution analysis, using a Nu Plasma multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS). Nd, Sr and Hf isotopic data are normalized, respectively, to 146Nd/144Nd = 0.7219, 86Sr/88Sr = 0.1194 and 179 Hf/177Hf = 0.7325. During period of measurement the mean value for 87Sr/86Sr of the SRM 987 standard was 0.710264 16 (n = 2), for 143Nd/144Nd of the JMC321 standard was 0.511115 4 (n = 3), and for 176Hf/177Hf of JMC475 standard was 0.282178 5 (n = 7). For the calculation of epsilon Hf (eHf) and Nd (eNd) we use a decay constant for 176Lu of 1.93 9 10-11 a-1 (Sguigna et al. 1982) and a decay constant for 147Sm of 6.54 9 10-12 a-1 ger 1977). Epsilon values have been calcu(Steiger and Ja lated as present-day values. 147Sm/144Nd values have been calculated using isotopic abundances: 147Sm = 14.99% and 144 Nd = 23.8%. Maximum errors for 147Sm/144Nd ratio are taken as 1%. The SmNd isochron calculation was done using Isoplot (Ludwig 1999). In situ Sr isotope analyses were carried out on three samples. The analyses were performed using a New Wave LUV213 laser ablation microprobe (LAM) attached to a Nu Plasma multi-collector ICPMS (MC-ICPMS). The laser spot size was 50100 lm. The BB-1 standard (87Sr/86Sr = 0.70444 7; n = 6) was analyzed as a

cross-check of analytical accuracy. Each analysis took *200 s, following the collection of 30 s gas background. Other analytical details are given by Adams et al. (2005). The trace-element compositions of minerals from seven xenoliths were determined in polished sections *100 lm thick using a LUV266 LAM attached to an Agilent 7500 Inductively Coupled Plasma Mass Spectrometry (LAMICPMS). NIST 610 was used as the external standard; internal standards were Ca for clinopyroxene, plagioclase and amphibole and Ti for oxides. The spot size was *40 lm. Samples were analyzed in runs of ca. ten analyses (two analyses of NIST 610 standard, one analysis of BCR-1, ve analyses of unknown points, two analyses of NIST 610 standard). Each analysis took *180 s, with gas background measurement of *55 s prior to ablation. Data were reduced using the in-house GLITTER online (van Achterbergh et al. 2001). Further analytical details are given by Belousova et al. (2001). In case of clinopyroxene and plagioclase grains, the analyses were performed in the core of the minerals to avoid possible late reaction rims, which in turn are too thin to be analyzed.

Petrology of the Hyblean gabbro xenoliths Petrographic and geochemical features of the Hyblean gabbros have been presented elsewhere (Sapienza and Scribano 2000; Scribano et al. 2006). Here we summarize the most relevant features. The Hyblean gabbros are medium- to coarse-grained rocks (Fig. 2), mainly composed of cumulitic plagioclase (An4080; Table 1) and diopsidic clinopyroxene (mg# = 7278; Al2O3 * 4.5 wt%, TiO2 * 0.9 wt%; Al2O3 and TiO2 are higher in samples FB11 and FB-f7; Table 2). These rocks have suffered more or less pronounced textural re-equilibration, which sometimes partially obliterates the primary igneous texture. However, there is a petrographic continuum from gabbros with clearly igneous microstructure (euhedral to subhedral, up to 4 mm plagioclase and up to 6 mm clinopyroxene, PL-I and CPX-I, with only local recrystallisation into polygonal neoblasts \0.5 mm, PL-II and CPX-II; Fig. 2a, b) to those with mainly granuloblastic microstructures (very rare or absent relict igneous phases set in a polygonal matrix of PL-II and CPX-II; Fig. 2c). Porphyroclastic samples represent the intermediate textural type (Fig. 2d). FeTi oxides are enclosed within silicate phases (ilmenite and Ti-magnetite, OX-I; Fig. 2b) or occur as interstitial grains (ilmenite, OX-II; Fig. 2a). Intercumulus pockets consist of mildly altered brownish crypto- to micro-crystalline matter enclosing ne-grained clinopyroxene, plagioclase, zeolites and large anhedral FeTi oxides (OX-III B 1 mm, sometime up to 4 mm; Table 3 and Fig. 2e, f). These oxides enclose irregular green

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4 Fig. 2 Photomicrographs showing the petrographic features of the studied Hyblean gabbros. a Foliation in gabbro FB-f4, dened by oriented clinopyroxene (CPX-I) and plagioclase (PL-I) porphyroclasts; interstitial FeTi oxides (OX-II) are present. b Local polygonal plagioclase and clinopyroxene neoblasts (PL-II and CPX-II) surround the igneous porphyroclasts; CPX-I hosts FeTi oxides (OX-I). c Granoblastic-textured gabbro FB11 characterized by a very few igneous relics (CPX-I and PL-I) set in a matrix of clinopyroxene and plagioclase neoblasts (CPX-II and PL-II). d Porphyroclastic texture in gabbro FB13 showing some relics of igneous plagioclase (PL-I) set in a polygonal matrix of clinopyroxene and plagioclase neoblasts (CPX-II and PL-II). e FeTi-rich intercumulus pockets enclosing large amoeboid FeTi oxide (OX-III) in gabbro FB80; green hercynitic spinel (SPL) occurs within OX-III; thin, exsolutionfree rim in CPX-I grains at contact with intercumulus pockets is visible. f Plagioclase grains (PL-I) show corrosion rims in contact with the intercumulus pockets in sample FB80; a OX-III grain occurs within this pocket

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hercynitic spinel (SPL; Fig. 2e), and can reach up to 18 vol% (Scribano et al. 2006). The modal abundance of the intercumulus pockets is generally higher in the more igneous-textured gabbros than in more metamorphic-textured ones. Clinopyroxene grains in contact with these pockets exhibit a thin exsolution-free rim (Fig. 2e), whereas plagioclase grains are strongly corroded (Fig. 2f); these features imply disequilibrium with intercumulus liquid, and almost disappear in the most metamorphictextured gabbros (Scribano et al. 2006; Fig. 2c). Clinopyroxene often contains exsolution lamellae of ilmenite. Rare grains and laths of brown amphibole (Ti-pargasite) occur within clinopyroxene in sample FB70; the Ti-pargasite grains show reaction rims of oxides at the contact with the host clinopyroxene. The whole-rock C1-normalized rare earth element (REE) patterns of all samples are similar (Fig. 3a), characterized by relatively unfractionated light REE (LREE)

(LaN/SmN * 1, rarely up to 2), a weak positive Eu anomaly (Eu/Eu* = 12) and depletion in heavy REE (HREE) relative to the LREE and middle REE (MREE) (LaN/YbN = 28; SmN/YbN = 35) (Scribano et al. 2006). When normalized to primitive mantle (PM) (Fig. 3b), all these rocks show enrichment of selected large ion lithophile elements (LILE; Sr, Rb and Ba) over Th, U and high eld strength elements (HFSE; Zr, Hf, Nb, Ta) (Scribano et al. 2006). The variably positive Ti anomaly reects the modal abundance of FeTi oxides.

Whole-rock SrNdHf isotope geochemistry Present-day SrNdHf isotope data are listed in Table 4 and plotted in Figs. 4 and 5. 143Nd/144Nd is very similar in all samples (average *0.5129 and eNd * +5, except for gabbro FB-e11 having 143Nd/144Nd = 0.513062), whereas

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Contrib Mineral Petrol (2009) 157:122 Table 1 Representative in situ major- and trace-element analyses for plagioclases from Hyblean gabbros FB50 PL_11 Elements (wt%) 49.38 SiO2 TiO2 b.d.l. Al2O3 32.18 FeOt 0.04 MnO 0.01 MgO 0.01 CaO 15.77 Na2O 3.09 K2O 0.04 Total 100.5 Ab mol% 26.1 An mol% 73.7 Or mol% 0.2 Elements (ppm) Rb 0.092 Ba 99.1 Th 0.141 U 0.051 Nb 0.143 Ta 0.007 Sr 2,039 Zr 1.58 Hf 0.025 Y 0.371 La 6.18 Ce 10.4 Pr 0.894 Nd 2.75 Sm 0.279 Eu 0.727 Gd 0.164 Tb 0.016 Dy 0.084 Ho 0.015 Er 0.049 Tm 0.004 Yb 0.036 Lu 0.004 Eu/Eua 9.5 LaN/SmN 12.8 PL_12 FB-f31 PL_13 PL_14 VB5 PL_13 PL_16 FB-f4 PL_12 PL_13 FB70 PL_12
a

FB11 PL_16 PL_12


a

FBf7 PL_15 PL_11 PL_15

47.95 b.d.l. 32.94 0.07 0.04 b.d.l. 16.64 2.31 0.03 100.0 20.1 79.8 0.1 0.546 106 0.059 0.019 0.173 0.011 2,062 1.63 0.044 0.370 5.94 8.94 0.862 2.84 0.277 0.866 0.234 0.012 0.116 0.014 0.014 0.003 0.029 0.004 10.0 12.4

50.92 b.d.l. 32 0.08 b.d.l. b.d.l. 12.17 4.22 0.16 99.6 38.2 60.9 1.0 0.164 134 0.073 0.031 0.446 0.018 2,208 2.87 0.047 0.290 4.39 7.27 0.794 2.71 0.306 0.921 0.148 0.018 0.079 0.008 0.025 0.005 b.d.l. 0.007 11.6 8.3

51.6 0.08 31.58 0.2 0.08 b.d.l. 11.37 4.47 0.21 99.6 41.0 57.7 1.3 0.134 123 0.020 b.d.l. 0.009 b.d.l. 1,957 0.21 b.d.l. 0.424 3.04 6.02 0.716 2.35 0.328 0.929 0.179 0.018 0.110 0.015 0.035 0.003 0.032 0.005 10.5 5.4

51.67 b.d.l. 31.5 0.14 b.d.l. b.d.l. 11.76 4.42 0.13 99.6 40.2 59.1 0.8 79.1 7,688 0.079 0.019 0.306 0.016 2,922 2.08 0.064 0.550 5.77 7.95 0.785 2.45 0.278 1.34 0.285 0.014 0.089 0.018 0.027 0.002 0.038 0.006 14.2 12.0

51.45 b.d.l. 31.82 0.15 b.d.l. b.d.l. 11.73 4.24 0.16 99.6 39.2 59.9 1.0 0.127 101 0.048 0.038 0.629 0.046 1,529 3.40 0.076 0.454 3.50 6.82 0.801 2.99 0.390 1.00 0.251 0.023 0.104 0.019 0.025 0.004 0.035 0.007 9.1 5.2

48.66 0.01 32.61 0.08 b.d.l. b.d.l. 16.55 2.54 0.04 100.5 21.7 78.1 0.2 0.112 77.6 0.062 b.d.l. 0.314 0.070 2,006 0.680 b.d.l. 0.126 5.08 7.98 0.777 2.76 0.217 0.845 b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. 13.6

49.02 b.d.l. 32.26 0.09 0.02 0.03 15.83 3.02 0.03 100.3 25.6 74.2 0.2 b.d.l. 75.1 0.051 0.051 0.172 0.041 1,922 1.34 b.d.l. 0.498 2.05 3.74 0.442 1.61 0.242 0.918 0.217 b.d.l. 0.18 0.03 b.d.l. b.d.l. b.d.l. b.d.l. 11.8 4.9

58.0 0.03 26.0 0.03 b.d.l. 0.01 8.38 6.65 0.29 99.4 58.3 40.1 1.6 0.069 464 b.d.l. 0.074 b.d.l. b.d.l. 1,936 9.97 b.d.l. 0.121 11.2 13.6 0.978 2.74 0.185 0.870 b.d.l. b.d.l. b.d.l. b.d.l. 0.026 b.d.l. b.d.l. b.d.l. 35.0

57.43 0.04 26.2 0.03 b.d.l. b.d.l. 8.45 6.69 0.24 99.1 58.0 40.6 1.4 0.103 482 b.d.l. b.d.l. b.d.l. b.d.l. 1,831 b.d.l. b.d.l. 0.133 10.9 13.8 1.06 2.76 0.213 1.05 0.087 b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. 19.8 29.7

49.85 0.01 31.51 0.02 b.d.l. 0.01 15.06 3.14 0.05 99.6 27.1 72.6 0.3 0.109 69.0 b.d.l. b.d.l. b.d.l. 0.018 1,688 b.d.l. b.d.l. 0.087 2.97 5.18 0.563 1.71 0.181 0.526 0.139 b.d.l. 0.05 b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. 9.6 9.5

49.98 0.02 31.70 0.05 b.d.l. b.d.l. 15.01 3.07 0.05 99.9 27.0 72.7 0.3 b.d.l. 64.11 b.d.l. b.d.l. b.d.l. b.d.l. 1,779 b.d.l. b.d.l. 0.104 3.04 5.24 0.512 1.74 0.221 0.498 0.064 b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. 9.8 8.0

53.5 b.d.l. 30.89 b.d.l. b.d.l. b.d.l. 10.16 4.99 0.16 99.7 46.6 52.4 1.0 4.13 474 b.d.l. b.d.l. b.d.l. b.d.l. 2,001 b.d.l. b.d.l. 0.143 6.99 10.5 0.848 2.45 0.136 1.21 b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. 29.8

53.35 b.d.l. 30.61 0.06 b.d.l. b.d.l. 10.34 5.1 0.15 99.6 46.7 52.4 0.9 0.356 332 b.d.l. b.d.l. b.d.l. b.d.l. 1,815 b.d.l. b.d.l. b.d.l. 6.55 9.79 0.689 1.89 b.d.l. 0.961 b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. b.d.l.

Rare earth element ratios are C1-normalized (Anders and Grevesse 1989) b.d.l. below detection limit a Data from Scribano et al. (2006)

Sr/86Sr ranges widely, from 0.703943 to 0.705192 (Fig. 4a). For comparison, elds for xenoliths and lavas from the Central Mediterranean area are also plotted in the

87

SrNd space (Fig. 4a). The Nd isotope composition of the Hyblean gabbros is similar to that of the Hyblean peridotites and basic granulites and to lavas from Linosa and Pantelleria

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Table 2 Representative in situ major- and trace-element analyses for clinopyroxenes and the amphibole (AMPH) from Hyblean gabbros FB-f31 CPX_10 CPX_5 CPX_6 CPX_1 CPX_4 CPX_1 CPX_2 CPX_1
a

FB50 CPX_3 AMPH


a

FB-f4 CPX_1
a

VB5 CPX_3 CPX_2

FB70

FB11

FB-f7 CPX_3

123
51.04 0.92 3.71 7.49 0.22 13.92 22.78 0.54 b.d.l. 100.6 77 0.088 1.96 0.160 0.045 2.21 0.150 67.1 79.8 3.05 17.3 4.43 16.9 3.21 17.9 5.17 1.82 5.10 0.716 4.10 0.749 1.71 0.663 1.62 3.75 3.65 0.667 1.53 0.657 0.645 4.59 4.54 1.67 1.59 1.30 4.24 0.542 3.67 0.539 1.52 4.57 4.50 3.96 14.9 14.4 13.5 2.52 2.44 2.21 3.35 20.0 6.18 1.67 5.54 0.808 5.10 0.821 2.12 11.6 11.4 11.5 17.1 2.72 2.75 3.39 4.75 15.6 15.5 13.7 21.7 23.0 4.34 17.1 3.36 20.3 6.49 1.93 6.61 0.892 5.30 0.933 2.25 1.97 2.46 2.41 4.90 4.00 56.7 57.1 53.4 158 98.1 54.4 53.7 567 47.8 63.7 70.5 103 4.00 26.4 5.28 20.9 4.20 23.2 6.81 2.32 7.41 1.008 6.29 1.080 2.63 0.120 0.076 b.d.l. 0.075 0.068 0.119 0.038 1.93 0.024 0.709 b.d.l. 0.068 b.d.l. 0.331 0.030 0.341 0.065 0.855 b.d.l. 0.453 0.113 66.3 178 5.31 39.0 12.22 42.0 7.50 37.2 9.35 3.11 8.60 1.25 7.70 1.41 3.61 0.131 0.095 b.d.l. 0.055 0.163 0.333 0.020 4.89 0.143 35.0 b.d.l. 0.960 7.22 b.d.l. 0.116 0.020 0.520 b.d.l. 0.098 0.481 b.d.l. b.d.l. b.d.l. 0.025 b.d.l. 0.659 0.149 71.7 179 5.49 38.9 12.28 42.4 7.56 37.1 9.41 3.17 8.59 1.28 7.38 1.40 3.51 78 78 78 76 77 78 74 72 100.1 100.0 100.4 100.4 99.9 100.2 99.9 99.5 97.8 62 10.2 671 1.00 0.287 41.3 2.66 423 176 5.29 43.6 21.10 66.7 10.97 51.8 11 4.72 11.6 1.55 9.52 1.72 4.44 b.d.l. b.d.l. 0.03 0.01 b.d.l. b.d.l. 0.01 b.d.l. 0.92 0.7 0.84 0.64 0.55 0.86 0.70 1.05 0.92 2.96 22.63 22.6 23.4 23.2 22.69 22.7 20.9 17.4 11.4 22.9 0.97 0.01 100.0 76 b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. 0.028 69.5 42.0 1.83 18.3 2.96 14.7 3.16 19.0 5.73 2.11 5.75 0.746 4.38 0.777 1.74 13.58 13.8 13.3 12.9 13.45 13.47 13.2 14.6 11.5 11.9 0.12 0.14 0.20 0.29 0.15 0.17 8.13 10.4 0.17 0.19 7.01 6.89 6.79 7.44 7.32 6.88 0.27 0.33 12.7 6.82 7.64 0.22 12.3 22.3 0.96 b.d.l. 101.0 74 b.d.l. 0.133 0.031 0.017 b.d.l. 0.028 68.9 43.4 1.80 19.1 3.08 15.2 3.32 19.9 5.86 2.23 5.83 0.830 4.29 0.785 1.88 4.38 4.4 4.55 4.78 4.54 5.04 5.04 4.71 13.3 7.80 7.89 50.82 0.84 50.6 0.73 50.6 0.86 49.9 1.29 50.28 0.64 50.43 0.76 50.4 0.98 50.2 0.98 40.4 4.37 47.5 1.87 47.9 1.75 49.21 1.05 6.93 7.5 0.23 12.57 21.45 0.94 b.d.l. 99.9 75 b.d.l. b.d.l. 0.196 0.049 0.186 0.081 57.3 65.1 2.40 21.7 6.14 24.1 4.74 24.4 6.66 2.93 6.13 0.911 4.96 0.926 2.16 49.94 0.82 6.26 7.23 0.09 12.87 21.77 0.97 b.d.l. 100.0 76 b.d.l. b.d.l. 0.213 0.027 0.118 0.045 59.8 63.5 2.45 21.9 5.99 23.8 4.50 23.8 6.72 2.85 6.16 0.871 5.49 0.846 2.25

CPX_2

CPX_4

Elements (wt%)

SiO2 TiO2

50.65 0.78

50.17 0.90

Al2O3

4.27

4.46

FeOt

7.46

7.40

MnO

0.26

0.26

MgO

13.61

13.54

CaO

23.07

22.83

Na2O

0.68

0.59

K2O

0.01

b.d.l.

Total

100.8

100.2

mg#

76

77

Elements (ppm)

Rb

0.053

0.824

Ba

1.53

20.7

Th

0.119

0.146

U Nb

0.030 0.237

0.041 1.79

Ta

0.030

0.140

Sr

56.5

94.3

Zr

72.9

81.5

Hf

2.90

3.33

12.3

17.7

La

3.68

4.48

Ce

15.1

17.1

Pr

2.76

3.31

Nd

14.5

18.0

Sm

3.87

5.05

Eu

1.43

1.76

Gd

3.49

5.14

Tb

0.524

0.715

Dy

2.94

4.14

Contrib Mineral Petrol (2009) 157:122

Ho Er

0.513 1.22

0.746 1.78

Contrib Mineral Petrol (2009) 157:122 CPX_3

7 Table 3 Representative in situ major-element, rare earth element, Nb and Ta data for oxides from Hyblean gabbros FB50_ox9 OX III FB50_ox11 OX III FB70_ox5 OX III

0.243

1.47

0.234

2.3 4.4 2.1 3.9

FB-f7

CPX_2

0.278

1.65

0.215

1.4

1.3

Elements (wt%) SiO2 0.12 52.25 0.54 39.28 0.37 7.09 0.06 b.d.l. 99.7 9.16 6.89 0.005 0.022 0.004 0.023 0.008 0.004 0.009 0.002 0.023 0.006 0.023 0.004 0.033 0.007 b.d.l. 54.08 0.57 37.63 0.54 8.55 0.07 b.d.l. 101.4 30.6 11.2 0.010 0.056 0.010 0.049 0.012 0.005 0.018 0.003 0.024 0.007 0.021 0.004 0.036 0.007 0.03 50.15 0.70 41.30 0.49 6.21 0.07 b.d.l. 99.0 114 9.40 0.006 0.017 0.003 0.027 b.d.l. 0.006 0.013 0.007 0.051 0.011 0.040 0.008 0.065 0.012 TiO2 Al2O3 FeOt MnO

CPX_3

0.206

1.32

0.178

1.3 4.3 1.4 4.7

CPX_1

0.214

FB11

1.18

0.178

1.1

1.1

MgO CaO Cr2O3

AMPH

0.514

3.55

0.473

3.3 3.3

1.2

Total Elements (ppm) Nb

CPX_3

0.426

0.391

2.68

2.5 3.4

1.0

Zr La Ce

CPX_1

0.473

FB70

0.426

3.03

2.2 3.0

1.0

Pr Nd Sm Eu Gd Tb

CPX_2

0.324

0.277

1.98

1.5 3.3

CPX_1

0.281

VB5

0.220

1.58

1.0

1.5 3.9

0.9

Dy Ho Er

CPX_4

0.243

0.250

1.91

1.4 3.1

0.8

Tm Yb Lu Rare earth element ratios are C1-normalized (Anders and Grevesse 1989)

CPX_1

FB-f4

0.107

0.600

0.089

3.1 6.3

0.9

b.d.l. below detection limit

CPX_6

0.187

0.157

1.13

Islands, and is within the ranges of the least enriched clinopyroxenes from Vulture peridotites and the least depleted clinopyroxenes from North Africa peridotites. By contrast, 87Sr/86Sr of the Hyblean gabbros is the highest among the samples showing 143Nd/144Nd * 0.5129. 87 Sr/86Sr and Rb content are positively correlated in 7 out of 12 samples (Fig. 4b). The other samples have higher Rb contents (up to 16 ppm) and variable 87Sr/86Sr. Hyblean peridotites and basic granulites have lower Rb contents and Sr isotope ratios than the other gabbros. 176 Hf/177Hf ranges from 0.282429 to 0.283032 (eHf = -6.6 to +14.8). HfNd isotopic values (epsilon notations) are plotted in Fig. 5a relative to the Terrestrial array of Vervoort et al. (1999). Most samples plot in the upper right quadrant (suprachondritic 176Hf/177Hf and 143Nd/144Nd) and only two samples (gabbros XLP1 and FB50) plot in the lower right quadrant (subchondritic 176Hf/177Hf). A few Hf data for lavas from Etna volcano and Hyblean Plateau are

1.3 3.8 1.3 3.8

CPX_5

FB-f31

0.175

1.17

0.165

1.1

1.0

b.d.l. below detection limit, mg# Mg/(Mg + Fetot)

CPX_10

0.220

0.185

1.27

1.9 3.9

1.1

Table 2 continued

LaN/YbN SmN/YbN

Eu/Eua

Tm

Yb

Lu

Data from Scribano et al. (2006)

CPX_4

0.212

1.33

0.188

1.9 3.6 2.0 3.7

CPX_2

0.158

FB50

0.136

1.01

1.1

1.0

123

Contrib Mineral Petrol (2009) 157:122

gabbros fall within this range. Sr and Hf isotope ratios are not correlated with one another (Fig. 5b). RbSr and LuHf systematics do not provide age constraints; however, SmNd data for nine gabbros yield an isochron age of 253 60 Ma (Fig. 6).

Trace-element compositions Plagioclase Representative trace-element analyses of plagioclases are listed in Table 1. Their REE patterns show the typical LREE-enriched shape (Fig. 7), with a strong positive Eu anomaly (Eu/Eu* = 920); HREE are often below detection limit (b.d.l.). PM-normalized multi-element diagrams for average plagioclases are characterized by marked positive Ba, Sr and Eu anomalies (Fig. 8) and variable Rb, Ba and HFSE abundances. In general, selected LILE and HFSE in plagioclase grains vary widely (Rb = b.d.l. to 79 ppm; Ba = 647,688 ppm; Nb = b.d.l. to 0.6 ppm; Zr = b.d.l. to 10 ppm; Table 1). Sample VB5 shows the highest average Rb, Ba, Th, Nb, Zr and Hf values. Some differences also exist among grains from the same sample: for instance, plagioclase grains in gabbro VB5 have widely variable contents of Rb (0.1379 ppm), Ba (101 7,688 ppm) and Sr (1,5292,922 ppm).
Fig. 3 a C1-normalized REE patterns and b PM-normalized traceelement compositions of Hyblean gabbros included in this study (after Scribano et al. 2006, modied). Normalizations to C1 and PM are after Anders and Grevesse (1989) and McDonough and Sun (1995), respectively

Clinopyroxene Representative trace-element analyses of clinopyroxenes are listed in Table 2. The C1-normalized REE patterns of all clinopyroxene cores are upward-convex and are nearly parallel (LaN/YbN = 1.33.1 and SmN/YbN = 36; Fig. 7). Eu anomalies are very small (Eu/Eu* = 0.81.4). Clinopyroxenes from sample FB70 show the highest

available in the literature (Fig. 5a). They are in the range of the gabbros with the highest eHf. The eld of Hyblean hydrothermal crustal zircons is also shown; half of the
Table 4 SrNdHf isotope compositions of Hyblean gabbro xenoliths Sample XLP1 VB5 FB50 FB80 FB-f4 FB-f31 FB-f7 FB-f32 FB-e11 FB13 FB70 FB11
87

Sr/86Sr

1 SE 5 9 6 8 4 6 5 9 8 9 4 7

143

Nd/144Nd

1 SE 9 20 7 6 8 9 11 6 8 7 9

147

Sm/144Nd

176

Hf/177Hf

1 SE 29 28 46 50 39 38 43 40 62 20 3 30

eNd 5.04 5.12 5.12 5.30 5.38 4.44 4.09 8.27 4.35 4.12 5.14

eHf -1.25 10.58 -6.55 11.46 5.03 6.42 5.81 1.22 14.78 12.98 10.43 7.21

0.704294 0.704477 0.704721 0.70479 0.705104 0.704431 0.704439 0.704726 0.705192 0.704883 0.704141 0.703943

0.512896 0.512901 0.512901 0.512910 0.512914 0.512866 0.512848 0.513062 0.512861 0.512849 0.512901

0.1663 0.1757 0.1642 0.1776 0.1657 0.1757 0.1447 0.2186 0.1465 0.1368 0.1741

0.282579 0.282913 0.282429 0.282938 0.282756 0.282795 0.282778 0.282648 0.283032 0.282981 0.282909 0.282818

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Contrib Mineral Petrol (2009) 157:122

Fig. 4 a 87Sr/86Sr versus 143Nd/144Nd plot for Hyblean gabbros. Fields for Hyblean basic granulites (Tonarini et al. 1996), Hyblean peridotite xenoliths (DOrazio 1994), peridotite clinopyroxenes from Monte Vulture (Downes et al. 2002) and North Africa (Beccaluva et al. 2008), lavas from Pantelleria Island (Esperanca and Crisci 1995; Civetta et al. 1998), Linosa Island (Civetta et al. 1998; Del Moro and Rottura, unpublished data), Vulture Mt (Peccerillo 2005 and references therein), Hyblean Plateau (Bianchini et al. 1999) and Etna Mt (Armienti et al. 2004 and references therein) are shown for comparison. CMR eld is after Lustrino and Wilson (2007).

b 87Sr/86Sr versus Rb plot for Hyblean gabbros. Fields for Hyblean basic granulites and peridotites (Tonarini et al. 1996) are shown for comparison. Three mixing curves are reported between the cumulate pile (Rb = 0.2 ppm; 87Sr/86Sr = 0.7027; clinopyroxene contribution is considered for Rb content) and hypothetical metasomatic agents with different Rb87Sr/86Sr characteristics: (a) Rb = 80 ppm, 87 Sr/86Sr = 0.705, (b) Rb = 10 ppm, 87Sr/86Sr = 0.710; (c) Rb = 2 ppm, 87Sr/86Sr = 0.710. Mixing curves were calculated using the expression given by Faure (1998)

overall REE content among these gabbros. Figure 8 shows the PM-normalized average clinopyroxene compositions: LILE, Nb and Ta values show the largest scatter (e.g., RbN = 0.10.5; BaN = 0.011.2; NbN = 0.042), whereas the other elements show similar contents and distribution in all samples. The patterns are characterized by a marked negative Sr anomalies (due to co-precipitation of plagioclase) and weak negative Zr and Ti anomalies. In the most metamorphic-textured gabbros (e.g., sample FB11), Rb and Ba contents are below the detection limit. Some differences between grains from the same sample have been observed: for example, clinopyroxene grains from gabbro FB50 show variable Ba (1.520.7 ppm). Amphibole The analysis of amphibole in gabbro FB70 is listed in Table 2. The C1-normalized REE pattern of the amphibole is parallel to that of the clinopyroxene from the same sample, but with higher abundances, and shows a weak positive Eu anomaly (Eu/Eu* = 1.2; Fig. 7). LREE are moderately enriched relative to the HREE (LaN/YbN = 3.3). When normalized to PM (Fig. 8), the amphibole shows higher

values than coexisting clinopyroxene: its pattern is characterized by positive Ba, Nb, and Ta anomalies, with BaN * 100, NbN * 63 and TaN * 72. FeTi oxides Representative trace-element analyses of FeTi oxides are listed in Table 3. Oxides are very poor in REE, with LREEN \ HREEN (Fig. 7). FeTi oxides concentrate variable amounts of HFSE such as Zr (=711 ppm) and Nb (=9114 ppm).

In situ Sr isotope data In situ Sr istope data for plagioclase (cores and rims) and the crypto- to micro-crystalline portions of intercumulus pockets in samples VB5, FB50 and FB11 are listed in Table 5 and plotted in Fig. 9. 87Sr/86Sr in plagioclase cores varies from 0.704841 to 0.702775, with a preponderance of relatively low values (*0.7027), whereas the crypto- to micro-crystalline portions of intercumulus pockets show much higher 87Sr/86Sr (up to 0.7055 in sample FB50).

123

10

Contrib Mineral Petrol (2009) 157:122

Fig. 6 SmNd isochron for the Hyblean gabbros. Gray squares indicate out of the trend samples, which were not considered in age calculation. Uncertainties (1r) are smaller than the symbol size

Discussion Petrogenesis of the Hyblean gabbros: cumulus and post-cumulus mixing processes On the basis of textural and geochemical evidences, Scribano et al. (2006) suggested that Hyblean gabbros represented MORB-type cumulates inltrated by late Fe Ti rich melts that may have been lter-pressed from a nearby cumulate mush. However, since no isotopic or in situ trace-element data were available for these xenoliths, the origin of either the cumulus phases (clinopyroxene + plagioclase) or the late FeTi rich melts could only be inferred from petrography and the whole-rock and mineral chemistry. The new data presented here shed more light on this issue. The trace-element composition of clinopyroxene raises questions about the possible co-precipitation with plagioclase: the negative Sr anomaly is not accompanied by a negative Eu anomaly, and thus clinopyroxene might have precipitated before plagioclase. The EuSr decoupling may be explained by the fact that cpx/liqDSr \ cpx/liqDEu (mineral/ liquid D = partition coefcient) in basaltic systems (e.g., Hart and Dunn 1993; Fujimaki et al. 1984). However, only very rarely do small clinopyroxene grains occur within plagioclase, as would be expected if clinopyroxene precipitated earlier than plagioclase. Therefore we favor the hypothesis of the simultaneous segregation of these phases. The crypto- to micro-crystalline intercumulus pockets bearing large FeTi-rich oxides can be regarded as originally melt pockets, and related to the late injection of FeTi-rich melt (Scribano et al. 2006).

Fig. 5 a eHf versus eNd and b 87Sr/86Sr plots for Hyblean gabbro xenoliths. Black array and dark gray eld indicate the terrestrial Hf Nd trend from Depleted Mantle (DM) to Crust (Vervoort et al. 1999 and references therein). Stars are data for Etna and Hyblean Plateau (from Gasperini et al. 2002); pale gray eld is that of the Hyblean hydrothermal zircons from Sapienza et al. (2007); suggested eld of SCLM is from Grifn et al. (2000); HIMU eld is from Salters and White (1998). Hf isotope composition of MARID is from Choukroun et al. (2005); Sr isotope composition of MARID is from Hawkesworth et al. (1990)

Plagioclase rims record varying degrees of isotopic equilibration between cores and the FeTi rich intercumulus pools. Rb content varies in the ranges 0.0277 ppm in plagioclase cores and 3.580 ppm in intercumulus pools. Sr content varies between 1,152 and 9,714 ppm in plagioclase cores and 1,0105,524 ppm in the pools (only one point up to 15,000 ppm). Plagioclase rims have Sr concentrations in the range 70610,667 ppm; 1 point has Sr = 16,000 ppm. Plagioclase rims have Rb contents in the range 0.669 ppm.

123

Contrib Mineral Petrol (2009) 157:122 Fig. 7 REE compositions of gabbros-forming minerals. Normalization is to C1 chondrite (Anders and Grevesse 1989)

11

An important issue concerns the nature of these late melts, i.e., residual after the cumulus phases crystallization or exotic. To unravel the question, we calculated the evolution of the liquid crystallizing the plagioclase + clinopyroxene taking the gabbro FB50 as example (Fig. 10; procedure is described in the gure caption). The comparison between the composition of the residual liquid and that of the intercumulus pockets clearly shows that the latter cannot be the residue after the plagioclase + clinopyroxene crystallization, given the signicant differences with the modeled REE abundance and distribution (Fig. 10). Moreover, cumulus clinopyroxene is rich in thin exsolution lamellae of ilmenite (Fig. 2a, b, e) and the initial Ti content of clinopyroxene should be even higher than that measured by microprobe in exsolution-free micro-volumes (see Table 2). It is

improbable that a liquid segregating such a Ti-rich clinopyroxene would evolve toward compositions able to produce a residual liquid containing abundant FeTi oxides. We cannot exclude the possibility that small quantities of residual liquid after plagioclase + clinopyroxene crystallization were present, but they have not been identied. Afterwards, these gabbroic bodies suffered variable metamorphic re-equilibration as attested by the spectrum of igneous to granoblastic microstructures. Having reconstructed the sequence of petrological processes suffered by the Hyblean gabbros, we can use the geochemical and isotopic data to constrain the nature of these processes. Although the whole-rock Nd isotope composition remains rather constant (143Nd/144Nd * 0.5129), both Sr and Hf isotopes indicate a complex mixing process.

123

12
87

Contrib Mineral Petrol (2009) 157:122

Fig. 8 PM-normalized trace-element distributions for average plagioclases, clinopyroxenes and amphibole for Hyblean gabbro xenoliths. Normalization to PM after McDonough and Sun (1995)

The horizontal array for Sr data suggests the presence of at least two components, one with 87Sr/86Sr B 0.7039, and the other more enriched in radiogenic Sr (87Sr/86Sr C 0.7051; Fig. 4a). In addition, eHf values do not distribute along the crustmantle array in HfNd space, but trend vertically toward negative values (Fig. 5a). These isotopic trends cannot be explained by crustal contamination, which would have required a simultaneous change of Nd isotope composition. A contribution by more than one component to the cumulate pile is strongly suggested by the decoupling between Sr and Hf isotopes (Fig. 5b), which also show that re-equilibration with the surrounding subcontinental lithospheric mantle (SCLM) alone cannot account for the Sr NdHf isotope features (Fig. 5). In situ Sr analyses of plagioclase and the crypto- to microcrystalline portions of intercumulus pockets from three selected gabbros (FB11, FB50 and VB5) can help to unravel this geochemical puzzle. Plagioclase cores and intercumulus pools are considered representative of the whole cumulate pile and the late FeTi-rich melts, respectively. The plot of

Sr/86Sr against Sr and Rb concentrations (Fig. 9) reveals that a simple binary mixing cannot explain the scatter of data. Plagioclase cores from all samples tend to have low 87 Sr/86Sr (*0.7027), low Rb (0.1 ppm) and variable Sr, but show signicant within-grain heterogeneity with 87Sr/86Sr up to 0.7048 and highly variable Rb and Sr concentrations. Within-sample variations were already evident in the traceelement data for plagioclase and clinopyroxene (Tables 1, 2). The within-grain variability is unlikely to depend on mantle source heterogeneities, but rather testies to the interaction between the cumulus phasesderived from a homogeneous mantle-derived magmaand an isotopically distinct agent. Such an interaction could result in a patchy geochemical zoning of plagioclase and clinopyroxene. The intercumulus pools show also radiogenic Sr-isotope compositions, up to 0.7055 in gabbro FB50. In this sample, plots of Rb and Sr contents against 87Sr/86Sr show a complex distribution (Fig. 9). In the Rb87Sr/86Sr plot, plagioclase cores and rims have low Rb contents (B10 ppm, except for two rim points with Rb *30 and *60 ppm) and Sr isotope ratios ranging from 0.703 to 0.705. However, analyses of intercumulus pools show a range of 87Sr/86Sr = 0.70440.7055, and higher Rb contents (up to *80 ppm). The Sr-87Sr/86Sr plot is not so well dened, since the analyses of plagioclase cores and rims also have very high Sr contents. Therefore, the plagioclase data suggest heterogeneities related to interaction between the cumulate pile and a low-Rb, high-87Sr/86Sr metasomatic component. Later, the inltrating FeTi-rich melts, characterized by 87Sr/86Sr * 0.7055, introduced signicant amounts of Rb and Sr. The whole-rock data are the expression of such a mixing (Fig. 9). These geochemical and textural observations, especially on gabbro FB50, allow us to sketch the relative time relationships between the metasomatic events. Plagioclase cores locally record the isotopic-geochemical features due to the interaction between the cumulate pile and the lowRb component. By contrast, the plagioclase rims texturally and geochemically reect variable degrees of re-equilibration with the late FeTi rich melt. Therefore, the plagioclase cores indicate that the cumulate pile was rstly affected by metasomatism driven by the low-Rb agent; afterward the FeTi-rich melt inltrated the previously metasomatized cumulates. The lowest-87Sr/86Sr plagioclase cores and the intercumulus pools constrain the characteristics of the cumulate pile and of the FeTi-rich melt, respectively, since they represent their direct crystallization/cooling products. The situation is more complex for the low-Rb metasomatic agent, whose geochemical features can only be inferred from the highest-87Sr/86Sr portions of the plagioclase cores. The geochemistry of these components has been estimated as follows:

123

Table 5 In situ Sr isotope analyses for plagioclase cores (PL-Cores) and rims (PL-Rims) and micro- to crypto-crystalline portions of the FeTi-rich intercumulus pools (micro-crypto INT-CU) from Hyblean gabbros FB50, FB11 and VB5 Gabbro FB11 Sr (ppm) 1,390 9,714 3,238 5,714 0.70387 0.7029 0.704088 0.703587 6,000 16,000 1,867 10,667 8,762 4,381 5,714 0.70464 0.70337 9,714 2,990 3,467 4,571 15,048 2,610 4,952 2,476 1,010 3,048 5,524 2,095 43 14 32 25 15 44 32 65 76 4.5 3.5 31 Micro-crypto INT-CU 0.70441 0.0001 4,593 0.0001 2,186 0.0001 6,581 4.0 1.0 80 5.5 0.70305 0.0001 1,860 4.4 6.5 0.7 0.70422 0.70505 0.0001 0.0001 3,907 7,919 0.8 6.3 7.4 0.70312 0.0000 1,791 0.9 0.6 0.70505 0.0001 5,372 7.4 58 0.70356 0.0001 706 5.9 3.8 PL-Rims 0.70309 0.0001 1,553 3.1 PL-Rims 0.704743 0.705302 0.704148 0.0001 2,186 0.1 0.702775 0.0002 3,791 6.3 0.704267 3.1 0.70286 0.0001 2,209 1.1 0.703815 0.00015 9.6E-05 9.8E-05 0.00011 9.6E-05 0.00005 0.0001 0.0001 5.5 0.70302 0.0001 1,631 0.02 0.704841 0.00012 11 0.70294 0.0001 1,572 2.4 0.702852 0.00012 1,180 2,427 2,606 2,834 1,152 2,716 1,856 757 1,180 2,827 2.4 PL-Cores 0.70296 0.0001 1,593 0.5 PL-Cores 0.703372 0.00013 1,584 Rb (ppm)
87

Gabbro FB50 Sr/ Sr


86

Gabbro VB5 Sr (ppm) Rb (ppm)


87

87

Sr/ Sr

86

2r Sr (ppm)

2r

Sr/86Sr 2r

Rb (ppm) 3.8 0.1 77 17 22 0.1 14 20 1.0 69 23

PL-Cores

0.704771

0.00019

0.704598

0.00009

0.703252

0.00009

Contrib Mineral Petrol (2009) 157:122

0.703680

0.00008

PL-Rims

0.704459

0.00006

0.704874

0.00005

0.703132

0.00009

0.704751

0.00004

0.704110 0.703407

0.00012 0.00007

0.704780

0.00006

Micro-crypto INT-CU

0.705224

0.00011

0.704532

0.00008

0.704599

0.00006

0.705063

0.00006

0.705130

0.00014

0.705014

0.00011

0.705122

0.00005

0.704933

0.00012

0.705514

0.00017

0.705070

0.00006

0.704380

0.00007

0.705172

0.00012

13

123

14 Fig. 9 In situ Rb and Sr concentrations versus in situ 87 Sr/86Sr for gabbros FB11, VB5 and FB50. Two mixing curves are shown between the cumulate pile and the two metasomatic agents: the low-Rb uid and the FeTi-rich melt (see Table 7 for the isotopic and geochemical features of the three components). Microcrypto INT-CU = micro- to crypto-crystalline portions of the intercumulus pockets. Mixing curves were calculated using the formulation reported in Faure (1998)

Contrib Mineral Petrol (2009) 157:122

(a)

Cumulitic pile (plagioclase + clinopyroxene OXI OXII): constrained by plagioclase cores, with Sr * 1,200 ppm, Rb * 0.1 ppm and 87Sr/86Sr * 0.7027. (b) Metasomatic agent 1: This metasomatic agent imposed cryptic metasomatism on the cumulate pile.

Because the patchy geochemical zoning in plagioclase is not associated with melt inclusions, we propose that the low-Rb agent was a separate uid. The trace-element data indicate that cumulus phases from gabbro FB11 are the least contaminated by late FeTi-rich melts (e.g., elements as HFSE, U and Th

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15

(c)

Fig. 10 PM-normalized REE composition of liquids in equilibrium with clinopyroxene from gabbro FB50. The hatched curves represent the residual liquid after various degrees (numbers in italics) of plagioclase + clinopyroxene fractional crystallization. The REE pattern of the initial magma has been calculated using the Dcpx/liquid of Hart and Dunn (1993); then, the composition of the residual liquid after different degrees of cumulus phases crystallization has been calculated taking into account the plagioclase/pyroxene modal ratio and Dcpx/liquid (Paster et al. 1974; Hart and Dunn 1993) and Dplag/liquid (Paster et al. 1974; McKenzie and ONions 1991; Bindeman et al. 1998 for An77). The composition of the intercumulus pockets (calculated by subtracting the mode-based chemical contribution of plagioclase + clinopyroxene from the whole-rock composition; Scribano et al. 2006) is shown for comparison. Normalization to PM after McDonough and Sun (1995)

in cumulus phases are b.d.l.s; Tables 1, 2 and Fig. 8). This is corroborated by textural and geochemical evidence: rare modal occurrence of intercumulus material (Fig. 2c); restriction of interaction with the intercumulus material to plagioclase rims (Fig. 9). Thus, this sample is the best candidate to constrain the geochemical features of the rst metasomatizing agent. LAM-data for sample FB11 show some variation only for Rb and Ba contents (Tables 1, 2). We infer that this uid was solute-poor, and carried

only relatively small concentrations of selected LILE such as Rb, Ba and Sr (87Sr/86Sr C 0.7055). Metasomatic agent 2 (FeTi-rich melt): Gabbro FB50 was selected to constrain the geochemical character of this metasomatic agent, because it contains analyzable FeTi-rich intercumulus pockets. The RbSr features of this component are taken as those of the intercumulus portions of these pockets (Sr up to *15,000 ppm, Rb up to *80 ppm, Rb/Sr * 0.005 and 87Sr/86Sr * 0.705). Other geochemical characters were inferred from a mass-balance calculation based on 1,000-point modal analyses of thin sections and the geochemistry of cumulus plagioclase and clinopyroxene (Table 6). We assumed that the OX-III are genetically related to the intercumulus pockets, and their geochemical contribution is included within them. Hence, the chemical composition of the intercumulus material is dened by the difference between the whole-rock analysis (Scribano et al. 2006) and the modally based geochemical contribution of clinopyroxene and plagioclase (Fig. 11). This approach may lead to an underestimation of Ti content in clinopyroxene, which increases in the overgrowth rims (Scribano et al. 2006). However, the proportion of the CPX-I rims is small relative to the whole-rock, and their Ti contribution is assumed to be negligible. The uncertainties related to this method (e.g., the withingrain chemical variation) indicate that the estimate must be considered only semiquantitative. As a whole the FeTi-rich melt introduced LILE (*95% of Rb, *70% of Sr, *80% of Ba) and HFSE (*90% of Nb and Ta, *60% of Zr, *40% of Hf) and contributed *40% of the REE (Fig. 11).

We have modeled this three-component mixing process, calculating the mixing curves between the cumulate pile and either the low-Rb uid and the FeTi rich melt. The geochemical and isotopic parameters of the cumulates and

Fig. 11 Trace-element distribution among the rockforming minerals in gabbro FB50. See Table 6 for modal abundances

123

16 Table 6 Trace-element mineral analyses of sample FB50 used for the mass balance calculation FB50 WR Elements (ppm) Rb Ba Th U Nb Ta La Ce Sr Nd P Hf Zr Sm Eu Tb Y Yb
a b a

Contrib Mineral Petrol (2009) 157:122 Table 7 Geochemical and isotopic characters of the three components used for the calculations of the mixing lines in Fig. 9 Cumulus plagioclase CPX_10 30.1 9.96 247 0.20 0.07 5.34 0.49 6.03 14.8 3,185 11.6 742 1.35 40.0 3.02 1.37 0.44 10.7 0.73 0.09 1.96 0.16 0.05 2.21 0.15 4.43 16.9 67.1 17.9 180 3.05 79.8 5.17 1.82 0.72 17.3 1.27 PL_12 41.8 0.55 106 0.06 0.02 0.17 0.01 5.94 8.94 2,087 2.84 141 0.04 1.63 0.28 0.87 0.01 0.37 0.03 INT-CU 28.1 9.71 202 0.19 0.09 5.47 0.44 2.23 6.02 2,293 4.98 798 0.68 35.9 1.30 0.45 0.21 5.37 0.32
b 87

Low-Rb uid 0.710 10 500 0.02

FeTi rich melt 0.705 80 15,000 0.005

Sr/86Sr

0.7027 0.1 1,200 0.00008

Rb Sr Rb/Sr

the metasomatic agents can cause some discrepancies tting between the data points and the mixing curves. Origin of the metasomatic agents: a possible MARID-type reservoir beneath the Hyblean Plateau The analysis reported in the previous section raises two questions: (1) are the two metasomatic agents (uid and FeTi-rich melt) related one another? (2) what kind of mantle reservoirs are required to explain the isotopic and geochemical features of these agents? The two metasomatic agents share a more or less radiogenic Sr isotope composition and a low Rb/Sr ratio (Table 7), but the uid is estimated to be much more diluted than the melt, which carried high levels of both HFSE (Nb, Ta, Zr, Hf) and LILE (Rb, Sr, Ba) (Fig. 11). The signicant Sr and Rb contents inferred in both metasomatic agents imply high levels of these elements in their source(s). In the upper mantle, these elements generally reside in amphibole and phlogopite, while the high concentrations of Fe and HFSE in the metasomatizing melt suggest an ilmenite- and rutilerich source. Such a mineral assemblage can correspond to more than one mantle source. For example it is equivalent to the MARID (micaamphibolerutileilmenitediopside) rocks found as xenoliths in some kimberlites (Dawson and Smith 1977; Gregoire et al. 2002) as well as to amphibole phlogopiteilmenite associations like those found as veins in composite mantle xenoliths from the Kerguelen Islands (Moine et al. 2001). These options are discussed below. Kramers et al. (1983) reported the trace-element compositions of MARID minerals: amphibole has Rb/ Sr * 0.06, phlogopite has Rb/Sr * 1.5, and apatite has Rb/Sr ( 1. None of these minerals alone can account for the geochemical features of each metasomatizing agent, but different contributions from amphibole and phlogopite (apatite?) could yield these features. Sweeney et al. (1993) experimentally investigated the behavior of MARID rocks during partial melting in the KNFMASH system. They found that dry melting of these rocks requires a quite high temperature (T * 1,200C) at pressure (P) * 30 Kbar; the addition of 10 wt% H2O lowers the melting point by *300C (Fig. 12). In dry experiments, phlogopite behaves as a restitic phase and completely disappears only above

Modal percentage are reported in italics Whole-rock data are from Scribano et al. (2006) INT-CU = intercumulus material composition (including OX-III)

FeTi rich melt were taken directly from plagioclase cores and the crypto- to micro-crystalline portions of the intercumulus pockets (Table 7). The uid responsible for the cryptic metasomatism can be constrained by the whole-rock data (see below). Figure 4b shows mixing lines between the cumulitic pile and possible metasomatic uids with different Rb87Sr/86Sr characteristics (a: Rb = 80 ppm, 87 Sr/86Sr = 0.705; b: Rb = 10 ppm, 87Sr/86Sr = 0.710; c: Rb = 2 ppm, 87Sr/86Sr = 0.710). The mixing curve b between the early plagioclase and a uid with a 10 ppm Rb and 87Sr/86Sr of 0.710 ts 7 out of 12 samples, including gabbro FB11, which is the sample that seems to have experienced the minimum degree of metasomatism by the FeTi-rich melt. A mixing curve for a uid with 87 Sr/86Sr = 0.7055 does not t the in situ Sr data (not shown in Fig. 9); in contrast, low-Rb points from the three gabbros on Fig. 9 are well explained by *50% mixing with an end-member having 87Sr/86Sr = 0.710 and Sr and Rb contents = 500 ppm and 10 ppm, respectively (Table 7). The highest Sr and Rb contents can be related to the late contribution of the FeTi-rich melt. Thus the whole-rock compositions can be explained as the result of such a mixing (see also Fig. 9), even if chemical heterogeneities in both

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17

Fig. 12 PT space showing the (vertically hatched) eld of crystallization of clinopyroxene + plagioclase ilmenite (Thompson 1972). The obliquely hatched area indicates the eld of Hyblean basic granulites (Punturo et al. 2000). The Moho depth is after Scarascia et al. (1994). Hyblean paleogeotherm is after Perinelli et al. (2008). Olivine gabbro/spinel gabbro transition curve is after Gasparik (1984). Spinel granulite/garnet granulite transition curve is after Irving (1974). Dry and wet MARID solidus curves are after Sweeney et al. (1993)

1,350C (see also Yoder and Kushiro 1969). Amphibole (Krichterite in the assemblage studied by Sweeney et al. 1993), which is unstable already below the solidus, is supposed to break down or to dehydrate prior to breakdown. The melting of HFSE- and Fe-rich phases is required to supply the signicant amounts of these elements in the Fe Ti-rich melt. Effective repositories for HFSE and Fe in the mantle are, respectively, titanate phasessuch as rutile and the lindsleyite-mathiasite series (LIMA)and ilmenite. Residual rutile in mantle sources can produce negative HFSE anomalies in the uid or melt in equilibrium (uid/ rutile D and melt/rutileD ? Nb, Ta \ Zr, Hf \ other elements; Jenner et al. 1993; Brenan et al. 1994; Stalder et al. 1998; Foley et al. 2000). Ilmenite can be assumed to behave similarly (Ayers and Watson 1993). The solubility of rutile in aqueous uids or hydrous melts increases with T and decreases with P (Ryerson and Watson 1987; Ayers and Watson 1993). Therefore, the geochemical and textural evidence can be explained by a thermal perturbation that initially led to the dehydration/melting of amphibole and

phlogopite (apatite), and later to the dissolution of rutile and ilmenite together with melting of amphibole and phlogopite. The Sr and Hf isotope ratios attest to the derivation of the Hyblean gabbros from isotopically distinct sources or a very heterogeneous single source. The MARID source itself is very heterogeneous (e.g., Hawkesworth et al. 1990; Choukroun et al. 2005), and different domains of a MARID-type source may have developed very different isotopic features due to their complex petrogenetic history (e.g., Choukroun et al. 2005). The isotopic variations shown by the Hyblean gabbros are compatible with the metasomatizing effect of agents derived from such a source, as indicated by arrows in Fig. 5. Alternatively, a mineral association made of amphibole phlogopiteilmenite can represent a possible candidate to generate metasomatic agents able to impart the geochemical features observed in our gabbros. Moine et al. (2001) interpreted amphibole-rich, phlogopiteilmenite-bearing veins as due to the interaction between the upper mantle and percolating highly alkaline melts similar to the host rock. Melts with such a composition actually erupted in the Hyblean Plateau in Cenozoic time, testifying that the Hyblean lithosphere was actually percolated by those melts. However, SrHf isotopic data do not t with an origin related to the Hyblean Cenozoic volcanics (Figs. 4a, 5a): they do not account for the high-87Sr/86Sr and the low- eHf, as would be expected in case of a genetic link. A possible explanation may be to invoke the co-participation of more factors: for example, a high 87Rb/86Sr in the amphibole phlogopiteilmenite assemblage and/or the possible re-equilibration with the surrounding environment. The above discussion does not allow us to categorically exclude one reservoir in favor of the other. However, the isotopic constraints and the comparison with the data available in literature lead us to favor the MARID-type reservoir. Parental liquids of Hyblean cumulitic gabbros With the assumption that metamorphic re-equilibration processes have not signicantly changed the composition of the cores of cumulus minerals, we have calculated the composition of the parental liquids in equilibrium with clinopyroxene from the Hyblean gabbros, using appropriate cpx/liquidD for basaltic liquids (Hart and Dunn 1993). For this calculation, the average analyses of clinopyroxenes from each samples have been used. Figure 13 shows the PM-normalized trace-element distribution of melts in equilibrium with Hyblean clinopyroxenes. The theoretical melts are very homogeneous from La to Yb, with marked enrichment of LREE over HREE (LaN/YbN = 1223) and a negative Sr anomaly. Sample FB70 shows the highest REE contents, in keeping with its slightly more evolved

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18

Contrib Mineral Petrol (2009) 157:122

Fig. 13 Composition of liquids at equilibrium with clinopyroxenes from analyzed Hyblean gabbros. The elds of a Hyblean Upper Miocene lavas (Bianchini et al. 1998; Rocchi et al. 1998; Perinelli 2000; Scribano et al. 2006), b the theoretical parental liquids of Hyblean pyroxenites (Nimis and Vannucci 1995), c the theoretical parental liquids in equilibrium with Hyblean peridotite clinopyroxenes and an hawaiitic glass vein cutting the HYB40 peridotite (Perinelli et al. 2008), are reported for comparison. cpx/liquidD of Hart and Dunn (1993) have been used for the calculation of all the parental liquids. Symbols as in Fig. 8

deserve further discussion: Sr and Ti anomalies may be related to the co-precipitation of plagioclase and oxides and Nb and Ba distributions probably depend on post-cumulus mixing with the FeTi-rich melt providing *80% of Ba and *90% of Nb (Fig. 11). Barium and Nb distributions in clinopyroxenes from all samples are quite scattered (BaN = 181,700; NbN = 6260). The lowest Ba and Nb contents are found in gabbro FB11, which is among the samples with low modal contents of intercumulus material and the least contaminated by late FeTi-rich melts. It is noteworthy that sample FB70, which is in general the richest in trace-elements, has a relatively low Nb content, and its Ba content is below detection. However, this sample carries amphibole, which is relatively rich in Nb and Ba (NbN * 63 and BaN * 102; Fig. 8). This feature, coupled with the petrographic evidence of reaction rims at the contact with the host clinopyroxene and the rough similarity to the clinopyroxene in trace-element distribution, supports a metasomatic origin for the FB70 amphibole. The parental melts of the clinopyroxenes have been compared with (1) the host rocks (Hyblean Upper Miocene lavas; Bianchini et al. 1998; Rocchi et al. 1998; Perinelli 2000; Scribano et al. 2006) (Fig. 13a), (2) the liquids in equilibrium with clinopyroxenes from Hyblean pyroxenites (Nimis and Vannucci 1995) (Fig. 13b), (3) the liquids metasomatizing the Hyblean peridotites (Perinelli et al. 2008) (Fig. 13c). In general, the comparison shows that the host basalt cannot be regarded as a possible parental melt for the cumulus phases; the HREE and ZrHf contents in the host basalt are lower than those of the clinopyroxene parental melt. Closer similarities can be observed between the calculated liquids and those in equilibrium with the Hyblean clinopyroxenites, although the lack of some elements in the data set prevents an effective comparison. The metasomatic melts in equilibrium with peridotitic clinopyroxenes are clearly very different from the parental melts of our gabbros. However, the pattern of the hawaiitic glass vein cutting the peridotite HYB40 resembles that of our gabbros, with the exception of very high Ba and Nb levels (Perinelli et al. 2008), which however may indicate a link with the metasomatic source of the FeTi-rich melt. Considering all of these data, we suggest that the melts that crystallized the cumulus clinopyroxenes show some similarity with the liquids in equilibrium with Hyblean clinopyroxenites and the hawaiitic vein cutting the Hyblean peridotite HYB40. Unfortunately there are no isotopic data to test the genetic links between these melts. Geological implications

character (e.g., lower An content in plagioclase; Table 1 and Scribano et al. 2006). The negative Sr and Ti anomalies and the scattered Ba and Nb data shown in Fig. 13

The geological interpretation of the Hyblean gabbros raises the questions of the geochemical and isotopic

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19

characterization of the source(s) within the petrological context of the Central Mediterranean area and a better denition of the nature of the Hyblean lithospheric microblock. The SrNd isotopic features of the Hyblean upper mantle are rather similar to those of lavas from Pantelleria and Linosa Islands, and partly overlap the data from Etnean and Hyblean Cenozoic lavas and the clinopyroxenes separated from North African peridotites (Fig. 4a). In the last decade, many authors have proposed a common mantle reservoir for the Cenozoic magmatic products in the Central Mediterranean area (Granet et al. 1995; Hoernle et al. 1995; Goes et al. 1999; Lustrino and Wilson 2007 and references therein) whose location (lower mantle vs. Transition Zone) and geochemical-isotopic afnity (e.g., HIMU- or FOZO-like) are still debated. However, the presence of such a common mantle reservoir (CMR in Fig. 4a; Lustrino and Wilson 2007) is widely accepted, and the observed isotopic variations are considered to reect the contingent geodynamic situations. In this scenario, the Hyblean lavas and xenoliths are expected to be among the least contaminated products, giving the best possibility of dening the geochemical and isotopic characteristics of this mantle reservoir (e.g., Sapienza et al. 2005). The Hyblean clinopyroxene + plagioclase cumulates probably were derived from this source. These asthenospheric magmas, in fact, permeate the lithosphere, and probably were stored at different lithospheric levels, giving rise to clinopyroxenite veins within the peridotite matrix, to gabbroic bodies, or even erupting on the surface. By contrast, the isotopic data show that the FeTi-rich melt that intruded the gabbro pile and formed the intercumulus pockets cannot be derived from such a source: a MARID-type source appears to be the best reservoir to t the geochemical and isotopic features of the metasomatizing agents. Since the MARID reservoir is considered to reside within the SCLM, we suggest that the lithosphere, as well as the asthenosphere, contributed geochemically and isotopically to the petrogenesis of the gabbros, and thus to the Hyblean crustal accretion. Interestingly, the Hf-isotope variation in the Hyblean gabbros is similar to that found in hydrothermal, lower crustal zircons from the same locality (Fig. 5; Sapienza et al. 2007). The UPb ages on these zircons dated this hydrothermal event to Permo-Triassic time (246 Ma), similar to the SmNd age obtained for nine gabbro samples (Fig. 6) and probably representing the gabbro crystallization age; those that lie off this trend appear to reect extensive post-cumulus metasomatism and/or were not cogenetic with the other samples. Such a convergence suggests that a genetic linkage exists among these phenomena. Another key point regards the lithospheric location of the studied gabbros. The mineral assemblage of the

gabbros does not allow PT estimates. However, the eld for clinopyroxene + plagioclase (ilmenite) crystallization in basaltic systems (Thompson 1972) indicates PT conditions of at least *1,100C and *0.8 GPa, well above the Hyblean paleogeotherm (Perinelli et al. 2008) (Fig. 12). The petrographic evidence, namely the lack of garnet and the presence of hercynitic spinel, suggests that the gabbro emplacement occurred at T * 1,200C and P = 0.80.9 GPa, corresponding to the crustmantle interface. This T is also consistent with that required for melting for a MARID domain under anhydrous conditions (Fig. 12). Therefore, we suggest that the gabbros can be related to magmatic underplating processes. Moreover, they lie below the presumed depth of the basic granulites of the lower crust (Punturo et al. 2000) (Fig. 12). These two xenolith populations are quite different (Scribano et al. 2006; see also Fig. 4): the FeTi-rich gabbroseven the more granuloblasticconsist of plagioclase + clinopyroxene + FeTi oxides (rarely enclosing hercynitic spinel) small amounts of intercumulus material, whereas the basic granulites are made of plagioclase + clinopyroxene + orthopyroxene + green Al-spinel. Furthermore, remnants of intercumulus pockets and/or anhedral FeTi oxides have never been reported in the basic granulites. Another salient question regards the nature of the Hyblean lithosphere. The suggestion of a MARID-type reservoir in the Hyblean SCLM strengthens the evidence for the continental nature of this micro-block. The geochemical and isotopic data clearly indicate that a signicant thermal/magmatic episode in Permo-Triassic time affected the old Hyblean continental lithosphere (Sapienza et al. 2007), causing a signicant perturbation of the paleogeotherm. Such an event was related to lithosphere thinning, which caused upwelling and melting of the asthenosphere and produced the gabbro pile; the same thermal event may have also caused the melting of ancient MARID-type domains in the progressively thinned SCLM. The uids produced by early breakdown of such a domain may have caused the cryptic metasomatism in the cumulitic gabbros as well as the lower crustal hydrothermal event described by Sapienza et al. (2007). The above inferences are compatible with rifting preceding an ocean opening, and the age of this thermal event is that often invoked for the opening of the Ionian Basin. However, more investigations are needed to better dene this scenario.

Concluding remarks The geochemical and isotopic study of selected gabbros from the Hyblean Plateau helps to unravel the geochemical and isotopic evolution of the underlying lithosphere. The main conclusions are summarized below:

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Contrib Mineral Petrol (2009) 157:122

(1)

(2)

(3)

The Hyblean gabbros consist of clinopyroxene + plagioclase FeTi oxides precipitated from alkalibasaltic melts rising from the asthenosphereascribable to the CMR of Lustrino and Wilson (2007)and emplaced near the crustmantle interface. The resulting cumulitic pile represents episodes of magmatic underplating. These gabbroic bodies subsequently underwent metasomatism and more or less pronounced re-equilibration. The combination of geochemical, isotopic and textural evidence suggests the contribution of two distinct, but possibly related, metasomatic agents to the cumulate pile: (1) *50% mixing with a high-87Sr/86Sr uid carrying relatively small amounts of Sr and Rb, and (2) inltration of solute-rich FeTi-rich melts supplying Fe, Ti, Rb, Sr and HFSE to the system. Both metasomatic events may be related to the progressive partial melting of a heterogeneous MARID-type reservoir within the SCLM. Thus the petrogenesis of the Hyblean gabbros could have involved both astenospheric and lithospheric reservoirs. Gabbro emplacement occurred in Permo-Triassic time, at the crustmantle interface. At that time a signicant thermal episode related to lithospheric thinning and asthenospheric upwelling caused the perturbation of the paleogeotherm. The heating may have caused melting of previously metasomatised lithospheric domains, producing uids and melts that percolated and enriched the nearby lithosphere. As a whole, this scenario is consistent with a rifting preceding the (Ionian?) ocean opening.

Acknowledgments We are grateful to Vittorio Scribano for providing samples. We thank Norman Pearson for his contributions to the analytical work and discussions of the results, and Suzy Elhlou, Peter Wieland and Carol Lawson for their invaluable assistance and guidance in the laboratory. Roberto Braga is thanked for the continuous and precious advices during preparation of the manuscript. Andrea Argnani is thanked for interesting discussions on geodynamic situation of the Central Mediterranean area. Alessandro Rottura and Aldo Del Moro are thanked for providing unpublished isotopic data of lavas from Linosa Island. Constructive criticism by Massimo Coltorti and Michel Gregoire signicantly improved the paper. Funding for ` this research was provided by a Marco Polo grant from the Universita di Bologna (GTS), MIUR 60% (LM) and an ARC Discovery Project (SYOR/WLG). Analytical data were obtained at GEMOC using instrumentation funded by ARC LIEF, and DEST Systemic Infrastructure Grants and Macquarie University. This is contribution 538 from the ARC National Key Centre for Geochemical Evolution and Metallogeny of Continents (www.es.mq.edu.au/GEMOC).

References
Adams CJ, Campbell HJ, Grifn WL (2005) Isotopic microanalysis of seawater strontium in biogenic calcite to assess subsequent rehomogenisation during metamorphism. Chem Geol 220:6782

` del Amore C, Carveni P, Scribano V, Sturiale C (1988) Facies ed eta vulcanismo nella fascia sudorientale della Sicilia (Pachino-Capo Passero). Boll Soc Geol Ital 107:481489 Anders E, Grevesse N (1989) Abundances of the elements; meteoritic and solar. Geochim Cosmochim Acta 53:197214 Argnani A (2005) Possible record of a Triassic ocean in the Southern Apennines. Boll Soc Geol Ital 124:109121 Armienti P, Tonarini S, DOrazio M, Innocenti F (2004) Genesis and evolution of Mt. Etna alkaline lavas: petrological and Sr-Nd-B isotope constraints. Period Mineral 73:2952 Ayers JC, Watson EB (1993) Rutile solubility and mobility in supercritical aqueous uids. Contrib Mineral Petrol 114:321330 Beccaluva L, Siena F, Coltorti M, Di Grande A, Lo Giudice A, Macciotta G, Tassinari R, Vaccaro C (1998) Nephelinitic to tholeiitic magma generation in a transtentional tectonic setting: an integrated model for the Iblean volcanism, Sicily. J Petrol 39:130 Beccaluva L, Bianchini G, Ellam RM, Marzola M, Oun KM, Siena F, Stuart FM (2008) The role of HIMU metasomatic components in the North African lithospheric mantle: petrological evidence from Gharyan lherzolite xenoliths, NW Libya. In: Coltorti M, Gregoire M (eds) Metasomatism in oceanic and continental lithospheric mantle. Geol Soc Lond Spec Publ, London, vol 293, pp 253277 Belousova EA, Grifn WL, Shee SR, Jackson SE, OReilly SY (2001) Two age populations of zircons from the Timber Creek kimberlites, Northern Territory, as determined by laser-ablation ICP-MS analysis. Aust J Earth Sci 48:757765 Ben-Avraham Z, Grasso M (1990) Collisional zone segmentation in Sicily and surrounding areas in the Central Mediterranean. Ann Tectonicae 4:131139 Bianchi F, Carbone S, Grasso M, Invernizzi G, Lentini F, Longaretti G, Merlini S, Mostardini F (1987) Sicilia orientale: prolo geologico Nebrodi-Iblei. Mem Soc Geol Ital 38:429458 Bianchini G, Clocchiatti R, Coltorti M, Joron JL, Vaccaro C (1998) Petrogenesis of mac lavas from the northernmost sector of the Iblean district (Sicily). Eur J Mineral 10:301315 Bianchini G, Bell K, Vaccaro C (1999) Mantle sources of the Cenozoic Iblean volcanism (SE Sicily, Italy): Sr-NdPb isotopic constraints. Mineral Petrol 67:213222 Bindeman IN, Davis AM, Drake MJ (1998) Ion microprobe study of plagioclase-basalt partition experiments at natural concentration levels of trace elements. Geochim Cosmochim Acta 62:1175 1193 Brenan JM, Shaw HF, Phinney DL, Ryerson FJ (1994) Rutileaqueous uid partitioning of Nb, Ta, Hf, Zr, U and Th: implications for high eld strength element depletions in islandarc basalts. Earth Planet Sci Lett 128:327339 Burollet FP, Mugniot JM, Sweeney P (1978) The geology of the Pelagian Block: the Margins and Basins of Southern Tunisia and Tripolitania. In: Nairm AEM, Kanes WH, Stehli FG (eds) The Ocean basins and margins, v.4b: the Western Mediterranean. Plenum Press, New York, pp 331359 Catalano R, Doglioni C, Merlini S (2001) On the mesozoic ionian basin. Geophys J Int 143:124 Choukroun M, OReilly SY, Grifn WL, Pearson NJ, Dawson JB (2005) Hf isotope of MARID (mica-amphibole-rutile-ilmenitediopside) rutile trace metasomatic processes in the lithospheric mantle. Geology 33:4548 Civetta L, DAntonio M, Orsi G, Tilton GR (1998) The geochemistry of volcanic rocks from Pantelleria Island, Sicily Channel: petrogenesis and characteristics of the mantle source region. J Petrol 39:14531491 Cristofolini R (1966) Le manifestazioni eruttive basiche del trias superiore nel sottosuolo di Ragusa (Sicilia sud-orientale). Period Mineral 35:128

123

Contrib Mineral Petrol (2009) 157:122 Dawson JB, Smith JV (1977) The MARID (mica-amphibole-rutileilmenite-diopside) suite of xenoliths in kimberlite. Geochim Cosmochim Acta 41:309323 Dewey JF, Helman ML, Turco E, Hutton DHW, Knott SD (1989) Kinematics of the western Mediterranean. In: Coward MP, Dietrich D, Park RG (eds) Alpine tectonics. Geol Soc Lond Spec Publ, London, vol 45, pp 265283 DOrazio M (1994) Natura ed evoluzione delle vulcaniti dellEtna e ` loro relazioni con il magmatismo Ibleo. Ph.D. thesis, Universita di Pisa Downes H, Kostoula T, Jones AP, Beard AD, Thirlwall M, Bodinier J-L (2002) Geochemistry and SrNd isotopic compositions of mantle xenoliths from the Monte Vulture carbonatite-melilite volcano, central southern Italy. Contrib Mineral Petrol 144:78 92 Esperanca S, Crisci GM (1995) The island of Pantelleria: a case for the development of DMM-HIMU isotopic compositions in a long-lived extensional setting. Earth Planet Sci Lett 136:167 182 Farrugia P, Panza GF (1981) Continental charcater of the lithosphere beneath the Ionian sea. In: Cassinis R (ed) The solution of the inverse problem in geophysical interpretation. Plenum, New York, pp 327334 Faure G (1998) Principles and applications of geochemistry, 2nd edn edn. Prentice Hall, Englewood Cliffs, p 589 Foley SF, Barth MG, Jenner GA (2000) Rutile/melt partition coefcients for trace elements and an assessment of the inuence of rutile on the trace element characteristics of subduction zone magmas. Geochim Cosmochim Acta 64:933938 Fujimaki H, Tatsumoto M, Aoki K-I (1984) Partition coefcients of Hf, Zr, and REE between phenocrysts and groundmasses. J Geophys Res 89:662672 Gasparik T (1984) Two pyroxene thermobarometry with new experimental data in the system CaO-MgO-Al2O3-SiO2. Contrib Mineral Petrol 87:8797 Gasperini D, Blichert-Toft J, Bosch D, Del Moro A, Macera P, Albarede F (2002) Upwelling of deep mantle material through a plate window: evidence from the geochemistry of Italian basaltic volcanics. J Geophys Res 107:23672385 Goes S, Spakman W, Bijwaard H (1999) A lower mantle source for central European volcanism. Science 286:19281931 Granet M, Wilson M, Achauer U (1995) Imaging a mantle plume beneath the French Massif Central. Earth Planet Sci Lett 136:281296 Gregoire M, Bell DR, le Roex AP (2002) Trace element geochemistry of phlogopite-rich mac mantle xenoliths: their classication and their relationship to phlogopite-bearing peridotites and kimberlites revisited. Contrib Mineral Petrol 142:603625 Grifn WL, Pearson NJ, Belousova E, Jackson SE, van Achterbergh E, OReilly SY, Shee SR (2000) The Hf isotope composition of cratonic mantle: LAM-MC-ICPMS analysis of zircon megacrysts in kimberlites. Geochim Cosmochim Acta 64:133147 Hart SR, Dunn T (1993) Experimental cpx/melt partitioning of 24 trace elements. Contrib Mineral Petrol 113:18 Hawkesworth CJ, Erlank AJ, Kempton PD, Waters FG (1990) Mantle metasomatism: isotope and trace-element trends in xenoliths from Kimberley, South Africa. Chem Geol 85:1934 Hoernle K, Zhang Y-S, Graham D (1995) Seismic and geochemical evidence for large-scale mantle upwelling beneath the eastern Atlantic and western and central Europe. Nature 374:3439 Irving AJ (1974) Geochemical and high pressure experimental studies on garnet pyroxenite and pyroxene granulite xenoliths from the Delegate basaltic pipes, Australia. J Petrol 15:140 Jenner GA, Foley SF, Jackson SE, Green DH, Fryer BJ, Longerich HP (1993) Determination of partition coefcients for trace elements in high pressure-temperature experimental run products by laser

21 ablation microprobe-inductively coupled plasma-mass spectrometry (LAM-ICP-MS). Geochim Cosmochim Acta 57:50995103 Kramers JD, Roddick JCM, Dawson JB (1983) Trace element and isotope studies on veined, metasomatic and MARID xenoliths from Bultfontein, South Africa. Earth Planet Sci Lett 65:90106 Lentini F (1984) Carta geologica della sicilia sud-orientale, scala 1:100, 000. S.E.L.C.A, Firenze Ludwig KR (1999) Isoplot/Ex 2.06 a geochronological toolkit for Microsoft Excel. Berkeley Geochronology Center Special Publication 1a:149 Lustrino M, Wilson M (2007) The circum-Mediterranean anorogenic Cenozoic igneous province. Earth Sci Rev 81:165 McDonough WF, Sun SS (1995) The composition of the Earth. Chem Geol 120:223253 McKenzie D, ONions RK (1991) Partial melt distributions from inversion of rare Earth element concentrations. J Petrol 32:1021 1091 Moine BN, Gregoire M, OReilly SY, Sheppard SMF, Cottin J-Y (2001) High eld strength element fractionation in the Upper Mantle: evidence from amphibole-rich composite mantle xenoliths from the Kerguelen Islands (Indian Ocean). J Petrol 42:21452167 Nimis P, Vannucci R (1995) An ion microprobe study of clinopyroxenes in websteritic and megacrystic xenoliths from Hyblean Plateau (SE Sicily, Italy): constraints on HFSE/REE/Sr fractionation at mantle depth. Chem Geol 124:185197 Niu Y, Gilmore T, Macie S, Greig A, Bach W (2002) Mineral chemistry, whole-rock compositions, and petrogenesis of Leg 176 gabbros: data and discussion. In: Natland JH, Dick HJB, Miller DJ, Von Herzen RP (eds) Proceedings of the Oceanic Drilling program, Scientic Results, vol 176, pp 160 [Online] Paster TP, Schauwecker DS, Haskin LA (1974) The behavior of some trace elements during solidication of the Skaergaard layered series. Geochim Cosmochim Acta 38:15491577 Peccerillo A (2005) Plio-quaternary volcanism in Italypetrology, geochemistry, geodynamics. Springer, Berlin, p 365 Perinelli C (2000) Modicazioni indotte dal metasmatismo ad alta pressione ed alta temperatura nelle peridotiti del mantello superiore in zone di rift attivo, di margine passivo e di ` di Pisa magmatismo dintraplacca. Ph.D. thesis, Universita Perinelli C, Sapienza GT, Armienti P, Morten L (2008) Metasomatism of the Upper Mantle beneath Hyblean Plateau (Sicily): evidence from pyroxenes and glass in peridotite xenoliths. In: Coltorti M, Gregoire M (eds) Metasomatism in Oceanic and Continental lithospheric mantle. Geol Soc Lond Spec Publ, London, vol 293, pp 197221 Punturo R, Kern H, Scribano V, Atzori P (2000) Petrophysical and petrological characteristics of deep-seated xenoliths from Hyblean Plateau, south-eastern Sicily, Italy: suggestions for a lithospheric model. Mineral Petrogr Acta 43:120 Rocchi S, Longaretti G, Salvadori M (1998) Subsurface Mesozoic and Cenozoic magmatism in south-eastern Sicily: distribution, volume and geochemistry magmas. Acta Vulcanol 10:395408 Ryerson FJ, Watson EB (1987) Rutile saturation in magmas: implications for Ti-Nb-Ta depletion in island arc basalts. Earth Planet Sci Lett 86:225239 Salters VJM, White WM (1998) Hf isotope constraints on mantle evolution. Chem Geol 145:447460 Sapienza G, Scribano V (2000) Distribution and representative whole-rock chemistry of deep-seated xenoliths from the Iblean Plateau, South-Eastern Sicily, Italy. Period Mineral 69:185204 Sapienza G, Hilton DR, Scribano V (2005) Helium isotopes in peridotite mineral phases from Hyblean Plateau xenoliths (southeastern Sicily, Italy). Chem Geol 219:115129 Sapienza GT, Grifn WL, OReilly SY, Morten L (2007) Crustal zircons and mantle suldes: Archean to Triassic events in the lithosphere beneath south-eastern Sicily. Lithos 96:503523

123

22 Sapienza GT, Avanzinelli R, Conticelli S (2008) Petrology and geochemistry of Cretaceous withinplate lavas from PachinoCapo Passero, Southeastern Sicily (in preparation) Scarascia S, Lozej A, Cassinis R (1994) Crustal structures of the Ligurian, Thyrrenian and Ionian sea and adjacent onshore areas interpreted from wide-angle seismic proles. Boll Geosica Teorica Appl 36:519 Scribano V (1986) The harzburgite xenoliths in a Quaternary basanitoid lava near Scordia (Hyblean plateau, Sicily). Rend Soc Ital Mineral Petrol 41:245255 Scribano V (1988) Petrological notes on lower-crustal nodules from Hyblean Plateau (Sicily). Period Mineral 57:4152 Scribano V, Sapienza G, Braga R, Morten L (2006) Gabbroic xenoliths in tuff-breccia pipes from the Hyblean Plateau: insights into the nature and composition of the lower crust underneath South-eastern Sicily, Italy. Mineral Petrol 86:6388 Sguigna AP, Larabee AJ, Waddington JC (1982) The half-life of 176 Lu by a c-c coincidence measurement. Can J Phys 60:361 364 Stalder R, Foley SF, Brey GP, Horn I (1998) Mineral-aqueous uid partitioning of trace elements at 9001200C and 3.05.7 GPa: new experimental data for garnet, clinopyroxene, and rutile, and implications for mantle metasomatism. Geochim Cosmochim Acta 62:17811801 ger E (1977) Subcommission on geochronology: Steiger RH, Ja convention on the use of decay constant in geo- and cosmochronology. Earth Planet Sci Lett 36:359362

Contrib Mineral Petrol (2009) 157:122 Sweeney P, Thompson AB, Ulmer P (1993) Phase relations of a natural MARID composition and implications for MARID genesis, lithospheric melting and mantle metasomatism. Contrib Mineral Petrol 115:225241 Thompson RN (1972) Melting behaviour of two Snake River lavas at pressures up to 35 kb. Carnegie Inst Wash Geophys Lab Yearb 71:406410 Tonarini S, DOrazio M, Armienti P, Innocenti F, Scribano V (1996) Geochemical features of Eastern Sicily lithosphere as probed by Hyblean xenoliths and lavas. Eur J Mineral 5:11531174 Trua T, Esperanca S, Mazzuoli R (1998) The evolution of the lithospheric mantle along the N. African Plate: geochemical and isotopic evidence from the tholeiitic and alkaline volcanic rocks of the Hyblean plateau, Italy. Contrib Mineral Petrol 131:307322 Vai GB (1994) Crustal evolution and basement elements in the Italian area: palaeogeography and characterization. Boll Geosica Teorica Appl 36:411434 van Achterbergh E, Ryan C, Jackson SE, Grifn WL (2001) Appendix 3 data reduction software for LA-ICP-MS. In: Sylvester P (ed) Laser-ablation-ICPMS in the earth sciences. Mineralogical Association of Canada Short Course, St Johns, Newfoundland, vol 29, pp 239243 Vervoort J, Blichert-Toft J, Patchett PJ, Albarede F (1999) Relationship between LuHf and SmNd isotopic systems in the global sedimentary system. Earth Planet Sci Lett 168:7999 Yoder HS, Kushiro I (1969) Melting of a hydrous phase: phlogopite. Am J Sci 267-A:558582

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