Contrib Mineral Petrol (2009) 157:4163 DOI 10.

1007/s00410-008-0319-8

ORIGINAL PAPER

Shoshonite and sub-alkaline magmas from an ultrapotassic volcano: SrNdPb isotope data on the Roccamonna volcanic rocks, Roman Magmatic Province, Southern Italy
Sandro Conticelli Sara Marchionni Davide Rosa Guido Giordano Elena Boari Riccardo Avanzinelli

Received: 7 February 2008 / Accepted: 3 June 2008 / Published online: 27 June 2008 Springer-Verlag 2008

Abstract The Roccamonna volcano is characterised by two stages of volcanic activity that are separated by volcano-tectonic caldera collapses. Ultrapotassic leucitebearing rocks are conned to the pre-caldera stage and display geochemical characteristics similar to those of other volcanoes in the Roman Province. After the major sector collapse of the volcano, occurred at ca. 400 ka, shoshonitic rocks erupted from cinder cones and domes both within the caldera and on the external anks of the pre-caldera Roccamonna volcano. On the basis of new trace element and SrNdPb isotope data, we show that the Roccamonna shoshonitic rocks are distinct from

Communicated by T.L. Grove.

Electronic supplementary material The online version of this article (doi:10.1007/s00410-008-0319-8) contains supplementary material, which is available to authorized users.
S. Conticelli S. Marchionni D. Rosa E. Boari R. Avanzinelli ` degli Studi di Dipartimento di Scienze della Terra, Universita Firenze, Via Giorgio La Pira, 4, 50121 Florence, Italy S. Conticelli (&) Consiglio Nazionale delle Ricerche, Istituto di Geoscienze e Georisorse, Sezioni di Firenze, Via Giorgio La Pira, 4, 50121 Florence, Italy e-mail: sandro.conticelli@uni.it G. Giordano ` di Roma III, Dipartimento di Scienze Geologiche, Universita Largo San Leonardo Murialdo, 1, 00100 Rome, Italy Present Address: R. Avanzinelli Bristol Isotope Group, Department of Earth Sciences, Wills Memorial Building, University of Bristol, Bistol BS8 1RJ, UK

shoshonites of the Northern Roman Province, but are very similar to those of the Neapolitan volcanoes. The last phases of volcanic activity erupted sub-alkaline magmas as enclaves in trachytic domes, and as lavas within the Monte Santa Croce dome. Ultrapotassic rocks of the pre-caldera composite volcano are plagioclase-bearing leucitites characterised by high levels of incompatible trace elements with an orogenic signature having troughs at Ba, Ta, Nb, and Ti, and peaks at Cs, K, Th, U, and Pb. Initial values of 87 Sr/86Sr range from 0.70926 to 0.70999, 143Nd/144Nd ranges from 0.51213 to 0.51217, while the lead isotope rations vary between 18.78818.851 for 206Pb/204Pb, 15.68515.701 for 207Pb/204Pb, and 39.04839.076 for 208 Pb/204Pb. Shoshonites show a similar pattern of trace element depletions and enrichments to the earlier ultrapotassic leucite-bearing rocks but have a larger degree of differentiation and lower concentrations of incompatible trace elements. On the other hand, shoshonitic rocks have Sr, Nd, and Pb isotopes consistently different than precaldera ultrapotassic leucite-bearing rocks. 87Sr/86Sr ranges from 0.70665 to 0.70745, 143Nd/144Nd ranges from 0.51234 to 0.51238, 206Pb/204Pb ranges from 18.924 to 19.153, 207Pb/204Pb ranges from 15.661 to 15.694, and 208 Pb/204Pb ranges from 39.084 to 39.212. High-K calcalkaline samples have intermediate isotopic values between ultrapotassic plagioclase leucitites and shoshonites, but the lowest levels of incompatible trace element contents. It is argued that ultrapotassic magmas were generated in a modied lithospheric mantle after crustal-derived metasomatism. Interaction between the metasomatic agent and lithospheric upper mantle produced a low-melting point metasomatised veined network. The partial melting of the veins alone produced pre-caldera leucite-bearing ultrapotassic magmas. It was possibly triggered by either postcollisional isotherms relaxation or increasing TC due

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increasing heat ow through slab tears. Shoshonitic magmas were generated by further melting, at higher temperature, of the same metasomatic assemblage with addition 1020% of OIB-like astenospheric mantle material. We suggest that addition of astenospheric upper mantle material from foreland mantle, owing through slab tearing after collision was achieved. Keywords SrNdPb isotopes Plagioclase leucitite Shoshonite Sub-alkaline basaltic andesite Roccamonna volcano Roman Magmatic Province Orogenic magmas Slab tearing Asthenospheric inow

(i.e., Vulsini, Vico, Sabatini, Colli Albani). Thus, Roccamonna together with the Middle Latin Valley district (Boari and Conticelli 2007; Frezzotti et al. 2007; Boari et al. 2008a, in press), represents a key area for the understanding the nature of the geochemical and isotopic transition from the Latian to the Neapolitan sector of the Roman Magmatic Province (Conticelli et al. 2004, 2007; Peccerillo 2005a). In the present study, major and trace element concentrations, together with Sr, Nd, and Pb isotope ratios have been determined for Roccamonna volcanic rocks with the aim of elucidating the genetic relationships between ultrapotassic leucite-bearing rocks and shoshonitic lavas.

Introduction Geological and volcanological background Roccamonna was the rst volcano on the Italian Peninsula to be investigated in detail (i.e. Appleton 1972; Ghiara et al. 1973; Cox et al. 1976; Carter et al. 1978; Taylor et al. 1979). Detailed petrographic and volcanologic studies dened the volcanic succession and the eruption styles (e.g. Giannetti and Luhr 1983; Luhr and Giannetti 1987; Cole et al. 1992, 1993; Valentine and Giannetti 1995; De Rita and Giordano 1996; Giannetti 1996a, b; Giordano 1998a, b), and discussed the nature of the xenolith assemblage (Giannetti and Luhr 1990). Roccamonna mac volcanic rocks have been used to address the issue of the genesis of Italian Potassic and ultrapotassic magmatism (e.g. Hawkesworth and Vollmer 1979; Vollmer and Hawkesworth 1980; Ellam et al. 1989; Beccaluva et al. 1991; Conticelli and Peccerillo 1992; Giannetti and Ellam 1994; DAntonio et al. 1996; Conticelli et al. 2002, 2007; Peccerillo 2005a), however, there have been no detailed studies of the distribution of major and trace elements and SrNdPb isotopes in the various phases of the Roccamonna volcano since the study of Appleton (1972). Conticelli et al. (2004) showed that low potassium series of Appleton (1972) is better dened as a shoshonitic series. Shoshonitic rocks are leucite-free and are characterised by lower K contents than ultrapotassic lavas. In Italy, shoshonitic rocks generally post-date the ultrapotassic magmatism (i.e. Tuscany, Vulsini, Vico; Conticelli et al. 1991, 2007; Perini et al. 2000, 2003, 2004), except in the Neapolitan area, where the present activity at Vesuvius is ultrapotassic. Geochemical and isotopic variations in the high-MgO rocks of the Roman Magmatic Province have been described by several authors (Beccaluva et al. 1991; DAntonio et al. 1996; Conticelli et al. 2002; Peccerillo 2005a). Recently Avanzinelli et al. (2008) have shown that the Neapolitan volcanoes are consistently different in their UTh disequilibria with respect to the volcanoes of Latium The Roccamonna volcano is part of the Auruncan District of Washington (1906). The volcano lies at the intersection of important NESW, NWSE and NS tectonic lineaments cut the MesozoicCenozoic Apennine carbonatic sequences (Accordi 1963; Incoronato et al. 1985; Accordi and Carbone 1988; Mattei et al. 1993; Giordano et al. 1995). The Roccamonna volcanics are located in the NEtrending Garigliano graben, lled by transgressive marine sedimentary sequence (Ippolito et al. 1973; Watts 1987; Giordano et al. 1995). The Roccamonna composite volcano is made up by lavas and pyroclastic rocks erupted in three main periods of activity, which accompanied the formation of the poly phased summit caldera (De Rita and Giordano 1996). Volcanic activity begun at 630 ka (Ballini et al. 1989a) with a phase dominated by leucite-bearing lava ows interbedded to minor ash fall and mud-ow deposits (Fig. 1). Peripheral dikes and eccentric monogenetic volcanoes were also emplaced in the area surrounding the volcano (Di Girolamo et al. 1991). The formation of the summit caldera sector collapse marked the passage to the second period of activity (De Rita and Giordano 1996). The second period is characterised by plinian paroxistic volcanic activity between 385 and 230 ka (Luhr and Giannetti 1987), with the eruption of ve main, caldera forming pyroclastic ow units (Giannetti and Luhr 1983; Luhr and Giannetti 1987; Ballini et al. 1989b; Cole et al. 1993; Bosi and Giordano 1997; Giordano 1998a, b) that are the Brown Leucitic Tuff and the succession of the White Trachytic Tuffs (De Rita et al. 1998). The third and last period of post-caldera activity spans between 155 and 50 ka (Cortini et al. 1973; Fornaseri 1985; Radicati di Brozolo et al. 1988). Leucite-free lavas have been poured out in the form of intra- and peri-caldera exogenous trachytic domes but small leucite-free mac

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08 10 12 14 16 18 20

43

Euganei (50 Ma)

LEGEND: TMP Tuscan Magmatic Province

RMP Roman Magmatic Province LuMP Lucanian Magmatic Province

Volcanic districts (composite volcanoes)

44

Monogenetic volcano, dykes, hypabissal body Aeolian Arc - calc-alkalic volcanoes Position and depth of present-day benioff zone

44

CMP

TMP

Limit of the Apennine front

Cenozoic to present time Withinplate rocks external to Apennine-Tyrrhenian system

42

LD-RMP

Pescosansonesco (70 Ma) Pietre Nere (70 Ma)

42

Roccamonfina
Middle Latin Valley

inflow
LuMP Vulture

ND-RMP Phlegrean
Pontine Is.

Ischia
45 0

Vesuvius

40

40
350

Ustica

Aeolian Arc

25 0 15 0

38
Etna Iblei Pantelleria Linosa

38

10

12

14

16

18

Fig. 1 Distribution of volcanism in Italy and geological sketch map of Roccamonna (redrawn after: Taylor et al. 1979; Cole et al. 1992; Conticelli et al. 2007). Inset shows the location of the Roccamonna Volcano with respect to the rest of the Roman Province and the denition of the Latian Districts of the Roman Magmatic Province (RMP-LD) and the Neapolitan District of the Roman Magmatic Province (RMP-ND). Note that the CMP represent the Corsica Magmatic Province as dened by Conticelli et al. (2008, in press). 1 Campanian Ignimbrite (erupted from Campi Flegrei caldera at 39 ka), late phase of post-caldera activity (Vezzara synthem; 15550 ka),

2 HKCA nal lavas, 3 Shoshonitic mac lava and pyroclastics from monogenetic centres, 4 Shoshonitic domes, 5 Yellow Trachytic Tuff, early phase of post-caldera activity (Riardo synthem; 385230 ka), 6 White Trachytic Tuffs, 7 Teano pyroclastic succession, 8 Brown Leucitic Tuff, 9 pre-caldera activity Leucite-bearing lava and pyroclastics (plagioclase leucitites) (Roccamonna synthem; 630 385 ka), 10 MesozoicCenozoic pre-orogenic carbonatic-terrigenous succession; 11 main extensional faults, 12 caldera rim, 13 scoria cones

lava ows are also found within the caldera (Cole et al. 1992), and in some nal monogenetic parasitic vents on the ank of the volcano (Fig. 1). For the purposes of this paper, the rst period of activity at Roccamonna (630400 ka) is named hereafter precaldera period, whereas the following two periods, the paroxysm (385230 ka) and the nal one (15550 ka), are collectively named post-caldera period.

Samples and analytical techniques Forty-nine fresh samples representative of the two stages of activity at the Roccamonna volcano have been selected for the present study. Their petrography, together with sample localities, is reported in Table 1. Major and trace elements on whole rocks were determined at the DST of Firenze University using XRF and wet

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Table 1 Samples and petrography Latitude Longitude Series Rock type Texture Petrography

123
41190 0000 N HKS HKS HKS HKS HKS HKS HKS HKS HKS HKS HKS HKS Lava Lava Lava Lava Strongly porphyritic, microcr. gdm Sub-aphyric, microcrystalline gdm Sub-aphyric, microcrystalline gdm Sub-aphyric, microcrystalline gdm Lava Strongly porphyritic, microcr. gdm Lava Sub-aphyric, microcrystalline gdm Lava Sub-aphyric, microcrystalline gdm Lava Sub-aphyric, microcrystalline gdm Dyke Sub-aphyric, microcrystalline gdm Lava Sub-aphyric, microcrystalline gdm Lava Sub-aphyric, microcrystalline gdm Lava Sub-aphyric, microcrystalline gdm 4119 30 N 41210 3500 N 41190 4200 N 41190 4700 N 4120 40 N 1353 18 E 13580 1900 E 13580 4700 E 13570 5500 E 13550 0100 E 13550 0400 E 13580 5300 E 41190 1700 N 41180 5900 N 41180 4500 N 4118 42 N 41180 4200 N 41230 0700 N
0 00 0 00 0 00 0 00

Sample

Locality

Pre-caldera stage (630385 ka) 13580 1800 E 13560 4500 E 12570 3300 E 13580 0100 E 13550 1100 E Cpx[diop] + Leu + Cpx + Plg + Op + Apa Cpx + Olv + Leu + Leu + Cpx + Plg + Phl + Op Leu + Cpx + Leu + Cpx + Plg + Op + Phl + Apa Leu(Apa) + Cpx + Leu + Cpx + Plg + Op Leu + Leu + Cpx + Plg + Op Cpx + Olv + Plg[rare] + Leu + Cpx + Plg + Phl + Op Leu(Apa) + Cpx + Leu + Plg + Cpx + Op + Apa Leu + Plg + Cpx + Leu + Plg + Cpx + Op + Apa Leu + Cpx + Leu + Plg + Cpx + Op + Apa Leu + Cpx + Leu + Cpx + Plg + Op + Apa Cpx + Plg + Bio[res] + Sph + Leu + Cpx + Plg + Op Plg + Cpx + Bio[res] + Op + Leu + Cpx + Plg + Op Olv[skel](Chr) + Cpx + Plg + Cpx + Op Cpx + Olv[skel](Chr) + Plg + Cpx + Op Sub-porphyritic, microcryst. gdm Sub-porphyritic, microcryst. gdm Sub-porphyritic, microcryst. gdm Sub-aphyric, microcrystalline gdm Lava Lava SHO SHO SHO Dome Dome Dome Sub-aphyric, microcrystalline gdm Sub-aphyric, microcrystalline gdm Porphyritic, cryptocrystalline gdm Porphyritic, cryptocrystalline gdm Porphyritic, microcrystalline gdm Olv[skel](Chr) + Cpx + Plg + Cpx + Phl + Op Olv[skel](Chr) + Cpx + Plg + Cpx + Op Olv[skel](Chr) + Cpx + Plg + Cpx + Phl + Op Lava Cpx + Olv + Bio[res] + Plg + Plg + Cpx + Op Olv + Cpx + Plg + Plg + Cpx + Olv + Op Olv(Chr) + Cpx + Plg + Cpx + Olv + Op Bio[res] + Cpx + Plg + Op + Plg + Cpx + Op + Bio + Glass Plg + Cpx + Bio[res] + Op + Plg + Cpx + Op + Bio 13570 5900 E Plg + Cpx + Bio[res] + Op + Plg + Cpx + Bio + Op + Apa

RMN 44

Caldera wall

RMN 18

Caldera rim

RMN 46

Vignola

RMN 03

Sipicciano

RMN 07

Zelloni

RMN 10

Caldera wall

Rmn 45

North Caldera rim

RMN 43

North Caldera rim

RMN 50

Caldera wall

RMN 05

San Carlo

RMN 06

San Carlo

RMN 47

Fosso Maltempo

Post-caldera stage, early phase (385155 ka) 41180 5900 N SHO SHO SHO SHO SHO SHO SHO SHO Lava Lava Lava Scoria Lava 4117 02 N 41170 3700 N 41170 0300 N 4117 37 N 41190 2600 N 41210 1900 N 41230 1800 N 4117 26 N 41170 4200 N 41180 3100 N
0 00 0 00 0 00

RMN 11 13590 0300 E 13550 3800 E 13580 5300 E 13550 3800 E 13560 4900 E 13590 1200 E 13590 0900 E 1357 20 E 13580 1400 E
0 00

Masseria Robetti

13580 2400 E

Porphyritic, cryptocristalline gdm Porphyritic, glassy gdm

RMN 14

Monte Atano

RMN 09

San Martino

RMN 16

Monte Atano

RMN 08

San Martino

RMN 04

Fontanelli

RMN 17

Colle Friello

Rmn 48

Paterno

RMN 28

Monte Santa Croce

RMN 25

Monte Santa Croce

Contrib Mineral Petrol (2009) 157:4163

RMN 38

Monte Santa Croce

Table 1 continued Latitude Longitude Series Rock type Dome Lava Dome Dome Dome Dome Lava Dome Dome Dome Dome Dome Enclave Porphyritic, pylotaxitic gdm Porphyritic, pylotaxitic gdm Strongly porphyritic, crypto gdm Sub-porphyritic, trachytic gdm Sub-porphyritic, pylotaxitic gdm Porphyritic, pylotaxitic gdm Porphyritic, microcrystalline gdm Porphyritic, microcrystalline gdm Porphyritic, cryptocrystalline gdm Sub-porphyritic, pylotaxitic gdm Porphyritic, microcrystalline gdm Porphyritic, microcrystalline gdm Porphyritic, microcrystalline gdm Plg + Bio[res] + Cpx + Op + Plg + Bio + Cpx + Op Cpx + Olv + Plg[res] + Op + Plg + Cpx + Op + Bio[res] Plg + Cpx + Bio[res] + Op + Sd + Plg + Cpx + Op + Bio + Apa Plg + Cpx + Plg + Cpx + Olv + Op Plg + Bio[res] + Cpx + Op + Plg + Cpx + Op + Bio Plg + Cpx + Bio[res] + Op + Plg + Op + Cpx + Bio Plg + Cpx + Bio[res] + Olv[cor] + Op + Plg + Cpx + Bio + Ga Plg + Bio[res] + Cpx + Op + Olv + Plg + Cpx + Op + Phl Bio[res] + Plg + Cpx + Op + Plg + Cpx + Bio + Op Plg + Cpx + Bio[res] + Op + Plg + Cpx + Op + Opx (?) Plg + Bio[res] + Cpx + Op + Plg + Bio + Cpx + Op Sd + Cpx + Sph + Sd + Plg + Cpx + Op Olv(Chr) + Cpx + Plg + Olv + Cpx + Op + Glass Sub-porphyritic, glassy gdm Porphyritic, visicular, glassy gdm Sub-porphyritic, mycrocryst. gdm Final lava Final lava HKCA HKCA 13580 2800 E HKCA Final lava Final lava Final lava Sub-porphyritic, glassy gdm Sub-porphyritic, glassy gdm Sub-porphyritic, pylotaxitic gdm Sub-porphyritic, glassy gdm Sub-aphyric, cryptocrystalline gdm Cpx + Olv(Chr) + Plg + Cpx + Glass + Xenolith of Dome Olv + Cpx + Plg + Opx(?) + Plg + Cpx + Olv + Glass Final lava Olv[idd](Chr) + Plg + Cpx + Bio + Plg + Cpx + Olv[idd] + gl Olv(Chr) + Cpx + Plg + Olv + Cpx + Glass Texture Petrography

Sample

Locality

RMN 23 SHO SHO SHO SHO SHO SHO SHO SHO SHO SHO SHO SHO HKCA 41230 4400 N 41180 0300 N 41180 0900 N 4117 35 N 41170 5900 N 41180 3000 N 41170 0400 N 41170 5900 N 41170 5600 N 41180 010000 N 41170 0200 N 4117 26 N
0 00 0 00

Monte Lattani 13590 1200 E 13580 4200 E 13580 3100 E 13580 1400 E 13570 4300 E 13590 4000 E 13580 5300 E 13590 0700 E 13590 0400 E 13580 5800 E 13580 3800 E 13570 2000 E

41180 0300 N

13580 4200 E

RMN 49

Annalise

RMN 24

Monte Lattani

RMN 01

Monte Lattani

Contrib Mineral Petrol (2009) 157:4163

RMN 27

Monte Santa Croce

RMN 30

Monte Santa Croce

RMN 42

Masseria SantAntonio

RMN 15

Near Monte Atano

RMN 21

Monte Lattani

RMN 22

Monte Lattani

RMN 20

Monte Lattani

RMN 13

Near Monte Atano

RMN 29

Monte Santa Croce

Post-Caldera stage, nal phase (\155 ka) 41180 0400 N HKCA HKCA HKCA HKCA HKCA 41180 0400 N 41180 3500 N 41180 4100 N 4118 44 N 41180 3100 N 41180 0800 N 41180 1200 N 13570 5900 E 13580 2400 E
0 00

RMN 31 13580 2000 E 13570 5200 E 13580 0300 E 13580 1300 E

Monte Santa Croce

13580 2000 E

Scoriaceous red lava Final lava at the vent

RMN 32

Monte Santa Croce

RMN 39

Ciannemaie

RMN 41

Ciannemaie-Robetti

RMN 40

Ciannemaie-Robetti

RMN 37

Ciannemaie

Olv[skel](Chr) + Plg + Cpx + Plg + Cpx + Olv + Glass Olv(Chr) + Plg + Cpx + Plg + Cpx + Olv + Glass Olv(Chr) + Cpx + Plg + Plg + Olv + Cpx + Glass Olv(Chr) + Plg + Cpx + Glass 45

RMN 33

Poggio Molara

123

RMN 34

Poggio Molara

46 Entries within brackets are minerals enclosed in the preceeding mineral; within squared brackets are textural feature of the mineral: res resorbed, idd iddingsited; in bold are the phenocrysts; in italics and underlined are the xenocrysts HKS plagioclase leucitite, SHO shoshonite, HKCA high-K calc-alkaline, Olv olivine, Chr chromite, Cpx clinopyroxene, Leu leucite, Bio biotite, Plg plagioclase, Op opaque, Apa apatite, Gl glass, Ga garnet, Sd sanidine, Sph sphene

Contrib Mineral Petrol (2009) 157:4163

Poggio Molara

Ciannemaie

Selletta

Poggio Molara

chemical methods. MgO and Na2O were determined by AAS, FeO by titration (after Shapiro and Brannock 1962), and LOI gravimetrically. XRF data were corrected for matrix effects following the methods of Franzini et al. (1972) for major elements, and that of de Vries and Jenkins (1971) for trace elements. REE, Ta, Hf, Th, Co, and Sc were analysed by INAA (DST, Firenze University) following the procedure described by Poli et al. (1977) and by ICP-MS (ACTLAB). Errors for trace elements are better that 10% for Co, Sc, Nd, Lu, Tb, and Th, and better than 5% for the other elements. Bias between INAA and ICPMS was evaluated using international reference samples as unknown, and was found to be within the range of analytical error. Sr, Nd, and Pb isotopes were analysed at the DST of the Firenze University following the procedures outlined by Avanzinelli et al. (2005). Digested rocks solutions were used for Sr and Nd purication through standard liquid chromatographic techniques. Sr and Nd isotopic ratios were measured by thermal ionisation mass spectrometry (TIMS) using a Thermonnigan Triton TI in a triple jumping multi-dynamic mode (Thirlwall 1991; see also Avanzinelli et al. 2005 for further details). Mass fractionation of Sr and Nd isotopes has been exponentially corrected with 86Sr/88Sr = 0.1194 and 146Nd/144Nd = 0.7219, respectively. 87Sr/86Srtriple average value for NBS 987 reference sample was 0.710251 12 (2r, n = 70): 143 Nd/144Ndtriple average value for La Jolla reference samples was 0.511845 7 (2r, n = 25). Pb was puried following the method described by Deniel and Pin (2001) using 100150 lm Sr-spec resins in quartz bres microcolumns. The Pb separation efciency was evaluated to be about 97%. Pb samples were loaded onto zone-rened Re laments, with addition of 0.5 ll of silica gel and 1 ll of high-purity H3PO4 and measured in static mode with a Thermonnigan Triton TI; average runs were measured at 1,400C and yielded *1.5 V of 208Pb. Mass bias was monitored with repeated measurements of SRM 981 reference standard and we obtained a mass discrimination factor (e) of 0.15% per a.m.u. The external reproducibility of the international reference standard SRM 981 was: 208 Pb/204Pb = 36.495 23; 207Pb/204Pb = 15.423 7; 206 Pb/204Pb = 16.888 6; 207Pb/206Pb = 0.91328 15; 208 208 Pb/207Pb = 2.3662 4; Pb/206Pb = 2.1610 7 (2r, n = 45).

Plg + Cpx + Olv + Plg + Cpx + Olv + Op Sub-porphyritic, mycrocryst. gdm Final lava HKCA 13580 0900 E 4118 21 N
0 00

Cpx + Olv(Chr) + Plg + Plg + Olv + Cpx

Petrography

Sub-porphyritic, pylotaxitic gdm

Sub-aphyritic, cryptocryst. gdm Final lava HKCA 13570 4400 E 41180 2600 N

Texture

Final lava

Rock type

HKCA

13580 2800 E

41180 1200 N

Locality

41170 0100 N

Latitude

13580 3300 E

Longitude

HKCA

Series

Final lava

Sub-porphyritic, glassy gdm

Plg + Cpx + Olv + Plg + Cpx + Op + Glass

Plg + Cpx + Olv + Op

Table 1 continued

Petrography and geochemistry Pre- and post-caldera volcanic rocks from Roccamonna are distinct in terms of their mineralogy and petrography (Table 1). Pre-caldera rocks are leucite-bearing with clinopyroxene and plagioclase ubiquitously present as

RMN 35

RMN 36

123

Sample

RMN 02

RMN 12

Contrib Mineral Petrol (2009) 157:4163 Fig. 2 Classication diagrams, K2O + Na2O versus SiO2 (total alkali silica; Le Bas et al. 1986) and K2O versus SiO2 (Peccerillo and Taylor 1976), for ultrapotassic rocks of Roccamonna volcano. Note that data are plotted on a volatile-free basis

47

B
UltrapotassicSeries (HKS)

Shoshonitic Series (SHO)

High-K Calk-alkalic Series Calk-alkalic Tholeiitic Series

phenocrysts, and olivine only in the most mac members. Apatite and opaque phases are ubiquitous in the groundmass. Resorbed biotite and titanite also occur in the most felsic samples. These rocks are ultrapotassic and range in composition from basanite to phonolite (Fig. 2). Foley (1992a) referred to Italian leucite-bearing rocks as plagioclase leucitites to distinguish them from within-plate leucitites in which Al2O3 is extremely low (e.g. Rogers et al. 1992, 1998). Post-caldera rocks are leucite-free, with ubiquitous clinopyroxene phenocrysts. Different phenocrysts are present with clinopyroxene depending on the degree of differentiation: olivine in the most mac samples, plagioclase and biotite in the intermediate to felsic products and sanidine, often as a megacryst, is restricted to the most felsic samples along with rare titanite. On the basis of chemical characteristics and temporal succession, the postcaldera lavas can be further divided into two groups. The early post-caldera lavas (400155 ka) are shoshonitic in composition and range from basalt to trachyte (Fig. 2a). The nal lavas (15550 ka) have the lowest total alkali and K2O contents, at comparable silica, of the entire Roccamonna sequence (Fig. 2). They are sub-alkaline basaltic andesites (Fig. 2a), that straddle the boundary between the shoshonite series and High-K calc-alkaline series (Fig. 2b). Pre- and post-caldera rocks show distinct trends in major and trace element variation diagrams with MgO (Fig. 3). Pre-caldera plagioclase leucitites show the highest levels of K2O, FeO, TiO2, Rb and most of the incompatible elements contents, and they increase with decreasing MgO contents (Fig. 3). Among post-caldera rocks, the nal sub-alkaline lavas (HKCA) have fairly homogeneous MgO contents (Table 2), whereas early post-caldera rocks (i.e. shoshonites) are enriched in SiO2, Na2O, and Nb at comparable MgO contents (Table 2; Fig. 3). Small differences are shown on spider diagrams normalised to primordial mantle between pre- and post-caldera rocks (Fig. 4). Plagioclase leucitites have large peaks at Cs and Pb, and small one at U and Sr; large through are present at Ba, Ta, Nb, and Ti, with minor through at Nd, P,

and Hf (Fig. 4). Normalised Ta/Nb is \1. Early post-caldera leucite-free rocks (i.e., shoshonites) have large peaks at Cs and Pb, but still smaller than those shown by plagioclase leucitites (Fig. 4). Thought at Ta, Nb, and Ti are shown, with minor ones at Ba, Nd, and P. Normalised Ta/ Nb is variable from \1 to [1. The nal post-caldera lavas (i.e., HKCA), show the smallest peak and through magnitudes. Signicant differences are shown by disappearance of Ba through and inversion of the normalised Ta/Nb values which are [1 (Fig. 4). A twofold behaviour is also shown by isotopic compositions (Table 3). Plagioclase leucitites (i.e. pre-caldera) have the highest initial 87Sr/86Sr (0.709260.70999) and the lowest initial 143Nd/144Nd values (0.512130.51217), respectively (Fig. 5). Little or no variation of initial 87 Sr/86Sr with decreasing MgO are shown by within either plagioclase-leucitites of pre-caldera phase or leucite-free post-caldera rocks (0.706650.70745), with nal subalkaline lavas intermediate (0.707480.70749) between pre- and post-caldera rocks (Fig. 5). On the whole 87Sr/86Sr and 143Nd/144Nd of Roccamonna rocks show a clear negative covariation straddling the elds of rocks from the Latian districts (RMP-LD) and the Neapolitan one (RMPND) of the Roman Magmatic Province (Fig. 6). The same covariation is observed for 208Pb/204Pb, 87Sr/86Sr, and 143 Nd/144Nd vs. 206Pb/204Pb diagrams (Fig. 7), with shoshonites showing the highest 206Pb/204Pb (18.924 19.153) and 208Pb/204Pb (39.08439.212) values and plagioclase leucitites the lowest 206Pb/204Pb (18.78818.851) and 208Pb/204Pb (39.04839.076) values (Table 3).

Discussion The origin of the extremely enriched trace element composition of Italian potassic and ultrapotassic volcanoes their fractionated LILE/HFSE and their isotopic signature has been thoroughly discussed in many studies about Italian magmatism (e.g. Conticelli et al. 2004; Peccerillo 2005a, for reviews). To briey summarise the genetic scenario, Italian magmas in general, and Roccamonna in

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48 Fig. 3 Differentiation diagrams for some major (wt.%) and trace (ppm) elements versus MgO wt.%. Note that leucite-bearing and leucite-free rocks plots along different trends

Contrib Mineral Petrol (2009) 157:4163

particular, have been generated in a sub-continental lithospheric mantle, enriched by the addition of crustal material, recycled probably as sedimentary melts via subduction (Peccerillo 1985, 2005a, b; Conticelli and Peccerillo 1992). Silica saturation of ultrapotassic has been controlled by XCO2 during partial melting of the metasomatised mantle source partial melting (Wendlandt and Eggler 1980a, b). In this scenario, the CO2-rich component might have been released during partial melting of CaCO3-rich subducted marly sediment (Conticelli et al. 2004; Avanzinelli et al. 2008). Then de-volatilisation of CaCO3 sedimentary component might provide the CO2 to increase the XCO2 and to provide the necessary CaO to re-fertilise the lithospheric refractory mantle source. High-ux of CO2, with typical crustal-derived oxygen isotopic values, has been recorded in the Roman Magmatic Province (e.g. Bertrami et al. 1990; Chiodini and Frondini 2001; Beaubien et al. 2003). In addition Conticelli et al. (2002, 2007) have shown that

initial 87Sr/86Sr and 143Nd/144Nd for Roman Magmatic Province anticorrelate pointing to a crustal reservoir with the isotopic composition intermediate between those of shales and limestones. Leucite-bearing rocks from Roccamonna volcano fall along this trend, with isotopic values typical of leucite-bearing rocks (plagio-leucitites, leucitites, and kamafugites) of the Roman Magmatic Province but slightly less enriched in radiogenic Sr (Fig. 6). Previous studies, however, have shown that Neapolitan ultrapotassic volcanoes (RMP-ND) display clear differences in many geochemical (Beccaluva et al. 1991) and isotopic (Peccerillo 2005a, and references therein) tracers respect with ultrapotassic volcanic rocks belonging to the northern district of the Roman Magmatic Province (RMPLD). The process responsible for this variation is still matter of debated and it might involves several different factors, such as: (1) the inuence of an asthenospheric component prior to metasomatism (Beccaluva et al. 1991;

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Contrib Mineral Petrol (2009) 157:4163 Table 2 Representative chemical analyses of Roccamonna rocks Series Sample Number SiO2 TiO2 Al2O3 Fe2O3 FeO MnO MgO CaO Na2O K2O P2O5 LOI Sum MgV Alk Sc V Cr Co Ni Cu Zn Ga Rb Sr Y Zr Nb Cs Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta Pre-caldera: leucite-bearing RMN 44 1 46.3 0.97 15.3 4.73 4.10 0.15 6.61 12.6 1.60 6.63 0.62 0.58 100.18 62.38 8.23 nd 312 164 34.5 72 109 83 18 322 1,784 38.9 226 10.5 31.0 1,460 105.4 210.8 24.9 90.0 18.4 3.70 12.9 1.81 7.32 1.19 2.96 0.367 2.16 0.311 6.38 0.54 RMN 18 2 48.2 0.89 16.6 3.99 4.01 0.15 5.78 10.2 1.99 7.29 0.51 0.76 100.27 61.46 9.28 29.6 267 154 30.6 54 nd nd nd 345 1,842 40.0 255 10.4 36.0 1,706 96.3 185.0 23.8 93.0 17.6 3.50 12.5 1.80 7.05 1.17 3.14 0.403 2.22 0.320 5.99 0.58 RMN 46 3 49.0 0.78 19.9 1.70 5.70 0.16 2.80 7.64 2.67 8.10 0.42 1.07 99.90 44.81 10.77 nd 239 bdl 24.4 21 40 86 21 358 1,890 39.3 279 10.3 25.1 1,460 122.0 244.4 24.5 90.0 16.0 3.29 11.1 1.49 6.82 1.18 3.28 0.448 2.71 0.389 5.83 0.52 RMN 45 7 50.8 0.69 19.9 3.12 3.48 0.17 1.78 7.02 2.69 8.65 0.37 0.93 99.65 37.25 11.34 nd 228 bdl 14.6 6 17 112 21 511 2,190 39.7 289 19.5 25.5 1,450 134.8 258.6 28.3 97.2 17.4 3.51 10.8 1.59 6.94 1.21 3.30 0.453 2.80 0.406 6.61 0.91 RMN 43 8 52.6 0.58 20.1 1.32 3.98 0.12 1.75 5.16 2.41 10.41 0.36 1.01 99.74 41.54 12.82 nd 141 3 15.4 11 43 85 19 606 1,670 38.4 256 18.2 46.3 1,280 98.3 185.1 19.6 65.5 11.5 2.31 7.44 1.08 4.82 0.82 2.33 0.323 2.02 0.292 4.3 0.87 Post-caldera: leucite-free shoshonites RMN 11 12 47.3 0.91 15.8 2.48 5.96 0.15 9.35 12.1 1.32 1.29 0.30 3.22 100.11 70.53 2.61 43.8 nd 350 43 74 nd nd nd 189 819 30 146 16 18.0 841 40.7 77 nd 36 7.66 1.88 nd 0.7 nd nd nd nd 1.73 nd 2.8 0.90 RMN 14 13 47.7 0.91 17.0 3.29 5.80 0.16 8.94 12.0 1.36 1.86 0.27 0.74 100.00 68.15 3.22 31.9 nd 330 40 76 nd nd nd 177 777 24 157 16 9.0 600 44 91 nd 44 9.29 2.27 nd 1.0 nd nd nd nd 1.88 nd 4.1 0.35 RMN 09 14 48.2 0.82 17.6 3.57 5.08 0.15 7.10 11.2 1.75 3.16 0.37 1.14 100.09 64.23 4.91 32.7 nd 313 39 56 nd nd nd 191 1,152 30 157 13 9.0 604 43.7 87 nd 42 9.06 2.03 nd 0.9 nd nd nd nd 1.92 nd 3.8 0.75 RMN 16 15 48.1 0.80 17.0 2.99 5.96 0.16 8.67 12.4 1.68 1.62 0.27 0.58 100.11 67.76 3.30 45.5 nd 330 47 74 nd nd nd 153 784 31 156 16 4.0 594 27.3 50 nd 26 6.04 1.63 nd 0.7 nd nd nd nd 1.64 nd 2.8 0.38 RMN 04 17 51.1 0.82 18.6 3.79 4.03 0.14 5.87 9.15 2.17 3.41 0.31 0.67 100.05 62.33 5.58 26.9 nd 240 36 47 nd nd nd 152 882 32 166 15 4.0 693 43.6 80 nd 38 7.70 1.77 nd 0.8 nd nd nd nd 2.33 nd 4.3 0.81

49

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50 Table 2 continued Series Sample Pb Th U Series Sample Number SiO2 TiO2 Al2O3 Fe2O3 FeO MnO MgO CaO Na2O K2O P2O5 LOI Sum MgV Alk Sc V Cr Co Ni Cu Zn Ga Rb Sr Y Zr Nb Cs Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho Pre-caldera: leucite-bearing RMN 44 50.6 36.7 8.68 RMN 18 51.5 43.0 9.21 RMN 46 61.7 47.9 11.5 RMN 45 71.6 46.3 11.4 RMN 43 52.3 40.4 9.8

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Post-caldera: leucite-free shoshonites RMN 11 8.71 7.8 1.7 RMN 14 8.11 7.5 2.3 RMN 09 12.9 7.6 2.0 RMN 16 5.67 4.3 1.0 RMN 04 16.9 13.0 3.3

Post-caldera: leucite-free shoshonites RMN 17 18 51.1 0.85 17.4 3.49 3.54 0.14 7.76 10.1 2.07 2.94 0.25 0.55 100.19 70.90 5.01 35.6 nd 300 35 66 nd nd nd 132 806 28 174 9 5.0 581 36.5 67 nd 31 6.45 1.60 nd 0.8 nd nd RMN 48 19 51.7 0.73 18.4 2.21 4.60 0.15 5.91 8.08 2.22 4.10 0.24 1.68 100.06 65.29 6.32 nd 201 254 24.7 51 59 61 16 146 723 35.4 150 11.9 3.67 630 70.5 100.1 13.2 50.4 9.89 2.23 8.30 1.27 6.10 1.13 RMN 24 25 54.4 0.73 18.3 2.09 4.37 0.14 3.14 7.25 2.86 4.93 0.30 1.75 100.18 51.30 7.79 nd 205 14 20.3 10 43 68 19 207 1,060 32.0 205 16.2 10.8 752 63.0 128.6 13.4 52.5 10.5 2.40 8.12 1.21 5.92 1.08 RMN 01 26 54.4 0.78 18.8 1.45 5.04 0.15 3.54 7.53 2.53 5.06 0.24 1.58 101.10 53.92 7.59 13.4 nd 25 16.4 14 nd nd nd 153 909 32 155 16 nd 587 62 114 nd 49 8.40 1.92 nd 1.0 nd nd RMN 30 28 55.2 0.73 19.0 4.14 2.46 0.16 3.04 6.24 2.89 4.45 0.24 1.36 99.86 50.76 7.34 nd 189 9 19.9 11 51 81 20 162 898 30.8 199 16.6 4.98 656 53.2 108.9 11.2 42.7 8.65 1.97 6.85 1.07 5.44 1.06 RMN 42 29 55.2 0.69 19.2 1.89 4.10 0.14 2.96 6.51 3.04 5.24 0.28 0.76 100.00 51.70 8.28 nd 195 14 19.1 9 36 69 20 230 1,070 33.8 228 18.4 14.4 792 69.0 138.4 14.4 55.2 10.7 2.45 8.11 1.26 6.15 1.14 RMN 22 32 58.0 0.62 18.7 2.86 2.60 0.13 2.68 5.57 2.97 4.86 0.20 0.83 100.00 52.08 7.83 nd 159 20 15.2 12 21 64 19 188 773 31.8 211 19.3 7.06 561 64.6 120.9 12.0 44.5 8.57 1.91 6.67 1.06 5.33 1.04

Post-caldera: leucite free HKCA RMN 29 35 52.3 0.83 19.0 2.13 6.21 0.16 4.67 8.67 2.08 2.86 0.18 0.88 100.00 54.65 4.94 nd 199 38 26.2 14 30 75 19 120 857 25.3 128 10.2 7.14 561 37.0 78.0 8.34 32.9 6.91 1.63 5.59 0.86 4.44 0.90 RMN 39 38 52.3 0.80 19.2 1.90 6.17 0.15 4.63 8.25 2.18 2.99 0.20 1.22 100.00 55.20 5.17 nd 212 37 25.2 16 26 93 21 118 910 28.1 136 11.0 6.62 626 42.0 81.9 9.27 36.5 7.44 1.69 6.05 0.94 4.83 0.97 RMN 33 42 53.4 0.80 18.6 1.92 6.09 0.15 4.44 8.58 2.16 3.00 0.18 0.63 100.00 54.36 5.16 nd 202 43 23.8 17 15 99 19 132 892 26.2 139 10.6 7.67 580 39.0 78.7 8.72 34.1 6.91 1.65 5.72 0.91 4.59 0.90 RMN 12 47 53.9 0.80 18.8 2.16 5.84 0.15 4.31 8.15 2.10 2.98 0.17 0.57 99.90 53.73 5.08 18.6 nd 24 24.4 14 nd nd nd 152 944 30 151 10 nd 572 42 71 nd 38 7.60 1.58 6.0 0.8 nd nd

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Contrib Mineral Petrol (2009) 157:4163 Table 2 continued Series Sample Er Tm Yb Lu Hf Ta Pb Th U Post-caldera: leucite-free shoshonites RMN 17 nd nd 2.06 nd 3.5 0.50 9.90 8.9 2.7 RMN 48 3.15 0.439 2.73 0.405 3.88 0.70 20.6 12.9 2.7 RMN 24 3.08 0.441 2.84 0.414 5.20 0.94 22.5 18.6 5.3 RMN 01 nd nd 2.86 nd 5.3 1.07 23 20 6 RMN 30 3.10 0.441 2.80 0.424 5.04 0.96 25.3 19.1 5.6 RMN 42 3.23 0.464 2.90 0.426 5.50 1.03 33.5 21.1 6.0 RMN 22 3.13 0.455 2.91 0.435 5.14 1.06 23.6 21.2 7.1 Post-caldera: leucite free HKCA RMN 29 2.61 0.368 2.34 0.347 3.47 0.70 17.1 8.8 2.1 RMN 39 2.84 0.405 2.48 0.373 3.65 0.70 20.0 9.5 2.2 RMN 33 2.61 0.378 2.51 0.373 3.72 0.70 17.8 9.2 2.2

51

RMN 12 nd nd 2.84 nd 3.5 0.69 15 9.7 2

Major elements have been determined by XRF; trace elements by ICP-MS; when in italic they have been determined by XRF and INAA

Peccerillo and Panza 1999); (2) variation in the composition of the metasomatic agent; (3) the presence of a further metasomatic event in the Neapolitan area (Peccerillo 2005a; Avanzinelli et al. 2008). In this context the Roccamonna volcano has many characteristics, in addition to geographic position, to represent a key point to solve this issue. Differently from the northermost Roman Volcanoes (RMN-LD) at Roccamonna volcano occur shoshonitic to high-K calc-alkalic rocks following silica undersaturated plagioclase leucitites. This shoshonitic volcanism is coeval to the appraisal and building up of the Neapolitan volcanoes (RMP-ND) (Conticelli et al. 2004, and references therein). On the basis of the incompatible trace element and Sr, Nd, and Pb data (Tables 2, 3) it is clear that Roccamonna shoshonites have many geochemical and isotopic similarities with Neapolitan shoshonites (RMP-ND), whereas pre-caldera plagioclase leucitites still fall well within the geochemical and isotopic eld of other ultrapotassic Roman volcanoes (RMP-LD) (Fig. 7). Boari and Conticelli (2007) have shown that coeval shoshonites also occur in the Middle Latin Valley monogenic volcanic eld, few km north of Roccamonna, associated to plagioclase leucitites, kamafugites and calc-alkalic magmatism. In that case extensive detailed studies on fresh rocks have shown that incompatible trace elements and isotopic characteristics of shoshonites and calc-alkalic magmas from Middle Latin Valley are not different from those of northernmost Roman magmas (RMP-LD) and therefore signicantly different from those of the Neapolitan volcanoes (RMPND) (Boari et al. 2008a, in press). Shallow level differentiation processes Before tackling any source process, it is necessary to investigate the effect of shallow level processes. The aim of this section is not to reproduce or model the evolution of the magmas in the shallow reservoir of Roccamonna

volcano, but to evaluate the possibility that the different series were cogenetic and related one to the other by crystal fractionation, crustal assimilation, or a combination of both (AFC). There is no doubt that pre-caldera and post-caldera volcanic rocks at Roccamonna volcano follow distinct differentiation trends (Fig. 3). Post-caldera leucite free rocks can be further divided into two groups: the early post-caldera shoshonitic rocks, and the late post-caldera high-K calc-alkalic rocks. Low pressure differentiation processes are then required for modelling the compositional variations within each group of rocks recognised. Small Sr and Nd isotopic variations with MgO decreasing are shown within each trend (Fig. 5), indicating that differentiation at low pressure of each trend is mainly driven by either fractional crystallisation (FC) or fractional crystallisation plus contamination (AFC). Post-caldera rocks with high-K calc-alkaline afnity have Sr and Nd isotopes intermediate between the plagioclase leucititic samples and the shoshonitic ones, but closer to the latter (Fig. 5), suggesting a possible derivation from shoshonites through either AFC or mixing plus crystal fractionation (MFC). Major element mass balance calculation performed on pre-caldera leucite-bearing rocks having similar initial 87 Sr/86Sr (from RMN 44 to RMN 45) has provided at the best an R2 = 1.1 for a fractionation of clinopyroxene (37.9 vol.%) + leucite (15.6 vol.%) + apatite (2.5 vol.%) + magnetite (13.5 vol.%). This assemblage is compatible with modal mineralogy of the choose end members, and is conrmed by trace element enrichment factors calculated. A plagioclase (7.7 vol.%) + clinopyroxene (9.2 vol%) + apatite (0.73 vol.%) + magnetite (6.9 vol.%) assemblage (R2 = 0.45) is argued to achieve the composition of the most evolved rocks at MgO levels lower than 2 wt.% (RMN 43), but differences in the 87Sr/86Sr and 143Nd/144Nd isotopes argue for open system processes. AFC does not model the isotopic composition of the most differentiated plagioclase

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Fig. 4 Patterns of incompatible trace elements normalised to the primordial mantle (Sun and Mc Donough 1989) for ultrapotassic rocks of the Roccamonna volcano. Element order in the abscissa follows the increasing compatibility of the elements according to Hoffman (1996). Note that pre-caldera plagioclase leucitites and postcaldera leucite-free rocks have similar normalised patterns, but Nb/Ta values are inverted passing from pre- to post-caldera ones

leucititic sample (RMN 43), whereas it might be explained by either bulk mixing or mixing plus crystal fractionation (MFC) between plagioclase leucitites and mac shoshonites (Fig. 8). Shoshonitic rocks show the largest differentiation range covering the entire MgO spectrum of Roccamonna rocks, from trachybasalts to trachytes (Fig. 2). Differentiation occurs with small but signicant isotopic variation suggesting that crystal fractionation plus assimilation dominated. The differentiation pathways followed by the0shoshonitic rocks are governed mainly by crystal fractionation of an assemblage made up by olivine (4.9%) + clinopyroxene (29.6%) + plagioclase (19.9%) +

magnetite (9.7%) biotite and sanidine in the most differentiated steps. Applying partition coefcients of Francalanci et al. (1987) and Foley and Jenner (2004) AFC has been modelled to account for Sr and Nd isotopic variations (Fig. 8). According to the geology of the area a limestone has been taken as contaminant (Mattei et al. 1993; Giordano et al. 1995). In Fig. 8 the AFC modelling (DePaolo 1981) for Sr/Th versus initial 87Sr/86Sr is reported. Starting from a mac parental magmas the entire trend of shoshonites can be modelled with an r (i.e. assimilation/crystallisation mass proportions) = 0.2. On the other hand, it is not possible to derive any plagioclaseleucititic composition with an AFC process starting from a mac shoshonitic end member (Fig. 8). Regarding late post-caldera leucite-free rocks (HKCA), they distinctively plot on a further different trend. AFC starting from a mac shoshonitic composition does not account completely for their genesis. In fact an r value [0.5 is needed (Fig. 8), which would results a far too high proportion of assimilated material. On the other hand a mixing process between mac shoshonite and some plagioclase leucitite magma might account for their genesis. The possibility of generating such enrichment in the incompatible trace element contents by crustal assimilation has been thoroughly discussed and discounted in previous works (e.g. Conticelli 1998; Murphy et al. 2002). Furthermore, the role of crustal contamination of such protoliths does not match with the strong degree of silica undersaturation of ultrapotassic leucite-bearing rocks. Recently Iacono Marziano et al. (2007) have called for strong involvement of sedimentary carbonate assimilation in the Italian rocks to justify the derivation of ultrapotassic leucite-bearing rocks from shoshonite. This general picture was already arise by several authors in the early twentieth century (e.g. Daly 1910; Rittmann 1933) and discounted by Savelli (1967). On the other hand, Iacono Marziano et al. (2007), on the basis of experimental data, justify the passage from shoshonite to either leucititic or plagioclase leucititic magmas through limestone assimilation plus clinopyroxene crystallisation. Our calculations (Fig. 8) clearly show that AFC is an important process in generating the geochemical and isotopic variation in postcaldera shoshonitic rocks but cannot reproduce the transition from post- to pre- caldera products, or vice versa. Other characteristic of Roccamonna volcano rocks argues against such a process. Analogously to Savelli (1967) we have found that ultrapotassic leucite-bearing rocks are enriched in incompatible trace elements respect with leucite-free (i.e. shoshonite and high-K calc-alkaline) ones, with limestones characterised by the lowest concentration levels (Fig. 9). In addition limestones from Apennine (Melluso et al. 2003, 2005a, b; Conticelli et al. 2002, 2007, 2008, in press; Boari et al. 2008a, in press)

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Table 3 Sr, Nd, and Pb isotopes on representative sample from Roccamonna 2 sigma
87

Sample

87

Sr/86Sr measured 2 sigma

Sr/86Sr initial

Nd/144Nd measured

143

Nd/144Nd initial

143

206

Pb/204Pb

207

Pb/204Pb

208

Pb/204Pb

Pre-caldera; leucite-bearing ultrapotassic rocks 0.000007 0.000005 0.000006 0.000007 0.000007 0.000008 0.000007 0.000004 0.000003 0.000004 0.000004 0.000007 0.000005 0.000008 0.000007 0.000005 0.000007 0.000003 0.000005 0.000007 0.000004 0.707492 nd 0.707476 0.707488 0.512270 0.512265 0.707492 0.512277 0.706975 0.512382 0.707122 nd nd 0.000003 0.000005 0.000004 0.000003 nd 0.707030 0.512369 0.707054 nd nd 0.000004 0.707454 0.512371 0.000005 0.706891 nd nd nd 0.512371 nd 0.512369 nd 0.512382 0.512277 0.512270 0.512265 nd 0.706812 0.706761 0.512342 nd 0.000003 nd 0.706654 0.512356 0.000010 0.512356 0.512342 nd 0.706786 0.512350 0.000004 0.512350 0.706687 0.512359 0.000009 0.512359 0.706662 0.512377 0.000007 0.512377 0.709255 0.512134 0.000007 0.512134 18.805 19.153 19.026 18.924 nd nd nd nd 19.069 nd 19.008 nd nd 18.886 18.890 18.896 nd 0.709852 0.512171 0.000004 0.512171 18.851 0.709987 nd nd nd nd 0.709834 0.512167 0.000005 0.512167 18.823 0.709529 0.512152 0.000003 0.512152 18.788 15.689 15.698 nd 15.701 15.685 15.680 15.661 15.674 nd nd nd nd 15.694 nd 15.693 nd nd 15.686 15.695 15.700 nd 39.048 39.052 nd 39.076 39.048 39.199 39.123 39.084 nd nd nd nd 39.212 nd 39.168 nd nd 39.088 39.101 39.118 nd

RMN 44

0.709533

Contrib Mineral Petrol (2009) 157:4163

RMN 18

0.709837

RMN 46

0.709991

RMN 45

0.709856

RMN 43

0.709261

Post-caldera; early phase, shoshonitic rocks

RMN 11

0.706663

RMN 14

0.706688

RMN 09

0.706788

RMN 16

0.706656

RMN 04 RMN 17

0.706813 0.706762

RMN 48

0.706892

RMN 24

0.707455

RMN 01

0.707055

RMN 30

0.707031

RMN 42

0.707123

RMN 22

0.706977

Post-caldera; nal phase, HKCA rocks

RMN 29

0.707492

RMN 39

0.707488

RMN 33

0.707476

RMN 12

0.707492

Initial values have been calculated on ages from literature (Cortini et al. 1973; Fornaseri 1985; Radicati di Brozolo et al. 1988); see text for further explanation

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trace elements (Peccerillo 1998, 2005b) due to their extremely low K and incompatible trace elements contents (Fig. 9). In addition sedimentary carbonate assimilation would also modify trace element signature of magmas imparting extremely high U/Th, which is not observed (Avanzinelli et al. 2008). By contrast, due to the very low REE contents, and then of Nd and Pb contents of limestones the trends observed for REE and 143Nd/144Nd and 206 Pb/204Pb should be the opposite of what observed at Roccamonna (Figs. 5, 6). In summary, the post-caldera MgO-rich leucite-free magmas, either shoshonitic or high-K calc-alkalic, cannot represent the parental magma of the entire Roccamonna succession. Geochemical and petrographic characteristics suggest that ultrapotassic plagioclase leucititic magmas and leucite free magmas, erupted, respectively, during pre- and post-caldera stages, are not cogenetic and they derive from different events of partial melting of a variably metasomatised upper mantle source. Origin of ultrapotassic parental magmas In the light of the above discussion we can safely assume that the strong fractionation between LILE and HFSE (Fig. 4) is a primary characteristics of Roman ultrapotassic leucite-bearing rocks, which has also been observed in volcanic island arcs where the budget of incompatible trace elements is clearly dominated by sediment addition (e.g. Aeolian Arc, Francalanci et al. 1993, 2007; Banda Arc, Vroon et al. 1993; Sunda arc, Whitford et al. 1979; Hoogewerff et al. 1997). Depletion of HFSE except Th (Fig. 4) with respect to LILE is attributed either to the original fractionation in the sedimentary reservoirs (Fig. 9)

Fig. 5 143Nd/144Nd and initial Roccamonna rocks

87

Sr/86Sr versus MgO wt.% for

have intermediate Sr isotope ratios between plagioclase leucitites and shoshonitic rocks, precluding any possibility to derive one from the other by limestone assimilation. It has been shown indeed, that limestone assimilation by ultrapotassic magmas has the effect of diluting incompatible
Fig. 6 143Nd/144Nd versus initial 87Sr/86Sr isotopic composition for the Italian potassic and ultrapotassic rocks. Fields have been drawn on the basis of data from Conticelli et al. (1992, 1997, 2002, 2007, 2008, in press), Conticelli (1998), Pappalardo et al. (1999), Perini et al. (2004), Avanzinelli et al. (2008), Boari et al. (2008a, b, in press) and authors unpublished data (e.g., Vulture, Vesuvius). A blow up of the inset is reported at the top-right hand side. Symbol size is larger than analytical error (2r)

Tyrrhenian Sea Floor

Pietre Nere

Vulture (LuMP)
Aeolian Arc RMP-ND (Neapolitan District) Mafic enclaves in TAP

Tus can Pro vinc e

RMP-LD (Latian Districts)

Tuscan Anatectic Province

Apennine Crustal Rocks

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Fig. 8 Sr/Th versus 87Sr/86Sr for the Roccamonna volcanic rocks with reported simulation pathways for AFC and bulk-mixing differentiation models. Lines for AFC refers to r = 0.2 and p 0.5, respectively. F = Mm/Mo (nal volume of magma/initial volume of magma); r = assimitared/crystallased rate. Partition coefcient used are after Francalanci et al. (1987) and Foley and Jenner (2004). Note that AFC with r = 0.2 is able to model the entire shoshonitic trend, whereas AFC is not able to model the differentiation within plagioclase leucitites

Fig. 7 143Nd/144Nd, and initial 87Sr/86Sr versus 206Pb/204Pb isotopic compositions for the Italian potassic and ultrapotassic rocks (in colour) with reported data for the Roccamonna Volcano (black, white and grey). Data sources Conticelli et al. (1992, 1997, 2002, 2007, 2008, in press), Conticelli (1998), Pappalardo et al. (1999), Perini et al. (2004), Avanzinelli et al. (2008), Boari et al. (2008a, b, in press) and authors unpublished data (e.g., Vulture, Vesuvius). TMP Tuscan Magmatic Province, RMP-LD Latian Districts of the Roman Magmatic Province, RMP-ND Neapolitan District of the Roman Magmatic Province, LuMP Lucanian Magmatic Province, PS Pescosansonesco dykes, PN Punta delle Pietre Nere dykes, LMP lamproites, SHO shoshonites, HKCA high-K calc-alkalic, KAM kamafugites, HKS plagioclase leucitites and leucitites

recycled into the mantle (Plank and Langmuir 1998) or to retention of Ta, Nb, Hf, Zr and Ti by a residual phase during recycled sediment partial melting (Nicholls et al. 1994; Elliott et al. 1997). Th is not readily partitioned into slab-derived uids, but can be efciently enriched in the metasomatising agent via partial melting of recycled sediments (Johnson and Plank 1999). Also Pb is efciently enriched within the mantle wedge by sediment-derived metasomatism. The high Th/Nb values shown by plagioclase leucititic pre-caldera rocks (Fig. 10) are clearly suggestive of melt dominated subduction component

(Elliott et al. 1997; Plank 2005). Shoshonites, on the other hand, show a linear decreasing of this ratio, with values \1, pointing towards the composition of the within plate alkali basalts of Pietre Nere (PN end member in Fig. 10) in the Adriatic foreland (Fig. 1). Production of silica-undersaturated melts (i.e. leucitebearing pre-caldera volcanic rocks) is thought to be due either to extremely high-P partial melting or to partial melting under extremely high XCO2 conditions of a metasomatised mantle source. Most of the geochemical and mineralogical characteristics of Roccamonna leucitebearing rocks are compatible with partial melting of a modally metasomatised lithospheric upper mantle similarly to other volcanic elds of the Roman region (i.e., RMPLD; Boari and Conticelli 2007; Boari et al. 2008a, in press). The same holds true for their extreme enrichment in Al2O3 which is also testied by the occurrence of modal plagioclase (Table 1). In this scenario, the CO2-rich component might have been acquired during partial melting of CaCO3-rich subducted marly sediment. Then devolatilisation of CaCO3 component might provide the CO2 for increase the XCO2 and the necessary CaO to refertilise the lithospheric refractory source, whereas melts from the silicoclastic components would have enriched in K and incompatible elements the mantle source of Roccamonna magmas. In Fig. 6 it is clear the decoupling between initial 87 Sr/86Sr and 143Nd/144Nd with Roman Magmatic Province pointing to a crustal reservoir with the isotopic composition intermediate between those of shales and limestones. Leucite-bearing rocks from Roccamonna volcano fall

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Fig. 9 Patterns of incompatible trace elements normalised to the primordial mantle (Sun and Mc Donough 1989) for Apennine crustal rocks (top) and comparison among the compositions of high-Mg plagioclase-leucitites (pre-caldera), shoshonites (post-caldera), and limestone from Lepini Mounts (bottom). Note that limestone have strongly lower normalised values than volcanic rocks, and different distributions. Assimilation of limestone plus crystal fractionation of clinopyroxene starting from the shoshonite would have affected dramatically U/Th, Nb/Ta, Ce/Pb, and Sr/Nd values, which are not fractionated by clinopyroxene

Fig. 10 Th/Nb versus Ta/Nb for the Roccamonna rocks. Data elds for Tuscan Magmatic Province (TMP), Roman Magmatic Province north of Roccamonna (RMP-LD), Roman Magmatic Province South of Roccamonna (RMP-ND), and Lucanian Magmatic Province (LuMP) are also reported in colour, as well as values for the Punta le Pietre Nere (PN) and Pescosansonesco (PS) within plate magmatic rocks from Adriatic plate. Data Sources Conticelli et al. (1992, 1997, 2002, 2004, 2007, 2008, in press), Conticelli (1998), Pappalardo et al. (1999), Perini et al. (2004), Avanzinelli et al. (2008), Boari et al. (2008a, b, in press) and authors unpublished data (e.g., Vulture, Vesuvius, Middle Latin Valley)

along this trend, with isotopic values typical of leucitebearing rocks (plagio-leucitites, leucitites, and kamafugites) of the Roman Magmatic Province but slightly less enriched in radiogenic Sr (Fig. 6). Avanzinelli et al. (2008) focussing attention of the southern Roman Province and using new Sr and Nd isotopes and UTh disequilibria modelled the observed compositional variation of MgOrich mac magmas of Southern Roman Province with the addition to the mantle wedge of a marl subducting sediment assemblage, estimated as a 50:50 mixing between the clay- and carbonate-rich components. Given the estimated composition of sediment melts, the authors calculated that less than 5% of recycled sediments melts is able to reproduce the SrNd isotope variation of the Roman Province. Roccamonna high-Mg plagioclase leucititic rocks from Roccamonna t perfectly this simulation. In Fig. 12 the plot of 208Pb/204Pb versus 206Pb/204Pb variations is reported for the entire set of Neogene to Quaternary rocks of the Italian Peninsula and in particular for the Roccamonna volcanic rocks. D-DMM, OIB, and CaCO3rich bulk sedimentary components with several different

simulations are also reported (Fig. 12). Focussing attention on ultrapotassic rocks (plagioclase leucitites), the Roccamonna ones fall well within the eld of northern volcanic district of the Roman Province (RMP-LD). Taking into account a D-DM mantle on one hand, and a bulk sedimentary component enriched in CaCO3, on the other one, less than 35% of recycled sediments melts is able to reproduce the Pb isotopic isotope variations of the ultrapotassic rocks of Roccamonna volcano, but also of the RMN-LD portion of the Roman Province (Fig. 12). Transition from ultrapotassic to shoshonitic magmas The two major issues that remain the centre of debate, when Roccamonna volcano is concerned, are the coexistence of ultrapotassic leucite-bearing and shoshonitic rocks in the same volcano, and the link between this shift in composition and the overall southward chemical variation observed in Italian volcanism jumping from the Latian districts (RMP-LD) to the Neapolitan one (RMP-ND) of the Roman Magmatic Province. As outlined in other papers (e.g. Peccerillo 2005a; Avanzinelli et al. 2008) Neapolitan rocks (RMP-ND) clearly differs from Latian districts rocks (RMP-LD) in at least three main features: they have (1) lower Sr and higher Nd and Pb isotope ratios (Peccerillo 2005a, and references

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Fig. 11 Zr/Nb vs. 206Pb/204Pb isotopic compositions for the Roccamonna Rocks Data elds for Tuscan Magmatic Province (TMP), Roman Magmatic Province north of Roccamonna (RMP-LD), Roman Magmatic Province South of Roccamonna (RMP-ND), and Lucanian Magmatic Province (LuMP) are also reported in colour, as well as values for the Punta le Pietre Nere (PN) and Pescosansonesco (PS) within plate magmatic rocks from Adriatic plate. Data sources Conticelli et al. (1992, 1997, 2002, 2007, 2008, in press), Conticelli (1998), Pappalardo et al. (1999), Perini et al. (2004), Avanzinelli et al. (2008), Boari et al. (2008a, b, in press) and authors unpublished data (e.g., Vulture, Vesuvius)

therein); (2) 238U excess testifying a recent U-enriched metasomatic event which is not present in the other Latian volcanic districts (i.e. Avanzinelli et al. 2008); (3) higher Nb suggesting the involvement of a rather fertile end member (e.g. OIB pre-metasomatism mantle wedge? Beccaluva et al. 1991). The Roccamonna volcano is the only volcanic district where both geochemical and isotopic signatures occur but temporarily separated. Pre-caldera plagioclase leucitites (HKS) have compositional and isotopic characteristics similar to those of the Latian districts (Figs. 10, 11, 12) of the Roman Magmatic Province (RMN-LD). Post-caldera shoshonites, on the other hand, have Nd (143Nd/144Nd = 0.5123420.512382) and Pb (e.g., 206Pb/204Pb = 18.924 19.153) higher than those of pre-caldera rocks and overlapping those of Neapolitan rocks (RMN-ND). Therefore, we believe it is important to relate the regional shift in the composition of Italian volcanism with that occurring in the different phases of the Roccamonna volcano in order to make the most of the clues that Roccamonna volcano might provide on the overall Italian volcanism. It is clear in Figs. 7 and 11 that the shoshonitic and the sub-alkaline basaltic andesitic rocks from Roccamonna fall always within the eld of Neapolitan rocks (RMP-ND) pointing towards the composition of Punta Pietre Nere volcanic rocks, though those of Monte Vulture (Lucanian Magmatic Province). However, few UTh isotope data on shoshonites and sub-alkaline lavas (authors unpublished data) show

Fig. 12 208Pb/204Pb vs. 206Pb/204Pb isotopic compositions for the Italian potassic and ultrapotassic rocks (in colour) with reported data for the Roccamonna Volcano (black, white and gray); for symbols about Italian rocks see Fig. 7. Data sources Conticelli et al. (1992, 1997, 2002, 2007, 2008, in press), Conticelli (1998), Pappalardo et al. (1999), Perini et al. (2004), Boari et al. (2008a, b, in press) and authors unpublished data (e.g., Vulture, Vesuvius). TMP Tuscan Magmatic Province, RMP-LD Latian Districts of the Roman Magmatic Province, RMP-ND Neapolitan District of the Roman Magmatic Province, LuMP Lucanian Magmatic Province, PS Pescosansonesco dykes, PN Punta delle Pietre Nere dykes. A marlstone has been taken as the sediment end member (see Avanzinelli et al. 2008 for a thorough discussion). Due to the lack of Pb data on Italian sediments we used the Pb isotopic composition of sediments subducting under Sunda arc (Plank and Langmuir 1998) as a proxy; indeed, the lithologic assemblage subducting under Sunda is made up by an alternation of limestone and clays, resembling subducting under Italy. The isotopic composition of Punta Pietre Nere (PN) has been taken as the within plate component uxed through slab tearing into the mantle wedge of the Italian Peninsula. Roccamonna plagioclase leucitites samples lie along with other Roman magmas (RMP-LD) on a mixing curve between D-DMM bulk and Marlstone sediments (dashed line with crosses). Shoshonites compositions can be reproduced by adding to the source of plagioclase leucitites magmas a variable amount (720%, dashed line with dots) of within plate asthenospheric component. On the contrary, the simple addition of marlstone sediments to the within-plate astenospheric mantle (dashed line with stars) does not t the isotope composition of Roccamonna shoshonitic rocks

near equilibrium isotopic composition and no sign of the 238 U excess characteristic of the Neapolitan region. This suggests that the recent addition of the U-enriched component affecting the Neapolitan region seems not to be effective beneath Roccamonna. The transition from plagioclase leucitites rocks to shoshonites has to be explained in terms of the general decrease in incompatible element, the change in SrNdPb isotope and the increase in Nb content (Figs. 10, 11). Two hypotheses has been proposed to explain this transition: (1) increasing country rock-vein interaction within the mantle wedge with increasing contribution of a within plate

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component from slab tears (Foley 1992b; Conticelli et al. 2002, 2007); (2) partial melting in different mantle wedge levels (Peccerillo and Panza 1999). Metasomatism within the upper mantle usually occurs along the main ow pathways of metasomatic agents. Reaction between metasomatic agents and the upper mantle produced a new mineralogy accommodated in a vein network (Foley 1992b). In the case of ultrapotassic magmatism vein network is established within the lithospheric portion of the mantle (e.g. Mitchell 2006). The metasomatic mineralogical assemblage has lower melting point than surrounding upper mantle (Foley 1992b). When veined mantle is within a mantle wedge at a destructive continental plate margin and collision come to end, in the back of the orogen extension brought to isotherms relaxation. Upraise of isotherms brought to partially melt the vein network, which has the lowest melting point of the mantle wedge; further isotherms relaxation brings also the surrounding mantle to melts and then interaction with purevein melt continuously change the composition of the produced magmas. An increasing diminution of the alkaline degree of the magmas and therefore of the total metasomatic signature within the incompatible trace element distribution is observed in some alkaline-ultrapotassic to potassic associations (i.e. Tuscan Magmatic Province, Conticelli et al. 2007; Trans Mexican Volcanic Belt, Maria and Luhr 2008) with increasing melting degree and thus increasing proportions of country rock over vein-mantle. In the case of Roccamonna Volcano we observe a decreasing alkaline degree and total abundance of incompatible elements passing from pre-caldera, leucite-bearing magmas, to early post-caldera, shoshonitic magmas, till late post-caldera, high-K calc-alkalic magmas (Figs. 2, 4). All these characteristics are consistent with the process of increasing interaction proportion of melts from surrounding mantle with respect to vein melts (i.e. leucite-bearing magma). Problems arise, however, when we consider the large variation in SrNdPb isotopes, for simple mass balance reasons. Given the difference in Sr, Nd and Pb content of the vein and the surrounding depleted mantle (Sun and Mc Donough 1989), the isotopic composition of any resulting melt would be strongly dominated by that of the vein. Higher degrees of melting and thus higher proportion of country rock would dilute the absolute concentration of those elements, but hardly change the isotopic composition of the melt. Another problem arises from the expected isotopic composition of the surrounding mantle: its low Sr and high Nd isotope ratios, respectively, would suite the versus of variation in the shoshonites; however, a depleted mantle is expected to have developed low U/Pb and Th/Pb and thus to have an unradiogenic signature, rather than the radiogenic one necessary to explain the increase in Pb isotopic ratios towards the

shoshonites (Figs. 10, 11). A high 206Pb/204Pb mantle component could be envisaged only suggesting the mantle wedge with an OIB signature prior to metasomatism (Beccaluva et al. 1991). A fertile OIB-like surrounding mantle would also have higher trace element composition, and thus potentially more leverage on the mass balance proportions of elements between vein and country rock, but more importantly it would bear high Nb concentration producing the Nb enrichment observed in the post-caldera shoshonites. This has been found recently in mantle xenoliths from Eifel volcanic eld. An OIB-like mantle wedge, however, cannot be suggested also for the ultrapotassic (plagioclase leucitites) precaldera rocks, which clearly follow a mixing trend between a D-DMM and marlstone sediment (Figs. 7, 12). In the frame of a veined mantle, it could be argued that the decrease in Zr/Nb in post-caldera rock reects their lower proportion of vein to country rock in the ultrapotassic precaldera rocks, but if mantle wedge had an OIB signature prior to the metasomatism, it is conceivable that this signature would be at some extent preserved also within the vein (Fig. 12). More information can be obtained from the mineral chemistry of separated phases in other Italian volcanoes. Cr-spinel inclusions in olivine crystals from Italian volcanic rocks (Boari et al. 2008b, in press) have given clues on the degree depletion of the pre-metasomatism mantle beneath Italy. Although no such data are available for Roccamonna, olivine-spinel pairs from the ultrapotassic leucite-bearing rocks from the Latian districts (Perini and Conticelli 2002; Boari and Conticelli 2007), comparable with pre-caldera rocks, suggest a highly depleted mantle; on the opposite a more fertile one is suggested by olivinespinel pairs measured in the Neapolitan districts volcanic rocks (e.g. Conticelli et al. 2004), which can be related to the post-caldera shoshonites. In summary trace element ratios, such as Zr/Nb, Th/Nb, and isotopic values all points to the OIB component similar to Punta Pietre Nere in the Adriatic foreland (Figs. 7, 10, 11, 12); therefore it is argued that an asthenospheric component with the trace element and isotopic compositions similar to the source of the Punta Pietre Nere magma is involved in the genesis of the post-caldera shoshonites. As outlined, earlier the presence of an astenosperic OIBlike component in the genesis of the southernmost Italian magmas (i.e. RMP-ND) had been claimed in previous studies (Beccaluva et al. 1991; Ayuso et al. 1998; Peccerillo and Panza 1999). According to the interpretation of Peccerillo and Panza (1999) the OIB-like signature of post caldera magmas could be interpreted with a metasomatised source within the mantle wedge located at a different, deeper and thus asthenospheric, level than that of pre-caldera ones, which would be instead located in the

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lithosphere. Here we propose a slight different interpretation when the asthenospheric, high Zr/Nb and radiogenic Pb-isotope component is added to the source of ultrapotassic plagioclase leucitites successively to their genesis to generate shoshonites. In the 208Pb/204Pb versus 206Pb/204Pb diagram (Fig. 12) Roccamonna shoshonitc rocks do not plot on a hypothetic mixing line between the PN endmember and the sedimentary component as expected if metasomatism occurred at different mantle levels. Instead, post caldera mixing trend start directly from the pre-caldera ones moving away toward the PN component, within a range of 10 and 20% of an OIB-like component added to the source of plagioclase leucitites. The fact that the OIBlike component is recorded late in the history of the Roccamonna volcano we might argue for its late arrival within the mantle wedge after the caldera formation. This agree also with the chronological differences within the Roman Magmatic Province being the Nepolitan volcanoes (RMP-ND) much younger than those of the Latian Districts (RMP-LD). The oldest shoshonitic event at Roccamonna volcano has been dated at 327 24 ka (40Ar/39Ar performed by M.A. Laurenzi 2006 personal communication), an age comparable to the beginning of magmatism in the Neapolitan Area (Brocchini et al. 2001). In summary all the available data on Roccamonna volcano suggest similar surrounding mantle for pre- and post-caldera rocks, but with an increasingly asthenospheric component late arrival. This would imply that partial melting occurs within the mantle wedge under high XCO2 to produce ultrapotassic leucite bearing rocks. The subsequent arrival of the OIB-like astenospheric component changed the geochemical isotopic compositions of the mantle source. In addition it increases also heat ow triggering larger degrees of partial melting that exhaust the sedimentary-derived CO2 providing magmas under low XCO2 partial melting conditions. The physical processes responsible for the arrival of asthenospheric material into the metasomatised mantle wedge can be discussed in relationship with the complex geodynamics of the Italian area. The peculiar arcuate morphology of the slab beneath the Italian peninsula following the south-eastward slab retreat (Lucente et al. 1999; Wortel and Spakman 2000) brought to the formation of ruptures of the downgoing slab (e.g. Faccenna et al. 2001). This phenomenon induces small slab tears to large plate windows, which might allow the inow of sub-slab asthenospheric mantle. U/Th disequilibria measured on Monte Vulture (Lucanian Magmatic Province; Fig. 1) have shown that inux of hot asthenospheric mantle material, undergoing adiabatic melting, invaded the Southernmost sector of the Italian Mantle wedge in recent times (\350 ka; Avanzinelli et al. 2008). Monte Vulture volcano is part of the Lucanian

Magmatic Province (LuMP) and is located offset with respect to the Apennine chain (Fig. 1) just at the edge of the present day Calabrian Arc, site of the still active subduction beneath the Aeolian Arc (e.g., Francalanci et al. 2007, and references therein). This suggests that hot asthenospheric material from the mantle behind or beneath the subducted slab enters the mantle wedge from the north-eastern corner of the Ionian subduction (Mattei et al. 2004). The arrival of sub-slab asthenospheric hot material through slab tears at Monte Vulture is testied by the composition of Lucanian magmatic rocks, which are characterised by intermediate geochemical and isotopic signatures between mantle wedge and within plate (e.g. Beccaluva et al. 2002; Downes et al. 2002; authors unpublished data). Carbonatites with transitional signatures, between within plate and arc magmatism, are also found at Monte Vulture volcano (DOrazio et al. 2007). Here, oblique upraise of the mantle pierced the slab tears formed as a consequence of the strong bending of the Adriatic slab during rolling back (Faccenna et al. 2001). The proximity of Monte Vulture to the trench and thus the limited vertical extension of the mantle wedge, makes it the volcano to be interested to higher extent by the by the asthenospheric ow. The trace elements and isotopic data of Roccamonna, however, are not as extreme as those of Monte Vulture (Figs. 8, 9). In addition, Monte Vulture plate-window is far away from the Roccamonna volcano. However, Lucente et al. (1999) have shown the presence of a slab tear also in correspondence of the Ortona-Roccamonna lineament (Fig. 1), which might has acted as a preferential way for sub-slab asthenospheric mantle inux into the mantle wedge. Then heating provided by the inux might have triggered larger partial melting of the mantle wedge.

Conclusion Roccamonna volcano is a composite volcano characterised by a two stage activity: a pre-caldera period characterised by leucite-bearing rocks (plagioclase-leucitite, HKS) and a post-caldera period with exclusively leucite-free shoshonites and sub-alkaline basaltic andesites. Magmas of each period of activity are not genetically related to those of the other one. Shoshonites and subalkaline basaltic andesites are not comagmatic with plagioclase leucitites (HKS). Within each period of activity shallow level differentiation mainly driven by crystal fractionation with minor crustal assimilation occurred. Leucite-bearing ultrapotassic magmas have been generated by partial melting of a metasomatised lithospheric mantle wedge, where a vein network of modally modied peridotite after metasomatism has been established.

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Contrib Mineral Petrol (2009) 157:4163 Ballini A, Frullani A, Mezzetti F (1989b) La formazione piroclastica del tufo trachitico bianco del vulcano di roccamonna. Boll Gruppo Naz Vulcanol 5(2):557574 Beaubien SE, Ciotoli G, Lombardi S (2003) Carbon dioxide and radon gas hazard in the Alban Hills area (Central Italy). J Volcanol Geotherm Res 123:6380 Beccaluva L, Di Girolamo P, Serri G (1991) Petrogenesis and tectonic setting of the Roman Volcanic Province, Italy. Lithos 26:191 221 Beccaluva L, Coltorti M, Di Girolamo P, Melluso L, Milani L, Morra V, Siena F (2002) Petrogenesis and evolution of Mt. Vulture alkaline volcanism (Southern Italy). Mineral Petrol 74:277297 Bertrami R, Buonasorte G, Ceccarelli A, Lombardi S, Pieri S, Scandifo G (1990) Soil gases in geothermal prospecting: two cases histories (Sabatini Volcanoes and Alban Hills, Latium, Central Italy). J Geophys Res 95:2147521481 Boari E, Conticelli S (2007) Mineralogy and petrology of Mg-rich calc-alkalic, potassic, and ultrapotassic associated rocks: the Middle Latin Valley monogenetic volcanoes, Roman Magmatic Province, Southern Italy. Can Mineral 45:14431469 Boari E, Tommasini S, Laurenzi MA, Conticelli S (2008a) Transition from ultrapotassic kamafugitic to sub-alkaline magmas: Sr, Nd, and Pb isotope, trace element and 40Ar39Ar age data from the Middle Latin Valley volcanic eld, Roman Magmatic Province. J Petrol (in press) Boari E, Avanzinelli R, Melluso L, Giordano G, Mattei M, Morra V, Conticelli S (2008b) Isotope geochemistry (SrNdPb) and petrogenesis of leucite-bearing rocks from Colli Albani volcano, Roman Magmatic Province, Central Italy: inferences on volcanic evolution. Bull Volcan (in press) Bosi V, Giordano G (1997) Stress eld evolution in central Italy during middle late pleistocene: new information from Southern Latium. Il Quat 10(2):631636 Brocchini D, Principe C, Castradori D, Laurenzi MA, Gorla L (2001) Quaternary evolution of the southern sector of the Campanian Plain and early Somma-Vesuvius activity: insights from the Trecase 1 well. Mineral Petrol 73:6791 Carter SR, Evensen NM, Hamilton PJ, ONions RK (1978) Continental volcanics derived from enriched and depleted source regions: Nd- and Sr-isotope evidence. Earth Planet Sci Lett 37:401408 Chiodini G, Frondini F (2001) Carbon dioxide degassing from the Albani Hills volcanic region, Central Italy. Chem Geol 177:6768 Cole PD, Guest JE, Duncan AM, Chester DK, Bianchi R (1992) Postcollapse volcanic history of calderas on a composite volcano: an example from Roccamonna, Southern Italy. Bull Volcan 54:504520 Cole PD, Guest JE, Duncan AM (1993) The emplacement of intermediate volume ignimbrite: a case study from Roccamonna volcano, Southern Italy. Bull Volcan 55:467480 Conticelli S (1998) Effects of crustal contamination on ultrapotassic Magmas with Lamproitic afnity: mineralogical, geochemical and isotope data from the Torre Alna Lavas and Xenoliths, Central Italy. Chem Geol 149:5181 Conticelli S, Peccerillo A (1992) Petrology and geochemistry of potassic and ultrapotassic alkalic volcanism in Central Italy: petrogenesis and interferences on the mantle source. Lithos 28:21240 Conticelli S, Francalanci L, Santo AP (1991) Petrology of the nal stage Latera lavas: mineralogical, geochemical and Sr-isotopic data and their bearing on the genesis of some potassic magmas in Central Italy. J Volcanol Geother Res 46:187212 Conticelli S, Manetti P, Menichetti S (1992) Petrology, chemistry, mineralogy and Sr-isotopic features of Pliocenic Orendites from

Metasomatic agent is clearly derived from melting and dehydratation of recycled carbonate-rich sediments. High-MgO shoshonites and sub-alkaline basaltic andesites have been generated from the interaction between the lithospheric mantle wedge and an asthenospheric OIB-like mantle component with very high 143Nd/144Nd, 206 Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb, but consistently lower Zr/Nb and 87Sr/86Sr than original metasomatised lithospheric mantle wedge. The most feasible process capable to add a within plate asthenospheric OIB component within the sub-italian mantle wedge is inux from slab tears, from the adjacent area, as shown by tomographic studies.
Acknowledgments We sincerely appreciate Sergio Chiesa, Angelo Peccerillo, and Piero Manetti for helps and discussions during the rst eld campaign in the late 1980s, Alice Farinelli for helps during the second eld campaign in the early new millenium, Lia M Todaro for help with AAS analyses, Lorella Francalanci for handling INA analyses on some samples, and at last but not the least Leone Melluso, Lorella Francalanci, Simone Tommasini, Giampiero E. Poli, and Angelo Peccerillo for stirring and focusing discussions. Maurizio Ulivi provided technical support for isotope analyses. Thoughtful reviews made by two anonymous peer-reviewers greatly improved the original manuscript. Editorial managing by Tim Grove is greatly appreciated. Financial support was provided by Firenze-Perugia Ph.D. consortium during the early eld campaign (19861987), by FIRB 2001 (grant # RBAU01FX8M_003) for the nal eld campaign (2003) and analytical work, and PRIN 2007 (grant # 2007NS22NZ_005), for the nal modelling.

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