Ackerman Et Al. (2013) - Alkaline Carb Metasomatism NEBavaria Xenol JPet

JOURNAL OF PETROLOGY
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2013
doi:10.1093/petrology/egt059
Journal of Petrology Advance Access published November 5, 2013
Alkaline and Carbonate-rich Melt Metasomatism and Melting of Subcontinental Lithospheric Mantle: Evidence from Mantle Xenoliths, NE Bavaria, Bohemian Massif
S S ACKERMAN1,2*, PETR S PAC EK3,4, TOMA MAGNA2, LUKA JAROMIR ULRYCH1, MARTIN SVOJTKA1, ERNST HEGNER5 AND KADOSA BALOGH6
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269, CZ-165 00, INSTITUTE OF GEOLOGY v.v.i., ACADEMY OF SCIENCES OF THE CZECH REPUBLIC, ROZVOJOVA ROV 3, CZ-118 21 PRAGUE 1, CZECH REPUBLIC CZECH GEOLOGICAL SURVEY, KLA II, CZ-141 34, PRAGUE 4, NI INSTITUTE OF GEOPHYSICS v.v.i., ACADEMY OF SCIENCES OF THE CZECH REPUBLIC, BOC HO 12, CZ-602 00, BRNO, CZECH REPUBLIC INSTITUTE OF EARTH PHYSICS, MASARYK UNIVERSITY, TVRDE T MU NCHEN, THERESIENSTRAE 41, DEPARTMENT OF EARTH AND ENVIRONMENTAL SCIENCES, UNIVERSITA R 18/C, DEBRECEN H-4026, INSTITUTE OF NUCLEAR RESEARCH, HUNGARIAN ACADEMY OF SCIENCES, BEMTE
PRAGUE 6, CZECH REPUBLIC

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NCHEN, GERMANY D-80333 MU

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RECEIVED JANUARY 29, 2013; ACCEPTED SEPTEMBER 20, 2013
Peridotite xenoliths hosted by Cenozoic basanite lava flows (212^235 Ma) occur at several localities in the western continuation of the Ohr e/Eger rift (Central European Volcanic Province) in NE Bavaria, Bohemian Massif. Detailed petrography, major and trace element compositions of whole-rock samples and selected mineral phases as well as Sr^Nd^Li isotopic compositions for a suite of mantle xenoliths from Zinst, Hirschentanz and T eichelberg document variable degrees of partial melting and metasomatism. Melting models based on whole-rock major element composition and Cr# of spinel indicate 6^30% melting in the spinel stability field. Subsequent metasomatism by alkaline and carbonate-rich melts resulted in modal and cryptic metasomatism, expressed by the presence of carbonate-bearing silicate melt pockets with complex secondary mineral assemblages and by enrichment in light rare earth elements, Li, Rb, U, Pb, high field strength elements and P.The carbonate is most probably associated with fractionation of the Na-rich
silicate melt. High P contents, variable but low to negative d7Li values from 25 to 97, coupled with 87Sr/86Sr ratios between 07032 and 07041 may reflect a significant contribution of recycled crustal material such as eclogite in the infiltrating melts responsible for metasomatism, although the Li isotope compositions may reflect kinetic modifications through diffusion. The trace element geochemistry of clinopyroxene, carbonate and melt pockets suggests that clinopyroxene plays a very important role in fractionation of the rare earth elements, high field strength elements and Sr, whereas carbonate does not host large quantities of incompatible trace elements except for Sr, Ba and, to a lesser extent, Th and U.
KEY WORDS: peridotite; metasomatism; subcontinental lithosphere; Sr^Nd^Li isotopes; microstructure
*Corresponding author. T elephone: 420-233087240. 420-220922670. E-mail address: ackerman@gli.cas.cz
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I N T RO D U C T I O N
Peridotite xenoliths in volcanic rocks provide important clues to the structural and chemical characteristics of the subcontinental lithospheric mantle. A number of studies have shown that the upper mantle sampled by spinel and garnet peridotite xenoliths is variably enriched in incompatible trace elements caused by infiltration of originally melt-depleted peridotites by melts or fluids of different composition, including those with basaltic and carbonatitic affinities (e.g. Frey & Green, 1974; Menzies & Hawkesworth, 1987; Yaxley et al., 1991; Ionov et al., 1993; Downes, 2001; Pearson et al., 2004). Such mantle enrichment (metasomatism or mantle refertilization) may result in precipitation of secondary clinopyroxene, amphibole, mica or apatite that are enriched in incompatible trace elements (e.g. Ionov et al.,1993, 1997; Gregoire et al., 2000b). Cenozoic alkaline anorogenic volcanism forms several important centres across Europe (Lustrino & Wilson, 2007), including those in Spain (Iberia, Canary Islands, Madeira), France (Massif Central), Italy (e.g. Veneto volcanic province, Sardinia), Germany (e.g. Kaiserstuhl, eske Eifel, Vogelsberg), the Czech Republic (e.g. C Hory volcanic complex), Str edohor | Mts., Doupovske Slovakia, Hungary (Pannonian Basin), Serbia, Bulgaria and Macedonia (Rhodope Massif). In western and central Europe, volcanic activity is associated with the development of the European Cenozoic Rift System (ECRIS) forming the Western and Central European Volcanic Province (CEVP), which stretches from the Massif Central in France through the Vosges and Schwarzwald (Black Forest) and Rhenish Massif to the Bohemian Massif and Lower Silesia (Wilson & Downes, 1991; Lustrino & Wilson, 2007). The NE^SW-trending Ohr e/ Eger Rift system in the Bohemian Massif represents the easternmost part of the continent-scale rift system within the CEVP (Fig. 1). Volcanic rocks from the Ohr e rift system contain abundant mantle xenoliths, which record mantle depletion by partial melting and subsequent enrichment by infiltration of basaltic melts at upper mantle conditions (Ackerman et al., 2007, 2012; Geissler et al., 2007; Puziewicz et al., 2011) and during exhumation in the host basalts (Puziewicz et al., 2011). Cenozoic volcanic rocks in the Upper Palatinate and Upper Franconia volcanic fields (NE Bavaria, Germany) commonly contain mantle xenoliths. Some of these exhibit unique, fine-grained symplectites after garnet, recording a complex history of interaction between garnet peridotite and melts or fluids both prior to entrainment of the xeno pac liths and during their ascent (S ek et al., 2013). Here, we present detailed petrographic descriptions, major and trace element compositions of whole-rock samples and single minerals, and Sr^Nd^Li isotopic compositions for a suite of mantle xenoliths from Zinst, Hirschentanz and T eichelberg to assess the conditions of the origin and
history of the ambient subcontinental lithospheric mantle. The major and trace element data and Sr^Nd^Li isotopic compositions and KÂr ages for the host basalts are used to discuss the possible relationship between the xenoliths and their host basalts. Our data suggest variable melting degrees in the spinel stability field and subsequent enrichment of the mantle protolith by alkali-rich melts resulting in both cryptic as well as modal metasomatism, the latter being evidenced by the presence of carbonate-bearing melt pockets in some xenoliths. We argue that the source of the infiltrating melts is most probably mantle peridotite, but some contribution from recycled crustal material such as eclogite is also possible.
GEOLOGIC A L S ET T I NG A N D ST U D I E D LOC A L I T I E S
The Bohemian Massif represents the largest relic of the European Variscan belt formed during the Devonian convergence and Carboniferous collision of Gondwana, Laurussia and intervening microplates (Franke, 2000; Matte, 2001). This terrane collage is recorded in the mantle lithosphere by domains with different seismic anisotropy (e.g. , 2010) correlatBabus ka et al., 2008; Babus ka & Plomerova ing with the major tectonic units of the Bohemian ^Barrandian and SaxMassifthe Moldanubian, T epla othuringian units (e.g. Franke, 1989; Matte et al., 1990). Cenozoic volcanic rocks in the Bohemian Massif are concentrated along major fault zones (grabens), forming one of the most prominent regions of the CEVP (Fig. 1). The western part of the Bohemian Massif, comprising Upper Palatinate (NE Bavaria) and adjacent Saxony, represents a prominent neotectonic mobile zone within central Europe located at the junction of two volcano-tectonic zones, the Ohr e Rift and the Cheb^Domaz lice Graben (Ulrych et al., 2000). The southernmost part of the Ohr e hory Mts. and the Rift structure between the Doupovske Cheb Basin continuing up to the Franconian Line is characterized by abundant volcanic rocks, mostly of the basaniteôlivine nephelinite series (Ulrych et al., 1999) of Late Oligocene to Early Miocene age (29^19 Ma; Ulrych et al., 1999). Rare Plio-Pleistocene volcanism (20^026 Ma; Ulrych et al., 2011) of olivine melilitite to olivine nephelinite occurs at the junction of the Ohr e and Cheb^Domaz lice Grabens. The continuation of the Ohr e Rift SW of the Cheb Basin towards NE Bavaria lacks the asymmetric geometry with two marginal faults that is characteristic of its central part. The position of the Moho discontinuity and thickness of the lithosphere in this area have been estimated at 26^31km and 90 km, respectively (Geissler et al., 2007; Babus ka et al., 2009). The Zinst locality (Zinster Kuppe: 288 Ma, T odt & Lippolt, 1975; 256 Ma, Horn & Rohrmu ller, 2005) comprises a basaltic volcanic breccia
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MANTLE XENOLITHS, NE BAVARIA
Fig. 1. (a) Map showing the location of Variscan basement terranes and Neogene to Quaternary volcanism in western and central Europe [RH, Rhenohercynian; S, Saxothuringian; M, Moldanubian; modified from Franke (1989) and Wilson & Downes (1991)]. (b) Simplified geological map of the Ohr e/Eger Rift (modified from Christensen et al., 2001) showing the location of the studied localities in NE Bavaria (Zinst, Hirschentanz, T eichelberg).
and a relic nepheline basanite lava flow. These basanites typically contain abundant peridotite xenoliths ranging from 3 to 10 cm in diameter, rarely up to 30 cm (Huckenholz & Kunzmann, 1993). No pyroxenite or lower crustal xenoliths have been reported from this locality. The Hirschentanz Hill locality is the conduit of a 25 m thick nepheline basanite lava sheet. Abundant xenoliths of peridotite as well as crustal xenoliths, mostly granitic in composition, are present (Huckenholz & Kunzmann, 1993). Both the geology of T eichelberg Hill as well as the overall petrographic and geochemical characteristics of the peridotite xenoliths are similar to those of Zinst (So llner, 1960).
A N A LY T I C A L M E T H O D S
Whole-rock major element analyses were performed at the Faculty of Science, Charles University, Prague, by conventional wet chemical techniques. The accuracy and external precision of the method has been assessed by analysis of peridotite PCC-1 (USGS) reference material and has been reported by Ackerman et al. (2007). Whole-rock trace element analyses were performed by inductively coupled plasma mass spectrometry (ICP-MS) using an Element 2 sector field system (Thermo-Finnigan) housed at the Institute of Geology v.v.i., Academy of Sciences CR, Prague. The precision of the analyses was better than 5%
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for all analyzed elements. Accuracy was monitored by repeated analyses of UB-N reference material, which yields an average precision better than 15% relative (Supplementary Data Table 1; supplementary material is available for downloading at http://www.petrology.oxfordjournals.org) for all elements with respect to reference values (Govindaraju, 1989). Trace element concentrations in clinopyroxene, carbonate and quench melt were determined by laser ablation (LA)-ICP-MS at the Institute of Geology v.v.i., Academy of Sciences CR, using an Element 2 ICP-MS system coupled with a UP-213 NdYAG LA system (New Wave Research), with analytical conditions as outlined by Ackerman et al. (2012). The laser was fired at a repetition rate of 20 Hz and an output energy of 6^7 J cm^2. Linear laser raster patterns of 100 mm in length and with 35^55 mm beam size were used for the analysis. The data were calibrated against an external standard of synthetic silicate glass, NIST SRM 612, using the recommended values of Jochum et al. (2011) to calculate absolute concentrations of trace elements in the analysed grains. The accuracy of the analyses (Supplementary Data Table 2) was monitored by analysing soda-lime float glass NIST 1830 (01wt % Al2O3) compared with the published values of Flem & dard (2002), Flem et al. (2002) and Berends-Montero Be et al. (2006). The relative standard deviation (% RSD) ranged between 3 and 15% for all elements except Tm, Pb and Ta, which had much poorer reproducibility (up to 60%). The time-resolved signal data were processed using the Glitter software (van Achterbergh et al., 2001). Major element analyses of mineral phases in most of the samples were carried out using a Cameca SX 100 electron microprobe coupled with wavelength-dispersive spectrometry (WDS) at the Institute of Geology v.v.i., Academy of Sciences CR, Prague, at an accelerating voltage of 15 kV, beam current of 20 nA, and a 2 mm beam. Synthetic and natural mineral phases were used as standards for corresponding elements. Some samples were analysed also by a Cameca SX 100 electron microprobe at the Masaryk pac ek University, Brno, using conditions described by S et al. (2013). The Sr^Nd isotopic analyses of clinopyroxene separates and host basalts were performed at the Universita t Mu nchen according to the procedures outlined by Hegner et al. (1995). Prior to the analyses, the clinopyroxene separates were leached at 708C in 6 M HCl for 1h and subsequently in 6M HNO3 for 1 h to remove possible grain boundary components. The 143Nd/144Nd and 87Sr/86Sr ratios of the clinopyroxene separates from peridotites were measured on a Triton thermal ionization mass spectrometer (ThermoFisher) in static data collection mode. The JNd-1 standard yielded 143Nd/144Nd 0512095 8 and the NIST 987 reference material yielded 87Sr/86Sr 0710246 8. Strontium and Nd isotopic compositions of
the whole-rock basalt samples were measured on an upgraded MAT 261 in dynamic triple mass collection mode. During these measurements, the JNd-1 standard 143 yielded Nd/144Nd 0512113 8 normalized to 146 144 Nd/ Nd 07219 (Wasserburg et al., 1981). The reference materials NIST 987 and BCR-1 yielded 87Sr/86Sr of 0710224 10 and 0704988 7, respectively (normalized to 86Sr/88Sr 01194). The long-term reproducibility of Sr and Nd isotopic ratios for the reference materials measured on both instruments overlaps, therefore no additional inter-laboratory instrumental bias correction was applied. The eNd values were calculated with the parameters of Bouvier et al. (2008) with present-day 147 Sm/144Nd 01960 and 143Nd/144Nd 0512630 for the chondritic uniform reservoir (CHUR). The analytical procedures for lithium (Li) isolation and purification by means of cation-exchange chromatography were performed at the Czech Geological Survey and followed methods outlined by Magna et al. (2004, 2006). Lithium isotopic compositions were measured with a Neptune multiple-collector (MC)-ICP-MS system housed at the Czech Geological Survey, Prague, Czech Republic, using L4 and H4 Faraday cups for simultaneous collection of 6Li and 7Li, respectively. Bracketing with the L-SVEC (Flesch et al., 1973) reference solution was applied to correct for instrumental mass bias (Magna et al., 2004). The international reference rock materials JP-1 (peridotite; GSJ), BHVO-2 (basalt) and DTS-2B (dunite; both USGS) were used to monitor the precision and accuracy of the analytical procedure. Their resulting d7Li values were 381 039 (n 5), 451 008 (n 4) and 739 010 (n 3), respectively; d7Li is calculated as d7Li () (7Li/6Lisample/7Li/6LiL-SVEC ^ 1) 1000 and all errors are given as 2s. A replicate measurement of JP-1, comprising new dissolution, full analytical procedure and isotope measurement yielded d7Li of 374 034 (n 4). These data are in full agreement with published values (Zack et al., 2003; Magna et al., 2006, 2008; Penniston-Dorland et al., 2012). KÂr dating was carried out at the Institute of Nuclear Research of the Hungarian Academy of Sciences, Debrecen, Hungary, using procedures described by Balogh (1985). In brief, samples were crushed to 03^ 01mm and split into two parts: one part was used for Ar determination and the other was pulverized for K abundance determination. Argon concentration was determined after Ar extraction by high-frequency induction heating in a vacuum system at 1300^15008C. Prior to gas extraction, a 38Ar spike was introduced into the extraction line. Argon isotopic composition was measured on a 908 deflection, 150 mm radius magnetic sector-type mass spectrometer at the Institute of Nuclear Research. The concentration of K was determined by flame photometry. Potassium and Ar abundance determinations were
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calibrated against inter-laboratory standards LP-6, HD-B1 and Asia 1/65 as well as atmospheric Ar. The error (1s) of the KÂr determinations is based on the long-term instrument stability. A 3% error was assigned to the K concentration, including a 1% uncertainty of the standards. The error of the 38Ar spike was 2% whereas the error of the measured isotopic ratios was 1%, including a possible fractionation in the extraction line. Data handling and plotting were performed using the GCDkit software (Janous ek et al., 2006).
M A N T LE X ENOL I T H S Texture and modal composition

The xenoliths from Zinst, Hirschentanz and T eichelberg (mostly 3^10 cm in diameter) are dominated by coarsegranular varieties with millimetre-sized grains. The textures are rarely well equilibrated, with olivine displaying a non-unimodal grain-size distribution and variable grain shapes. Rare transitions to high-strain, porphyroclastic textures in some xenoliths suggest late deformation. Some coarser-grained xenolith types host unusual, high aspect ratio tabular grains of olivine with straight crystal faces. The coarse-grained, complex symplectitic intergrowths of pyroxene with spinel, frequently observed at other localities in the Bohemian Massif (e.g. Medaris et al., 1999; Matusiak-Malek et al., 2010), are mostly absent. However, a specific group of xenoliths from Zinst hosts other types of plagioclase-bearing spinel^pyroxene symplectites with much smaller grain size, complex structures and several structurally distinct concentric zones. These symplectites pac ek et al. (2013) and interwere described in detail by S preted as pseudomorphs after garnet, indicating a complex pressure^temperature and chemical evolution. In this study, only one sample of this type (ZIN14) is included. The xenolith samples studied can be grouped into three main textural types based on their olivine grain-size distribution and grain shape (Fig. 2, Table 1), as follows. Type 1 peridotites with equigranular to weakly inequigranular olivine of average grain size 1^2 mm in diameter (10ZIN1-6, ZIN11, ZIN14, ZIN19, ZINx5, HIR3-6, HIR16; Fig. 2a). Samples with strain-free olivine predominate over those with moderately strained olivine. Olivine typically exhibits irregular, curvilinear grain boundaries. Samples with partly equilibrated grain boundaries (straight boundaries and 1208 triple junctions in some grains) are rare. Sample ZIN14 containing fine-grained spheroidal spinel^pyroxene symplectite with interstitial plagioclase hosted in pyroxene-rich domains (05^2 mm large) is classified as a Type 1a xenolith. Coarse-grained symplectitic intergrowth of pyroxene with spinel was found in a single sample from Zinst (10ZIN1, T ype 1b). Type 2 peridotites show abundant, small (02^05 mm), strain-free olivine neoblasts at grain boundaries of larger (1^5 mm), weakly to moderately strained grains of
Fig. 2. Photomicrographs showing the typical textures of the NE Bavaria mantle xenoliths. (a) Type 1, medium-grained, equigranular to slightly inequigranular lherzolite with curved olivineôlivine and lobate orthopyroxene grain boundaries (sample HIR 6). (b) Type 2, porphyroclastic texture with finer olivine neoblasts in grain boundary regions of coarser, strained phases (sample ZIN9). (c) Type 3, medium-grained lherzolite with preferentially elongated tabular olivine grains (sample ZINx8). Grains with lobate boundaries are orthopyroxene.
olivine, and strain-free grains of pyroxene (porphyroclastic types; ZIN9 and ZINx2; Fig. 2b). In these samples, microstructural relations suggest that the olivine neoblasts were formed by grain-size reduction by dynamic recrystallization and later probably affected by a static growth.
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T able 1: Summary of main petrographic features and modal compositions of NE Bavaria mantle xenoliths
Sample Locality Textural type Carbonate-bearing melt pockets ol opx cpx sp Lithology Bulk modal composition (wt %) Bulk Mg#
10ZIN1 10ZIN2 10ZIN3 10ZIN4 10ZIN5 10ZIN6 ZIN9 ZIN11 ZIN14* ZIN19 ZIN27 ZINx2 ZINx5 ZINx8 HIR3 HIR4 HIR5 HIR6 HIR16 TEI2B
Zinst Zinst Zinst Zinst Zinst Zinst Zinst Zinst Zinst Zinst Zinst Zinst Zinst Zinst Hirschentanz Hirschentanz Hirschentanz Hirschentanz Hirschentanz Teichelberg
1b 1 1 1 1 1 2 1 1a 1 3 2 1 3 1 1 1 1 1 3
x x x
lherzolite/harzburgite lherzolite harzburgite lherzolite harzburgite/lherzolite lherzolite lherzolite lherzolite lherzolite lherzolite/harzburgite dunitewehrlite lherzolite lherzolite/harzburgite lherzolite/harzburgite lherzolite lherzolite/harzburgite lherzolite lherzolite lherzolite/harzburgite lherzolite/harzburgite
80 80 84 69 81 72 63 67 55 80 89 72 86 76 60 82 65 74 79 82
13 12 12 17 15 17 25 18 29 14 2 16 8 19 27 10 26 12 15 11
6 7 3 13 4 10 11 12 13 6 7 10 5 5 12 6 8 12 6 5
1 1 1 1 51 1 1 3 3 51 2 2 1 51 1 2 1 2 51 2
914 911 912 907 911 904 905 898 870 917 907 898 918 912 912 914 906 910 911 911
GPS coordinates for the studied localities: Zinst 4985408"N, 1185635"E; Hirschentanz 4985926"N, 1281156"E; Teichelberg 4985721"N, 1280957"E. ol, olivine; opx, orthopyroxene; cpx, clinopyroxene; sp, spinel. (See text for explanation of textural types.) Bulk Mg# 100[Mg/(Mg Fetot)]. pac ek et al., 2013). *Sample ZIN14 contains garnet pseudomorphs (S
Type 3 peridotites contain high-aspect ratio strain-free tabular grains of olivine with semi-planar-parallel faces. In samples TEI2B and ZIN27 both tabular grains and moderately strained grains with irregular or curvilinear grain boundaries are present (Fig. 2c). In contrast, sample ZINx8 contains only strain-free grains. The aspect ratio of the tabular grains is typically 3^4 and exceeds a value of five in some strained grains. Strong shape-preferred orientation is observed in equigranular (1^2 mm) samples ZIN27 and ZINx8, whereas in inequigranular sample TEI2B randomly oriented tabular grains, up to 25 cm in size, are hosted in a finer-grained (05^5 mm) matrix. Neither amphibole nor phlogopite was observed in the samples, which is consistent with previous observations on mantle xenoliths from the Bohemian Massif (e.g. Ackerman et al., 2007; Matusiak-Malek et al., 2010; Puziewicz et al., 2011). Whole-rock major element compositions were inverted ' de using the least-squares inversion method of Albare (1995) to four-phase, OlÔpx^Cpx^Spl modal compositions, using their average mineral compositions in the given sample (Table 1). However, for samples ZIN11 and
ZIN14 relatively large errors are expected, taking into account the presence of carbonate-bearing melt pockets and anorthite-bearing symplectites. In general, the modal composition of the xenoliths from the three studied localities is broadly similar. Of the 20 samples studied, 13 are spinel lherzolites with variable (6^13 wt %) clinopyroxene contents, whereas six samples are harzburgites or transitional harzburgite^lherzolite (3^6 wt % clinopyroxene); one sample (ZIN27) exhibits a transitional composition between dunite and wehrlite (Fig. 3). Spinel contents in all samples are low and olivine and clinopyroxene abundances are negatively correlated.
Melt pockets
In addition to the primary mineral assemblages, many samples host a significant amount of variably shaped patches filled by aggregates of finely crystallized minerals and glass, clearly formed by quenching of a liquid phase, hereafter referred to as melt pockets. These features, pac ek et al. (2013), occur as either described briefly by S variably shaped, up to several millimetres diameter, rounded domains hosted in peridotite, or irregular patches
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These grains are mostly rounded, oval-shaped or vermicular (Fig. 4b, c and f). In the case of clinopyroxene, the small grains are sometimes linked to relics of larger grains (if present) with undulating margins and complicated embayments, sometimes clearly derived from resorbed primary clinopyroxene (Fig. 4c). Orthopyroxene also exhibits undulating boundaries when in contact with the melt pockets, but it is not usually associated with a large number of small isolated grains in the matrix compared with clinopyroxene (Fig. 4b). Spongy or sieve-textured spinel clusters are often found within the fine-grained quench, often exhibiting homogeneous cores, representing primary spinel grains (Fig. 4d^f). Larger, euhedral microphenocrysts are usually absent in carbonate-free pockets.
Carbonate^silicate pockets
Fig. 3. T ernary OlÔpx^Cpx diagram showing the modal compositions of the NE Bavarian mantle xenoliths.
in fine-grained symplectites after garnet, or grain boundary veinlets. Whereas some of these pockets are clearly linked to the host basanite, some other, less abundant pockets are apparently isolated, located far from xenolith margins and without feeder channels. The two types of pockets with different structural and chemical features are very similar to those described by Zinngrebe & Foley (1995) from Eifel mantle xenoliths. Similar to the classification scheme used by those researchers, the former type of pockets clearly associated with the host basanite are here referred to as Type I and the latter, which represent the focus of this study, as Type II. Based on their composition, two main varieties of the Type II pockets can be distinguished: (1) carbonate-free silicate melt pockets, which are most common; (2) relatively rare composite carbonate^silicate pockets. These two varieties of pockets are described separately below, but many features of the silicate domains are common to both varieties as, for example, documented by backscattered electron (BSE) images of the composite pockets in Fig. 4.
Silicate pockets
The silicate melt pockets have a glassy appearance under the optical microscope. Scanning electron microscope (SEM) and cathodoluminescence (CL) images reveal the presence of small (5 5 mm) feldspar grains with slight compositional zoning within a micrometre-sized quench, which sometimes dominates the pockets. The local presence of strictly amorphous glass was not tested, but seems to be likely, based on compositions and substructure. Small (typically 3^30 mm) grains of clinopyroxene (cpx 2), and sometimes olivine (ol 2) and spinel are often clearly visible within an apparently homogeneous matrix.
The composite carbonate^silicate pockets often exhibit a more or less well-developed core^rim structure with a carbonate zone in the core and a silicate zone forming the rim (e.g. Fig. 4a and e). In addition to pocket cores, carbonate is present in variable amounts as small irregular domains within the silicate zone (Fig. 4a^f). The silicate zone is sometimes reduced to a thin film forming the margins of pockets, but is always present. The structure of the silicate zone is similar to that in carbonate-free pockets considering its fine-grained quench with feldspar and often small rounded grains of clinopyroxene and olivine as well as the sieve- or spongy-textured spinel. Unlike in most carbonate-free pockets, some composite pockets contain larger subhedral to euhedral phenocrysts of olivine or clinopyroxene as well as other less common phases that are hosted in the fine-grained matrix (Fig. 4d^f). The carbonate zone is dominated by a very fine-grained aggregate of carbonate grains with a grain size below the resolution of the optical microscope. The fine-grained carbonate hosts euhedral or subhedral microphenocrysts of olivine, clinopyroxene, orthopyroxene and feldspar, and subsidiary phases apparently isolated or growing from walls of the zone (Fig. 4b and d^f). It is evident from BSE and CL images that the composition of the carbonate often varies significantly, both between two neighbouring pockets and within a single pocket (Fig. 4a, b and d). In this study, three samples containing melt pockets were analyzed in detail, representing the three main types of carbonate^silicate pocket, as follows. Spinel lherzolite sample ZIN14 hosts 50^800 mm diameter irregular pockets (Fig. 4a) in fine-grained orthopyrox pac ek ene^spinel symplectites pseudomorphing garnet (S et al., 2013). The carbonate zone that dominates in some pockets hosts olivine crystals with well-developed crystal faces growing from the margin of the silicate zone. The silicate zone is devoid of phenocrystsonly partly resorbed pyroxene and spinel are present (Fig. 4b and c). Small-scale intermingling of carbonate domains with the silicate zone in complex geometrical relations is common.
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Fig. 4. Back-scattered electron (BSE) images showing the morphology of the silicate^carbonate melt pockets. ol, olivine; opx, orthopyroxene; cpx, clinopyroxene; spl, spinel; afs, alkali feldspar; cb, carbonate; ilm, ilmenite; ap, apatite; quench, fine-grained aggregate with quenched crystals of feldspar and small grains of cpx and ol, possibly containing glass. (a) Complexly shaped chain of pockets with alternating silicate and carbonate zones hosted in fine-grained orthopyroxene^spinel symplectite pseudomorphing garnet, sample ZIN14. Part of the pocket is outlined pac ek et al., 2013). Noteworthy features for clarity. (b) Detail of melt pocket in orthopyroxene^spinel symplectite, sample ZIN14 (modified from S are the euhedral olivine and intimate association of carbonate with quenched silicate melt, and the compositional difference of the carbonates indicated by their different BSE greyscale in (a) and (b). (c) Melt pocket located at the margin of a primary clinopyroxene grain, sample ZIN14. The partly resorbed pyroxene and related small rounded grains in a glassy matrix should be noted. (d) Melt pocket in sample TEI2B. The similar structure and mineral composition of the phenocrysts (cpx, Mg-ilm) in both carbonate (upper left) and silicate (lower right) zones should be noted. (e) Carbonate-dominated core of a spheroidal melt pocket in sample ZIN11. The drusy arrangement of feldspar crystals, euhedral microphenocrysts of cpx and irregular grains of quartz in microcrystalline carbonate matrix should be noted. (f) Detail of a melt pocket in ZIN11. The sieve-textured reaction rim of primary spinel and association of carbonate domains with apatite and Mg-ilmenite should be noted. (continued)
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Fig. 4. Continued
Lherzolite sample TEI2B hosts 4 1mm diameter, simple pockets (Fig. 4d). The imaged pocket has a non-concentric structure with a dominant silicate zone. Both the carbonate and silicate zones host subhedral phenocrysts of clinopyroxene (cpx 2partly skeletal) and needle-shaped ilmenite. Spinel exhibits sieve-textured reaction rims when in contact with the pocket. Sample ZIN11 (a lherzolite with a large number of grain-boundary silicate and carbonate veinlets and fluid or melt inclusions) hosts 3^6 mm diameter spheroidal pockets with dominant silicate zones and well-developed carbonate cores (Fig. 4e). The silicate zone hosts numerous larger, subhedral phenocrysts of olivine and rare ilmenite and zoned spinel with a sieve-textured reaction rim in a fine-grained matrix. Small, rounded clinopyroxene grains (cpx 2) are common in the matrix, similar to sample ZIN14 and the carbonate-free pockets described above. Carbonate hosts euhedral microphenocrysts of clinopyroxene and zoned needle-shaped orthopyroxene (opx 2, Fig. 4e), ilmenite (Ilm), rutile, apatite (Ap; sometimes with quasi-spherical habit), crichtonite group (Ti^Zr-rich oxide) minerals (C-rich), and irregular quartz (Qtz) grains. One particular large carbonate pocket has a geode-like appearance with radially oriented crystals of alkali feldspar growing from its margin (Fig. 4e).
Whole-rock major and trace element geochemistry

The major element compositions of the studied xenoliths are presented in Table 2. Except for two carbonate-bearing xenoliths (ZIN11, ZIN14), the major element composition of all the samples is characteristic of a variably melt-depleted
mantle assemblage with Mg# between 898 and 917, Al2O3 contents between 089 and 195 wt %, low TiO2 contents of 001^014 wt % and variable but high Cr contents between 1320 and 3970 ppm. The ZIN27 dunite^ wehrlite differs from the other samples in having a low SiO2 content of 407 wt %. A negative correlation is apparent between MgO and SiO2, Al2O3, CaO and Na2O for most samples (Fig. 5). This feature has also been recognized in other mantle-derived rocks worldwide (Bodinier & Godard, 2004; Pearson et al., 2004) including those sampling the European subcontinental lithospheric mantle (Downes, 2001). In contrast, all NE Bavarian xenoliths are variably enriched in P2O5 (002^029 wt %; Table 2) when compared with the primitive upper mantle (PUM, 002 wt %; McDonough & Sun, 1995). Two carbonatebearing xenoliths (ZIN11, ZIN14) exhibit lower Mg#s of 898 and 870, respectively, and have the highest Al2O3 (27 wt %), CaO and Na2O contents (32^40 and 029^057 wt %, respectively) of the whole xenolith suite at a given SiO2 content. With the exception of one refractory harzburgite (10ZIN3), the Ca/Al ratios for the xenolith suite vary from 13 to 25; thus, they are higher than that of PUM (11; McDonough & Sun, 1995). The K2O contents of the xenolith suite are rather low (5 010 wt %) except for sample ZIN11 with 026 wt %. Trace element concentrations in whole-rock samples are presented in Table 2 and their primitive-mantle normalized distributions are shown in Fig. 6. All NE Bavaria xenoliths show slight to large enrichments in the light rare earth elements (LREE) relative to heavy REE (HREE), with PUM-normalized LaN/YbN ratios between 29 and 23. The highest REE contents are found in the carbonate-
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T able 2: Whole-rock major and trace element compositions of NE Bavaria mantle xenoliths
Sample: Rock: 10ZIN1 lherz 10ZIN2 lherz 10ZIN3 harz 10ZIN4 lherz 10ZIN5 lherz 10ZIN6 lherz ZIN9 lherz ZIN11 lherz ZIN14 lherz ZIN19 lherz
wt % SiO2 TiO2 Al2O3 Fe2O3 FeO MnO MgO CaO Na2O K2O P2O5 H2O H2O CO2 Total ppm Cr Ni Rb Sr Y Zr Nb Cs La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta Pb Th U Mg# 1323 2361 18 13 021 31 12 0052 0541 113 0099 0353 0051 0017 0058 0006 0029 0005 0020 0003 0022 0005 008 003 12 0071 0065 914 2226 2208 19 27 027 37 16 0033 0208 0763 0114 0580 0126 0038 0105 0014 0064 0011 0033 0005 0031 0005 007 006 b.d. 0039 0088 911 2349 2298 17 29 034 56 13 0056 0687 145 0151 0609 0117 0045 0123 0017 0081 0015 0042 0006 0035 0005 013 009 13 0115 0065 912 2275 1907 22 44 069 11 23 0071 130 302 0370 163 0318 0102 0301 0040 0174 0030 0086 0010 0065 0009 031 039 06 0125 0110 907 1427 2201 24 16 022 38 12 0085 0488 106 0113 0462 0082 0025 0085 0011 0051 0009 0030 0004 0030 0005 008 008 20 0085 0092 911 2698 1955 36 141 046 93 39 0197 155 283 0290 111 0186 0061 0199 0024 0105 0018 0055 0007 0045 0007 021 032 23 0101 0231 904 2208 1797 37 30 078 21 18 0013 0531 133 0194 099 0240 0082 0228 0035 0182 0034 0105 0015 0102 0017 043 014 064 0058 0135 905 3267 1630 64 113 174 19 48 0025 312 617 0695 279 0530 0186 0573 0079 0387 0072 0215 0027 0181 0027 042 031 049 0175 0136 898 2676 1333 06 114 043 97 051 0007 0383 0907 0111 0515 0122 0046 0127 0020 0104 0020 0058 0007 0052 0008 027 004 022 0054 0023 870 1901 1812 24 32 060 12 22 0013 116 256 0287 121 0244 0083 0259 0036 0163 0028 0080 0010 0061 0009 028 014 034 0066 0059 917 4236 001 118 208 552 012 4417 137 010 003 002 046 008 220 9970 4274 002 119 207 578 011 4369 178 013 004 003 054 075 075 9962 4218 006 111 169 628 011 4545 085 001 004 024 044 024 095 9965 4354 006 195 179 583 011 4084 285 032 010 004 048 053 111 9955 4276 003 108 192 609 011 4465 117 013 009 003 048 021 096 9971 4291 007 149 206 599 012 4137 237 017 007 006 042 043 197 9950 4426 004 189 243 532 011 3994 236 008 001 017 060 154 044 9919 4214 018 275 236 573 012 3895 322 057 026 026 054 094 112 9914 4392 010 269 394 593 012 3547 404 029 004 018 052 111 112 9947 4248 009 089 188 548 012 4434 128 006 001 025 065 120 058 9931
(continued)
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T able 2: Continued
Sample: Rock: wt % SiO2 TiO2 Al2O3 Fe2O3 FeO MnO MgO CaO Na2O K2O P2O5 H2O H2O CO2 Total ppm Cr Ni Rb Sr Y Zr Nb Cs La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta Pb Th U Mg# 2307 1895 24 30 029 57 21 002 111 231 0269 112 0219 0074 0239 0039 0152 0032 008 0015 0062 0018 015 018 063 0064 0080 907 2363 1771 15 11 024 29 020 0024 0253 119 0114 0498 0112 0043 0132 0027 0113 0027 0067 0014 006 0018 008 001 075 0032 0034 898 1719 1834 21 12 014 37 061 0019 0487 104 0121 0492 0096 0036 0108 0022 0072 0018 0042 0011 004 0015 009 004 047 0045 0051 918 2134 1768 15 20 037 60 084 0024 0985 233 0290 128 0269 0095 0278 0046 0183 0038 0098 0018 0088 0023 016 006 11 0146 0172 912 2876 1673 23 28 035 25 20 0020 0529 153 0171 0666 0119 0035 0117 0014 0068 0014 0046 0007 0047 0007 004 014 22 0047 0073 912 3462 1787 35 66 062 87 37 0028 1842 351 0360 138 0239 0080 0255 0032 0148 0026 0078 0010 0065 0010 019 023 052 0153 0088 914 2108 1746 17 111 028 51 095 0019 0489 138 0175 0698 0100 0028 0107 0014 0062 0013 0043 0006 0043 0008 011 006 20 0062 0066 906 1456 1788 25 101 13 19 57 0020 2972 651 0777 316 0570 0182 0581 0074 0334 0059 0172 0020 0132 0020 041 038 051 0127 0305 910 1821 1751 30 57 088 11 49 0026 2548 589 0657 251 0404 0150 0426 0050 0210 0037 0112 0013 0085 0013 023 024 049 0141 0167 911 3971 1892 16 22 042 96 21 0048 0671 153 0195 091 0196 0063 0189 0026 0117 0020 0057 0007 0045 0007 023 014 035 0050 0118 911 4074 010 091 198 641 012 4496 148 014 007 019 058 098 068 9934 4334 005 154 294 580 011 4185 198 015 007 017 030 086 022 9938 4216 006 096 174 578 012 4586 112 013 009 016 028 069 032 9947 4384 008 136 187 566 012 4292 129 009 006 029 042 106 030 9936 4481 003 186 212 499 011 4014 274 010 001 017 034 154 035 9931 4174 009 116 178 599 012 4504 129 012 002 029 031 086 040 9921 4392 004 157 199 562 012 3991 292 005 001 015 037 182 081 9930 4243 014 156 203 569 012 4247 246 022 005 016 032 105 068 9938 4238 008 094 243 546 012 4379 106 015 009 017 062 145 041 9915 4216 007 135 191 596 012 4397 133 009 002 017 045 104 047 9911 ZIN27 dunwehr ZINx2 lherz ZINx5 harz ZINx8 harz HIR3 lherz HIR4 lherz HIR5 lherz HIR6 lherz HIR16 lherz TEI2B lherz
lherz, lherzolite; harz, harzburgite; dun, dunite; wehr, wehrlite; Mg# 100[Mg/(Mg Fetot)]; b.d., below detection limit.
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Fig. 5. Whole-rock major element variations of MgO (wt %) vs SiO2, TiO2, Al2O3, CaO, Na2O and P2O5 (wt %) in NE Bavarian xenoliths. The primitive mantle composition (McDonough & Sun, 1995) is shown by an asterisk. Continuous-line black and grey arrows represent the batch melting trends of Niu (1997) and Herzberg (2004), respectively. The dashed line represents a fractional melting trend from Niu (1997).
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Fig. 6. Primitive-mantle normalized REE and trace element patterns for bulk xenolith samples. Normalizing values from McDonough & Sun (1995).
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bearing lherzolite ZIN11 (Fig. 6). Some of the samples with low total REE contents tend to have U-shaped REE patterns, but none of the samples exhibit apparent Eu anomalies. In addition, distinct enrichments in the large ion lithophile elements (LILERb, Cs), Sr, Pb and U are recorded in the peridotite samples (Fig. 6). Uranium and Th are strongly fractionated from each other (UN/ThN 17^ 96, mean 52) with the lowest value found in carbonatebearing xenolith ZIN11. With the exception of two samples (ZINx2, ZINx5), the xenoliths show significant Nb^Ta enrichment and Zr^Hf depletion relative to PUM. Zirconium/Hf ratios are moderately fractionated (ZrN/ aN ratios vary HfN 097^17, mean 12) whereas NbN/T greatly between 033 and 23 (Fig. 7).
Mineral chemistry
The major mineral phases in the NE Bavarian xenolith suite comprise olivine, orthopyroxene, Cr-diopside and spinel. These mineral phases are homogeneous at the intra-grain (core to rim) and inter-grain scale; their representative compositions are given in Table 3. The mineral chemistry of the symplectite-bearing xenoliths has been re pac ek et al. (2013); only data for sample ZIN14 ported by S are given in this study. Olivine (ol 1 and ol 2) exhibits similar, Mg-rich compositions with Mg# (100[Mg/(Mg Fetot)]) values ranging from 902 to 917, with the lowest Mg# found in carbonate-bearing xenoliths ZIN11 and ZIN14. Orthopyroxene (opx 1) is magnesian with Mg# between 907 and 919, and Al2O3 and Cr2O3 contents showing a large variation between 20^48 wt % and 033^078 wt %, respectively. Most orthopyroxene grains have lowTiO2 contents 5010 wt %. However, several samples (ZIN11, ZIN19, ZIN27, ZINx8 and HIR16) have variable, and higher, TiO2 concentrations between 013 and 023 wt %. Clinopyroxene occurs in two textural varietiesprimary clinopyroxene (cpx 1), which occurs in the peridotite matrix, and secondary clinopyroxene, which occurs within the carbonate-bearing melt pockets (cpx 2). The Mg# of cpx 1 (Cr-diopside) varies from 896 to 925, with Al2O3 contents varying from 27 to 62 wt %, Cr2O3 contents from 04 to 28 wt % and Na2O contents from 05 to 18 wt %. In contrast, cpx 2 is augite with a high Al2O3 content of 61^11wt % and highly variable CaO and Na2O contents of 126^227 wt % and 074^32 wt %, respectively (Table 4). Additionally, it is strongly enriched in TiO2 (up to 70 wt %; Table 3). The variations between Mg# and Al, Ti (a.p.f.u.) for cpx 1 and cpx 2 are shown in Fig. 8. Spinel compositions exhibit significant variations in Mg# from 683 to 795 and Cr# (100[Cr/(Cr Al)]) from 193 to 521, plotting within the olivine^spinel mantle array (OSMA; Arai, 1994; Fig. 9).
Fig. 7. ZrN/HfN vs NbN/TaN and ThN vs UN/ThN for the NE Bavaria xenoliths. The large high field strength element (Zr, Hf, Nb, Ta) fractionation and overall U enrichment should be noted.
Representative analyses of the principal mineral phases within carbonate-bearing pockets from samples ZIN11, ZIN14 and TEI2B are listed in Table 4. Carbonates from samples ZIN11 and ZIN14 have variable MgO contents ranging from 17 to 189 wt %, corresponding to 41^439 mol % of the magnesite component (100[Mg/ (Mg Fe Ca)]), whereas that from the melt pocket within sample TEI2B has a generally lower magnesite component of 05^174 mol %. Interstitial quenched melt in the melt pockets shows a broad range of compositions between samples, but also within a single sample. In ZIN11 and ZIN14, it has an intermediate composition with SiO2 and CaO contents of 530^582 wt % and 85^105 wt %, respectively, and low TiO2 of 5023 wt %. However, that from ZIN14 is significantly enriched in MgO (72 wt %). The quenched melt
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T able 3: Representative major element composition (wt %) of olivine, orthopyroxene, clinopyroxene and spinel from NE Bavaria mantle xenoliths
Olivine Sample: 10ZIN1 10ZIN2 10ZIN3 10ZIN4 10ZIN5 10ZIN6 ZIN9 ZIN11 ZIN14 ZIN19
SiO2 FeO MnO MgO CaO NiO Total Mg#
4126 853 014 4948 001 039 9980 912
4120 876 013 4909 007 035 9960 909
4111 843 010 4948 008 039 9959 913
4095 905 013 4896 008 039 9956 906
4093 900 013 4902 007 039 9954 907
4085 931 015 4894 007 039 9970 904
4124 839 014 4960 008 040 9986 913
4059 952 017 4924 012 038 10002 902
4123 926 014 4942 009 038 10052 907
4118 827 012 4975 008 040 9980 915
Olivine Sample: ZIN27 ZINx2 ZINx5 ZINx8 HIR3 HIR4 HIR5 HIR6 HIR16 TEI2B
SiO2 FeO MnO MgO CaO NiO Total Mg#
4128 872 011 4949 007 039 10007 910
4132 869 014 4928 008 039 9991 910
4135 807 011 4985 009 037 9994 917
4148 944 011 4798 010 035 9946 901
4102 844 011 5007 007 041 10013 914
4097 854 013 5006 001 041 10012 913
4115 889 012 4957 008 042 10024 909
4103 835 012 5013 007 041 10011 915
4130 861 012 4986 008 038 10036 912
4131 831 011 4998 006 041 10027 915
Orthopyroxene Sample: 10ZIN1 10ZIN2 10ZIN3 10ZIN4 10ZIN5 10ZIN6 ZIN9 ZIN11 ZIN14 ZIN19
SiO2 TiO2 Al2O3 Cr2O3 FeO MnO MgO CaO Na2O Total Mg#
5687 001 201 033 585 013 3431 027 001 9980 913
5574 001 345 056 562 011 3298 077 008 9933 913
5575 012 308 078 527 010 3317 096 010 9935 918
5506 004 424 060 577 011 3268 089 008 9947 910
5562 002 337 061 581 016 3309 084 005 9955 910
5576 005 297 052 591 013 3313 082 008 9938 909
5554 003 403 060 538 010 3303 088 020 9978 916
5552 016 482 060 581 017 3192 097 014 10012 907
5586 010 477 061 594 014 3245 093 017 10095 907
5626 023 281 077 525 006 3347 102 012 9999 919
(continued)
in the TEI2B melt pocket is richer inTiO2 (095 wt %) and Na2O (157 wt %), but significantly poorer in CaO (034 wt %). The homogeneous quench (glass) from the same pocket is even richer in TiO2 (149 wt %) and yields
low totals (95 wt %), which may indicate modest concentrations of volatile components such as H2O and/or CO2. Both types of quench in TEI2B melt pocket have elevated P2O5 contents of 020^028 wt %.
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T able 3: Continued
Orthopyroxene Sample: ZIN27 ZINx2 ZINx5 ZINx8 HIR3 HIR4 HIR5 HIR6 HIR16 TEI2B
5605 013 278 075 543 011 3352 095 010 9982 917
5544 009 405 066 563 011 3295 087 010 9990 913
5598 010 321 077 523 010 3326 105 015 9986 919
5642 020 309 077 564 006 3244 099 010 9971 911
5564 002 353 061 533 012 3362 087 005 9979 918
5650 005 208 051 579 014 3427 065 002 10001 913
5548 003 361 069 581 012 3327 096 005 10002 911
5578 001 331 064 531 011 3388 083 007 9994 919
5519 016 423 074 553 011 3283 100 016 9995 914
5649 005 261 061 532 012 3399 082 010 10011 919
Clinopyroxene Sample: 10ZIN1 10ZIN2 10ZIN3 10ZIN4 10ZIN5 10ZIN6 ZIN9 ZIN11 ZIN14 ZIN19
5296 b.d. 327 037 296 006 1809 2151 054 9974 916
5302 003 404 090 279 007 1639 2131 123 9978 913
5218 016 540 108 294 006 1612 2037 143 9973 907
5239 006 356 092 283 008 1690 2198 073 9946 914
5233 017 429 131 305 007 1627 2100 134 9983 905
5292 009 494 104 286 009 1657 1975 137 9974 912
5266 045 618 112 320 009 1552 1930 178 9974 896
5341 030 565 108 301 008 1603 2032 131 10120 896
5280 054 390 151 282 004 1686 1966 139 9952 914
Clinopyroxene Sample: ZIN27 ZINx2 ZINx5 ZINx8 HIR3 HIR4 HIR5 HIR6 HIR16 TEI2B
5297 033 396 153 271 002 1680 1983 134 9948 917
5270 030 518 114 296 008 1620 1945 140 9939 907
5310 025 439 278 159 007 1695 1905 144 9961 916
5324 052 426 123 300 002 1646 1969 149 9991 907
5308 005 369 086 261 007 1728 2105 082 9950 922
5300 012 273 118 257 002 1776 2089 066 9892 925
5274 006 370 288 094 1733 005 2113 062 9945 915
5310 002 388 105 263 006 1699 2080 105 9958 920
5239 047 562 128 309 007 1627 1881 160 9961 904
5276 025 498 200 279 005 1592 1857 208 9938 911
(continued)
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T able 3: Continued
Spinel Sample: 10ZIN1 10ZIN2 10ZIN3 10ZIN4 10ZIN5 10ZIN6 ZIN9 ZIN11 ZIN14 ZIN19
TiO2 Al2O3 Cr2O3 V2O3 FeO MnO MgO CaO ZnO NiO Total Mg# Cr#
001 3597 2955 013 1724 b.d. 1621 b.d. 009 021 9942 697 355
004 3726 2924 010 1463 b.d. 1757 003 010 025 9930 748 347
053 2988 3707 013 1468 b.d. 1677 001 005 025 9937 736 454
015 4531 2188 013 1301 b.d. 1876 b.d. 006 031 9960 768 245
010 3579 2975 020 1636 b.d. 1709 001 010 029 9968 732 358
036 3480 3249 017 1487 b.d. 1693 001 009 029 10000 727 385
008 4273 2466 009 1285 b.d. 1891 b.d. 009 031 9971 781 279
035 4442 2192 009 1336 014 1922 001 005 032 9971 720 245
017 4937 1758 010 1255 014 2028 b.d. 010 035 10062 742 193
132 2467 3995 022 1671 b.d. 1652 b.d. 008 025 9974 740 521
Spinel Sample: ZIN27 ZINx2 ZINx5 ZINx8 HIR3 HIR4 HIR5 HIR6 HIR16 TEI2B
TiO2 Al2O3 Cr2O3 V2O3 FeO MnO MgO CaO ZnO NiO Total Mg# Cr#
072 2717 3953 016 1565 b.d. 1632 b.d. 009 024 9987 724 494
028 4271 2379 011 1312 b.d. 1894 b.d. 007 032 9934 784 272
044 3101 3591 015 1531 b.d. 1707 001 004 025 10018 740 437
095 2847 3627 015 1783 b.d. 1587 b.d. 008 024 9986 702 461
007 3847 2862 009 1373 b.d. 1839 b.d. 008 029 9974 773 333
012 2827 3737 019 1793 b.d. 1531 b.d. 023 016 9957 683 470
009 3599 2988 015 1534 b.d. 1777 b.d. 008 029 9958 757 358
001 3653 3067 010 1454 b.d. 1757 001 010 029 9991 748 360
044 4083 2518 011 1339 b.d. 1912 b.d. 009 028 9945 795 293
056 3240 3427 016 1471 b.d. 1718 001 007 026 9960 745 415
b.d., below detection limit; Mg# 100[Mg/(Mg Fe)]; Cr# 100Cr/(Cr Al)].
Feldspar has a highly variable composition. In sample ZIN11, alkali feldspar (Ab67An5Or28) is predominant and is accompanied by rare plagioclase (Ab61An35Or4), occurring mostly in silicate pockets. Feldspar in ZIN14 melt pockets is similar in composition (Ab54An44Or2) to plagioclase from ZIN11. In contrast, feldspar in the silicate quench within melt pockets in sample TEI2B (fsp quench; Fig. 4d) is almost pure albite in composition (Ab95An3Or2) and has a higher TiO2 content of 21wt %. Needle-shaped opx 2 grains (Fig. 4e) hosted by carbonate in ZIN11 have significantly lower Mg# of 833 compared with opx 1 with Mg# of 907.
Apatite contains 055 wt % Cl and 370^384 wt % F. Crichtonite has the composition of loveringite with 27^ 41wt % CaO, 115^123 wt % Cr2O3 and 37^55 wt % ZrO2 (Table 4).
Trace element geochemistry of clinopyroxene, carbonate and melt

Primary clinopyroxene (cpx 1) in four spinel lherzolites (10ZIN2, 10ZIN5, ZINx2, HIR6) and secondary clinopyroxene (cpx 2), carbonate and quenched melt from three carbonate-bearing lherzolite samples (ZIN11, ZIN14, TEI2B) were analysed for their trace element
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T able 4: Representative mineral analyses (wt %) of carbonate-bearing pockets within samples ZIN11, ZIN14 and TEI2B
ZIN14 Afs Pl Quench Cb Cb Ilm Crich Ap Cpx 2 Ol 2 Pl Quench Cb Cb Cb Cpx 2 Pl Quench TEI2B Quench Cb Cb Cb
Sample:
ZIN11
Mineral:
Cpx 2
Opx 2
Ol 2
SiO2 n.a. n.a. n.a. n.a. b.d. 002 b.d. 181 n.a. 931 624 n.a. n.a. n.a. 005 003 b.d. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 006 006 n.a. n.a. 10124 n.d. n.a. n.d. 025 10179 n.a. n.a. n.a. n.a. n.a. 10047 875 n.a. n.d. n.a. n.a. n.a. n.a. n.a. 9992 902 n.d. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 10110 n.d. n.d. b.d. b.d. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 9968 n.d. n.d. n.a. 007 n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 5273 990 341 042 004 012 n.a. n.a. 008 002 002 001 023 372 1049 3806 3353 n.a. n.a. 003 012 001 n.a. 002 n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 5281 997 440 5287 n.a. n.a. n.a. n.a. n.a. n.a. 009 n.a. n.a. n.a. 024 n.a. n.a. 072 n.a. n.a. n.a. 011 125 013 b.d. n.a. n.a. n.a. n.a. 9997 440 004 022 n.a. 384 n.a. n.a. n.a. 055 n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 5477 987 45 4104 098 n.a. b.d. n.a. 268 005 b.d. n.a. n.a. 009 n.a. n.a. 004 n.a. 007 n.a. n.a. n.a. b.d. n.a. n.a. n.a. n.a. b.d. n.a. n.a. n.a. 009 n.a. 082 052 340 5430 1754 020 1294 419 039 1634 4755 718 1418 1891 n.a. 165 5320 n.a. n.a. n.a. n.a. n.a. n.a. 008 n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 5495 1000 4 1 013 010 007 026 040 011 002 006 b.d. 431 5026 n.a. n.a. 002 004 005 n.a. 009 n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 5490 992 107 004 970 654 016 415 1122 014 190 025 010 007 n.a. 224 n.a. n.a. n.a. n.a. n.a. n.a. 1194 038 019 102 327 004 1411 2267 074 b.d. n.a. n.a. n.a. 020 n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 9940 884 n.d. n.a. 137 b.d. n.a. 073 1021 2691 2262 002 000 002 612 n.a. 7027 n.a. n.a. n.a. n.a. n.a. n.a. 6693 072 023 352 207 2353 069 001 014 001 089 1397 040 n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 9958 n.d. n.d. n.a. 023 n.a. 2599 n.a. 022 n.a. n.a. 756 729 075 002 b.d. b.d. b.d. b.d. 003 b.d. b.d. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 10042 n.d. n.d. 009 n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 10081 n.d. n.d. 064 675 846 010 003 032 005 2559 1968 n.a. 006 b.d. b.d. 096 787 497 005 b.d. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 10077 n.d. n.d. 022
4280
5652
4128
6695
5889
5823
006
007
021
4989
4055
5784
5298
006
003
003
4772
5789
5735 095 2600 003 047 004 010 034 1572 074 b.d. b.d. n.a. n.a. 020 n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 10174 n.d. n.d.
5709 149 2297 b.d. 046 002 011 080 1167 030 006 016 n.a. n.a. 028 n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 9491 n.d. n.d.
n.a. n.a. n.a. n.a. 672 047 699 4098 n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 5515 650 174
TiO2
697
039
n.a.
Al2O3
1096
006
n.a.
Cr2O3
129
005
n.a.
FeOtot
315
1078
972
MnO
008
027
020
MgO
1581
3014
5019
CaO
1261
177
025
Na2O
320
005
n.a.
K 2O
107
b.d.
n.a.
BaO
010
n.a.
n.a.
VOLUME 0
18
SrO
004
n.a.
n.a.
ZnO
008
n.a.
n.a.
V2O3
016
n.a.
n.a.
P 2O5
n.a.
n.a.
n.a.
Cl
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
NUMBER 0
Nb2O5
n.a.
n.a.
n.a.
Sc2O3
n.a.
n.a.
n.a.
ZrO2
n.a.
n.a.
n.a.
WO3
n.a.
n.a.
n.a.
Y2O3
n.a.
n.a.
n.a.
La2O3
n.a.
n.a.
n.a.
MONTH 2013
Ce2O3
n.a.
n.a.
n.a.
Total
9832
10002
10164
Mg#
899
833
902
Mag
n.d.
n.d.
n.d.
Cpx 2, clinopyroxene II; Ol 2, olivine 2; Afs, alkali feldspar; Pl, plagioclase; Cb, carbonate; Ilm, ilmenite; Crich, crichtonite; Ap, apatite; n.a., not analyzed; n.d., not determined; b.d., below detection limit; Quench, quenched melt; Mg# 100[Mg/(Mg Fe)]; Mag 100[Mg/(Mg Fe Ca)].
ACKERMAN et al.
Fig. 9. Variation of Mg# in olivine and Cr# in spinel for the NE Bavaria xenoliths. OSMA (olivine^spinel mantle array) from Arai (1994).
Fig. 8. Compositional variations in primary (cpx 1) and secondary (cpx 2) clinopyroxene from the NE Bavarian xenolith suite. (a) Variation of Mg# vs Ti content (a.p.f.u.). (b) Variation of Mg# vs Al content (a.p.f.u.).
concentrations by LA-ICP-MS (Table 5). With the exception of ZIN14, the primitive mantle-normalized REE and incompatible trace element patterns of cpx 1 in all samples are similar (Fig. 10). Despite the fact that some samples exhibit convex-upward REE patterns with LaN/SmN and SmN/YbN ratios of 05^07 and 17^68, respectively, the REE distribution in clinopyroxenes generally is similar to that in their corresponding whole-rocks. On the other hand, the clinopyroxenes are significantly depleted in Rb, Pb and U when compared with the whole-rocks, suggesting that these elements reside in some as yet unidentified phase and/or at grain boundaries enriched in these elements (e.g. Zindler & Jagoutz, 1988; Eggins et al., 1998; Hiraga et al., 2004; Harvey et al., 2012). Clinopyroxene 1 in ZIN14 exhibits a peculiar sinusoidal REE pattern with higher HREE contents than in the other analysed clinopyroxenes (Fig. 10). Clinopyroxene 2, present specifically in melt-bearing domains, was successfully analysed only in lherzolite TEI2B (Table 5), where it forms small
idiomorphic grains (5 100 mm) within the carbonate-bearing melt pocket (Fig. 4d). All analysed grains in this pocket (average of three grains in Table 5) are strongly enriched in incompatible trace elements, in particular LREE, Sr, Nb and Ba, with the highest total trace element concentrations among all the analysed minerals, but significant depletion in Pb, Zr, and Hf (Fig. 10). The REE abundances in the carbonates in lherzolites ZIN11, ZIN14 and TEI2B are very low and mostly below the detection limit, with the exception of La, Ce, Pr and Nd in ZIN14 and TEI2B. Strontium and Ba contents in carbonates from ZIN11 and ZIN14 are higher than in the coexisting cpx 2 and vary in the range 143^187 ppm and 75^90 ppm, respectively. In comparison, carbonate from sample TEI2B (Fig. 4d) is strongly enriched in Sr (1065 ppm) and Ba (769 ppm). These contents are similar to those reported from carbonates found in mantle xenoliths from Spitsbergen and Mongolia (Ionov, 1998) but significantly lower than those of carbonates found in Kerguelen mantle xenoliths (Moine et al., 2004). Quenched melt in the carbonate-bearing pocket in TEI2B exhibits an LREE-enriched REE pattern (Fig. 10) with LaN/YbN of 41 and is strongly enriched in Rb (54 ppm) and HFSE.
87
Sr/86Sr and 143Nd/144Nd variations in clinopyroxene
The measured Nd^Sr isotope compositions of four (10ZIN2, 10ZIN5, ZINx2, HIR6) clinopyroxene separates from Zinst and Hirschentanz xenoliths are listed in Table 6 and plotted in Fig. 11. The 143Nd/144Nd ratios display a limited range between 0512813 and 0512928, which corresponds to present-day eNd values of 39 to 58. In
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T able 5: T race element compositions of clinopyroxenes, carbonates and melt from NE Bavaria mantle xenoliths
Sample: Mineral: 10ZIN2 Cpx 1 10ZIN5 Cpx 1 ZINx2 Cpx 1 HIR6 Cpx 1 ZIN11 Cpx 1 ZIN11 Cb ZIN14 Cpx 1 ZIN14 Cb TEI2B Cpx 1 TEI2B Cpx 2 TEI2B Cb TEI2B Melt
ppm Li Rb Sr Y Zr Nb Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta Pb Th U 20 50006 242 63 26 21 0078 26 14 31 16 35 11 26 031 15 025 064 0080 056 0082 035 019 011 0055 0008 33 002 129 39 55 11 0043 17 80 18 86 16 045 11 013 073 015 044 0064 045 0067 018 012 012 011 0019 11 50005 91 71 23 14 010 29 11 17 75 17 058 17 026 15 029 074 0095 060 0079 082 025 006 0045 0009 12 50005 339 50 16 082 015 93 26 38 16 25 070 18 022 11 019 051 0069 050 0079 054 013 012 022 0031 16 046 122 10 47 21 54 53 13 18 76 19 070 20 032 19 040 10 016 099 015 13 034 044 053 015 b.d. 007 187 b.d. 15 037 75 b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. 0123 b.d. 011 18 03 62 14 13 11 25 38 71 086 34 12 051 19 040 26 061 16 025 14 021 050 014 030 10 014 b.d. b.d. 143 13 42 092 9 062 074 017 060 b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. 10 b.d. 026 32 009 163 11 90 27 025 53 22 42 22 55 18 40 055 25 043 09 013 07 012 24 058 017 023 0072 14 086 411 33 218 19 35 32 73 13 65 14 40 12 15 79 13 32 037 22 029 57 36 014 11 011 b.d. 010 1065 5002 021 b.d. 769 014 015 0024 b.d. b.d. 046 b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. 014 0053 0023 b.d. 54 167 19 33 42 119 86 14 14 48 068 024 079 0070 036 0070 018 0029 014 0027 050 30 025 18 028
n.a., not analyzed; b.d., below detection limit; Cpx 1, primary clinopyroxene 1; Cpx 2, secondary clinopyroxene 2; Cb, carbonate.
three samples, the Nd composition is paralleled by 87 Sr/86Sr ratios from 070321 to 07035, not much different from the Nd^Sr isotopic composition of the host basalts (Fig. 11). In contrast, lherzolite 10ZIN5 has a much more radiogenic 87Sr/86Sr composition of 070414, at an eNd similar to those of the other cpx samples and host basalts (Fig. 11). The Sr^Nd isotope compositions overlap the range reported for spinel peridotite xenoliths sampled by the Cenozoic volcanism of the ECRIS (see Downes, 2001, and references therein). With the exception of 10ZIN5, the Sr^ Nd isotopic compositions of samples from this study broadly resemble that of the assumed plume material (Wilson & Downes, 1991) and ambient upwelling mantle (Hoernle et al., 1995) involved in the genesis of the CEVP.
However, the NE Bavarian xenoliths studied here do not show the vertical array of 87Sr/86Sr and 143Nd/144Nd ratios reported for other Cenozoic mantle peridotite and pyroxenite xenoliths from the Bohemian Massif (Ackerman et al., 2007, 2012).
Lithium systematics
Whole-rock Li contents as well as Li isotopic compositions in the NE Bavaria peridotite xenolith suite are listed in Table 7 and plotted in Fig. 12. The samples show no to modest Li enrichment (14^58 ppm) compared with pristine modally non-metasomatized mantle xenoliths (in general between 12 and 20 ppm Li; Seitz & Woodland, 2000; Magna et al., 2006; Jeffcoate et al., 2007; Magna et al.,
20
ACKERMAN et al.
2008; Pogge von Strandmann et al., 2011; Fig. 12). This is in agreement with other studies of metasomatically overprinted mantle xenoliths (e.g. Rudnick & Ionov, 2007; Aulbach et al., 2008; Zhang et al., 2010; Tang et al., 2011; Su et al., 2012; Fig. 12). Peridotites from Hirschentanz show less variability in Li abundance (14^29 ppm) and d7Li (^25 to 25) compared with those from Zinst (15^58 ppm Li; d7Li from 97 to 12). Lithium
Fig. 10. Primitive-mantle normalized REE and trace element patterns for primary clinopyroxene (cpx 1), secondary clinopyroxene (cpx 2) and melt. Normalizing values from McDonough & Sun (1995).
abundances do not correlate with modal contents of olivine, orthopyroxene or clinopyroxene, suggesting both the negligible influence of mineralogy on Li distribution and the absence of a principal carrier phase of Li in the suite. This conclusion is reinforced by the observation that, for example, samples 10ZIN5 and ZIN19 differ by 2 ppm Li despite their lherzolitic affinity, with near-identical modal compositions, whereas similar Li contents are found in lherzolites HIR3 and HIR4 with very distinct modal mineral assemblages. Similarly, Li abundances do not correlate with either major or trace element contents in the whole suite, suggesting decoupling of Li from the other trace elements during secondary processes. The presence of a secondary carbonate component in three lherzolites ZIN11, ZIN14 and TEI2B imparts insignificant and/or non-systematic changes to Li contents, suggesting low Li abundance in carbonates. Lithium isotope compositions show a huge departure towards low d7Li compared with pristine mantle xenoliths (Magna et al., 2006, 2008; Jeffcoate et al., 2007; Pogge von Strandmann et al., 2011; Fig. 12). Interestingly, d7Li values correlate positively with modal olivine in the Hirschentanz and T eichelberg samples but are negatively correlated for the Zinst locality (Fig. 13a), whereas the opposite is observed for d7Li vs modal clinopyroxene and orthopyroxene in the respective localities (not shown). The vulnerability of d7Li to post-magmatic modification in clinopyroxene, olivine and, to a lesser extent, orthopyroxene has been recognized (e.g. Seitz et al., 2004; Rudnick & Ionov, 2007; Zhang et al., 2010; Su et al., 2012). d7Li values do not vary in any systematic way with other indices of magmatic fractionation (e.g. Zr/Hf, La/Sm) and/or fluid activity (e.g. Sr/Y, Rb/Nb) and may thus be regarded as an independent parameter of metasomatic processes. However, whole-rock d7Li values correlate negatively with Li/Yb (Fig. 13b), which itself shows an extreme range between 18 and 143 in the whole suite and is far higher than Li/Yb variability in metasomatized (5 40; e.g. Brooker et al., 2004; Ionov & Seitz, 2008; Pogge von Strandmann et al., 2011) and pristine mantle xenoliths
T able 6: Rb^Sr and Sm^Nd concentrations and isotopic data for clinopyroxenes from NE Bavaria mantle xenoliths
Sample Rb (ppm) Sr (ppm)
87
Rb/86Sr
87
Sr/86Sr(m)
Sm (ppm)
Nd (ppm)
147
Sm/144Nd
143
Nd/144Nd(m)
eNd
10ZIN2 10ZIN5 ZINx2 HIR6
002 50005 50006 50005
129 339 242 91
00004 n.d. n.d. n.d.
0703208 7 0704139 7 0703234 7 0703470 7
16 25 35 17
86 16 16 75
011 0095 013 014
0512858 8 0512831 6 0512928 8 0512813 7
44 39 58 36
Rb, Sr, Sm and Nd concentrations were determined by ICP-MS; m, measured ratio; error given as 2sm; eNd corresponds to the measured ratio using for CHUR 143Nd/144Nd 0512630 and 147Sm/144Nd 01960 (Bouvier et al., 2008); n.d., not determined.
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Fig. 11. Measured 87Sr/86Sr vs 143Nd/144Nd and eNd values for clinopyroxene from NE Bavarian mantle xenoliths together with the composition of the host basalts (dark grey field). Light grey field represents the composition of CEVP basalts (data sources: Alibert et al., 1983, 1987; Blusztajn & Hart, 1989; Bendl et al., 1993; Ulrych et al., 1998, 2000, 2002; Lustrino & Wilson, 2007); the medium-grey field indicates the isotopic composition of peridotite and pyroxenite xenoliths from the Cenozoic volcanic rocks of the Bohemian Massif (Ackerman et al., 2007, 2012). BSE, present-day Bulk Silicate Earth composition; DMM, Depleted MORB Mantle composition (Workman & Hart, 2005).
(3^6; e.g. Magna et al., 2008; Pogge von Strandmann et al., 2011) as well as melt derivatives of the upper mantle (Li/ Yb generally 54; Ryan & Langmuir, 1987).
H O S T B A S A LT S
Host basalts from Zinst, Hirschentanz and T eichelberg are basanitic in composition following the classification of Le Maitre (2002), with SiO2 395^440 wt %, Na2O K2O 35^38 wt % and Mg# between 779 and 784 (Table 8). PotassiumÂr dating yields indistinguishable ages of 212 11 Ma (Zinst), 235 12 Ma (Hirschentanz) and 221 11 Ma (T eichelberg) (Table 9). These ages, however, are significantly younger than previously reported KÂr determinations of 288 18 Ma and 256 10 Ma for Zinst (T odt & Lippolt, 1975; Horn & Rohrmu ller, 2005). Trace element concentrations and Sr^Nd^Li isotopic data for the host basalts are reported in Tables 7, 8 and 10. All rocks are similarly enriched in LREE (LaN/ YbN 172^245), LILE, Th and U relative to the primitive mantle, coupled with depletions in Pb, Zr and Hf. The initial Sr^Nd isotopic composition of the host basalts is uniform, with initial 87Sr/86Sr ranging from 07033 to 07035 and 143Nd/144Nd between 051280 and 051283,
corresponding to eNd from 40 to 46. These data are similar to those for other Cenozoic volcanic rocks of the Bohemian Massif (Lustrino & Wilson, 2007; Ulrych et al., 2011). The Li isotopic composition (23 to 42) is within the range of other intra-plate alkaline volcanic rocks from central Europe (Magna & Rapprich, 2012) as well as from other localities (Ryan & Kyle, 2004; Halama et al., 2007, 2008; Hamelin et al., 2009). However, the d7Li of the host basalts appears to be shifted towards higher values relative to the average d7Li of the xenoliths, similar to what was reported for Cenozoic alkaline basalts in central Asia hosting frequent peridotite xenoliths (Magna et al., 2008).
DISCUSSION Partial melting in the mantle source of the xenolith samples

There are several lines of evidence that the xenolith suite (except for ZIN11 and ZIN14) experienced prior melt extraction: (1) negative correlation between Mg# and Al content in primary clinopyroxene (Fig. 8a); (2) negative correlation between some major oxides (e.g. SiO2, Al2O3, CaO) and MgO whole-rock contents (Fig. 5); (3) high
22
ACKERMAN et al.
T able 7: Lithium concentrations and isotopic compositions of NE Bavaria mantle xenoliths and their host basalts
Sample Lithology Li (ppm) d7Li () 2s
10ZIN1 10ZIN2 10ZIN3 10ZIN4 10ZIN5 10ZIN6 ZIN9 ZIN11 ZIN14 ZIN19 ZIN27 ZINx2 ZINx5 ZINx8 HIR3 HIR4 HIR5 HIR6 HIR16 TEI2B B-10 B-9 B-11
lherzolite lherzolite harzburgite lherzolite harzburgite lherzolite lherzolite lherzolite lherzolite lherzolite dunitewehrlite lherzolite lherzolite lherzolite lherzolite lherzolite lherzolite lherzolite lherzolite lherzolite Zinst basanite Hirschentanz basanite Teichelberg basanite
270 248 303 247 429 339 343 576 150 211 518 267 486 283 169 180 141 230 286 248 60 61 58
345 311 324 007 437 202 134 176 116 670 801 375 967 004 252 228 073 098 254 133 231 318 422
019 016 020 036 053 026 025 029 025 020 018 013 033 003 008 017 025 056 015 013 045 030 013
(Niu, 1997; Herzberg, 2004; Walter, 2004), Cr# in spinel (Hellebrand et al., 2001, 2005) or trace element (REE, Y) composition of clinopyroxene (Johnson et al., 1990; Norman, 1998). However, calculations based on the trace element composition of clinopyroxene clearly yield too low F, which is not consistent with the whole-rock major element and modal composition. This is probably due to REE, Y or cpx addition during metasomatism and/or a high proportion of Yb and Y hosted by orthopyroxene (e.g. McDonough et al., 1992; Eggins et al., 1998). A more robust estimate of the amount of melt depletion should be obtained from the major element (MgO, SiO2, Al2O3) and modal composition of the xenoliths (except for samples ZIN11 and ZIN14 with whole-rock major element compositions strongly affected by metasomatism) and the experimental grids of Herzberg (2004) and Walter (2004) for spinel or garnet peridotite. Using this approach, the NE Bavaria xenoliths define trends consistent with a wide range of partial melting degrees from F 15 to 30% (Figs 14 and 15) with the highest calculated F for the cpx-poor xenoliths. Similar results (F 6^26%) can be obtained using the calculation of Niu (1997) based on whole-rock MgO contents (Table 11). Alternatively, partial melting degrees for spinel peridotites can be estimated from Cr# in spinel (Hellebrand et al., 2001). Using a modified version of this calibration (Hellebrand et al., 2005), partial melting degrees of 8 to 18% can be inferred for all xenoliths.
Origin of melt pockets

The origin of glass- or melt-bearing pockets and/or veinlets enclosed in mantle xenoliths remains a matter of debate. The following processes have been identified as crucial for the formation of melt pockets: breakdown of amphibole or mica (e.g. Frey & Green, 1974; Neumann & Wulff-Pedersen et al., 1997; Yaxley et al., 1997; Yaxley & Kamenetsky, 1999), breakdown of orthopyroxene and spinel (Dautria et al., 1992), reaction of peridotite with migrating melts and fluids in the upper mantle (e.g. Ionov et al., 1994; Zinngrebe & Foley, 1995; Neumann & Wulff-Pedersen, 1997; Schiano et al., 1998; Ishimaru & Arai, 2009), or late intrusion of the host magma into the xenoliths (e.g. Klu gel, 1998, 2001; Miller et al., 2012). The formation of silicate and carbonate^silicate melt pockets in the xenoliths from NE Bavaria was discussed in pac brief by S ek et al. (2013), who studied the origin of unusual fine-grained opx^spl^pl symplectites pseudomorphing garnet. Type II pockets are hosted preferentially in these symplectites and in some cases there is clear structural evidence that these are older than both Type I pockets and the veinlets in the proximity of the symplectites. Based on the textural features, mineralogy and bulk chem pac ek et al. (2013) suggested that istry of the melt pockets, S whereas the veinlets and Type I pockets are probably associated with melt intrusion from the host basanite, it is
Mg# of olivine and pyroxenes; (4) lower HREE contents in whole-rock samples compared with primitive mantle (Fig. 6). On the other hand, the absence of a correlation between whole-rock TiO2, Na2O and MgO contents, clinopyroxene modal abundance and whole-rock Cr#, and only weak positive correlation between Mg# of olivine and Cr# of spinel (r 069; Fig. 9) suggests some perturbation of major element systematics and possible clinopyroxene addition during later stages of metasomatism. A negative correlation between SiO2, CaO, Al2O3 and MgO in peridotites (Fig. 5) is usually ascribed to variable degrees of partial melting, implying preferential melting of clinopyroxene and spinel (e.g. Frey & Green, 1974; Mysen & Kushiro, 1977; Frey & Prinz, 1978). However, whereas the compositional trends of CaO vs MgO fit well the batch melting model of Niu (1997), compositional trends in our xenolith suite exhibit lower contents of SiO2 and Al2O3 for a given MgO than would be expected from the model compositions of Niu (1997) and Herzberg (2004). Partial melting degrees (F) can be estimated using the major element and modal composition of the whole-rock
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Fig. 12. The d7Li vs Li variation in NE Bavaria mantle xenoliths (symbols as in Fig. 3). Data for other xenoliths worldwide are also plotted; only measured whole-rock values were considered and no d7Li values reconstructed from analyses of individual mineral phases were included. Date sources: Mongolia, Magna et al. (2006, 2008) and Pogge von Strandmann et al. (2011); Vitim, Avacha, Ionov & Seitz (2008), Halama et al. (2009) and Pogge von Strandmann et al. (2011); T ok, Pogge von Strandmann et al. (2011); Zabargad, Brooker et al. (2004); Gakkel Ridge, Gao et al. (2011); South Korea, Kil (2010). Two whole-rock analyses with high d7Li values from Zabargad (Brooker et al., 2004) are indicated with arrows, as they plot outside the range of the figure.
difficult to explain the Type II pockets by metasomatic reaction with the xenolith-entraining magma. The generally high Na content and a local presence of carbonate in the Type II pockets requires a chemically open system. On the other hand, in terms of the high contents of Si and Al, usually low Ti, and much higher Na2O/ K2O (10 to 26 compared with 3^4 in the host basanite) (Table 4), the quenched silicate melts differ significantly from the host basanite itself (Table 8) or from any products expected to result from reaction between the primary phases and significant volume of basanite. At the same time, the absence of relict amphibole or mica and low K contents in the quenched melt are factors against any significant contribution of OH-bearing minerals to its origin. Therefore, similar to many previous studies of melt pockets in mantle xenoliths (e.g. Ionov et al., 1994; Zinngrebe & Foley, 1995; Neumann & Wulff-Pedersen, 1997, 2001; Neumann et al., 2002; Rampone et al., 1997), we suggest that the Type II melt pockets most probably record an older metasomatic reaction, which pre-dated the infiltration of the host magma and took place in the mantle. The highly variable composition of the quenched melt in all the pockets suggests that its formation is not controlled by fractional crystallization only (e.g. Ionov
et al., 1994). Structural evidence for the resorption and metasomatic reaction of primary phases (clinopyroxene, spinel; Fig. 4c, d and f) suggests reaction of the primary peridotite (devoid of hydrous phases) with percolating melts. The mineralogy and bulk composition of the pockets indicate that these melts had a high Na content, low K content and were CO2-bearing. Based on the structural position of the Type II pockets (or domains of metasomatic melting) within the external parts of very unstable sym pac ek et al. (2013) suggested that this metasomplectites, S atic event occurred immediately after the onset of hightemperature breakdown of relict garnet in the protolith of the peridotites and probably shortly before the eruption of the Zinst basanite. The mineralogy and mineral chemistry of the melt pockets found in the three samples selected for detailed study reveal some important similarities as well as differences. Whereas the melt pockets in samples ZIN14 and TEI2B contain a similar mineral association (cpx2/ ol2 cb plg melt spl2 ilm), the melt pockets in ZIN11 exhibit a more complex mineral association of cb ol/cpx2 afs melt ap ilm crich, resulting in the prominent K and LREE enrichment in the latter (Table 2). This is most easily explained by an additional
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T able 8: Whole-rock major and trace element compositions of host basalts

Sample: Rock: Locality: wt % SiO2 TiO2 Al2O3 Fe2O3 FeO MnO MgO CaO Na2O K2O P2O5 H2O H2O CO2 Total ppm Sc Rb Sr Y Zr 22 23 754 20 192 64 048 455 42 82 10 40 76 25 76 10 47 08 23 026 17 023 45 69 26 57 13 23 34 922 22 259 77 095 523 52 101 12 51 93 29 89 12 53 09 25 028 17 025 59 55 22 57 16 25 26 993 23 286 98 069 571 66 123 15 58 10 31 98 12 54 09 26 029 18 026 66 78 26 74 17 4395 175 1086 430 736 018 1499 1077 282 071 059 035 096 024 9983 4148 212 1098 520 728 019 1438 1128 279 089 075 046 136 063 9979 3946 257 1090 607 692 020 1384 1262 271 110 083 052 158 028 9960 B-10 Basanite Zinst B-9 Basanite Hirschentanz B-11 Basanite Teichelberg
Fig. 13. (a) d7Li vs modal olivine in the NE Bavaria xenolith suite (symbols as in Fig. 3). (b) d7Li vs Li/Yb in NE Bavaria peridotites compared with other localities. Data sources as in Fig. 12. Yb data from Stosch et al. (1986), Brooker et al. (2004), Ionov et al. (2005, 2006), Kil (2007; Yb in cpx only), Liu et al. (2008; Yb in cpx only), Magna et al. (2008), Halama et al. (2009) and Ionov (2010). PM, primitive mantle, Li/Yb from Jagoutz et al. (1979) (see main text for d7Li in the primitive mantle).
Nb Cs Ba La Ce Pr Nd Sm Eu
overprint of an older metasomatic association by later, post-entrainment metasomatic reaction with the mobile components of the host basanite infiltrating into the xenolith.
Gd Tb Dy Ho Er
Alkaline and carbonate-rich melt metasomatism

Mantle metasomatism by percolating melts or fluids of various compositions represents the key process of mantle enrichment (e.g. Frey & Green, 1974; Menzies & Hawkesworth, 1987; Downes, 2001). This includes metasomatism by (alkaline) basaltic melts (e.g. Bodinier et al., 1990; Zanetti et al., 1996; Witt-Eickschen et al., 1998; Ionov et al., 1999; Coltorti et al., 2007; Gregoire et al., 2009, 2010),
Tm Yb Lu Hf Ta Pb Th U
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alkaline or Fe^Ti-rich fluids or melts (e.g. Ionov, 1998; Gregoire et al., 2000a; Kalfoun et al., 2002), carbonatitic melts (e.g. Y axley et al., 1991; Ionov et al., 1993; Rudnick et al., 1993; Coltorti et al., 1999; Gorring & Kay, 2000) and subduction-related fluids or melts (e.g. Zanetti et al., 1999; Gregoire et al., 2001; Coltorti et al., 2007; Y oshikawa et al., 2010). The xenolith suite in this study shows similar, distinct signs of pervasive melt infiltration resulting in modal (melt pockets) and cryptic metasomatism. The evidence includes LREE, Li, Rb, U, Nb, Ta, Pb and P enrichments in all xenolith samples, variable d7Li values from 25 to 97 and the presence of carbonate-bearing silicate melt pockets in some xenoliths. The mineralogy and mineral chemistry of the melt pockets in the xenolith suite and the whole-rock major and trace element data support overprinting of the xenoliths by Na^P^CO2-rich metasomatic agents and may suggest a combination of alkaline and carbonatitic melt metasomatism. However, the geochemical data show no simple correlation between the extent of metasomatism, such as CaO/Al2O3 or Mg#, and incompatible trace element enrichment and indicators of alkaline and carbonatitic metasomatism (e.g. Ti/Eu vs LaN/YbN; Coltorti et al., 1999). This may, in part, be due to the fact
T able 9: Results of KÂr ages for NE Bavaria volcanic rocks

Sample Locality K (%)
40
Ar(rad)
3 1
40
Ar(rad)
Age (Ma)
1s
(cm STP g ) 5454 107 7201 107 8315 107
(%)
B-10 B-9 B-11
Zinst Hirschentanz Teichelberg
0658 0782 0963
327 327 379
212 235 221
11 12 11
that alkaline and carbonatitic metasomatism often results in contrasting metasomatic effects (e.g. Ti enrichment for alkaline melts vs Ti depletion usually observed in carbonatitic melt metasomatism; Bizimis et al., 2003), trace element fractionation during melt percolation (e.g. Navon & Stolper, 1987) and/or modal metasomatism resulting in the formation of new phases such as cpx 2, carbonate, apatite and Ti^Zr oxides within melt pockets (e.g. Neumann et al., 2000, 2002). Alkali-rich silicate melts typically have elevated CO2 contents (Brey & Green, 1976), probably reflecting an origin by low-degree melting of a carbonated peridotitic source (e.g. Edgar, 1987, and references therein). Interaction of such melts with peridotite usually results in the precipitation of K-rich hydrous phases such as amphibole or mica, coupled with LREE^HFSE enrichment and lower Mg# values in the peridotites (Dawson & Smith, 1982; Hawkesworth et al., 1984; Menzies & Hawkesworth, 1987; Bodinier et al., 1988; Fabries et al., 1989; Harte & Hawkesworth, 1989; Wulff-Pedersen et al., 1996; Ionov et al., 1997; Gregoire et al., 2000b; Puziewicz et al., 2011). This would be in agreement with the overall LREE enrichment observed in the NE Bavaria xenoliths (Fig. 6) and lower Mg# of the whole-rocks and mineral phases, coupled with elevated HFSE contents in most samples. However, except for sample ZIN11, which contains melt pockets with predominant alkali feldspar, the K enrichment is only minor, expressed by low K2O contents in whole-rocks and the presence of Na-rich plagioclase within the melt pockets in samples ZIN14 and TEI2B. On the other hand, the elevated whole-rock Ca/Al ratios, coupled with LREE and LILE enrichment and Zr^Hf and U^Th fractionation, as well as the abundance of apatite, are often considered as characteristic signatures of carbonatitic metasomatism (Yaxley et al., 1991, 1998; Hauri et al., 1993; Ionov et al., 1993, 1994; Rudnick et al., 1993; Coltorti et al., 1999; Lenoir et al., 2000). All these signatures can also be recognized in the NE Bavaria xenolith suite (Table 2, Figs 6 and 7) together with the presence of
T able 10: Rb^Sr and Sm^Nd concentrations and isotopic data for xenolith-hosting basalt samples from Zinst, Hirschentanz and T eichelberg, NE Bavaria, Bohemian Massif
Sample Locality Age Rb Sr
87
Rb/86Sr
87
Sr/86Sr(m)
87
Sr/86Sr(t) Sm
Nd
147
Sm/144Nd
143
Nd/144Nd(m)
143
Nd/144Nd(t) eNd(t)
(Ma) (ppm) (ppm)
(ppm) (ppm)
B-10 B-9 B-11
Zinst
212
23 34 26
754 922 993
0088 0107 0076
0703479 9 0703465 9
0703454 0703425
76 93 10
40 51 58
01151 01114 01055
0512827 11 0512828 9 0512856 9
0512811 0512811 0512841
41 41 47
Hirschentanz 235 Teichelberg 221
0703337 10 0703316
Rb, Sr, Sm and Nd concentrations were determined by ICP-MS; m, measured ratio; error given as 2sm; eNd corresponds to the measured ratio using for CHUR 143Nd/144Nd 0512630 and 147Sm/144Nd 01960 (Bouvier et al., 2008).
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ACKERMAN et al.
Fig. 14. Melt extraction estimates for the NE Bavaria xenoliths based on whole-rock major element composition (MgO, Al2O3, SiO2). The melt extraction curves at 1 and 2 GPa were constructed using the experimental data of Herzberg (2004). Figure adopted from Harvey et al. (2012).
carbonate within melt pockets in samples ZIN14 and TEI2B and the more complex cb ol/cpx2 melt ap ilm crich mineral assemblage found in sample ZIN11. Except for the presence of Ti-rich phases, the mineralogy of the melt pockets in sample ZIN11 is similar to that described from Svalbard mantle xenoliths (Amundsen et al., 1987; Ionov et al., 1993) interpreted as a product of mantle metasomatism by carbonate-rich fluids (Ionov et al., 1993, 1996). Although these three xenoliths could be considered as products of carbonatitic metasomatism, their low whole-rock Mg# values, overall enrichment in HFSE and the presence of cpx2 in carbonate-bearing melt pockets significantly enriched in TiO2 (up to 70 wt %) are factors against simple interaction between peridotite and a pure carbonatitic melt, because such a melt is markedly depleted in HFSE as a result of preferential partitioning into residual pargasite, clinopyroxene, and ilmenite (Green & Wallace, 1988). The clear association of carbonateâpatite with alkaline melt pockets, the presence of large (up to 1mm) carbonate pockets hosted in silicate melt pockets and the low REE contents in the carbonates (Table 5) compared with quenched carbonatitic melts (e.g. Moine et al., 2004) are features strongly in favour of the carbonate occurrence being connected with magmatic fractionation of an alkaline and/or alkali^carbonate melt (e.g. Giuliani et al., 2012). Such a conclusion is in agreement with the occurrence of wehrlite and apatitebearing clinopyroxenites in the nearby area, interpreted as the products of alkaline^carbonatitic melts (Geissler et al., 2007).
Fig. 15. Whole-rock major element variations of FeO (wt %) vs SiO2, Al2O3 and MgO (wt %) for NE Bavaria xenoliths. Batch melt extraction curves for 1, 2, 3, 5 and 7 GPa melting of primitive mantle (McDonough & Sun, 1995) adopted from Walter (2004).
The incompatible element composition of the alkaline silicate melt invading the peridotites cannot be calculated from the composition of the clinopyroxene and Dcpx/melt, because the clinopyroxene does not represent the only phase contributing to the trace element budget (see below). On the other hand, owing to the clear modal metasomatism in some xenoliths, the composition of the melt has been inferred from the complex mineralogy and chemical composition of the melt pockets. It has been shown above that the melt pockets have compositions different from those of the host basalts, indicating an origin by melt infiltration at upper mantle conditions. The composition of the silicate melt quench (intermediate SiO2 contents of 509^590 wt % and TiO2/Al2O35007) most probably reflects reaction between an infiltrating alkali basaltic melt and peridotite (Neumann & Wulff-Pedersen, 1997) rather than a primary melt composition. Its alkali-rich composition (Na2O K2O up to 96 wt %), coupled with the presence of plagioclase (ZIN14, TEI2B) or alkali feldspar
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T able 11: Calculated partial melting degrees for NE Bavaria mantle xenoliths
Sample Locality Lithology Cpx mode (vol. %) F (%)1 F (%)2
the separation of an immiscible CO2-rich melt or fluid (Schiano & Clocciatti, 1994; Schiano et al., 1994; Harvey et al., 2010) and precipitation of carbonate and quartz, as observed in sample ZIN11. Additionally, very high F and Cl contents in apatite (384 and 055 wt %, respectively) point to elevated contents of these elements in the infiltrating melt.
10ZIN1 10ZIN2 10ZIN3 10ZIN4 10ZIN5 10ZIN6 ZIN9 ZIN11 ZIN14 ZIN19 ZIN27 ZINx2 ZINx5 ZINx8 HIR3 HIR4 HIR5 HIR6 HIR16 TEI2B
1 2
Zinst Zinst Zinst Zinst Zinst Zinst Zinst Zinst Zinst Zinst Zinst Zinst Zinst Zinst Hirschentanz Hirschentanz Hirschentanz Hirschentanz Hirschentanz Teichelberg
lherzolite/harzburgite lherzolite harzburgite/lherzolite lherzolite harzburgite/lherzolite lherzolite lherzolite lherzolite lherzolite lherzolite dunitewehrlite lherzolite lherzolite/harzburgite lherzolite/harzburgite lherzolite lherzolite lherzolite lherzolite lherzolite/harzburgite lherzolite/harzburgite
6 7 3 13 4 10 11 12 13 6 7 10 5 5 12 6 8 12 6 5
14 14 17 10 14 15 12 11 8 18 18 12 16 17 14 17 14 14 12 16
20 19 24 9 22 11 6 n.d. n.d. 21 23 13 26 16 7 23 6 15 19 19
The source of the infiltrating melts: evidence for a recycled component?

The mantle source of the magmatism within the major part of the Ohr e/Eger Rift has been evaluated based on the compositions of volcanic rocks occurring within the rift and on its shoulders (Haase & Renno, 2008). At least three mantle source components can be distinguished using Sr^Nd^Pb isotopic data and incompatible trace element systematics. Volcanic rocks in the western continuation of the rift, including the Zinst, Hirschentanz and T eichelberg localities, show considerable enrichment in incompatible elements, suggesting either lower degrees of partial melting and/or enriched mantle sources, represented by amphibole-bearing mantle peridotite (Haase & Renno, 2008). Although the peridotites investigated here provide no evidence for the presence of either amphibole or low degrees of partial melting, we do see evidence for an enriched mantle source. We argue below that this enrichment may be the result of recycled (subducted) crustal lithologies within the upper mantle column. The NE Bavarian xenoliths occur in volcanic rocks that intruded the Saxothuringian tectonic unit of the Bohemian Massif, the evolution of which is closely connected with eastward subduction of oceanic crust (Saxothuringian ^Barrandian unit during Devonocean) beneath the T epla sek & ian^Carboniferous times (Franke, 2000; Konopa Schulmann, 2005; Schulmann et al., 2009). Relics of oceanic crust preserved as eclogites and metabasites are widespread within the Saxothuringian terrane (e.g. Stosch & Lugmair, 1990; Schma dicke et al., 1992). The xenolith-bearing localities are close to the Saxothuringian^Moldanubian terrane boundary and a triple junction of the mantle lithosphere domains that are characterized by different , 2010). However, seismic anisotropy (Babus ka & Plomerova there is no direct evidence for a different chemical composition of these domains (e.g. Haase & Renno, 2008). The trace element and isotopic similarity between the primitive Cenozoic basalts of the Bohemian Massif and Permo-Carboniferous volcanic rocks from the same area led Ulrych et al. (2002) to propose that their HIMU-like mantle source already existed in Permian times and was formed by Devonian subduction-related metasomatism of the mantle lithosphere. The importance of pyroxenite and/or eclogite in the generation of basalt magmas was discussed by Hirschmann & Stolper (1996) and Sobolev et al. (2007), who suggested the involvement of 2^20 vol. % of recycled crust (eclogite
Degree of partial melting based on Cr# of spinel (Hellebrand et al., 2001, 2005). Degree of partial melting based on whole-rock MgO content (Niu, 1997). n.d. not determined.
(ZIN11) and Al Na-rich cpx 2 within the pockets are features strongly in favour of reaction between peridotite and alkali-rich basaltic melt. The trace element compositions of cpx 2 and the quenched melt (Fig. 10) provide more details on the incompatible element composition of this infiltrating melt, which was apparently strongly enriched in REE (up to 229 ppm total REE in cpx 2) and Zr^Nb, but significantly depleted in U, Th and Pb. The absence of hydrous metasomatic phases such as amphibole and/or mica in our xenolith suite points to high CO2/H2O ratios in the infiltrating alkaline melt, which is in agreement with experimental studies (Green & Wallace, 1988). Elevated CO2 contents in the garnet peridotite sources of basalts from the Ohr e/Eger Rift were suggested by Haase & Renno (2008). Further evidence for elevated CO2 contents in the upper mantle of the western part of the rift is provided by CO2-rich gas emanations with 3He/4He and d13C compositions implying their derivation from the mantle (Weinlich et al., 1999). Fractionation of such a CO2-bearing silicate melt will result in increasing CO2 contents and CO2/SiO2 ratio in the residual melt, which would lead to
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ACKERMAN et al.
or pyroxenite) during mantle melting. Melting experiments on carbonated eclogite (Hammouda, 2003; Dasgupta et al., 2004; Yaxley & Brey, 2004) suggest that eclogite will melt preferentially over peridotite, and that melting of a mixed peridotiteêclogite source can produce alkali basalts with variable Mg#s that are lower than those of typical peridotite-derived melts (Kogiso & Hirschmann, 2006). Such melts can, in turn, be responsible for metasomatism that will lower the Mg#, as is apparent in some of the peridotites from this study (e.g. ZIN11, ZIN14). A similar scenario was suggested for Fe-rich peridotites from Calatrava, Spain (Bianchini et al., 2010), which contain carbonate-bearing melt pockets with compositions almost identical to those of the NE Bavaria xenoliths. Further support for recycled material in the source of infiltrating melts may be provided by high P contents in the whole-rocks (002^029 wt % P2O5; Table 2) compared with primitive mantle values. Although some of these high P contents can be explained by the occurrence of apatite within melt pockets in some xenoliths, they can also be connected with the presence of discrete P-bearing glasses interpreted as percolating melts originating from partial melting of subducted sedimentary material by Rosenbaum et al. (1997). The Sr^Nd^Li isotopic systematics represent powerful tools for tracing recycled components (e.g. Medaris et al., 1995; Ishikawa et al., 2007; Penniston-Dorland et al., 2010; Melchiorre et al., 2011; Zeng et al., 2011). The relatively high 87 Sr/86Sr ratios between 07033 and 07035 at 143 Nd/144Nd of 051281^051284 in volcanic rocks from Zinst, Hirschentanz and T eichelberg (Table 10) are similar to those reported by Haase & Renno (2008), which those researchers interpreted to reflect mixing between two mantle components with similar Nd isotopic composition, but variable Sr isotopic ratios between 07032 and 07036. Whereas the clinopyroxenes from the mantle xenoliths have Nd isotope compositions similar to those of the host basalts and other xenoliths from the CEVP, harzburgite 10ZIN5 from Zinst has a significantly more radiogenic 87 Sr/86Sr of 07041 (Fig. 11). Despite the limited amount of data, the radiogenic 87Sr/86Sr in 10ZIN5 coupled with a 143 Nd/144Nd similar to that of the host basalts and three other lherzolites analyzed for their Sr^Nd isotopic compositions (10ZIN2, ZINx2, HIR6) may provide evidence for selective overprinting of the Sr in the Zinst samples by Sr-rich melts or fluids derived from a subducting slab and/ or the presence of recycled material in the source of the melts. Most of the xenoliths in this study are variably enriched in Li compared with the primitive mantle, with substantial enrichments in clinopyroxene (up to 33 ppm; Table 5) suggesting significant Li addition from the infiltrating melt. The large variations in d7Li (25 to 97) are similar to those reported for peridotites metasomatized by
subducted crustal materials (Zhang et al., 2010), and for mantle xenoliths that have interacted with Na-carbonatitic melts (Su et al., 2012). The low d7Li values in the NE Bavaria xenoliths are paralleled by high to extreme Li/Yb ratios (18^143; Fig. 13b) that are fairly uncommon for mantle xenoliths worldwide and far from the Li/Yb of 45 estimated for the terrestrial upper mantle (Jagoutz et al., 1979). These high Li/Yb ratios appear to result from slight Li enrichment (2^3 pristine mantle Li abundance; Ryan & Langmuir, 1987) coupled with large Yb depletion (in general 5009 ppm), probably caused by large degrees of melting that exhausted a substantial proportion of the HREE. Similarly low Yb contents have been found in Avacha spinel harzburgites (Ionov, 2010) with Li/Yb ranging from 38 to 109 but with largely normal mantle d7Li values (Ionov & Seitz, 2008; Pogge von Strandmann et al., 2011). The larger range in both d7Li and Li/Yb for the Zinst suite relative to the Hirschentanz^T eichelberg suite appears to be related to a greater extent of physical disturbance in the former suite, as supported by petrographic evidence. This, coupled with non-uniform correlation between d7Li and Al2O3, may hint at different processes controlling the d7Li variations and may imply easier invasion of metasomatizing fluids into the Zinst suite of xenoliths. Two alternatives may be assessed to explain the observed extreme variation of Li isotope compositions in mantle xenoliths toward negative values: (1) mixing with a lowd7Li reservoir and/or overprinting by low-d7Li fluids or melts; (2) kinetic fractionation during ingress of Li. Both alternatives must be considered equal, or they may even be combined. Recent Os isotope data for NE Bavaria xenoliths appear to provide some support for a contribution of recycled crustal material in the percolating melts (Ackerman et al., 2013). The mechanism of kinetic isotope fractionation cannot be evaluated with the current dataset because of the lack of relevant in situ data; further studies are required to resolve this. (1) Low d7Li values have been reported for rocks such as granulites (d7Li as low as 18; T eng et al., 2008) and eclogites (d7Li as low as 22; Zack et al., 2003; Marschall et al., 2007; Halama et al., 2011). In parallel, a low-d7Li crustal reservoir has been advocated by Hamelin et al. (2009) in the petrogenesis of evolved alkaline volcanic rocks (benmoreites, trachytes) from the Massif Central and explained by assimilation of an isotopically light lower crustal component, such as a metapelite. However, melting of even a small portion of such a metapelitic source could not reproduce the major and trace element variations as well as the very low d7Li observed in the NE Bavaria xenoliths (see Qiu et al., 2011). Lithium contents in granulites (5 23 ppm, but usually below 5 ppm; T eng et al., 2008) and garnet-bearing metapelites (5 11ppm; Qiu et al., 2011) are too low to explain the observed enrichment in
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clinopyroxene; granulites or their melts will also probably have different trace element characteristics (e.g. Bea & Montero, 1999; Janous ek et al., 2004). Tang et al. (2012) have suggested that eclogites could be the ultimate source of the low-d7Li melt or fluid that metasomatized peridotite xenoliths from the North China Craton whereas Su et al. (2012) have advocated carbonatite melts as the low-d7Li component. Secondary carbonate probably has very low Li contents; the ZIN11, ZIN14 and TEI2B carbonates are indeed highly depleted in Li (Table 5). T o a certain extent, this may disqualify carbonate metasomatism as a source of elevated Li concentrations. Moreover, those samples with abundant carbonate do not show a systematic d7Li bias from the other NE Bavaria xenoliths. The presence of eclogitic lithologies in the mantle beneath the Bohemian Massif may be assigned to Devonian^Carboniferous subduction of Saxothuringian lithosphere (e.g. Schulmann et al., 2009). A simplified binary-mixing scenario between pristine mantle and a nearby Mu nchberg eclogite is plotted in Fig. 12. Preferential melting of Li-rich eclogites could account for the observed negative [Li]^d7Li variation and the apparent scatter could easily be explained by non-uniform Li abundance and variable d7Li signature in clinopyroxene. Such heterogeneous distribution of Li isotopes has been observed in many examples (e.g. Zack et al., 2003; Nishio et al., 2004; Rudnick & Ionov, 2007; Tang et al., 2011). We note that clinopyroxene from pristine peridotites usually has d7Li higher than olivine and orthopyroxene (Magna et al., 2006; Jeffcoate et al., 2007). However, the absence of a correlation between Li contents, degree of metasomatism (e.g. Ca/Al) and d7Li, as well as rather low Li/Yb ratios in eclogites, are all factors against simple mixing of peridotite with infiltrating melts. (2) Kinetic effects have been observed to severely modify the intrinsic intra-mineral Li isotope systematics of clinopyroxene and orthopyroxene from peridotite mantle xenoliths (e.g. Lundstrom et al., 2005; Jeffcoate et al., 2007; Rudnick & Ionov, 2007; Aulbach et al., 2008; Ionov & Seitz, 2008; Aulbach & Rudnick, 2009). It is important to stress that clinopyroxene, in particular, inherits very low d7Li values through faster 6Li diffusion, whereas olivine is more resistant to diffusive modification (Jeffcoate et al., 2007; Parkinson et al., 2007; Rudnick & Ionov, 2007). The superior speed of 6Li in diffusion has been evidenced in natural mantle settings by newly formed melt pockets coexisting with clinopyroxene that is isotopically light relative to that coexisting with melting olivine (Magna et al., 2008). High Li contents associated with low d7Li in clinopyroxene are often considered a hallmark of diffusive ingress of light Li (Rudnick & Ionov, 2007; Tang et al., 2011). We stress that Li contents in cpx1 and cpx2 from the NE Bavaria suite (Table 5) are not uniformly high, neither are peridotites with high-Li clinopyroxene associated with low bulk d7Li values. Nevertheless, it is still conceivable
that part of the variation can be explained by recent diffusive influx of Li from the surrounding melt (see Aulbach et al., 2008); further detailed investigations are required to resolve this. It is interesting to note that mantle xenoliths always have lower d7Li than their respective host alkali basalts (see Magna et al., 2008). This can be illustrated by comparing the average Li content and Li-isotope composition of xenolith samples with the lowest Li/Yb and d7Li values in the respective host basanites, which are clearly off by 4 16. A similar difference of 4 has been recorded between moderately LREE-depleted spinel lherzolite and its host basalt from Atsagin Dush, Mongolia (Magna et al., 2008). It may be feasible for Li isotopes to kinetically exchange between an alkali basaltic melt and peridotite over a short time interval en route to the surface (Lundstrom et al., 2005; Aulbach et al., 2008); however, we cannot evaluate these observations with the results of Rudnick & Ionov (2007) owing to the lack of whole-rock xenolith data in their study, although they envisaged infiltration of Li from the host basalt.
Constraints on trace element distribution within minerals

Mass-balance calculations show that four analysed clinopyroxenes (10ZIN2, ZINx2, ZIN14 and TEI2B) host most of the REE and Y. In contrast, clinopyroxenes from samples 10ZIN5, HIR6 and ZIN11 host only up to 40^70% of the middle rare earth elements (MREE), HREE and Y, and less than 40% of La and Ce. With regard to HFSE, clinopyroxenes can account for variable proportions between 20^30% (10ZIN5, HIR6) and 70^100% of the total HFSE inventory (10ZIN2, ZIN11, ZIN14, ZINx2, TEI2B). Except for sample ZIN14, in which the clinopyroxene is strongly enriched in Th and U (Table 5), clinopyroxene hosts only a small fraction of the bulk-rock Th and U budget (5 30% Th and 5 10% U). The Sr budget is variably controlled by clinopyroxene (10^80%), with the lowest values calculated for samples with abundant carbonates (ZIN11, ZIN14). This is in agreement with our trace element analyses of carbonate, suggesting that it plays only a limited role as a host of incompatible trace elements, except for Sr, Ba and, to a lesser extent, Th and U. On the other hand, Sr and Ba can be largely accommodated in feldspar (e.g. Gregoire et al., 2000a). The very low Rb concentrations in cpx1 (05 ppm) compared with high whole-rock Rb contents (19^25 ppm) suggest that, for the samples with carbonate-bearing pockets (ZIN11, ZIN14, TEI2B), Rb distribution is controlled solely by the presence of feldspar and/or Rb-rich silicate melt (e.g. TEI2B with 54 ppm Rb; Table 5). For samples without secondary melt pockets (Table 1), it is likely that Rb is hosted in some as yet unidentified phase(s) and/or grain boundary component (e.g. Bedini & Bodinier, 1999). Very low Pb contents detected in clinopyroxenes compared with
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Fig. 16. Whole-rock trace element composition of melt pocket-bearing samples (ZIN11, ZIN14, TEI2B) and the host basalts.
whole-rocks suggest only a limited role (5 20% of total Pb budget) for clinopyroxene in Pb partitioning among mineral phases. Gregoire et al. (2000b) argued that olivine can control the Pb budget in the upper mantle. However, we suggest that mantle sulphides, occasionally present in the xenolith suite, may control Pb owing to the capability of sulphide to concentrate up to several parts per million of Pb (Hart & Gaetani, 2006; Burton et al., 2012; L. Ackerman, unpublished data).
CONC LUSIONS
Peridotite mantle xenoliths from Zinst, Hirschentanz, and T eichelberg (NE Bavaria, Bohemian Massif) are hosted in Cenozoic basanite lava flows (212^235 Ma), forming part of the Central European Volcanic Province. Whole-rock major element variations and spinel chemistry suggest variable (6^30%) degrees of melt extraction from their protolith in the spinel stability field and subsequent pervasive enrichment by alkaline and carbonate-rich melts that resulted in modal and cryptic metasomatism. The evidence includes progressive Li, LREE, Rb, U, Pb, HFSE and P enrichment and the presence of carbonate-bearing silicate melt pockets. The clear association of carbonate and apatite with alkaline melt pockets and the presence of large domains with carbonate within some of the silicate melt pockets strongly suggest that the carbonate occurrence is connected with the fractionation of an alkaline silicate melt and/or alkali^carbonate melt, rather than representing metasomatism by a pure carbonatitic melt.
The Sr^Nd^Li isotopic systematics with variable Sr/86Sr ratios between 07032 and 07041 and significantly negative d7Li values down to 97 may indicate an important contribution of recycled crustal material such as eclogite in the infiltrating melts. This might be connected with the geodynamic setting of the host basalts that intruded the Saxothuringian basement terrane, the evolution of which was closely connected with eastward dipping subduction of oceanic lithosphere (Saxothuringian ocean) during Devonian^Carboniferous times. Alternatively, kinetic diffusive fractionation could have played an important role in 7Li/6Li modifications with predominant enrichment in light Li isotope compositions in those xenoliths whose protoliths were most severely deformed by previous tectonic events. The trace element geochemistry of clinopyroxene, carbonate, and silicate melt pockets implies that clinopyroxene controls most of the MREE HREE, HFSE and, to a lesser extent, also the LREE and Sr whole-rock budgets. Carbonate plays only a subordinate role as a host of incompatible trace elements, except for Sr, Ba and, to a lesser extent, Th and U. In contrast, Rb distribution can be controlled by the presence of feldspar and/or Rb-rich silicate melt in melt pocket-bearing xenoliths.
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for microprobe analyses, We thank Vlasta Bo hmova for whole-rock ICP-MS analyses, Matous kova uris ova for help with LA-ICP-MS analyses, D a rka S Jana Jitka
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and Vladislav Chrastny M| kova for maintenance of the clean lab and MC-ICP-MS facility, and Vojte ch Janous ek for helpful discussions. Detailed reviews by Jason Harvey, Roberta Rudnick and an anonymous reviewer helped to improve the paper significantly.
F U N DI NG
This research was supported by the projects 205/09/1170, P210/12/1990 and P210/12/0573 (Czech Science Foundation) and the Scientific Programme CEZ: AV0Z30130516 and RVO67985831 of the Institute of Geology v.v.i., Academy of Sciences of the Czech Republic.
SUPPLEMENTARY DATA
Supplementary data for this paper are available at Journal of Petrology online.
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JOURNAL OF PETROLOGY

Journal of Petrology Advance Access published November 5, 2013

Downloaded from http://petrology.oxfordjournals.org/ by guest on November 6, 2013

PRAGUE 6, CZECH REPUBLIC

NCHEN, GERMANY D-80333 MU

RECEIVED JANUARY 29, 2013; ACCEPTED SEPTEMBER 20, 2013

KEY WORDS: peridotite; metasomatism; subcontinental lithosphere; Sr^Nd^Li isotopes; microstructure

*Corresponding author. T elephone: 420-233087240. 420-220922670. E-mail address: ackerman@gli.cas.cz

MANTLE XENOLITHS, NE BAVARIA

MANTLE XENOLITHS, NE BAVARIA

M A N T LE X ENOL I T H S Texture and modal composition

MANTLE XENOLITHS, NE BAVARIA

MANTLE XENOLITHS, NE BAVARIA

Whole-rock major and trace element geochemistry

MANTLE XENOLITHS, NE BAVARIA

MANTLE XENOLITHS, NE BAVARIA

MANTLE XENOLITHS, NE BAVARIA

SiO2 FeO MnO MgO CaO NiO Total Mg#

4126 853 014 4948 001 039 9980 912

4120 876 013 4909 007 035 9960 909

4111 843 010 4948 008 039 9959 913

4095 905 013 4896 008 039 9956 906

4093 900 013 4902 007 039 9954 907

4085 931 015 4894 007 039 9970 904

4124 839 014 4960 008 040 9986 913

4059 952 017 4924 012 038 10002 902

4123 926 014 4942 009 038 10052 907

4118 827 012 4975 008 040 9980 915

SiO2 FeO MnO MgO CaO NiO Total Mg#

4128 872 011 4949 007 039 10007 910

4132 869 014 4928 008 039 9991 910

4135 807 011 4985 009 037 9994 917

4148 944 011 4798 010 035 9946 901

4102 844 011 5007 007 041 10013 914

4097 854 013 5006 001 041 10012 913

4115 889 012 4957 008 042 10024 909

4103 835 012 5013 007 041 10011 915

4130 861 012 4986 008 038 10036 912

4131 831 011 4998 006 041 10027 915

MANTLE XENOLITHS, NE BAVARIA

Trace element geochemistry of clinopyroxene, carbonate and melt

MANTLE XENOLITHS, NE BAVARIA

Sr/86Sr and 143Nd/144Nd variations in clinopyroxene

MANTLE XENOLITHS, NE BAVARIA

10ZIN2 10ZIN5 ZINx2 HIR6

002 50005 50006 50005

129 339 242 91

00004 n.d. n.d. n.d.

0703208 7 0704139 7 0703234 7 0703470 7

011 0095 013 014

0512858 8 0512831 6 0512928 8 0512813 7

DISCUSSION Partial melting in the mantle source of the xenolith samples

MANTLE XENOLITHS, NE BAVARIA

Origin of melt pockets

MANTLE XENOLITHS, NE BAVARIA

T able 8: Whole-rock major and trace element compositions of host basalts

Alkaline and carbonate-rich melt metasomatism

T able 9: Results of K^Ar ages for NE Bavaria volcanic rocks

(cm STP g ) 5454 107 7201 107 8315 107

B-10 B-9 B-11

Zinst Hirschentanz Teichelberg

0658 0782 0963

327 327 379

212 235 221