Riccardo Tribuzio

Rare earth element redistribution during high-pressure–low-temperature metamorphism in ophiolitic Fe-gabbros (Liguria, northwestern Italy): Implications for light REE mobility in subduction zones

To unravel the rare earth element (REE) redistribution during high-pressure–low-temperature metamorphism, we have analyzed by ion microprobe all the minerals from representative Fe-gabbros from Ligurian metaophiolites (northwestern Italy). Contrary to what is observed for fresh Fe-gabbros, the clinopyroxene contribution to the whole-rock REE inventory of blueschists and eclogitized Fe-gabbros is minor or negligible. In both blueschists and eclogites, REE are redistributed among newly formed minerals. In blueschists, lawsonite is the major REE carrier and concentrates almost all the light REE (LREE) in the rock, whereas titanite plays an important role for middle and heavy REE (MREE, HREE). In eclogites, LREE and HREE mainly reside in accessory allanite and garnet, respectively. The development of blueschist and eclogite facies mineral assemblages in mafic oceanic crust, due to subduction to 35–65 km depths, was not accompanied by release of significant amounts of LREE to the overlying mantle wedge. Owing to the stability of lawsonite and epidote at ultra-high-pressure conditions, subduction of mafic rocks is considered an effective mechanism to bring LREE to great depth within the mantle.

The association of continental crust rocks with ophiolites in the Northern Apennines (Italy): implications for the continent-ocean transition in the Western Tethys

Abstract The Late Cretaceous sedimentary melanges from the External Liguride Units of the Northern Apennines include large slide-blocks of ophiolites and lower and upper continental crust rocks representative of a continent-ocean transition between the Internal Liguride oceanic domain and the thinned continental margin of the Adria plate. The slide-blocks preserve a record of the long-lived history of rifting which led to opening of the Jurassic Western Tethys Basin. The External Liguride ophiolites consist of: (1) undepleted spinel-peridoties, partly re-equilibrated under plagioclase-facies conditions, which were interpreted as unroofed subcontinental mantle; (2) rare gabbroic rocks (mainly troctolite to olivine-bearing gabbro) probably crystallised from N-MORB magmas; and (3) basalts with N- to T-MORB affinity covered by late Callovian-early Oxfordian radiolarian cherts. Both gabbroic rocks and basalts locally intrude the mantle peridotites and postdate their re-equilibration to plagioclase-facies conditions. The slide-blocks of lower continental crust are composed of gabbro-derived mafic granulites and felsic granulites. The latter include quartzo-feldspathic granulites and rare quartz-poor to quartz-free charnockitic rocks. In both mafic and felsic granulites, granulite-facies re-equilibration was followed by a retrograde metamorphic evolution to amphibolite-, greenschist- and subgreenschist-facies conditions. Retrogression is commonly accompanied by deformations progressively changing from plastic to brittle. The upper crustal rocks occurring as slide-blocks consist of Hercynian granitoids with orogenic affinity, mainly biotite-bearing granodiorites and peraluminous two-mica leucogranites. Locally, the granitoids are intruded by basaltic dykes or capped by basaltic flows and radiolarian cherts. The granitoids underwent polyphase brittle deformations under subgreenschist-facies conditions which predated the basalt emplacement. The tectono-metamorphic evolution recorded by the slide-blocks of the External Liguride Units started in the Late Carboniferous-Early Permian (about 290 Ma), with the emplacement at deep crustal levels of the gabbroic protoliths for the mafic granulites. The associated felsic granulites likely represent the remnants of the lower continental crust intruded by the gabbro-derived granulites. Mafic and felsic granulites subsequently underwent tectonic exhumation in Permo-Triassic times, as testified by the development of granulite- to amphibolite-facies ductile shear zones. The granulites were finally exhumed to shallow levels, probably in association with the subcontinental mantle, in Late Triassic-Middle Jurassic times. The latter period was most likely characterized by extensive brittle faulting at shallow crustal levels, thus giving rise to extensional allochthons formed by stretched slices of granitoids. The Western Tethys opening is finally testified by the basalt intrusion and effusion in the Late Jurassic, followed by deep-sea pelagic sedimentation. The External Liguride crustal stratigraphy can be regarded as a fossil example of the transitional realm at the continent-ocean boundary. This reconstruction fits well with the available data on the present-day continental margins derived from passive lithosphere stretching.

Origin of titanian pargasite in gabbroic rocks from the Northern Apennine ophiolites (Italy): insights into the late-magmatic evolution of a MOR-type intrusive sequence

Abstract Gabbroic rocks from Northern Apennine ophiolites contain accessory titanian pargasite, in interstices between plagioclase and clinopyroxene, and as rims around interstitial Fe–Ti-oxide phases. The origin of titanian pargasite has been evaluated by combining major, volatile and trace element microanalyses. Titanian pargasites show variable amounts of F and low Cl (0.03–0.23 and ≤0.03 wt%, respectively), and mg# value ranging from 0.78 to 0.70 and from 0.61 to 0.53 in Mg- and Fe-rich rocks, respectively. Geothermometric calculations based on amphibole–plagioclase equilibrium yield temperatures of 900±50°C and 840±50°C for Mg- and Fe-rich rocks, respectively. Titanian pargasites are characterized by LREE depletion, nearly flat HREE and variable negative Eu anomalies. Total REE contents in titanian pargasites are higher and lower than in associated clinopyroxenes and apatites, respectively. In the chondrite-normalized patterns of titanian pargasites, Ba, K and Sr are markedly depleted relative to LREE, whereas Nb, Zr and Ti are slightly enriched to slightly depleted relative to neighboring REE. A separate of titanian pargasite from a Fe-rich gabbroic rock was analyzed for Sr isotopic composition; its initial 87Sr/86Sr falls within the range of modern N-MORB and is consistent with those of fresh Mg-rich gabbroic rocks. Titanian pargasite most likely formed by an igneous liquid with relatively high H2O content (4.4–6.1 wt%) and a slight LREE enrichment. The origin of this liquid has been ascribed to the percolation in the gabbroic crystal mush of a H2O-rich agent of igneous origin, WHICH could be a trondhjemite liquid or an exsolved fluid. Probably, such interaction triggered a post-cumulus crystallization process that finally yielded the precipitation of titanian pargasite.

Evolution of gabbroic rocks of the Northern Apennine ophiolites (Italy): Comparison with the lower oceanic crust from modern slow-spreading ridges

Field and petrographic relationships together with major and trace element mineral chemistry have allowed us to determine the igneous to high-temperature metamorphic evolution of the gabbroic rocks of the Northern Apennine ophiolites. Gabbroic rocks formed by the intrusion of liquids of normal mid-oceanic-ridge (N-MORB) type in a heterogeneous mantle section under low-pressure conditions. These liquids underwent an igneous-differentiation process controlled by fractional crystallization, most likely associated with late percolation in the gabbroic cumulate pile of a volatile-bearing igneous agent, possibly a trondhjemite-type liquid. Such an igneous-differentiation process produced highly evolved liquids that gave rise to Fe-rich rocks (mostly Fe-Ti oxide-bearing diorites). The gabbroic rocks underwent high-temperature (T 900 °C) recrystallization in ductile shear zones in the absence of seawater-derived fluids. The gabbroic rocks of the Northern Apennine ophiolites bear striking similarities to those recovered from modern slow-spreading ridges, such as the Southwest Indian Ridge, the Mid-Atlantic Ridge (at its intersection with the Kane Fracture Zone, i.e., the MARK area), and the Mid-Cayman Rise. The Northern Apennine ophiolites are interpreted to represent a fossil analogue of a magma-poor slow-spreading center that formed as a result of continental lithospheric extension.

Amphibole evolution in Variscan eclogite-amphibolites from the Savona crystalline massif (Western Ligurian Alps, Italy): Controls on the decompressional P-T-t path

Abstract The Variscan metamorphic evolution of eclogite-amphibolites from the Savona Crystalline Massif is marked by the occurence of calcic amphiboles. Microtextural relations together with coupled electron microprobe and X-ray investigations on amphiboles pointed out a complex decompressional evolution. A prograde stage of the evolution in the eclogite facies (temperature conditions estimated as ca. 620°C) is recorded by compositional zoning and inclusions in garnet. The eclogitic event (pressure conditions 12kbar) produced assemblages of garnet, omphacite, Ca-amphibole, zoisite, quartz and rutile. Composition and zoning of matrix eclogitic amphiboles reveal that the subsequent evolution in the eclogite facies contemplates a late re-equilibration under lower conditions of temperature (ca. 540°C) and pressure. The eclogitic amphiboles are pargasitic to edenitic hornblendes, and are marked by rather high Na contents at the M4 site (up to 0.5 apfu). The forming of coarse-grained diopside-plagioclase symplectites and of amphibole-plagioclase coronas represent the early results of the destabilization of omphacites and garnets in the amphibolite facies. Pressure conditions of this stage have been estimated of ca. 10 kbar, while temperature conditions are poorly constrained. However, the increase in edenite (NaAlSi −1 ) at the outermost rims of the matrix eclogitic amphiboles and the very high values of edenite and tschermack (Al 2 Mg −1 Si −1 ) components in the coronitic amphiboles (subsilicic pargasites) suggest that temperature increase accompanied the early decompression to the amphibolite facies. Subsequent retrogression in the low-grade amphibolite facies resulted in the complete breakdown of omphacite, producing finer-grained symplectites. This stage is also recorded by the amphibole growth (magnesio-hornblendes to edenitic hornblendes with negligible Na amounts at the M4 site) at the expense of the clinopyroxene symplectites and as outward rims around the coronitic amphiboles. Frequently, amphibolites are completely recrystallized and do not retain any relic of high pressure assemblages. Temperature conditions for this late amphibolitic event have been estimated of ca. 510°C, while pressure conditions are inferred in the range 4–7 kbar. Such a complicated decompressional evolution is indicative of complex uplift tectonics after a subduction event.

Mafic and ultramafic pods with eclogitic relics from the Proterozoic Nagssugtoqidian mobile belt of East Greenland

Abstract The cores of amphibolitic and ultramafic pods within the basement complex of the Nagssugtoqidian mobile belt of East Greenland preserve metastable relics of older high-pressure assemblages. The bulkrock geochemistry of amphibolites indicates that their protoliths derive from low-pressure crystal fractionation (mainly controlled by plagioclase, pyroxene and olivine) of tholeiitic melts of probable MORB affinity. Amphibolites from the cores of the pods are corona-textured and provide microtextural evidence of a polyphase retrogression subsequent to a high-T eclogitic event, producing omphacite-garnet assemblages. Symplectitic intergrowths of Ca-clinopyroxene and plagioclase are the result of the unmixing of the older omphacite, whilst garnet is partly replaced by a fine-grained pseudomorph of orthopyroxene, anorthitic plagioclase and magnetite. This suggests subsequent partial re-equilibration in the intermediate-pressure granulite facies, producing clinopyroxene-orthopyroxene-plagioclase-magnetite assemblages. The final event in the amphibolite facies was controlled by the influx of dominantly hydrous fluids. According to kinetic constraints, the amphibolites developed coronitic or granoblastic textures. The coronas consist of plagioclase and hornblende between remaining garnet and unmixed clinopyroxene. Re-crystallized granoblastic amphibolites do not retain relics; according to the bulk rock chemistry, plagioclase and hornblende coexist with either garnet or clinopyroxene. Adjacent ultramafic rocks conform with this metamorphic evolution, being retrogressed from the spinel ±amphibole lherzolite facies to the tremolite-chlorite peridotite facies. Estimated equilibrium conditions for the final amphibolite facies event are T = 600 + 70°C and P = 5.2 ± 1 kbar. Mafic and ultramafic pods from the basement complex of the Nagssugtoqidian mobile belt of East Greenland probably represent fragments of an oceanic crust which was subjected to a subduction event of Proterozoic age.

Origin of prismatine from the Sondalo granulites (Central Alps, northern Italy)

A granulite from the Sondalo femic complex, Italian Central Alps, contains prismatine, the boron-rich member of the kornerupine group. This is the first report of prismatine in the Alps. The granulite consists of albite-rich plagioclase + cordierite + sillimanite + rutile + hercynite + corundum + quartz and is interpreted as a restite formed after partial melting of amphibolite-facies tourmaline-bearing metasediments at about 900°C and 0.8 GPa. Prismatine grains, which form a coarse aggregate with tourmaline, biotite and albitic plagioclase, have inclusions of sapphirine, hercynite and corundum. Secondary-ion mass spectrometry (SIMS) analyses on prismatine gives B 2 O 3 = 2.30–2.89 wt.%, Li 2 O = 0.067–0.125 wt.%, BeO = 0.005–0.007 wt. %, F = 0.32–0.49 wt. % and H 2 O = 0.90–1.02 wt.%. The cell parameters a and c and V of the Sondalo prismatine fit with the B 2 O 3 co-variation reported in literature. We propose a mechanism of prismatine formation involving the breakdown of tourmaline during the anatexis of the amphibolite-facies metasediments and the development of prismatine as a refractory phase. No intervention of a metaso-matic boron-rich fluid is required. The possible tourmaline breakdown process is the reaction 7.82 tourmaline + 1.03 biotite + 2.41 sapphirine + 3.22 quartz = 8.00 prismatine + 5.93 melt + 1 B 2 O 3 .

In situ U-Pb geochronology of baddeleyite-zircon pairs using laser-ablation ICPMS: the case-study of quartz gabbro from Varney Nunatak (central Victoria Land, Antarctica)

In situ U-Pb geochronology was carried out by laser-ablation ICPMS on baddeleyite and zircon from a quartz gabbro of the Varney Nunatak intrusion (central Victoria Land, Antarctica). Back-scattered electron images reveal that baddeleyite grains from the investigated rock are partially substituted by zircon. Baddeleyite replacement by zircon is attributed to a late magmatic reaction between early fractionating minerals (plagioclase + sub-ophitic clinopyroxene + ilmenite + baddeleyite) with a silica oversaturated melt enriched in volatiles and incompatible elements. The development of fine-grained aggregates of clinopyroxene + amphibole + ilmenite around sub-ophitic clinopyroxene provides further evidence for this reaction. Homogeneous domains of baddeleyite were analysed by laser-ablation ICPMS and yielded crystallisation ages for the quartz gabbros of 488 ±3 Ma. U-Pb analyses on zircon define a population at 486 ± 6 Ma, coeval with the U-Pb baddeleyite crystallization age, and a population at 525 ± 10 Ma, representing an inherited component. This finding indicates that the parent magma of the quartz gabbro was contaminated with upper crustal rocks. The gabbroic rocks of Varney Nunatak are associated with peraluminous granites and late basalt dykes. The similar whole-rock and clinopyroxene major and trace element concentrations in the quartz gabbros and basalts is suggestive for a genetic relationship. The emplacement age, whole-rock compositions and highly enriched Nd isotope signature (ɛ Nd (488 Ma) of −7.7 to −6.8) of the Varney Nunatak association are similar to those of other igneous units from central Victoria Land. The association developed during the post-collisional phase of the Ross orogeny.

SIMS analysis of REE in pyroxenes and amphiboles from the Proterozoic Ikasaulak intrusive complex (SE Greenland): implications for LREE enrichment processes during post-orogenic plutonism

Abstract Rare-earth and selected trace elements (Ti, Cr, V, Sr and Zr) have been analyzed by secondary ion mass spectrometry (SIMS) in pyroxenes and amphiboles from both the lower and upper zones of the post-orogenic Proterozoic Ikasaulak intrusive complex (Nagssugtoqidian mobile belt of southeast Greenland). The orthopyroxenes from the harzburgites and olivine-orthopyroxenites (lower zone) are LREE-depleted. In contrast. orthopyroxenes from gabbros (the most mafic members of the upper zone) display U-shaped chondrite-normalized patterns and REE contents which increase from core to rim. In the lower zone, clinopyroxene coexists with pargasitic amphibole, both exhibiting unusually high LREE, Sr and Zr contents. In the upper zone, clinopyroxene is less LREE-enriched and is replaced by late- or post-magmatic hornblende. The variations observed in both the major- and trace-element composition of the ferromagnesian phases indicate that the Ikasaulak intrusive complex did not result from a single magma injection. An early injection of magma was responsible for the lower zone and strongly interacted with the country rocks. Fractional crystallization of this magma was probably accompanied by metasomatism effected by highly LREE-enriched hydrous fluids (Ce abundances up to 1300 × chondrite). The most mafic members from the upper zone were derived from a late injection of magma. This magma probably mixed with the residual liquid of the earlier injection, thus retaining the geochemical signature of the contamination processes which had occurred in the lower zone. Mixing and assimilation processes led the pyroxenes to concentrate REE contents higher than those theoretically predicted on the basis of the usual distribution coefficients for basaltic systems. The late growth of hornblende is unrelated to the LREE-enrichment processes. The ion microprobe analyses of the main mafic rock types of the Ikasaulak intrusive complex indicate that: (i) the parental magmas (tholeiites probably marked by a slight LREE-enrichment) were contaminated during the early cumulus processes; (ii) the degree of LREE-enrichment and HFSE (high field strength elements) depletion in parental magmas, as deduced from the whole-rock chemistry, may be overestimated.

Evolution of recycled crust within the mantle: Constraints from the garnet pyroxenites of the External Ligurian ophiolites (northern Apennines, Italy)

The pyroxenite-peridotite sequence from the External Ligurian (northern Apennines, Italy) ophiolites is evidence of the evolution of recycled crust within the mantle. We present new major and trace element and Nd-Hf isotopic compositions of garnet clinopyroxenites and websterites from this mantle section. The garnet clinopyroxenites display clinopyroxene and bulk-rock rare earth element patterns with distinct positive Eu anomalies, which argue for the involvement of plagioclase-rich precursors in their origin. We propose that the garnet clinopyroxenites formed by crystallization of eclogite-derived melts that underwent negligible interaction with the host peridotites. The garnet websterites are interpreted to have been produced by reactions between the eclogite-derived melts and peridotites, thereby giving rise to hybrid, second-stage pyroxenites with a crustal geochemical fingerprint. In our petrogenetic scenario, a rifting-related event at ca. 220 Ma caused melting of eclogites originating from a mid-oceanic ridge basalt–type gabbroic sequence. These mafic protoliths underwent a long-lived evolution of recycling in the mantle (1.5–1.0 Ga). We show that heterogeneity of crustal protoliths, age of recycling, and interaction with the host peridotites may lead to a significant compositional and isotopic diversity of crust-derived mantle pyroxenites.