ALBERT

Notes: The analytical capabilities of laser ablation (LA)-ICP-MS in determining Li, Be and B at trace levels in geological samples have been tested on a series of glass reference materials and natural samples. The LA-ICP-MS instrument used consisted of a sector-field ICP-MS coupled with a laser ablation microprobe operating at either 266 or 213 nm wavelength. Reference glasses from NIST (SRM 612, 614 and 616) and MPI-DING (KL2-G, ML3B-G, StHs6/80-G, GOR128-G, GOR132-G, T1-G and ATHO-G) were selected to develop the analytical method and to assess the best instrumental configuration. A series of calcic amphiboles with different Li, Be and B concentrations were also analysed using both LA-ICP-MS and SIMS to test the applicability of the method to natural minerals. Results indicated that with a spot size of 40 μm the agreement between measured and reference values of Li, Be and B is generally better than 10% for NIST SRM 612 and 20% for NIST SRM 614. Average reproducibility at the 2s level was 10% for Li, 20% for Be and 15% for B. Limits of detection were approximately 100 ng g-1 for Be and B and 200 ng g-1 for Li. These results were confirmed by analyses carried out on natural amphiboles and compared well in terms of precision and accuracy with those commonly achieved by SIMS.

Notes: Abstract The Finero peridotite massif is a harzburgite that suffered a dramatic metasomatic enrichment resulting in the pervasive presence of amphibole and phlogopite and in the sporadic occurrence of apatite and carbonate (dolomite)-bearing domains. Pyroxenite (websterite) dykes also contain phlogopite and amphibole, but are rare. Peridotite bulk-rock composition retained highly depleted major element characteristics, but was enriched in K, Rb, Ba, Sr, LREE (light rare earth elements) (LaN/YbN = 8–17) and depleted in Nb. It has high radiogenic Sr (87Sr/86Sr(270) = 0.7055–0.7093), low radiogenic Nd (ɛNd(270) = −1 to −3) and EMII-like Pb isotopes. Two pyroxenite – peridotite sections examined in detail show the virtual absence of major and trace element gradients in the mineral phases. In both rock types, pyroxenes and olivines have the most unfertile major element composition observed in Ivrea peridotites, spinels are the richest in Cr, and amphibole is pargasite. Clinopyroxenes exhibit LREE-enriched patterns (LaN/YbN ∼16), negative Ti and Zr and generally positive Sr anomaly. Amphibole has similar characteristics, except a weak negative Sr anomaly, but incompatible element concentration ∼1.9 (Sr) to ∼7.9 (Ti) times higher than that of coexisting clinopyroxene. Marked geochemical gradients occur toward apatite and carbonate-bearing domains which are randomly distributed in both the sections examined. In these regions, pyroxenes and amphibole (edenite) are lower in mg## and higher in Na2O, and spinels and phlogopite are richer in Cr2O3. Both the mineral assemblage and the incompatible trace element characteristics of the mineral phases recall the typical signatures of “carbonatite” metasomatism (HFSE depletion, Sr, LILE and LREE enrichment). Clinopyroxene has higher REE and Sr concentrations than amphibole (amph/cpxDREE,Sr = 0.7–0.9) and lower Ti and Zr concentrations. It is proposed that the petrographic and geochemical features observed at Finero are consistent with a subduction environment. The lack of chemical gradients between pyroxenite and peridotite is explained by a model where melts derived from an eclogite-facies slab infiltrate the overhanging harzburgitic mantle wedge and, because of the special thermal structure of subduction zones, become heated to the temperature of the peridotite. If the resulting temperature is above that of the incipient melting of the hydrous peridotite system, the slab-derived melt equilibrates with the harzburgite and a crystal mush consisting of harzburgite and a silica saturated, hydrous melt is formed. During cooling, the crystal mush crystallizes producing the observed sequence of mineral phases and their observed chemical characteristics. In this context pyroxenites are regions of higher concentration of the melt in equilibrium with the harzburgite and not passage-ways through which exotic melts percolated. Only negligible chemical gradients can appear as an effect of the crystallization process, which also accounts for the high amphibole/clinopyroxene incompatible trace element ratios. The major element refractory composition is explained by an initially high peridotite/melt ratio. The apatite, carbonate-bearing domains are the result of the presence of some CO2 in the slab-derived melt. The CO2/H2O ratio in the peridotite mush increased by crystallization of hydrous phases (amphibole and phlogopite) locally resulting in the unmixing of a late carbonate fluid. The proposed scenario is consistent with subduction of probably Variscan age and with the occurrence of modal metasomatism before peridotite incorporation in the crust.

Notes: Abstract Spinel–peridotite facies mantle xenoliths in Cenozoic alkali basalts of the Pico Cabuji volcano (Rio Grande do Norte State, Northeast Brazil) and the adjacent South Atlantic oceanic island of Fernando de Noronha are studied for: (1) the information they provide on the composition of the lithospheric component in the erupted basalt geochemistry, and (2) to check the effects of the Fernando de Noronha plume track on the mantle lithosphere. Xenoliths from Pico Cabuji are protogranular lherzolites and porphyroclastic harzburgites recording average equilibrium temperatures of 825 ± 116 and 1248 ± 19 °C, respectively. Pressure in the porphyroclastic xenoliths ranges from 1.9 to 2.7 GPa (Ca-in-olivine geobarometer). Both groups show major element chemical variation trends in whole-rock and Ti and HREE (Er, Yb) variations in clinopyroxene consistent with fractional melting and basalt extraction. REE (rare earth element) profiles of clinopyroxenes vary from LREE (La, Ce) enriched (spoon shaped) to LREE depleted in the protogranular group, whereas they are slightly convex upward in most porphyroclastic clinopyroxenes. HFSE (Ti and Zr) negative anomalies are in general modest in the clinopyroxenes of both groups. Xenoliths from Fernando de Noronha have textural variations similar to those of Pico Cabuji. Protogranular and porphyroclastic samples have similar temperature (1035 ± 80 °C) and the pressure is 1–1.9 and 2.3 GPa, respectively. Whole-rock chemical variation trends overlap and extend further than those of Pico Cabuji. The trace element profiles of the clinopyroxenes of the porphyroclastic xenoliths are enriched in La up to 30 × PM and are smoothly fractionated from LREE to HREE, with deep, negative, Zr and Ti anomalies. The geochemical heterogeneities of the xenoliths from both localities are interpreted in terms of reactive porous percolation. The porphyroclastic xenoliths from Pico Cabuji represent the lower part of a mantle column (the head of a mantle diapir, at the transition conductive–adiabatic mantle), where OIB infiltration triggers melting, and the protogranular xenoliths the top of the mantle column, chromatographically enriched by percolation at a low melt/rock ratio. This interpretation may also apply for Fernando de Noronha, but the different geochemical signature recorded by the clinopyroxenes requires a different composition of the infiltrated melt. Nd and Sr isotopes of the Pico Cabuji porphyroclastic clinopyroxenes (143Nd/144Nd= 0.51339–0.51255, 87Sr/86Sr=0.70275–0.70319) and of Fernando de Noronha (143Nd/144Nd=0.51323–0.51285, 87Sr/86Sr=0.70323–0.70465) plot on distinct arrays originating from a similar, isotopically depleted composition and trending to low Nd–low Sr (EMI) and low Nd–high Sr (EMII), respectively. Correlation of the isotope variation with geochemical parameters indicates that the isotopic variation was induced by the metasomatic component, of EMI type at Pico Cabuji and of EMII type at Fernando de Noronha. These different components enriched a lithosphere isotopically similar to DMM (depleted MORB mantle) at both localities. At Fernando de Noronha, the isotopic signature of the metasomatic component is similar to that of the ∼ 8 Ma old lavas of the Remedios Formation, suggesting that this is the age of metasomatism. At Pico Cabuji, the mantle xenoliths do not record the high 87Sr/86Sr component present in the basalts. We speculate that the EMII component derives from a lithospheric reservoir, which was not thermally affected during mantle metasomatism at Pico Cabuji, but was mobilized by the hotspot thermal influence at Fernando de Noronha. This interpretation provides a plausible explanation for the presence of distinct metasomatic components at the two localities, which would be difficult to reconcile with their genetic relationship with the same plume.

Notes: Abstract SIMS analyses have been carried out on clinopyroxenes, plagioclases and amphiboles of six gabbroic samples from Holes 921–924 of the Ocean Drilling Program Leg 153 sited in the MARK area of the Mid-Atlantic Ridge at the ridge–transform intersection, to investigate the rare earth, trace and volatile element distribution in the lower ocean crust during igneous crystallization and higher grade metamorphic conditions. The metagabbros underwent granulite to subgreenschist facies conditions through three main tectono-metamorphic phases: (1) ductile regime (750 〈 T 〈 1000 °C and P ≈ 0.3 GPa); (2) transitional regime (600 〈 T 〈 700 °C and P ≈ 0.2 GPa); (3) brittle regime (350 ≤ T 〈 600 °C and P 〈 0.2 GPa). Igneous clinopyroxenes show C1-chondrite normalized patterns depleted in LREE, and nearly flat for HREE. The rare earth and trace element distributions in igneous clinopyroxenes and plagioclases indicate that these minerals act as REE reservoirs, and comprise the main contribution to the overall rock content. The abundances in igneous minerals reflect the degree of fractionation of the parent liquids. In metamorphic clinopyroxenes recrystallized in anhydrous assemblages, the REE and trace elements patterns mimic those of the primary ones. Conversely, clinopyroxene re-equilibrated in amphibole-bearing assemblages shows a significant increase in REE, Ti, Zr, Y and V, a negative Eu anomaly, and slight decreases in Sr and Ba. An overall increase of REE and some trace elements is evident in hydrous assemblages, with preferential partitioning in the amphibole. It shows high Ti (18196–22844 ppm), LREE depleted patterns and LaN/SmN=0.10–0.33, LaN/YbN=0.10–0.30. Amphiboles from granoblastic assemblages show homogeneous patterns with no or a positive anomaly for TiN and negative anomalies for SrN and ZrN. Volatiles in amphibole are low, with Cl/F 〈 1; H2O% is significantly lower than the stoichiometric ratio (1.33–1.53%). The composition of the clinopyroxene and amphibole recrystallized in low-strain domains records evidence of incomplete re-equilibration, and element diffusion and partitioning is in part controlled by the textural site. The possible origins of the fluids involved in the metamorphic recrystallization are discussed: (1) remobilization from igneous amphibole; (2) exsolution from evolved melts; (3) introduction of seawater-derived fluids modified in rock-dominated systems; (4) injection of highly evolved hydrous melts during the metamorphic process.