Carlos J. Garrido

Unraveling the sequence of serpentinization reactions: petrography, mineral chemistry, and petrophysics of serpentinites from MAR 15°N (ODP Leg 209, Site 1274)

[1] The results of detailed textural, mineral chemical, and petrophysical studies shed new light on the poorly constrained fluid-rock reaction pathways during retrograde serpentinization at mid-ocean ridges. Uniformly depleted harzburgites and dunites from the Mid-Atlantic Ridge at 15� N show variable extents of static serpentinization. They reveal a simple sequence of reactions: serpentinization of olivine and development of a typical mesh texture with serpentine-brucite mesh rims, followed by replacement of olivine mesh centers by serpentine and brucite. The serpentine mesh rims on relic olivine are devoid of magnetite. Conversely, domains in the rock that are completely serpentinized show abundant magnetite. We propose that low-fluid-flux serpentinization of olivine to serpentine and ferroan brucite is followed by later stages of serpentinization under more open-system conditions and formation of magnetite by the breakdown of ferroan brucite. Modeling of this sequence of reactions can account for covariations in magnetic susceptibility and grain density of the rocks. Citation: Bach, W., H. Paulick, C. J. Garrido, B. Ildefonse, W. P. Meurer, and S. E. Humphris (2006), Unraveling the sequence of serpentinization reactions: petrography, mineral chemistry, and petrophysics of serpentinites from MAR 15� N (ODP Leg 209, Site 1274), Geophys. Res. Lett., 33, L13306,

Hydrothermal alteration and microbial sulfate reduction in peridotite and gabbro exposed by detachment faulting at the Mid-Atlantic Ridge, 15°20′N (ODP Leg 209): A sulfur and oxygen isotope study

Whole rock sulfur and oxygen isotope compositions of altered peridotites and gabbros from near the 15°20′N Fracture Zone on the Mid-Atlantic Ridge were analyzed to investigate hydrothermal alteration processes and test for a subsurface biosphere in oceanic basement. Three processes are identified. (1) High-temperature hydrothermal alteration (∼250–350°C) at Sites 1268 and 1271 is characterized by 18O depletion (2.6–4.4‰), elevated sulfide-S, and high δ34S (up to ∼2 wt% and 4.4–10.8‰). Fluids were derived from high-temperature (>350°C) reaction of seawater with gabbro at depth. These cores contain gabbroic rocks, suggesting that associated heat may influence serpentinization. (2) Low-temperature (<150°C) serpentinization at Sites 1272 and 1274 is characterized by elevated δ18O (up to 8.1‰), high sulfide-S (up to ∼3000 ppm), and negative δ34S (to −32.1‰) that reflect microbial reduction of seawater sulfate. These holes penetrate faults at depth, suggesting links between faulting and temperatures of serpentinization. (3) Late low-temperature oxidation of sulfide minerals caused loss of sulfur from rocks close to the seafloor. Sulfate at all sites contains a component of oxidized sulfide minerals. Low δ34S of sulfate may result from kinetic isotope fractionation during oxidation or may indicate readily oxidized low-δ34S sulfide derived from microbial sulfate reduction. Results show that peridotite alteration may be commonly affected by fluids ± heat derived from mafic intrusions and that microbial sulfate reduction is widespread in mantle exposed at the seafloor.

Seismic properties of an asthenospherized lithospheric mantle: constraints from lattice preferred orientations in peridotite from the Ronda massif

Above a mantle plume, the lithosphere is thermally ‘eroded’. It is however not clear whether heating and partial melting of the lithosphere may erase the mineral lattice preferred orientation (LPO) inherited from previous tectonic events or if, in the absence of large-scale flow, this fabric is preserved. To evaluate the effect of heating and partial melting on the seismic properties of the lithospheric mantle, we have measured the LPO and computed the seismic properties of peridotites from the Ronda massif (Spain). In this massif, a narrow (9 400 m) coarsening front separates a porphyroclastic peridotite domain, interpreted as old lithospheric mantle, from a coarse-granular peridotite domain produced by annealing and limited partial melting (6 6.5%) of the porphyroclastic peridotites. The olivine LPO in the porphyroclastic peridotites is moderate. The [100] and [001] axes are distributed within the foliation with a maximum of [100] parallel to the lineation, and the [010] axes are concentrated close to the normal to the foliation. The olivine LPO does not vary drastically across the coarsening front: the LPO strength decreases slightly and symmetry of the pattern progressively turns more orthorhombic. On the other hand, the strength of the orthopyroxene LPO increases. The consistency of olivine LPO translates to similar seismic properties of peridotites in the two domains. Especially, the anisotropy of both compressional and shear waves (P- and S-waves) remains almost unchanged across the entire massif. These results support that heating and partial melting (asthenospherization) of the lithospheric mantle do not necessarily obliterate the minerals LPO inherited from previous tectonic events. The ‘structural memory’ of the lithosphere may therefore be preserved even in the ‘asthenospherized’ mantle. In a region of asthenosphere^lithosphere interaction, tomography studies would indicate a largely attenuated lithosphere from the presence of a shallow lowvelocity anomaly while S-wave splitting measurement yields delays between arrivals of the fast and slow split waves requiring a larger lithosphere thickness. This apparent discrepancy may be resolved considering the existence of a ‘ghost lithosphere’ having lithospheric characteristics regarding anisotropy studies and asthenospheric properties regarding seismic waves velocities. fl 2001 Elsevier Science B.V. All rights reserved.

Garnet lherzolite and garnet-spinel mylonite in the Ronda peridotite: Vestiges of Oligocene backarc mantle lithospheric extension in the western Mediterranean

Uplift and exhumation of vast exposures of diamond facies, subcontinental mantle peridotite in the Western Mediterranean arc are attributed to tectonic scenarios including pure extension, transpression or subduction followed by delamination-driven or rollback-driven stretching. In the Ronda peridotite (southern Spain) the strong overprint of low-pressure assemblages has precluded accurate determination of the pressure and temperature conditions for the onset of exhumation that formed the spinel tectonite and garnet-spinel mylonite domain in this massif. Here we report unequivocal petrographic evidence for the existence of prekinematic, coarse-grained garnet lherzolite assemblages from the garnet-spinel mylonite domain of the Ronda peridotite. Application of well-calibrated geothermobarometers yields prekinematic minimum equilibration conditions of 2.4–2.7 GPa and 1020–1100 °C, demonstrating that the Ronda peridotite equilibrated at ∼85 km depth before shearing. We also show the existence of synkinematic garnet and spinel assemblages that overprinted garnet lherzolite assemblages at 800–900 °C and 1.95–2.00 GPa. The decompressional cooling path and high pressure recorded by garnet-spinel mylonites rule out their formation by near-isobaric cooling above a subduction-collision wedge or during or after the emplacement of the peridotite massif into the crust. Ronda garnet-spinel mylonites represent the vestiges of subcontinental mantle ductile shear zones formed at early stages of lithosphere extension during backarc extension in the western Mediterranean. Southward to westward retreat of the African slab during the Oligocene-Early Miocene accounts for intense backarc lithosphere extension and development of the Ronda extensional shear zone, coeval with extreme thinning of the Alboran domain overlying crust.

Origin of the island arc Moho transition zone via melt-rock reaction and its implications for intracrustal differentiation of island arcs: Evidence from the Jijal complex (Kohistan complex, northern Pakistan)

If the net fl ux to the island arc crust is primitive arc basalt, the evolved composition of most arc magmas entails the formation of complementary thick ultramafi c keels at the root of the island arc crust. Dunite, wehrlite, and Cr-rich pyroxenite from the Jijal complex, constituting the Moho transition zone of the Kohistan paleo‐island arc (northern Pakistan), are often mentioned as an example of high-pressure cumulates formed by intracrustal fractionation of mantle-derived melts, which were later extracted to form the overlying mafi c crust. Here we show that calculated liquids for Jijal pyroxenites-wehrlites are strongly rare earth element (REE) depleted and display fl at or convex-upward REE patterns. These patterns are typical of boninites and are therefore unlike those of the overlying mafi c crust that have higher REE concentrations and are derived from light rare earth element (LREE)‐enriched melts similar to island arc basalt. This observation, along with the lower 208 Pb/ 204 Pb and 206 Pb/ 204 Pb ratios of Jijal pyroxenites-wehrlites relative to gabbros, rejects the hypothesis that gabbros and ultramafi c rocks derive from a common melt via crystal fractionation. In the 208 Pb/ 204 Pb versus 206 Pb/ 204 Pb diagram, ultramafi c rocks and gabbros lie on the same positive correlation, suggesting that their sources share a common enriched mantle 2 (EM2) signature but with a major depleted component contribution for the ultramafi c rocks. These data are consistent with a scenario whereby the Jijal ultramafi c section represents a Moho transition zone formed via melt-rock reaction between subarc mantle and incoming melt isotopically akin to Jijal gabbroic rocks. The lack in the Kohistan arc of cogenetic ultramafi c cumulates complementary to the evolved mafi c plutonic rocks implies either (1) that a substantial volume of such ultramafi c cumulates was delaminated or torn out by subcrustal mantle fl ow from the base of the arc crust in extraordinarily short time scales (0.10‐0.35 cm/yr), or (2) that the net fl ux to the Kohistan arc crust was more evolved than primitive arc basalt.

Primitive Cretaceous island-arc volcanic rocks in eastern Cuba: the Téneme Formation

The Teneme Formation is located in the Mayari-Cristal ophiolitic massif and represents one of the three Cretaceous volcanic Formations established in northeastern Cuba. Teneme volcanics are cut by small bodies of 89.70 ± 0.50 Ma quarz-diorite rocks (Rio Grande intrusive), and are overthrusted by serpentinized ultramafics. Teneme volcanic rocks are mainly basalts, basaltic andesites, andesites, and minor dacites, and their geochemical signature varies between low-Ti island arc tholeiites (IAT) with boninitic affinity (TiO2 < 0.4 %; high field strength elements << N-type MORB) and typical oceanic arc tholeiites (TiO2 = 0.5-0.8 %). Basaltic rocks exhibit low light REE/Yb ratios (La/Yb < 5), typical of intraoceanic arcs and are comparable to Maimon Formation in Dominican Republic (IAT, pre Albian) and Puerto Rican lavas of volcanic phase I (island arc tholeiites, Aptian to Early Albian). The mantle wedge signature of the Teneme Formation indicates a highly depleted MORB-type mantle source, without any contribution of E-MORB or OIB components. Our results suggest that Teneme volcanism represents a primitive oceanic island arc environment. If the Late Cretaceous age (Turonian or early Coniacian) proposed for Teneme Formation is correct, our results indicate that the Cretaceous volcanic rocks of eastern Cuba and the Dominican Republic are not segments of a single arc system, and that in Late Cretaceous (Albian-Campanian) Caribbean island arc development is not represented only by calc-alkaline (CA) volcanic rocks as has been suggested in previous works.

Backarc basin inversion and subcontinental mantle emplacement in the crust: kilometre-scale folding and shearing at the base of the proto-Alborán lithospheric mantle (Betic Cordillera, southern Spain)

To constrain the latest evolutionary stages and mechanisms of exhumation and emplacement of subcontinental peridotites in the westernmost Mediterranean, we present here a detailed structural study of the transition from granular spinel peridotite to plagioclase tectonite in the western Ronda Peridotite (Betic Cordillera, southern Spain). We show that the plagioclase tectonite foliation represents an axial surface particularly well developed in the reverse limb of a downward facing moderately plunging and moderately inclined synform at the base of the Ronda massif. The fold limbs are cut by several mylonitic and ultramylonitic shear zones with top-to-the-SW sense of shear. After restoring the middle to late Miocene vertical-axis palaeomagnetic rotation and the early Miocene tectonic tilting of the massif, these studied structures record southward-directed kinematics. We propose a geodynamic model in which folding and shearing of an attenuated mantle lithosphere occurred by backarc basin inversion during late Oligocene (23–25 Ma) southward collision of the Alborán Domain with the palaeo-Maghrebian passive margin, leading to the intracrustal emplacement of peridotites in the earliest Miocene (21–23 Ma).

A Late Oligocene Suprasubduction Setting in the Westernmost Mediterranean Revealed by Intrusive Pyroxenite Dikes in the Ronda Peridotite (Southern Spain)

Contrasting tectonic reconstructions of the westernmost Mediterranean have been proposed to explain the origin of the Alboran marine basin contemporaneously with Cenozoic convergence between the African and European plates. Cr-rich pyroxenites in the Ronda massif record the geochemical processes occurring in the subcontinental mantle of the Alboran domain in the Late Oligocene, thus constraining the geodynamic scenario of Cenozoic extension in the western Mediterranean lithosphere. Clinopyroxene in intrusive Cr-rich websterite dikes crosscutting the Ronda peridotite is strongly depleted in Nb-Ta and enriched in light rare earth elements, as typically observed in arc magmas, and is in trace element equilibrium with Neogene subduction-related lavas from the western and central Mediterranean. Sr-Nd-Pb radiogenic isotopes indicate that the mantle source of the Ronda pyroxenite dikes was contaminated by a subduction component released by detrital sediments likely deposited in passive continental margins. Rather than convective removal or delamination of the lithospheric root, our data strongly support Alboran geodynamic models that envisage slab rollback as the tectonic mechanism responsible for the Miocene lithospheric thinning. The Ronda Cr-rich pyroxenite dikes represent the earliest unambiguous manifestation of subduction-related magmatism in the western Mediterranean and testify to the involvement of terrigenous sediments in the primitive stages of subduction.

The architecture of the European-Mediterranean lithosphere: A synthesis of the Re-Os evidence

Rhenium-depletion model ages ( T RD ) of sulfides in peridotite xenoliths from the subcontinental mantle beneath central Spain (the Calatrava volcanic field) reveal that episodes of mantle magmatism and/or metasomatism in the Iberia microplate were linked to crustal growth events, mainly during supercontinent assembly and/or breakup at ca. 1.8, 1.1, 0.9, 0.6, and 0.3 Ga. A synthesis of available in situ and whole-rock Os-isotope data on mantle-derived peridotites shows that this type of mantle (maximum T RD of ca. 1.8 Ga) is widespread in the subcontinental mantle of Europe and Africa outboard from the Betics-Maghrebides-Appenines front. In contrast, the mantle enclosed within the Alpine domain records T RD as old as 2.6 Ga, revealing a previously unrecognized Archean domain or domains in the central and western Mediterranean. Our observations indicate that ancient fragments of subcontinental lithospheric mantle have played an important role in the development of the present architecture of the Mediterranean lithosphere.

Combined microstructural and mineralogical phase characterization of gallstones in a patient-based study in SW Spain - Implications for environmental contamination in their formation

This study explores the environmental impact of metal exposure on humans through detailed phase and structural characterization of gallstones from two environmentally contrasting populations in Huelva Province (SW Spain). A total of 42 gallstone samples, obtained after surgical intervention at the Riotinto Hospital, were studied by powder X-ray diffraction (XRD), Fourier Transformed Infra-Red spectroscopy (FTIR), FTIR-μ-ATR (Attenuated Total Reflection) coupled with an optical microscope, and by Environmental Scanning Electron Microscope with Energy Dispersive X-ray Spectroscopy (ESEM-EDS), and subsequently classified according to their phase composition and structure. Additionally, the patients were enquired for their living habits in order to analyze the source of possible exposure to metal contamination. The gallstones were classified into pure, mixed and composite cholesterol stones, black and brown pigment stones, and carbonate stones. The patients from the study group residing in a region with acknowledged metal contamination of both natural and anthropogenic origin have a higher risk of metal exposure through contaminated soil, particle matter in the air, and consumption of local water and food products. According to our findings, the metal exposure is related to a higher tendency of forming black pigment stones in the study group in comparison to the control group residing in a natural park with nearly pristine environmental conditions. Moreover, the gallstones from the study group showed to contain more abundant metal components, such as Cu, Fe, Ni, and Zn, than those from the control group. To our knowledge this is the first study to examine the regional environmental impact of metal exposure on human gallstones.