Fe-Ni-Co-O-S Phase Relations in Peridotite-Seawater Interactions

Serpentinization of abyssal peridotites is known to produceextremely reducing conditions as a result of dihydrogen (H₂,aq)release upon oxidation of ferrous iron in primary phases toferric iron in secondary minerals by H₂O. We have compiled andevaluated thermodynamic data for Fe–Ni–Co–O–Sphases and computed phase relations in fO₂,g–fS₂,g andaH₂,aq–aH₂S,aq diagrams for temperatures between 150 and400°C at 50 MPa. We use the relations and compositions ofFe–Ni–Co–O–S phases to trace changesin oxygen and sulfur fugacities during progressive serpentinizationand steatitization of peridotites from the Mid-Atlantic Ridgein the 15°20'N Fracture Zone area (Ocean Drilling ProgramLeg 209). Petrographic observations suggest a systematic changefrom awaruite–magnetite–pentlandite and heazlewoodite–magnetite–pentlanditeassemblages forming in the early stages of serpentinizationto millerite–pyrite–polydymite-dominated assemblagesin steatized rocks. Awaruite is observed in all brucite-bearingpartly serpentinized rocks. Apparently, buffering of silicaactivities to low values by the presence of brucite facilitatesthe formation of large amounts of hydrogen, which leads to theformation of awaruite. Associated with the prominent desulfurizationof pentlandite, sulfide is removed from the rock during theinitial stage of serpentinization. In contrast, steatitizationindicates increased silica activities and that high-sulfur-fugacitysulfides, such as polydymite and pyrite–vaesite solidsolution, form as the reducing capacity of the peridotite isexhausted and H₂ activities drop. Under these conditions, sulfideswill not desulfurize but precipitate and the sulfur contentof the rock increases. The co-evolution of fO₂,g–fS₂,gin the system follows an isopotential of H₂S,aq, indicatingthat H₂S in vent fluids is buffered. In contrast, H₂ in ventfluids is not buffered by Fe–Ni–Co–O–Sphases, which merely monitor the evolution of H₂ activitiesin the fluids in the course of progressive rock alteration.The co-occurrence of pentlandite–awaruite–magnetiteindicates H₂,aq activities in the interacting fluids near thestability limit of water. The presence of a hydrogen gas phasewould add to the catalyzing capacity of awaruite and would facilitatethe abiotic formation of organic compounds. KEY WORDS: serpentinization; ODP Expedition 209; sulfide; oxygen fugacity; sulfur fugacity; hydrothermal system; metasomatism; Mid-Atlantic Ridge     

Zircon Hf isotope perspective on the origin of granitic rocks from eastern Bavaria, SW Bohemian Massif

The petrogenetic potential of in situ laser ablation Hf isotope data from melt precipitated zircons was explored through the analyses of about 700 individual crystals derived from about 20 different granitic intrusions covering the Variscan basement segment of eastern Bavaria, SE Germany. In combination with geochemical features, four major suites of granitic rocks can be distinguished: (1) NE Bavarian redwitzites (52–57 wt% SiO₂, intrusion ages around 323 Ma) have chondritic εHf(t) values (+0.8 to –0.4). The redwitzites are hybrid rocks and the Hf data are permissive of mixing of a mantle progenitor and crustal melts. (2) Various intermediate rock types (dioritic dyke, granodiorite, palite, 59–63 wt% SiO₂, 334–320 Ma) from the Bavarian Forest yield negative εHf(t) values between –3.4 and –5.1. These values which apparently contradict a mantle contribution fingerprint an enriched (metasomatized) mantle component that was mixed with crustal material. (3) Voluminous, major crust forming granites sensu stricto (67–75 wt% SiO₂, 328–298 Ma) are characterized by a range in εHf(t) values from –0.5 to –5.6. Different crustal sources and/or modification of crustal melts by various input of juvenile material can explain this variation. (4) Post-plutonic (c. 299 Ma) porphyritic dykes of dacitic composition (64–67 wt% SiO₂) from the southern Bavarian Forest have chondritic εHf(t) values (+0.6 to –1.1) and display large intergrain Hf isotope variation. The dykes form a separate petrogenetic group and the Hf data suggest that the zircons crystallized when a pristine mantle-derived parental melt was modified by infiltration of crustal material. The zircon Hf data form a largely coherent positive array with the whole-rock Nd data and both systems yield similar two-stage depleted mantle model ages (1.1–1.7 Ga).     

Reflectance anisotropy and syn-deformational coalification of the Jewel seam in the Cadomin area, Alberta, Canada

The Jewel seam of the Cadomin area is complexly folded and cut by several thrust faults. Vitrinite reflectance anisotropy was determined from twenty oriented coal blocks, collected from various structural positions. Five of the blocks have uniaxial anisotropies, five have biaxial positive anisotropies, the remaining ten are biaxial negative. The biaxial coals display maximum reflectance axes parallel to nearby fold axes, which suggests a relationship between vitrinite anisotropy and deformation. The biaxial vitrinite reflectance ellipsoids result from superposition of tectonic strains on a primary, sedimentary burial related, uniaxial anisotropy. A tectonic stress field was probably present during the later stages of sedimentary burial and subsequent deformation.Coalification resulted largely from pre-deformational, sedimentary burial, but the final coalification stage was syn-deformational, as illustrated by the intersection of isorank surfaces and the Jewel seam and the biaxial vitrinite reflectance anisotropy.     

Geochemical constraints on the modes of carbonate precipitation in peridotites from the Logatchev Hydrothermal Vent Field and Gakkel Ridge

The ultramafic-hosted Logatchev Hydrothermal Field (LHF) at 15°N on the Mid-Atlantic Ridge and the Arctic Gakkel Ridge (GR) feature carbonate precipitates (aragonite, calcite, and dolomite) in voids and fractures within different types of host rocks. We present chemical and Sr isotopic compositions of these different carbonates to examine the conditions that led to their formation. Our data reveal that different processes have led to the precipitation of carbonates in the various settings. Seawater-like ⁸⁷Sr/⁸⁶Sr ratios for aragonite in serpentinites (0.70909 to 0.70917) from the LHF are similar to those of aragonite from the GR (0.70912 to 0.70917) and indicate aragonite precipitation from seawater at ambient conditions at both sites. Aragonite veins in sulfide breccias from LHF also have seawater-like Sr isotope compositions (0.70909 to 0.70915), however, their rare earth element (REE) patterns show a clear positive europium (Eu) anomaly indicative of a small (< 1%) hydrothermal contribution. In contrast to aragonite, dolomite from the LHF has precipitated at much higher temperatures (~ 100 °C), and yet its ⁸⁷Sr/⁸⁶Sr ratios (0.70896 to 0.70907) are only slightly lower than those of aragonite. Even higher temperatures are calculated for the precipitation of deformed calcite veins in serpentine–talc fault schists form north of the LHF. These calcites show unradiogenic ⁸⁷Sr/⁸⁶Sr ratios (0.70460 to 0.70499) indicative of precipitation from evolved hydrothermal fluids. A simple mixing model based on Sr mass balance and enthalpy conservation indicates strongly variable conditions of fluid mixing and heat transfers involved in carbonate formation. Dolomite precipitated from a mixture of 97% seawater and 3% hydrothermal fluid that should have had a temperature of approximately 14 °C assuming that no heat was transferred. The much higher apparent precipitation temperatures based on oxygen isotopes (~ 100 °C) may be indicative of conductive heating, probably of seawater prior to mixing. The hydrothermal calcite in the fault schist has precipitated from a mixture of 67% hydrothermal fluid and 33% seawater, which should have had an isenthalpic mixing temperature of ~ 250 °C. The significantly lower temperatures calculated from oxygen isotopes are likely due to conductive cooling of hydrothermal fluid discharging along faults. Rare earth element patterns corroborate the results of the mixing model, since the hydrothermal calcite, which formed from waters with the greatest hydrothermal contribution, has REE patterns that closely resemble those of vent fluids from the LHF. Our results demonstrate, for the first time, that (1) precipitation from pure seawater, (2) conductive heating of seawater, and (3) conductive cooling of hydrothermal fluids in the sub-seafloor all can lead to carbonate precipitation within a single ultramafic-hosted hydrothermal system.     

The DAV and Periadriatic fault systems in the Eastern Alps south of the Tauern window

Alpine deformation of Austroalpine units south of the Tauern window is dominated by two kinematic regimes. Prior to intrusion of the main Periadriatic plutons at ~30 Ma, the shear sense was sinistral in the current orientation, with a minor north-side-up component. Sinistral shearing locally overprints contact metamorphic porphyroblasts and early Periadriatic dykes. Direct Rb-Sr dating of microsampled synkinematic muscovite gave ages in the range 33-30 Ma, whereas pseudotachylyte locally crosscutting the mylonitic foliation gave an interpreted ⁴⁰Ar-³⁹Ar age of ~46 Ma. The transition from sinistral to dextral (transpressive) kinematics related to the Periadriatic fault occurred rapidly, between solidification of the earlier dykes and of the main plutons. Subsequent brittle-ductile to brittle faults are compatible with N-S to NNW-SSE shortening and orogen-parallel extension. Antithetic Riedel shears are distinguished from the previous sinistral fabric by their fine-grained quartz microstructures, with local pseudotachylyte formation. One such pseudotachylyte from Speikboden gave a ⁴⁰Ar-³⁹Ar age of 20 Ma, consistent with pseudotachylyte ages related to the Periadriatic fault. The magnitude of dextral offset on the Periadriatic fault cannot be directly estimated. However, the jump in zircon and apatite fission-track ages establishes that the relative vertical displacement was ~4-5 km since 24 Ma, and that movement continued until at least 13 Ma.     

Jurassic and Cretaceous rhyncholites (Cephalopod jaws) from the North Atlantic Ocean (Deep Sea Drilling Project Leg 1–79) and their European Counterparts

Well-established species of non-nautilid jaws (Rhynchoteuthis, Palaeoteuthis, andLeptocheilus) from the European Continent and North Africa have been found in Pliensbachian and Oxfordian to Barremian beds of the North Atlantic Ocean (Deep Sea Drilling Project boreholes 1-547B). The rhyncholites from DSDP cores demonstrate stratigraphic condensation, redeposition, and changing palaeoceanographical conditions during the late Jurassic. Being characteristic Tethyan organisms such rhyncholites can also be used as index fossils and indicators for palaeobiogeography, palaeobathymetry, and palaeoclimate. Most likely the rhyncholites described here could be calcified upper jaws of Phylloceratid or Lytoceratid ammonites.

---

Zusammenfassung In den DSDP-Bohrungen 1-547B im Nordatlantik sind nicht-nautilide Cephalopoden-Oberkiefer bekannter Arten des europäischen Festlands (Rhynchoteuthis, Palaeoteuthis, Palaeotheutis, undLeptocheilus) im Pliensbachium und vom Oxfordium bis Barremium verbreitet. Die DSDP-Rhyncholithenfunde zeigen stratigraphische Kondensation, Umlagerung und einen Wechsel in den Faziesbedingungen während des Oberen Jura an. Ebenso können solche Rhyncholithen als charakteristische Tethys-Elemente für Aussagen über die Biostratigraphie, Paläobiogeographie und als Paläoklima-Indikatoren verwendet werden. Höchstwahrscheinlich stellen die hier beschriebenen Rhyncholithen karbonatische Oberkiefer von Phylloceraten und Lytoceraten dar.

---

Résumé Les couches du Pliensbachien et de l'Oxfordien-Barrémien de l'Atlantique nord (site DSDP 1-547B) renferment des machoires de céphalopodes non nautiloïdes appartenant à des espèces connues sur les continents européen et nord-africain (Rhynchoteuthis, Palaeoteuthis, Palaeotheutis etLeptocheilus). Ces fossiles témoignent d'une condensation stratigraphique, d'un remaniement et d'un changement des conditions de facies au cours du Jurassique supérieur. Comme ces rhyncholites sont des organismes caractéristiques de la Téthys, ils peuvent être utilisés comme des indicateurs de paléobiogéographie, de paléobathymétrie et des paléoclimats. Selon toute vraisemblance, les rhyncholites en question ici sont des machoires supérieures calcifiées de phylloceratides ou de lytoceratides.

---

1–547 DSDP , (Rhynchoteuthis, Palaeoteuthis, Palaeotheutis Leptocheilui) . , . . . , , , . , .

     

Zur Stratigraphie der grobklastischen Fazies im Oxfordium des Wiehengebirges

Zusammenfassung Der Fund vonPeltoceratoides instabiliformis n. sp. in Steinbrüchen am Gehn nordwestlich von Osnabrück (Abb. 3) liefert weitere Kriterien, daß der Wiehengebirgssandstein, dessen stratigraphische Stellung wegen Mangel charakteristischer Fossilien unsicher ist, ins höhere Oxfordium zu stellen ist. Diese grobklastische Fazies vertritt im Wiehengebirge im wesentlichen die für das Wesergebirge typische kalkige Fazies des Korallenooliths. Anschließend wird zu einer neueren paläogeographischen Mitteilung über den Korallenoolith Nordwestdeutschlands kurz Stellung genommen.

---

In quarries at the Gehn NW of Osnabrück, several specimens ofPeltoceratoides instabiliformis n. sp. have been found. This gives further indications to the stratigraphic position of the Wiehengebirgs sandstone — which is uncertain, due to the lack of characteristic fossils — to be of Upper Oxfordian age. In the Wiehengebirge though, this coarse clastic facies substitutes to a large extent the calcareous facies of the Korallenoolith typical for the Wesergebirge.A recent paleogeographic report on the Korallenoolith of NW-Germany is then briefly discussed.

---

Résumé LesPeltoceratoides instabiliformis n. sp. découverts dans des carrières du Gehn au nord-ouest d'Osnabrück fournissent d'autres indices affirmant que le grès du Wiehengebirge dont la position stratigraphique est incertaine faute de fossiles caractéristiques doit être attribué à l'Oxfordien supérieur. Dans le Wiehengebirge, ce faciès clastique à grain grossier remplace dans l'essentiel le faciès calcaire du Korallenoolith typique pour le Wesergebirge.Il suit une brève critique d'une communication paléogéographique récemment parue sur le Korallenoolith du Nord-Ouest de l'Allemagne.

---

. Peltoceratoides instabiliformis n. sp. . . , . - .

---

---

Herrn Professor Dr.Roland Brinkmann zum 70. Geburtstag gewidmet.     

Comparison of seismic activity for Llaima and Villarrica volcanoes prior to and after the Maule 2010 earthquake

Llaima and Villarrica are two of the most active volcanoes in the Chilean Southern Volcanic Zone and presently show contrasting types of activity. Llaima is a closed vent edifice with fumarolic activity, while Villarrica has an open vent with a lava lake, continuous degassing and tremor activity. This study is focused on characterizing the relationships between volcanic and seismic activity in the months before and after the 2010 M8.8 Maule earthquake, which was located in NNW direction from the volcanoes. Time series for tremors, long-period and volcano-tectonic events were obtained from the catalogue of the Volcanic Observatory of the Southern Andes (OVDAS) and from the SFB 574 temporary volcanic network. An increase in the amount of tremor activity, long-period events and degassing rates was observed at Villarrica weeks before the mainshock and continued at a high level also after it. This increase in activity is interpreted to be caused by enhanced magma influx at depth and may be unrelated to the Maule event. In Llaima, an increase in the volcano-tectonic activity was observed directly after the earthquake. The simultaneous post-earthquake activity at both volcanoes is consistent with a structural adjustment response. Since this enhanced activity lasted for more than a year, we suggest that it is related to a medium-term change in the static stress. Thus, the Maule earthquake may have affected both volcanoes, but did not trigger eruptions, from which we assume that none of the volcanoes were in a critical state.     

Yaxcopoil-1 and the Chicxulub impact

CSDP core Yaxcopoil-1 was drilled to a depth of 1,511 m within the Chicxulub crater. An organic-rich marly limestone near the base of the hole (1,495 to 1,452 m) was deposited in an open marine shelf environment during the latest Cenomanian (uppermost Rotalipora cushmani zone). The overlying sequence of limestones, dolomites and anhydrites (1,495 to 894 m) indicates deposition in various carbonate platform environments (e.g., sabkhas, lagoons). A 100-m-thick suevite breccia (894–794 m) identifies the Chicxulub impact event. Above the suevite breccia is a dolomitic limestone with planktic foraminiferal assemblages indicative of Plummerita hantkeninoides zone CF1, which spans the last 300 ky of the Maastrichtian. An erosional surface 50 cm above the breccia/dolomite contact marks the K/T boundary and a hiatus. Limestones above this contact contain the first Tertiary planktic foraminifera indicative of an upper P. eugubina zone P1a(2) age. Another hiatus 7 cm upsection separates zone P1a(2) and hemipelagic limestones of planktic foraminiferal Zone P1c. Planktic foraminiferal assemblages of Zone Plc to P3b age are present from a depth of 794.04 up to 775 m. The Cretaceous carbonate sequence appears to be autochthonous, with a stratigraphic sequence comparable to late Cretaceous sediments known from outside the Chicxulub crater in northern and southern Yucatan, including the late Cenomanian organic-rich marly limestone. There is no evidence that these sediments represent crater infill due to megablocks sliding into the crater, such as major disruption of sediments, chaotic changes in lithology, overturned or deep dipping megablocks, major mechanical fragmentation, shock or thermal alteration, or ductile deformation. Breccia units that are intercalated in the carbonate platform sequence are intraformational in origin (e.g., dissolution of evaporites) and dykes are rare. Major disturbances of strata by the impact therefore appear to have been confined to within less than 60 km from the proposed impact center. Yaxcopoil-1 may be located outside the collapsed transient crater cavity, either on the upper end of an elevated and tilted horst of the terrace zone, or even outside the annular crater cavity. The Chicxulub site thus records a large impact that predates the K/T boundary impact and mass extinction.