Mineralogical and morphological constraints on the reduction of Fe(III) minerals by Geobacter sulfurreducens

The biologically-mediated reduction of synthetic samples of the Fe(III)-bearing minerals hematite, goethite, lepidocrocite, feroxhyte, ford ferrihydrite, akaganeite and schwertmannite by Geobacter sulfurreducens has been investigated using microbiological techniques in conjunction with X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). This combination of approaches offers unique insights into the influence of subtle variations in the crystallinity of a given mineral on biogeochemical processes, and has highlighted the importance of (oxyhydr)oxide crystallite morphology in determining the changes occurring in a given mineral phase. Problems arising from normalising the biological Fe(III) reduction rates relative to the specific surface areas of the starting materials are also highlighted. These problems are caused primarily by particle aggregation, and compounded when using spectrophotometric assays to monitor reduction. For example, the initial rates of Fe(III) reduction observed for two synthetic feroxyhytes with different crystallinities (as shown by XRD and TEM studies) but almost identical surface areas, differ substantially. Both microbiological and high-resolution TEM studies show that hematite and goethite are susceptible to limited amounts of Fe(III) reduction, as evidenced by the accumulation of Fe(II) during incubation with G. sulfurreducens and the growth of nodular structures on crystalline goethite laths during incubation. Lepidocrocite and akaganeite readily transform into mixtures of magnetite and goethite, and XRD data indicate that the proportion of magnetite increases within the transformation products as the crystallinity of the starting material decreases. The presence of anthraquinone-2,6-disulfonate (AQDS) as an electron shuttle increases both the initial rate and longer term extent of biological Fe(III) reduction for all of the synthetic minerals examined. High-resolution XPS indicates subtle but measurable differences in the Fe(III):Fe(II) ratios at the mineral surfaces following extended incubation. For example, for a poorly crystalline schwertmannite, deconvolution of the Fe2p_3/2 peak suggests that the Fe(III):Fe(II) ratio of the near-surface regions varies from 1.0 in the starting material to 0.9 following 144 h of incubation with G.sulfurreducens, and to 0.75 following the same incubation period in the presence of 10 μM AQDS. These results have important implications for the biogeochemical cycling of iron.     

Fundamental changes in the activity of the natrocarbonatite volcano Oldoinyo Lengai, Tanzania

On September 4, 2007, after 25 years of effusive natrocarbonatite eruptions, the eruptive activity of Oldoinyo Lengai (OL), N Tanzania, changed abruptly to episodic explosive eruptions. This transition was preceded by a voluminous lava eruption in March 2006, a year of quiescence, resumption of natrocarbonatite eruptions in June 2007, and a volcano-tectonic earthquake swarm in July 2007. Despite the lack of ground-based monitoring, the evolution in OL eruption dynamics is documented based on the available field observations, ASTER and MODIS satellite images, and almost-daily photos provided by local pilots. Satellite data enabled identification of a phase of voluminous lava effusion in the 2 weeks prior to the onset of explosive eruptions. After the onset, the activity varied from 100 m high ash jets to 2–15 km high violent, steady or unsteady, eruption columns dispersing ash to 100 km distance. The explosive eruptions built up a ∼400 m wide, ∼75 m high intra-crater pyroclastic cone. Time series data for eruption column height show distinct peaks at the end of September 2007 and February 2008, the latter being associated with the first pyroclastic flows to be documented at OL. Chemical analyses of the erupted products, presented in a companion paper (Keller et al. 2010), show that the 2007–2008 explosive eruptions are associated with an undersaturated carbonated silicate melt. This new phase of explosive eruptions provides constraints on the factors causing the transition from natrocarbonatite effusive eruptions to explosive eruptions of carbonated nephelinite magma, observed repetitively in the last 100 years at OL.     

On the occurrence,trace element geochemistry,and crystallization history of zircon from in situ ocean lithosphere

We characterize the textural and geochemical features of ocean crustal zircon recovered from plagiogranite, evolved gabbro, and metamorphosed ultramafic host-rocks collected along present-day slow and ultraslow spreading mid-ocean ridges (MORs). The geochemistry of 267 zircon grains was measured by sensitive high-resolution ion microprobe-reverse geometry at the USGS-Stanford Ion Microprobe facility. Three types of zircon are recognized based on texture and geochemistry. Most ocean crustal zircons resemble young magmatic zircon from other crustal settings, occurring as pristine, colorless euhedral (Type 1) or subhedral to anhedral (Type 2) grains. In these grains, Hf and most trace elements vary systematically with Ti, typically becoming enriched with falling Ti-in-zircon temperature. Ti-in-zircon temperatures range from 1,040 to 660°C (corrected for a _TiO2 ≈ 0.7, a _SiO2 ≈ 1.0, pressure ≈ 2 kbar); intra-sample variation is typically ~60–150°C. Decreasing Ti correlates with enrichment in Hf to ~2 wt%, while additional Hf-enrichment occurs at relatively constant temperature. Trends between Ti and U, Y, REE, and Eu/Eu* exhibit a similar inflection, which may denote the onset of eutectic crystallization; the inflection is well-defined by zircons from plagiogranite and implies solidus temperatures of ~680–740°C. A third type of zircon is defined as being porous and colored with chaotic CL zoning, and occurs in ~25% of rock samples studied. These features, along with high measured La, Cl, S, Ca, and Fe, and low (Sm/La)_N ratios are suggestive of interaction with aqueous fluids. Non-porous, luminescent CL overgrowth rims on porous grains record uniform temperatures averaging 615 ± 26°C (2SD, n = 7), implying zircon formation below the wet-granite solidus and under water-saturated conditions. Zircon geochemistry reflects, in part, source region; elevated HREE coupled with low U concentrations allow effective discrimination of ~80% of zircon formed at modern MORs from zircon in continental crust. The geochemistry and textural observations reported here serve as an important database for comparison with detrital, xenocrystic, and metamorphosed mafic rock-hosted zircon populations to evaluate provenance.     

Dolomitization and the mineralization of the Marl Slate (N. E. England)

The Marl Slate, the English equivalent of the Kupferschiefer, has been studied with particular reference to the relationships between dolomitization and the origin of the metal sulphides. Dolomite occurs as: 1) discontinuous lenses of ferroan dolomicrite, 2) micronodules of finely crystalline dolospar in association with length-slow chalcedony and 3) discrete laminae of ferroan or non-ferroan dolospar. The ferroan dolomicrite has excess CaCO₃, and is more abundant in the lower, sapropelic facies of the Marl Slate. It is considered to have formed by the penecontemporaneous alteration of calcium carbonate under hypersaline conditions. Small micronodules (typically about 0.3 mm in diameter) are also more abundant in the sapropelic Marl Slate. These frequently contain cores of length-slow chalcedony (quartzine) fibres and sometimes quartz megacrysts. Textural observations clearly indicate that this silica is of authigenic origin and the dolomite/chalcedony micronodules are interpreted as diagenetic replacements of a calcium sulphate mineral such as anhydrite. The discrete laminae of finely crystalline dolospar are often inter-laminated with calcite in the upper part of the Marl Slate. This dolomite is also calcium rich and represents a replacement, possibly of anhydrite, during a later phase of diagenesis. Metal sulphides occur in two distinct forms: as disseminated framboidal pyrite and as discrete lenses of pyrite, chalcopyrite, galena, sphalerite and rarer sulphides. The framboidal pyrite originated during early diagenesis by reaction of sulphide, produced by reduction of sulphate by organic material and micro-organisms, with iron also released in the reducing environment. The sulphide lenses are often in intimate association with dolospar, length-slow chalcedony and authigenic quartz megacrysts. This indicates that the lenses were produced during diagenesis by the reduction and replacement of calcium sulphate (anhydrite). Various sources, such as co-precipitation with dolomite precursors and the underlying Yellow Sands, may have supplied metals which were mobilized and transported by connate brines as diagenesis progressed.     

Stability of openings in jointed rock

The slide line approach is combined with the finite element method to represent the action of a removable block on a lined tunnel. The present paper examines the strength and ductility required of the tunnel liner to resist the forces imposed by a block when the surrounding rock mass is subjected to explosive loading. Key block theory developed by Goodman and Shi provides the conceptual framework for simplifying a general jointed domain to a manageable size for analysis with finite element models.     

The generation and preservation of multiple hurricane beds in the northern Gulf of Mexico

Cores collected from Mississippi Sound and the inner shelf of the northeast Gulf of Mexico have been examined using ²¹⁰Pb and ¹³⁷Cs geochronology, X-radiography, granulometry, and a multi-sensor core logger. The results indicate that widespread event layers were probably produced by an unnamed hurricane in 1947 and by Hurricane Camille in 1969. Physical and biological post-depositional processes have reworked the event layers, producing regional discontinuities and localized truncation, and resulting in an imperfect and biased record of sedimentary processes during the storms. The oceanographic and sedimentological processes that produced these event beds have been simulated using a suite of numerical models: (1) a parametric cyclone wind model; (2) the SWAN third-generation wave model; (3) the ADCIRC 2D finite-element hydrodynamic model; (4) the Princeton Ocean Model; (5) a coupled wave–current bottom boundary layer-sedimentation model; and (6) a model for bed preservation potential as a function of burial rate and bioturbation rate. Simulated cores from the Mississippi Sound region are consistent with the observed stratigraphy and geochronology on both the landward and seaward sides of the barrier islands.