Biochemical evolution II: Origin of life in tubular microstructures on weathered feldspar surfaces

Mineral surfaces were important during the emergence of life on Earth because the assembly of the necessary complex biomolecules by random collisions in dilute aqueous solutions is implausible. Most silicate mineral surfaces are hydrophilic and organophobic and unsuitable for catalytic reactions, but some silica-rich surfaces of partly dealuminated feldspars and zeolites are organophilic and potentially catalytic. Weathered alkali feldspar crystals from granitic rocks at Shap, north west England, contain abundant tubular etch pits, typically 0.4–0.6 μm wide, forming an orthogonal honeycomb network in a surface zone 50 μm thick, with 2–3 × 106 intersections per mm2 of crystal surface. Surviving metamorphic rocks demonstrate that granites and acidic surface water were present on the Earth’s surface by ∼3.8 Ga. By analogy with Shap granite, honeycombed feldspar has considerable potential as a natural catalytic surface for the start of biochemical evolution. Biomolecules should have become available by catalysis of amino acids, etc. The honeycomb would have provided access to various mineral inclusions in the feldspar, particularly apatite and oxides, which contain phosphorus and transition metals necessary for energetic life. The organized environment would have protected complex molecules from dispersion into dilute solutions, from hydrolysis, and from UV radiation. Sub-micrometer tubes in the honeycomb might have acted as rudimentary cell walls for proto-organisms, which ultimately evolved a lipid lid giving further shelter from the hostile outside environment. A lid would finally have become a complete cell wall permitting detachment and flotation in primordial “soup.” Etch features on weathered alkali feldspar from Shap match the shape of overlying soil bacteria.

Biochemical evolution III: Polymerization on organophilic silica-rich surfaces, crystal–chemical modeling, formation of first cells, and geological clues

Catalysis at organophilic silica-rich surfaces of zeolites and feldspars might generate replicating biopolymers from simple chemicals supplied by meteorites, volcanic gases, and other geological sources. Crystal–chemical modeling yielded packings for amino acids neatly encapsulated in 10-ring channels of the molecular sieve silicalite-ZSM-5-(mutinaite). Calculation of binding and activation energies for catalytic assembly into polymers is progressing for a chemical composition with one catalytic Al–OH site per 25 neutral Si tetrahedral sites. Internal channel intersections and external terminations provide special stereochemical features suitable for complex organic species. Polymer migration along nano/micrometer channels of ancient weathered feldspars, plus exploitation of phosphorus and various transition metals in entrapped apatite and other microminerals, might have generated complexes of replicating catalytic biomolecules, leading to primitive cellular organisms. The first cell wall might have been an internal mineral surface, from which the cell developed a protective biological cap emerging into a nutrient-rich “soup.” Ultimately, the biological cap might have expanded into a complete cell wall, allowing mobility and colonization of energy-rich challenging environments. Electron microscopy of honeycomb channels inside weathered feldspars of the Shap granite (northwest England) has revealed modern bacteria, perhaps indicative of Archean ones. All known early rocks were metamorphosed too highly during geologic time to permit simple survival of large-pore zeolites, honeycombed feldspar, and encapsulated species. Possible microscopic clues to the proposed mineral adsorbents/catalysts are discussed for planning of systematic study of black cherts from weakly metamorphosed Archaean sediments.

Triassic redbeds in the Malaguide Complex (Betic Cordillera — Spain): petrography, geochemistry and geodynamic implications

Sandstone petrography and mudstone mineralogy and geochemistry of Triassic mudstones and sandstones from continental redbeds of the Malaguide Complex (Betic Cordillera, southern Spain) provide useful information on provenance, palaeoclimate and geodynamics during the early stages of the Pangea break-up, and on their diagenetic evolution. The sandstones are quartzarenites to sub-litharenites, with minor lithic fragments and rare feldspars. The mudstone samples show a PAAS like elemental distribution. The samples likely record recycling processes from their metasedimentary basement rocks that significantly affected the weathering indices, and monitors cumulative effects, including a first cycle of weathering at the source rocks. Sandstone composition and chemical–mineralogical features of mudstones record a provenance derived from continental block and recycled orogen that were weathered under warm and episodically wet climate. Source areas were located towards the east of the present-day Malaguide outcrops, and were formed by fairly silicic rock types, made up mainly of Palaezoic metasedimentary rocks, similar to those of the Paleozoic underlying series, with subordinate contributions from magmatic–metamorphic sources, and a rare supply from mafic metavolcanic rocks. Clay-mineral distribution of mudstones is dominated by illite and illite/smectite mixed-layer that result from differences in provenance, weathering, and burial/temperature history. Illite crystallinity values, illitization of kaolinite, occurrence of typical authigenic minerals and apatite fission-track studies, coupled with a subsidence analysis of the whole Malaguide succession suggest burial depths of at least 4–6 km with temperatures of 140–160 °C, typical of the burial diagenetic stage, and confirm the Middle Miocene exhumation of the Betic Internal Domain tectonic stack topped by the Malaguide Complex.

An insight into the breakup of Gondwana: Identifying events through low-temperature thermochronology from the basement rocks of Madagascar

Fission track analysis was applied to the Precambrian suites of Madagascar in order to identify the lower-temperature cooling histories and their relationships to the Phanerozoic events that affected the island. Apatite ages range from 431 to 68 Ma, and zircon ages range from 452 to 238 Ma. Thermochronologically, the island can be divided into a southern, central, and northern region each with a subdivision on an east-west basis. The southern region is sharply separated from the central region by strongly contrasting apparent apatite ages over the northwest-southeast striking Ranotsara Shear Zone (RSZ). The change in apparent ages over the RSZ is indicative of later reactivation along younger brittle faults. The central region has the oldest ages of the island and has a diffuse contact to the third region northward. Along the entire western margin of the Precambrian basement initial Paleozoic exhumation was followed by heating (burial by sediments) during Jurassic and Cretaceous times. A decrease in ages along the eastern margin from 119 to 68 Ma coincides with the predicted positions of the Marion hot spot after effects of erosion are considered. On the other hand, these ages may represent progressive opening of the margin in a southward direction together with associated denudation of the rift shoulder. The eastern part of the central region has remained very stable since at least Devonian times, undergoing only long-term very slow exhumation at rates of 1–5 m/Myr.

Mineralogical composition of the upper 300m of Hole 302-M0002A

During the Arctic Coring Expedition (ACEX), a 428-m-thick sequence of Upper Cretaceous to Quaternary sediments was penetrated. The mineralogical composition of the upper 300 m of this sequence is presented here for the first time. Heavy and clay mineral associations indicate a major and consistent shift in provenance, from the Barents-Kara - western Laptev Sea region, characterized by presence of common clinopyroxene, to the eastern Laptev-East Siberian seas in the upper part of the section, characterized by common hornblende (amphibole). Sea ice originating from the latter source region must have survived at least one summer melt cycle in order to reach the ACEX drill site, if considering modern sea ice trajectories and velocities. This shift in mineral assemblages probably represents the onset of a perennial sea ice cover in the Arctic Ocean, which occurred at about 13 Ma, thus suggesting a coeval freeze in the Arctic and Antarctic regions.

Chemical and mineral compositions of cherty and siliceous-clayey rocks from accretionary complexes in Sikhote Alin

The paper reports results of a study of clastic heavy mineral assemblages and geochemical features of some assemblages in several Permian-Mesozoic cherty and siliceous-clayey sequences of the Sikhote Alin Region. They are composed of pelagic and hemipelagic sediments of the Panthalassa (Paleopacific) Ocean. Four typical mineral assemblages and their environments are established. In one of the ocean segments, where the sedimentary cover formed during Late Paleozoic - Early Cretaceous, the Permian pelagic domain was characterized by the amphibole-pyroxene assemblage with heavy minerals derived from ophiolites. The Triassic-Jurassic stage was marked by development of the clinopyroxene assemblage with heavy minerals derived from intraplate alkaline volcanic complexes. Middle-Late Jurassic hemipelagic sediments host the zircon-clinopyroxene assemblage with greater role of continental environments and presence of volcanic products of the convergence zone. Another segment of the ocean accumulated red cherts and siliceous-clayey sediments during Jurassic - Early Cretaceous under influence of island-arc volcanism.

Geochemistry of basalts from ODP Leg 49, North Atlantic Ocean

The geochemistry of basalts recovered from seven sites in the North Atlantic is described with particular reference to minor elements. Three sites (407, 408, and 409) along the same mantle flow line, transverse to the Reykjanes Ridge at about 63°N, provide information on the composition of basalts erupted over a 34-m.y. interval between 2.3 and 36 m.y. ago. At Site 410, at 45°N, penetration into 10 m.y.-old crust west of the ridge axis permits comparisons with young basalts dredged from the median valley at 45°N. Three sites in the FAMOUS area at about 36°N provided material from very young (1 m.y.) basaltic crust (Site 411), and material to test the geochemical coherence of basalts of different ages (1.5 and 3.5 m.y.) on either side of a fracture zone (Sites 412 and 413). These sites complement earlier data from dredged and drilled sites (Leg 37) in the FAMOUS area. At Site 407, four geochemically distinct basalt units occur, with different normative and rare-earth element (REE) characteristics, and there is a clear correlation with magnetic stratigraphy. Yet there is a remarkable consistency in incompatible element ratios between these units, indicating derivation from an essentially similar mantle source. The basalts from the younger sites, 408 and 409, show a similar range of normative and REE variation, but incompatible element ratios are identical to those at Site 407, indicating that basalts at all three sites were produced from a mantle source which was geochemically relatively uniform. Rare-earth differences between the basalts can be interpreted in terms of variations in the degree and depth of partial melting causing HREE (+Y) retention in the source, although there may be some inter-site differences with respect to REE. A similar picture is presented at 45°N. Apparently a range of tholeiitic, transitional, and alkalic basalts were being erupted 10 m.y. ago, which have almost identical geochemical characteristics to those recently erupted in the median valley at 45°N. Incompatible element ratios are markedly different from those recorded at the Reykjanes Ridge. Basalts recovered from the FAMOUS sites are geochemically similar to previous samples recovered from the FAMOUS area, and their incompatible element ratios are similar, but not identical, to those at 45°N. However, total trace element levels are consistently lower than in 45°N basalts, which might imply smaller degrees of partial melting and/or greater depths of magma generation at 45°N, or higher trace element levels in the mantle source at 45°N. Few of the basalts recovered on Leg 49 have the geochemical characteristics of typical "MORB" (e.g., Nazca Plate, Leg 34). The data strongly support models invoking geochemical inhomogeneity in the source regions of basalts produced at the Mid-Atlantic Ridge. However, the data also introduce an additional time factor into such models and demonstrate the uniformity of the mantle source at a particular ridge sector (over periods in excess of 30 m.y.), while emphasizing the marked differences along the ridge. Mixing models invoking "depleted" and "enriched" mantle sources would seem to be inadequate to account for the observed variations.

Composition of bottom sediments from the anoxic Mogil'noe Lake, Kil'din Island (Barents Sea)

In summer 2006 integrated geological, geochemical, hydrological, and hydrochemical studies were carried out in the relict anoxic Mogil'noe Lake (down to 16 m depths) located in the Kil'din Island in the Barents Sea. Chemical and grain size compositions of bottom sediments from the lake (permanently anoxic basin) and from the Baltic Sea deeps (periodically anoxic basins) were compared. Vertical location of the hydrogen sulfide layer boundary in the lake (9-11 m depths) was practically the same from 1974 up to now. Concentrations of suspended matter in the lake in June and July 2006 appeared to be close to its summer concentrations in seawater of the open Baltic Sea. Muds from the Mogil'noe Lake compared to those of the Baltic Sea deeps are characterized by fluid and flake consistency and by pronounced admixtures of sandy and silty fractions (probably of eolic origin). Lacustrine mud contains much plant remains; iron sulfides and vivianite were also found. Concentrations of 22 elements determined in lacustrine bottom sediments were of the same levels as those found here 33 years ago. Concentrations also appeared to be close to those in corresponding grain size types of bottom sediments in the Baltic Sea. Low C_org/N values (aver. 5.0) in muds of the Mogil'noe Lake compared to ones for muds of the Baltic Sea deeps (aver. 10) evidence considerable planktogenic component in organic matter composition of the lacustrine muds. No indications were reveled for anthropogenic contaminations of the lacustrine bottom sediments with toxic metals.

(Table T2) Integrated intensity (peak area) of matrix minerals of ODP Hole 173-1068A

Mass-wasting deposits characterize the Upper Jurassic(?) to Lower Cretaceous sedimentary record of the Iberia Abyssal Plain. These deposits include olistostromes at Site 897, olistostromes and/or possible rock-fall deposits at Site 899, a breccia succession at Site 1068, slumped and fractured deposits at Site 1069, and a breccia succession at Site 1070. Whereas the exact origin of these deposits is uncertain, the regional common occurrence of middle to upper Mesozoic mass-wasting deposits suggests that they record the early rifting evolution of the west Iberia margin. This data report presents both qualitative and semiquantitative results from XRD analyses of the breccia matrix at Site 1068. In this study the matrix is defined as the fine-grained particles (as viewed through a binocular microscope) plus cement. Results are based on analytical methods that aimed to isolate the desired matrix from larger clast contamination prior to XRD analyses. In addition, the breccia was sampled at a higher resolution than was conducted aboard ship, producing a more complete description of downcore matrix mineralogical changes. The data presented here may be used to (1) further justify the subunit designation of Unit IV made aboard ship, (2) help determine to what degree the matrix and the larger clasts (studied in thin section aboard ship; Shipboard Scientific Party, 1998, doi:10.2973/odp.proc.ir.173.106.1998) are compositionally distinct, (3) help identify the extent of hydrothermal fluid migration in the breccia, and (4) support the proposed shipboard hypothesis that the Site 1068 breccia succession resulted from multiple mass-wasting.