Cavernous weathering,dynamical instability and self‐organization

Cavernous weathering may be conceptualized as a self‐reinforcing process, characterized by positive feedback within the weathering system. A morphometric study of caverns in the Valley of Fire State Park, Nevada, USA, demonstrates the applicability of a dynamically unstable, or conditionally unstable, model of cavernous weathering systems. Outcrop surfaces displaying caverns tend to show increasing fragmentation of the surface in the early stages of cavernous weathering, succeeded by convergent evolution of the surface in which caverns tend to grow and coalesce. A paradoxical relationship exists between the weathering system output at the scale of individual forms and the outcrop scale: caverns tend toward minimum interior surface area by developing a spheroidal form, yet the outcrop surface tends toward maximum exposed surface area by increasing the degree of fragmentation of the surface. Copyright © 2004 John Wiley & Sons, Ltd.     

Palaeomagnetic data from Ediacaran (Vendian) sediments of the Arkhangelsk region, NW Russia: An alternative apparent polar wander path of Baltica for the Late Proterozoic–Early Palaeozoic

The study area is situated along the Zolotica river in NW Russia, located within the Kola–Dvyna Rift System in the Baltic Shield that developed during Meso and Neoproterozoic times. A 9-m thick section made up of shallow marine sediments of Upper Ediacaran age was sampled in this locality. Two volcaniclastic levels from the middle part of the section yielded an age of 556 Ma. (U/Pb SHRIMP-II on zircons). Two magnetic components were successfully isolated, component A (Decl = 157.1, Incl = 68.0, ₉₅ = 1.9°, N = 575 in situ) carried by magnetite and component B (Decl = 120.3, Incl = − 31.7, ₉₅ = 3.9°, N = 57, bedding corrected), carried by haematite. While component A is thought to represent a younger overprint direction, the in situ direction for component B on the other hand, is dissimilar to any expected younger direction and is considered to be primary magnetisation in origin, acquired during or soon after deposition of the sediments in the Late Ediacaran. The corresponding palaeomagnetic pole for component A in situ is located at Lon = 55.4°E, Lat = 31°N, A₉₅ = 2.7° and for component B at Lon = 110°E, Lat = 28.3°S, A₉₅ = 3.8°, N = 57. Combined with other palaeomagnetic poles of the same tectonostratigraphic unit an alternative apparent polar wander path for the Late Proterozoic–Early Palaeozoic of Baltica is proposed. Such an alternative path shows that after the mid Cryogenian (750 Ma), the poles that were situated over South Africa (p.d.c.) moved to the east until they reached Australia during the Late Ediacaran (555 Ma) where they remained approximately stationary until the beginning of the Cambrian (545 Ma). Finally, they moved to the northwest until they reached the Arabian Peninsula in the Early Ordovician. Palaeolatitudes indicate that Baltica situated near the equator from the Cryogenian through to the Ediacaran moving gradually to the south at c. 1 cm/yr. During the Late Early Ediacaran, the plate suddenly began to drift northward at c. 8 cm/yr and in the boundary with the Cambrian it was positioned in low to intermediate latitudes. Finally, Baltica began to move back to the south at c. 13 cm/yr until in the Early Ordovician, reaching intermediate to high southern latitudes.     

The synoptic meaning of helicity

Summary Helicity, a scalar quantity resulting from the inner product of velocity and vorticity, has until now mostly been used in the field of mesoscale meteorology and boundary layer meteorology. Goals of this paper are the derivation of the flux form of the helicity equation in general form without neglection of friction and Coriolis force and the examination of helicity patterns of larger scales. The general helicity equation is approximated for the synoptic and frontal scale by use of the scale analysis. High helicity values are bounded to fronts, such that helicity determines their positions. Finally the helicity patterns at different heights and helicity sources and sinks are discussed for a case study of a cyclogenesis over the Atlantic.With 6 Figures     

Influence of Mn oxides on the reduction of uranium(VI) by the metal-reducing bacterium Shewanella putrefaciens

The potential for Mn oxides to modify the biogeochemical behavior of U during reduction by the subsurface bacterium Shewanella putrefaciens strain CN32 was investigated using synthetic Mn(III/IV) oxides (pyrolusite [β-MnO₂], bixbyite [Mn₂O₃] and K⁺-birnessite [K₄Mn₁₄O₂₇ · 8H₂O]). In the absence of bacteria, pyrolusite and bixbyite oxidized biogenic uraninite (UO₂[s]) to soluble U(VI) species, with bixbyite being the most rapid oxidant. The Mn(III/IV) oxides lowered the bioreduction rate of U(VI) relative to rates in their absence or in the presence of gibbsite (Al[OH]₃) added as a non-redox-reactive surface. Evolved Mn(II) increased with increasing initial U(VI) concentration in the biotic experiments, indicating that valence cycling of U facilitated the reduction of Mn(III/IV). Despite an excess of the Mn oxide, 43 to 100% of the initial U was bioreduced after extended incubation. Analysis of thin sections of bacterial Mn oxide suspensions revealed that the reduced U resided in the periplasmic space of the bacterial cells. However, in the absence of Mn(III/IV) oxides, UO₂(s) accumulated as copious fine-grained particles external to the cell. These results indicate that the presence of Mn(III/IV) oxides may impede the biological reduction of U(VI) in subsoils and sediments. However, the accumulation of U(IV) in the cell periplasm may physically protect reduced U from oxidation, promoting at least a temporal state of redox disequilibria.     

Variations in organic geochemistry and lithology of a carbonate sequence deposited in a backplatform basin (Triassic, Hungary)

The variations in the organic matter quantity and quality were studied with respect to the mineral composition of the carbonate sequences accumulated on a gentle slope (Zl-1 well) and at the toe of the slope (Rzt-1 well) located between a Late Triassic carbonate platform and a backplatform basin. Parallel variations observed in mineral composition and organic geochemical features of the successions appeared to be controlled by the change in climate and by sea-level fluctuations. The repetitive sea-level changes resulted in a variation in the carbonate-rich basin facies and in the mineralogically heterogenous slope and toe-of-slope ones. According to Rock Eval pyrolysis, organic petrography and carbon isotope ratios, the immature organic matter is of predominantly marine origin and composed of mainly liptinites in both of the studied boreholes. The results of the GC and GC/MS analyses of the saturated hydrocarbon fractions of bitumens together with the composition of kerogen pyrolysates reveal a predominant algal input with a minor variable bacterial and subordinate terrestrial contribution for the Rzt-1 borehole. In the Zl-1 borehole a significantly higher proportion of the bacterial biomass contributed to the organic precursors. The δ¹³C values and the composition of the kerogen pyrolysates together with the results of the maceral analysis and GC data suggest a relatively higher, but moderate, higher plant derived contribution in the slope facies and at the top of the toe-of-slope facies. The elementary composition of kerogens and Rock Eval data display type II-S kerogen in the basin and the slope facies, and type I-II-S one in the toe-of-slope facies. Variations in the hydrogen content of the organic matter mainly reflect variations in the preservation conditions and in primary productivity. The presence of the 2,6,10,15,19-pentamethyleicosane and the extremely low pristane/phytane ratios indicate a relatively high methanogenic bacterial activity and strongly anoxic depositional conditions in the Rzt-1 well, especially in two most organic-rich toe-of-slope facies.     

Combining IR and X‐ray microtomography data sets: Application to Itokawa particles and to Paris meteorite

In the near future, a new generation of sample return missions (Hayabusa2, OSIRIS‐REx, MMX, etc.) will collect samples from small solar system bodies. To maximize the scientific outcome of laboratory studies and minimize the loss of precious extraterrestrial samples, an analytical sequence from less destructive to more destructive techniques needs to be established. In this work, we present a combined X‐ray and IR microtomography applied to five Itokawa particles and one fragment of the primitive carbonaceous chondrite Paris. We show that this analytical approach is able to provide a 3‐D physical and chemical characterization of individual extraterrestrial particles, using the measurement of their 3‐D structure and porosity, and the detection of mineral and organic phases, and their spatial co‐localization in 3‐D. We propose these techniques as an efficient first step in a multitechnique analytical sequence on microscopic samples collected by space missions.     

Possible effects of human impacts on epibenthic communities and coral rubble features in the marine Park of Bunaken (Indonesia)

Indo-Pacific coral reefs are considered among the most complex and biodiversified ecosystems in the world. Their existence is threatened by both natural and anthropogenic factors. Therefore, the assessment of anthropogenic disturbances is necessary to protect and manage these marine natural resources. In Bunaken Marine Park (North Sulawesi, Indonesia) epibenthic assemblages and coral rubble features at four impacted sites (each of them located close to villages and frequently exploited as recreational diving spots), and four well preserved sites (far from villages and scarcely frequented by divers), were investigated at 6, 12 and 18 m depth, in order to identify possible reef modifications. The assemblages were sampled by way of photographs. Coral rubble cover was estimated both by way of photographs and along belt transects, while grain size and the living fraction of the coral rubble were assessed by direct samples. The data showed significant differences between the study sites and between depths with regard to human activity. The hard coral cover and the assemblage heterogeneity are higher in control sites than in the impacted site where, especially in shallow water, the mechanical damage can strongly affect the assemblage structure.     

Reduction of pertechnetate [Tc(VII)] by aqueous Fe(II) and the nature of solid phase redox products

The subsurface behaviour of ⁹⁹Tc, a contaminant resulting from nuclear fuels reprocessing, is dependent on its valence (e.g., IV or VII). Abiotic reduction of soluble Tc(VII) by Fe(II)_(aq) in pH 6-8 solutions was investigated under strictly anoxic conditions using an oxygen trap (<7.5 × 10⁻⁹ atm O₂). The reduction kinetics were strongly pH dependent. Complete and rapid reduction of Tc(VII) to a precipitated Fe/Tc(IV) form was observed when 11 μmol/L of Tc(VII) was reacted with 0.4 mmol/L Fe(II) at pH 7.0 and 8.0, while no significant reduction was observed over 1 month at pH 6.0. Experiments conducted at pH 7.0 with Fe(II)_(aq) = 0.05-0.8 mmol/L further revealed that Tc(VII) reduction was a combination of homogeneous and heterogeneous reaction. Heterogeneous reduction predominated after approximately 0.01 mmol/L of Fe(II) was oxidized. The heterogeneous reaction was more rapid, and was catalyzed by Fe(II) that adsorbed to the Fe/Tc(IV) redox product. Wet chemical and Fe-X-ray absorption near edge spectroscopy measurements (XANES) showed that Fe(II) and Fe(III) were present in the Fe/Tc(IV) redox products after reaction termination. ⁵⁷Fe-Mössbauer, extended X-ray adsorption fine structure (EXAFS), and transmission electron microscopy (TEM) measurements revealed that the Fe/Tc(IV) solid phase was poorly ordered and dominated by Fe(II)-containing ferrihydrite with minor magnetite. Tc(IV) exhibited homogeneous spatial distribution within the precipitates. According to Tc-EXAFS measurements and structural modeling, its molecular environment was consistent with an octahedral Tc(IV) dimer bound in bidentate edge-sharing mode to octahedral Fe(III) associated with surface or vacancy sites in ferrihydrite. The precipitate maintained Tc(IV)_aq concentrations that were slightly below those in equilibrium with amorphous Tc(IV)O₂·nH₂O_(s). The oxidation rate of sorbed Tc(IV) in the Fe/Tc precipitate was considerably slower than Tc(IV)O₂·nH₂O_(s) as a result of its intraparticle/intragrain residence. Precipitates of this nature may form in anoxic sediments or groundwaters, and the intraparticle residence of sorbed/precipitated Tc(IV) may limit ⁹⁹Tc remobilization upon the return of oxidizing conditions.     

Fe-solid phase transformations under highly basic conditions

Hyperalkaline and saline radioactive waste fluids with elevated temperatures from S-SX high-level waste tank farm at Hanford, WA, USA accidentally leaked into sediments beneath the tanks, initiating a series of geochemical processes and reactions whose significance and extent was unknown. Among the most important processes was the dissolution of soil minerals and precipitation of stable secondary phases. The objective of this investigation was to study the release of Fe into the aqueous phase upon dissolution of Fe-bearing soil minerals, and the subsequent formation of Fe-rich precipitates. Batch reactors were used to conduct experiments at 50 °C using solutions similar in composition to the waste fluids. Results clearly showed that, similarly to Si and Al, Fe was released from the dissolution of soil minerals (most likely phyllosilicates such as biotite, smectite and chlorite). The extent of Fe release increased with base concentration and decreased with Al concentration in the contacting solution. The maximum apparent rate of Fe release (0.566 × 10⁻¹³ mol m⁻² s⁻¹) was measured in the treatment with no Al and a concentration of 4.32 mol L⁻¹ NaOH in the contact solution. Results from electron microscopy indicated that while Si and Al precipitated together to form feldspathoids in the groups of cancrinite and/or sodalite, Fe precipitation followed a different pathway leading to the formation of hematite and goethite. The newly formed Fe oxy-hydroxides may increase the sorption capacity of the sediments, promote surface mediated reactions such as precipitation and heterogeneous redox reactions, and affect the phase distribution of contaminants and radionuclides.     

Analysis of State of Stress During The 1997 Earthquake Swarm In Western Bohemia

Focal mechanisms of 70 events of the January 1997 earthquake swarm were analysed using the Gephart and Forsyth method to determine the state of stress in the West Bohemia/Vogtland region and to reveal possible stress variations during the swarm activity. The method was applied to the whole set of 70 focal mechanisms and to several subsets distinguishing magnitudes of events and the spatial and temporal distribution of the swarm. The three representative stress models A ( ₁ ,A: 0/45 (az/dip), ₂ A: 134/35, ₃ A: 243/25), B ( ₁ ,B: 162/38, ₂ B: 263/14, ₃ B: 10/49), and C ( ₁ C: 135/30, ₂ C: 1/50, ₃ C: 239/23) which could characterise the state of stress in the region were found. Model C can be considered to be the most probable stress model because of its consistency with the European stress field. The results of the stress analysis applied to the individual subsets of focal mechanisms indicate that the state of stress was more uniform during the first phase of the swarm. To distinguish between the fault plane and the auxiliary plane of fault plane solutions a statistical approach was used. The results showed that the fault planes striking NW-SE and dipping 45° to NE were activated during the swarm.