Origin of SiO2-rich components in ordinary chondrites

Silica-rich objects are common minor components in ordinary chondrites (OC), occurring as fragments and as chondrules. Their typical paragenesis is orthopyroxene + SiO₂ (with bulk SiO₂ >65 wt%) and occasionally with additional olivine and/or spinel. Individual silica-rich components (SRC) have previously been studied in various types of OCs, although there is only one comprehensive study of these objects by Brigham et al. [Brigham, C.A., Murrell, M.T., Yabuki, H., Ouyang, Z., El Goresy, A., 1986. Silica-bearing chondrules and clasts in ordinary chondrites. Geochim. Cosmochim. Acta 50, 1655-1666]. Several different explanations of how SRCs formed have been published. The main question is how silica-enrichment was achieved, because CI-chondritic atomic Mg/Si-ratio is 1.07 and as a consequence only olivine and pyroxene, but no free silica should be stable. There are two basic possibilities for the SiO₂-enrichment: (1) a RedOx-mechanism or magmatic fractionation on the parent body and (2) fractional condensation or recycling of chondrule mesostasis in the solar nebula. To better constrain the origin of these objects, we measured major and rare earth elements in SRCs of various types of ordinary chondrites, and in addition, we studied silica polymorphism in these objects using an in situ micro-Raman technique. Bulk chondrule compositions define mixing lines between the compositions of olivine and pyroxene. The SRCs extend these lines to an SiO₂ end member. In contrast, magmatic trends grossly deviate from these mixing lines. Concentrations of CaO, Al₂O₃, and REE in the pyroxenes of the SRCs are low (0.01 to 1× CI) and the CI-normalized REE-patterns are virtually flat, typical of bulk chondrules, but untypical of magmatic trends. We therefore conclude that SiO₂-rich objects are not of magmatic origin. They are the result of fractional condensation in the solar nebula. The silica in SRCs occurs mainly as tridymite and sometimes as cristobalite or—in very rare cases—as quartz. Some SiO₂-phases yielded a yet unknown micro-Raman spectrum, which we were unable to identify. The often chondrule-like shape of SRCs as well as the presence of high-temperature SiO₂-polymorphs lead to the following model for the origin of SRCs: formation of SiO₂-rich precursors in the solar nebula by fractional condensation, reheating to temperatures between 1140 and >1968 K, thereby forming the SRCs,—probably during the chondrule-forming process—followed by rapid cooling.     

Does reactive surface area depend on grain size? Results from pH 3, 25 °C far-from-equilibrium flow-through dissolution experiments on anorthite and biotite

Laboratory determined mineral weathering rates need to be normalised to allow their extrapolation to natural systems. The principle normalisation terms used in the literature are mass, and geometric- and BET specific surface area (SSA). The purpose of this study was to determine how dissolution rates normalised to these terms vary with grain size. Different size fractions of anorthite and biotite ranging from 180-150 to 20-10 μm were dissolved in pH 3, HCl at 25 °C in flow through reactors under far from equilibrium conditions. Steady state dissolution rates after 5376 h (anorthite) and 4992 h (biotite) were calculated from Si concentrations and were normalised to initial- and final- mass and geometric-, geometric edge- (biotite), and BET SSA. For anorthite, rates normalised to initial- and final-BET SSA ranged from 0.33 to 2.77 × 10⁻¹⁰ mol_feldspar m⁻² s⁻¹, rates normalised to initial- and final-geometric SSA ranged from 5.74 to 8.88 × 10⁻¹⁰ mol_feldspar m⁻² s⁻¹ and rates normalised to initial- and final-mass ranged from 0.11 to 1.65 mol_feldspar g⁻¹ s⁻¹. For biotite, rates normalised to initial- and final-BET SSA ranged from 1.02 to 2.03 × 10⁻¹² mol_biotite m⁻² s⁻¹, rates normalised to initial- and final-geometric SSA ranged from 3.26 to 16.21 × 10⁻¹² mol_biotite m⁻² s⁻¹, rates normalised to initial- and final-geometric edge SSA ranged from 59.46 to 111.32 × 10⁻¹² mol_biotite m⁻² s⁻¹ and rates normalised to initial- and final-mass ranged from 0.81 to 6.93 × 10⁻¹² mol_biotite g⁻¹ s⁻¹. For all normalising terms rates varied significantly (p ? 0.05) with grain size. The normalising terms which gave least variation in dissolution rate between grain sizes for anorthite were initial BET SSA and initial- and final-geometric SSA. This is consistent with: (1) dissolution being dominated by the slower dissolving but area dominant non-etched surfaces of the grains and, (2) the walls of etch pits and other dissolution features being relatively unreactive. These steady state normalised dissolution rates are likely to be constant with time. Normalisation to final BET SSA did not give constant ratios across grain size due to a non-uniform distribution of dissolution features. After dissolution coarser grains had a greater density of dissolution features with BET-measurable but unreactive wall surface area than the finer grains. The normalising term which gave the least variation in dissolution rates between grain sizes for biotite was initial BET SSA. Initial- and final-geometric edge SSA and final BET SSA gave the next least varied rates. The basal surfaces dissolved sufficiently rapidly to influence bulk dissolution rate and prevent geometric edge SSA normalised dissolution rates showing the least variation. Simple modelling indicated that biotite grain edges dissolved 71-132 times faster than basal surfaces. In this experiment, initial BET SSA best integrated the different areas and reactivities of the edge and basal surfaces of biotite. Steady state dissolution rates are likely to vary with time as dissolution alters the ratio of edge to basal surface area. Therefore they would be more properly termed pseudo-steady state rates, only appearing constant because the time period over which they were measured (1512 h) was less than the time period over which they would change significantly.     

Early diagenesis of trace metals (Cd, Cu, Co, Ni, U, Mo, and V) in the freshwater reaches of a macrotidal estuary

Vertical profiles from the water column, including the maximum turbidity zone (MTZ) to the consolidated sediment were sampled in September 2000 in the freshwater reaches of the Gironde Estuary during a complete neap tide-spring tide cycle. The vertical distributions of dissolved major redox parameters and metals (Mn, Fe, Cd, Cu, V, Co, Ni, Mo, and U) were determined. Reactive particulate metal fractions were also determined from selective leaching. The studied system is characterized by density layers functioning at different time-scales, consisting of two mobile layers, i.e., the liquid (LM) and the soft mud (SM), overlying consolidated sediments (CS). This results in a three-zone diagenetic regime where (1) O₂ dynamics are fast enough to show depletion in the rapidly mixed LM sequence (tidal time-scale), (2) denitrification occurs on the weekly time-scale mixing SM sequence, and (3) the Mn, Fe, and sulfate cycling occurs in the CS layer (annual time-scale). The studied trace metals show differential behavior during early diagenesis: (1) Cd, Cu, and V are released into pore water preferentially from organic matter in the SM, (2) Co, Ni, and U are released in the CS from Mn and Fe oxides during reductive dissolution, and (3) Mo from both processes. Transient conditions (i.e., oscillations of redox fronts and reoxidation processes), due to the dynamics of the mobile layers, strongly influence the trace metal distributions as inducing resolubilization (Cd, Cu, and Mo). In the CS, authigenic metal phases accumulate, either by direct precipitation with sulfides (Cu, Cd) or co-precipitation with Fe-sulfides (Mo). Microbially mediated reduction of Fe oxides is proposed to control U removal from pore water by reduction of U(VI) to U(IV) at depth. However, a significant fraction of the trace metals is trapped in the sediment in exchangeable forms, and therefore is susceptible to be mobilized due to resuspension of estuarine sediment during strong river flood periods and/or dredging activities.     

Laboratory condensation of refractory dust in protosolar and circumstellar conditions

In order to better understand condensation processes that took place in the solar nebula and to evaluate the effect of kinetics on the condensed matter, we have built an experimental apparatus for studying condensation of multi-elemental refractory gases at high-temperature and low-pressure. The condensation of a Mg-Si-rich gas, with solar interelement ratios of Ca, Al, Mg and Si, and of a Ca-Al-rich gas under a total pressure of ∼4 × 10⁻³ bar at temperatures from 1045 to 1285 °C and for run times of 4-60 min results in direct formation of crystalline oxides or silicates such as corundum, spinel, anorthite, melilite, Al-diopside, forsterite and enstatite. The mineralogy of the condensates, close to that predicted at equilibrium, varies with the duration of an experiment and the temperature of condensation. The chemical reactions between gas and condensates are rapid enough to attain a steady state in less than one hour. The condensation results in chemical fractionation of the gas, i.e. a depletion of the gas in refractory elements at high temperature. Finally, besides revealing the textures of refractory crystals, which condense from a gas of complex chemical composition, this study shows that certain phases, such as spinel, have favored kinetics of condensation. Our experimental results confirm that refractory inclusions in primitive meteorites could have formed by condensation from a hot nebular gas. Similarly, we confirm that crystalline grains can condense at high temperature in the outflows of evolved stars. In both cases, our results indicate that kinetic processes certainly influence grain mineralogy. Kinetic processes must thus be taken into account in modeling the pressure-temperature conditions of circumstellar environments.     

Transfer and early diagenesis of biogenic silica oxygen isotope signals during settling and sedimentation of diatoms in a temperate freshwater lake (Lake Holzmaar, Germany)

We have investigated the transfer of oxygen isotope signals of diatomaceous silica (δ¹⁸O_diatom) from the epilimnion (0-7 m) through the hypolimnion to the lake bottom (∼20 m) in freshwater Lake Holzmaar, Germany. Sediment-traps were deployed in 2001 at depths of 7 and 16 m to harvest fresh diatoms every 28 days. The 7 m trap collected diatoms from the epilimnion being the main zone of primary production, while the 16 m trap collected material already settled through the hypolimnion. Also a bottom sediment sample was taken containing diatom frustules from approximately the last 25 years. The δ¹⁸O_diatom values of the 7 m trap varied from 29.4‰ in spring/autumn to 26.2‰ in summer according to the temperature dependence of oxygen isotope fractionation and represent the initial isotope signal in this study. Remarkably, despite the short settling distance δ¹⁸O_diatom values of the 7 and the 16 m trap were identical only during spring and autumn seasons while from April to September δ¹⁸O_diatom values of the 16 m trap were roughly ∼1.5‰ enriched in ¹⁸O compared to those of the 7 m trap. Isotopic exchange with the isotopically lighter water of the hypolimnion would shift the δ¹⁸O_diatom value to lower values during settling from 7 to 16 m excluding this process as a cause for the deviation. Dissolution of opal during settling with intact organic coatings of the diatom cells and near neutral pH of the water should only cause a minor enrichment of the 16 m values. Nevertheless, opal from the bottom sediment was found to be 2.5‰ enriched in ¹⁸O compared to the weighted average of the opal from the 7 m trap. Thus, resuspension of bottom material must have contributed to the intermediate δ¹⁸O_diatom signal of the 16 m trap during summer. Dissolution experiments allowed further investigation of the cause for the remarkably enriched δ¹⁸O_diatom value of the bottom sediment. Experiments with different fresh diatomaceous materials show an increase of opaline ¹⁸O at high pH values which is remarkably reduced when organic coatings of the cells still exist or at near neutral pH. In contrast, high pH conditions do not affect the δ¹⁸O_diatom values of sub-fossil and even fossil opal. IR analyses show that the ¹⁸O enrichment of the sedimentary silica is associated with a decrease in Si-OH groups and the formation of Si-O-Si linkages. This indicates a silica dehydroxylation process as cause for the isotopic enrichment of the bottom sediment. Silica dissolution and dehydroxylation clearly induce a maturation process of the diatom oxygen isotope signal presumably following an exponential behaviour with a rapid initial phase of signal alteration. The dynamics of this process is of particular importance for the quantitative interpretation of sedimentary δ¹⁸O_diatom values in terms of palaeothermometry.     

Models of oxic respiration, denitrification and sulfate reduction in zones of coastal upwelling

Coastal upwelling zones support some of the highest rates of primary production in the oceans. The settling and subsequent decomposition of this organic matter promotes oxygen depletion. In the Eastern tropical North and South Pacific and the Arabian Sea, large tracts of anoxic water develop, where intensive N₂ production through denitrification and anammox accounts for about 1/3 of the total loss of fixed nitrogen in the marine realm. It is curious that despite extensive denitrification in these waters, complete nitrate removal and the onset of sulfate reduction is extremely rare. A simple box model is constructed here to reproduce the dynamics of carbon, oxygen and nutrient cycling in coastal upwelling zones. The model is constructed with five boxes, where water is exchanged between the boxes by vertical and horizontal mixing and advection. These primary physical drivers control the dynamics of the system. The model demonstrates that in the absence of nitrogen fixation, the anoxic waters in a coastal upwelling system will not become nitrate free. This is because nitrate is the limiting nutrient controlling primary production, and if nitrate concentration becomes too low, primary production rate drops and this reduces rates of nitrate removal through N₂ production. With nitrogen fixation, however, complete nitrate depletion can occur and sulfate reduction will ensue. This situation is extremely rare in coastal upwelling zones, probably because nitrogen-fixing bacteria do not prosper in the high nutrient, turbid waters as typically in these areas. Finally, it is predicted here that the chemistry of the upwelling system will develop in a similar matter regardless whether N₂ production is dominated by anaerobic ammonium oxidation (anammox) or canonical heterotrophic denitrification.     

Effect of hydrogen limitation and temperature on the fractionation of sulfur isotopes by a deep-sea hydrothermal vent sulfate-reducing bacterium

The fractionation of sulfur isotopes by the thermophilic chemolithoautotrophic Thermodesulfatator indicus was explored during sulfate reduction under excess and reduced hydrogen supply, and the full temperature range of growth (40-80 °C). Fractionation of sulfur isotopes measured under reduced H₂ conditions in a fed-batch culture revealed high fractionations (24-37‰) compared to fractionations produced under excess H₂ supply (1-6‰). Higher fractionations correlated with lower sulfate reduction rates. Such high fractionations have never been reported for growth on H₂. For temperature-dependant fractionation experiments cell-specific rates of sulfate reduction increased with increasing temperatures to 70 °C after which sulfate-reduction rates rapidly decreased. Fractionations were relatively high at 40 °C and decreased with increasing temperature from 40-60 °C. Above 60 °C, fractionation trends switched and increased again with increasing temperatures. These temperature-dependant fractionation trends have not previously been reported for growth on H₂ and are not predicted by a generally accepted fractionation model for sulfate reduction, where fractionations are controlled as a function of temperature, by the balance of the exchange of sulfate across the cell membrane, and enzymatic reduction rates of sulfate. Our results are reproduced with a model where fractionation is controlled by differences in the temperature response of enzyme reaction rates and the exchange of sulfate in and out of the cell.     

Magnetostratigraphic evidence from the Cold Creek bar for onset of ice-age cataclysmic floods in eastern Washington during the Early Pleistocene

This study provides a detailed magnetostratigraphy of sediments composing the Cold Creek cataclysmic flood bar in the Pasco Basin, Washington. Our interpretation suggests onset of Missoula floods or similar events prior to 1.1 myr, later than previously suggested by Bjornstad et al. [Bjornstad, B.N., Fecht, K.R., Pluhar, C.J., 2001. Long history of pre-Wisconsin, Ice Age cataclysmic floods: evidence from southeastern Washington State. Journal of Geology 109 (6), 695-713]. Nonetheless these data suggest that Channeled Scabland features formed over a much longer timespan than commonly cited, that continental ice sheets of the early Pleistocene reached as far south as those of the late Pleistocene, and that similar physiography existed in eastern Washington and perhaps Montana to both generate and route Missoula-flood-like events. This study adds paleomagnetic polarity results from 213 new samples of silts and sands derived from nine new drill cores penetrating the Cold Creek cataclysmic flood bar to our previous database of 53 samples from four boreholes, resulting in a much more robust and detailed magnetostratigraphy. Rock magnetic studies on these sediments show pure magnetite to be the predominant remanence-carrying magnetic mineral, ruling out widespread remagnetization by secondary mineralization. The magnetostratigraphy at eastern Cold Creek bar is characterized by a normal polarity interval bracketed by reversed polarities. Equating the normal zone with the Jaramillo subchron (0.99-1.07 myr) affords the simplest correlation to the magnetic polarity timescale. Western Cold Creek bar was likely deposited during the Brunhes chron (0-0.78 myr) since it exhibits mainly normal polarities with only two thin reversed-polarity horizons that we interpret as magnetic excursions during the Brunhes.     

Total organic carbon in soils and its relation with manganese concentrations in soils and vegetation close to an abandoned manganese mine

This study aimed at quantifying the total organic carbon (TOC) present in soils within the proximity of the Kgwakgwe Mn oxide ore abandoned mine, Botswana, and establish its relationship with Mn concentrations in soils and vegetation based on multivariate and Geographical Information Systems (GIS) analytical techniques. Four hundred soil samples and 200 vegetation set samples were obtained from a 4 km² area close to the abandoned mine. The TOC in soil samples were determined using a carbon/hydrogen/moisture determinator, and Mn concentrations in soils and vegetation by atomic absorption spectrophotometry. Results were processed using the statistical package for social science (SPSS), GIS, and Remote Sensing (RS) techniques with the Integrated Land and Water Information System (ILWIS), Geosoft Oasis Montaj and ArcGIS software packages. The values for TOC in the soil samples from the study area ranged from 0 wt % to 7.91 wt %, with a mean of 1.90 wt %, and at the control area, from 4.07 wt % to 4.86 wt %. The range of concentrations of Mn in soils was from 36 mg/g to 24908 mg/g and for Mn concentrations in the vegetation samples from 26 mg/g to 3611 mg/g with a mean of 598 mg/g. Results of correlation coefficients depicted very weak negative association except Mn in soils/Mn in leaves which was weak but positive. The statistical data yielded four clusters as follows: cluster one consisted mainly of Mn in leaves, cluster two was constituted of Mn in soils, and cluster four had TOC. Cluster three was dominated by the three parameters but with negative t statistic. The spatial presentation of data presented revealed little or no vegetation in the south eastern area and those close to the mine workings, and some significant vegetation in the north western part of the study area. The low TOC in the soils is associated to low vegetation cover which is considered to have been influenced by the soil clay fraction mineralogy and high concentrations of Mn.     

High rate anaerobic treatment of Sago wastewater using HUASB with PUF as carrier

Sago industry is one of the major small-scale sectors in India and over 800 units are located in the southern State of Tamilnadu. Processing of sago generates enormous quantities of high strength wastewater requiring systematic treatment prior to disposal. The present study is an attempt to treat the sago wastewater using Hybrid Upflow Anaerobic Sludge Blanket (HUASB) reactor, which offers the advantages of both fixed film and up flow anaerobic sludge blanket treatment. HUASB reactor with a volume of 5.6 L was operated at Organic Loading Rates varying from 10.7 to 24.7 kg COD/m³.day. After 130 days of startup, the reactor produced appreciable decrease in COD of wastewater and removed solids efficiently. The COD removal varied from 91–87%. While the removal of Total Solids was in the range of 61–57%, that of volatile solids varied from 70–67%. The ideal OLR for the reactor was 23.5 kg COD/m³.day. The findings of the study open up newer possibilities of design low cost and compact onsite treatment systems with very short retention periods.