Modelling weathering processes at the catchment scale: The WITCH numerical model

A numerical model of chemical weathering in soil horizons and underlying bedrock (WITCH) has been coupled to a numerical model of water and carbon cycles in forest ecosystems (ASPECTS) to simulate the concentration of major species within the soil horizons and the stream of the Strengbach granitic watershed, located in the Vosges Mountains (France). For the first time, simulations of solute concentrations in soil layers and in the catchment river have been performed on a seasonal basis. The model is able to reproduce the concentrations of most major species within the soil horizons, as well as catching the first-order seasonal fluctuations of aqueous calcium, magnesium and silica concentrations. However, the WITCH model underestimates concentrations of Mg²⁺ and silica at the spring of the catchment stream, and significantly underestimates Ca²⁺ concentration. The deficit in calculated calcium can be compensated for by dissolution of trace apatite disseminated in the bedrock. However, the resulting increased Ca²⁺ release yields important smectite precipitation in the deepest model layer (in contact with the bedrock) and subsequent removal of large amount of silica and magnesium from solution. In contrast, the model accurately accounts for the concentrations of major species (Ca, Mg and silica) measured in the catchment stream when precipitation of clay minerals is not allowed. The model underestimation of Mg²⁺ and H₄SiO₄ concentrations when precipitation of well crystallized smectites is allowed strongly suggests that precipitation of well crystallized clay minerals is overestimated and that more soluble poorly crystallized and amorphous materials may be forming. In agreement with observations on other watersheds draining granitic rocks, this study indicates that highly soluble trace calcic phases control the aqueous calcium budget in the Strengbach watershed.     

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.     

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.     

Exposure ages from relict lateral moraines overridden by the Fennoscandian ice sheet

Lateral moraines constructed along west to east sloping outlet glaciers from mountain centred, pre-last glacial maximum (LGM) ice fields of limited extent remain largely preserved in the northern Swedish landscape despite overriding by continental ice sheets, most recently during the last glacial. From field evidence, including geomorphological relationships and a detailed weathering profile including a buried soil, we have identified seven such lateral moraines that were overridden by the expansion and growth of the Fennoscandian ice sheet. Cosmogenic ¹⁰Be and ²⁶Al exposure ages of 19 boulders from the crests of these moraines, combined with the field evidence, are correlated to episodes of moraine stabilisation, Pleistocene surface weathering, and glacial overriding. The last deglaciation event dominates the exposure ages, with ¹⁰Be and ²⁶Al data derived from 15 moraine boulders indicating regional deglaciation 9600 ± 200 yr ago. This is the most robust numerical age for the final deglaciation of the Fennoscandian ice sheet. The older apparent exposure ages of the remaining boulders (14,600-26,400 yr) can be explained by cosmogenic nuclide inheritance from previous exposure of the moraine crests during the last glacial cycle. Their potential exposure history, based on local glacial chronologies, indicates that the current moraine morphologies formed at the latest during marine oxygen isotope stage 5. Although numerous deglaciation ages were obtained, this study demonstrates that numerical ages need to be treated with caution and assessed in light of the geomorphological evidence indicating moraines are not necessarily formed by the event that dominates the cosmogenic nuclide data.     

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.     

Color removal from industrial wastewater with a novel coagulant flocculant formulation

Chemically enhanced wastewater treatment is attracting substantial interest among the currently employed chemical unit processes in wastewater treatment. Coagulation-flocculation has received considerable attention for yielding high pollutant removal, especially color removal. This investigation presents a novel formulation of coagulation-flocculation for color removal from industrial wastewater and illustrates its efficiency, with aid of measurement of solid sludge content, suspended solid content, percentage of solid recovery, UV absorption in wastewater effluent from two automotive factories. The results show that the novel formulation can remove color content from wastewater efficiently. The treated wastewater had UV absorption close to distillated water and color was removed up to 96% by flocculation / coagulation treatment.     

Determination of adsorption efficiency based on cation exchange capacity related to red earth, bone meal and pulverised fly ash as ameliorants to lead contaminated soils

Efficient treatment strategies to reduce the toxicity of metal contaminated soil using cost effective techniques such as naturally available ameliorants and industrial waste have emerged. Three easily available amendments were determined: Bone meal, red earth/mud and pulverised fly ash (PFA). The application of ameliorants offered a possible alternative in situ remediation of contaminated sites without disruption to the ecosystem profile. In comparison to other ameliorants Red earth/mud was found to be efficient in intercepting lead leaching from soil amended with different lead compounds based on CEC (Cmol/g). This was associated with the heterogeneous adsorbency principle in red mud which is associated with its ability to bind metal ions (M²⁺) onto one or two types of surface sites at pH< 6.0. However areas that need to be studied and assessed (for public health concerns) critically for wide spread application of all the ameliorants include off-site effects of the ameliorants.