Reactive Mineral Surfaces Research Articles

Evolution of carbon fluxes during initial soil formation along the forefield of Damma glacier, Switzerland

Soil carbon (C) fluxes, soil respiration and dissolved organic carbon (DOC) leaching were explored along the young Damma glacier forefield chronosequence (7–128 years) over a three-year period. To gain insight into the sources of soil CO2 effluxes, radiocarbon signatures of respired CO2 were measured and a vegetation-clipping experiment was performed. Our results showed a clear increase in soil CO2 effluxes with increasing site age from 9 ± 1 to 160 ± 67 g CO2–C m−2 year−1, which was linked to soil C accumulation and development of vegetation cover. Seasonal variations of soil respiration were mainly driven by temperature; between 62 and 70 % of annual CO2 effluxes were respired during the 4-month long summer season. Sources of soil CO2 effluxes changed along the glacier forefield. For most recently deglaciated sites, radiocarbon-based age estimates indicated ancient C to be the dominant source of soil-respired CO2. At intermediate site age (58–78 years), the contribution of new plant-fixed C via rhizosphere respiration amounted up to 90 %, while with further soil formation, heterotrophically respired C probably from accumulated ‘older’ soil organic carbon (SOC) became increasingly important. In comparison with soil respiration, DOC leaching at 10 cm depth was small, but increased similarly from 0.4 ± 0.02 to 7.4 ± 1.6 g DOC m−2 year−1 over the chronosequence. A strong rise of the ratio of SOC to secondary iron and aluminium oxides strongly suggests that increasing DOC leaching with site age results from a faster increase of the DOC source, SOC, than of the DOC sink, reactive mineral surfaces. Overall, C losses from soil by soil respiration and DOC leaching increased from 9 ± 1 to 70 ± 17 and further to 168 ± 68 g C m−2 year−1 at the <10, 58–78, and 110–128 year old sites. By comparison, total ecosystem C stocks increased from 0.2 to 1.1 and to 3.1 kg C m−2 from the young to intermediate and old sites. Therefore, the ecosystem evolved from a dominance of C accumulation in the initial phase to a high throughput system. We suggest that the relatively strong increase in soil C stocks compared to C fluxes is a characteristic feature of initial soil formation on freshly exposed rocks.

The influence of vegetation and soil type on the speciation of iron in soil water

Soluble organic matter derived from exotic Pinus species has been shown to form stronger complexes with iron (Fe) than that derived from most native Australian species. It has also been proposed that the establishment of exotic Pinus plantations in coastal southeast Queensland may have enhanced the solubility of Fe in soils by increasing the amount of organically complexed Fe, but this remains inconclusive. In this study we test whether the concentration and speciation of Fe in soil water from Pinus plantations differs significantly from soil water from native vegetation areas. Both Fe redox speciation and the interaction between Fe and dissolved organic matter (DOM) were considered; Fe – DOM interaction was assessed using the Stockholm Humic Model. Iron concentrations (mainly Fe2+) were greatest in the soil waters with the greatest DOM content collected from sandy podosols (Podzols), where they are largely controlled by redox potential. Iron concentrations were small in soil waters from clay and iron oxide‐rich soils, in spite of similar redox potentials. This condition is related to stronger sorption on to the reactive clay and iron oxide mineral surfaces in these soils, which reduces the amount of DOM available for electron shuttling and microbial metabolism, restricting reductive dissolution of Fe. Vegetation type had no significant influence on the concentration and speciation of iron in soil waters, although DOM from Pinus sites had greater acidic functional group site densities than DOM from native vegetation sites. This is because Fe is mainly in the ferrous form, even in samples from the relatively well‐drained podosols. However, modelling suggests that Pinus DOM can significantly increase the amount of truly dissolved ferric iron remaining in solution in oxic conditions. Therefore, the input of ferrous iron together with Pinus DOM to surface waters may reduce precipitation of hydrous ferric oxides (ferrihydrite) and increase the flux of dissolved Fe out of the catchment. Such inputs of iron are most probably derived from podosols planted with Pinus.

Role of Bacterial Biomass in the Sorption of Ni by Biomass-Birnessite Assemblages

Birnessites precipitated by bacteria are typically poorly crystalline Mn(IV) oxides enmeshed within biofilms to form complex biomass-birnessite assemblages. The strong sorption affinity of bacteriogenic birnessites for environmentally important trace metals is relatively well understood mechanistically, but the role of bacterial cells and extracellular polymeric substances appears to vary among trace metals. To assess the role of biomass definitively, comparison between metal sorption by biomass at high metal loadings in the presence and absence of birnessite is required. We investigated the biomass effect on Ni sorption through laboratory experiments utilizing the birnessite produced by the model bacterium, Pseudomonas putida. Surface excess measurements at pH 6-8 showed that birnessite significantly enhanced Ni sorption at high loadings (up to nearly 4-fold) relative to biomass alone. This apparent large difference in affinity for Ni between the organic and mineral components was confirmed by extended X-ray absorption fine structure spectroscopy, which revealed preferential Ni binding to birnessite cation vacancy sites. At pH ≥ 7, Ni sorption involved both adsorption and precipitation reactions. Our results thus support the view that the biofilm does not block reactive mineral surface sites; instead, the organic material contributes to metal sorption once high-affinity sites on the mineral are saturated.

Interfacial reactivity of radionuclides: emerging paradigms from molecular-level observations

AbstractOver the past few decades an increasing array of molecular-level analytical probes has provided new detailed insight into mineral and radionuclide interfacial reactivity in subsurface environments. This capability has not only helped change the way mineral surface reactivity is studied but also how field-scale contaminant migration problems are addressed and ultimately resolved. Here we review relatively new interfacial reactivity paradigms and assess their implications for future research directions. Specific examples include understanding the following: the role of site-to-site electron conduction at mineral surfaces and through bulk mineral phases and the effects of local chemical environment on the stability of intermediate species in oxidation-reduction reactions and the importance of mechanistic reaction pathways for defining possible reaction products and thermodynamic driving force. The discussion also includes examples of how detailed molecular/microscopic characterization of field samples has changed the way complex contaminant migration problems are conceptualized and modelled.

Bio-dissolution of colloidal-size clay minerals entrapped in microporous silica gels

Four colloidal-size fractions of strongly anisotropic particles of nontronite (NAu-2) having different ratios of basal to edge surfaces were incubated in the presence of heterotrophic soil bacteria to evaluate how changes in mineral surface reactivity influence microbial dissolution rate of minerals. To avoid any particle aggregation, which could change the reactive surface area available for dissolution, NAu-2 particles were immobilized in a biocompatible TEOS-derived silica matrix. The resulting hybrid silica gels support bacterial growth with NAu-2 as the sole source of Fe and Mg. Upon incubation of the hybrid material with bacteria, between 0.3% and 7.5% of the total Fe included in the mineral lattice was released with a concomitant pH decrease. For a given pH value, the amount of released Fe varied between strains and was two to twelve-fold higher than under abiotic conditions. This indicates that complexing agents produced by bacteria play an important role in the dissolution process. However, in contrast with proton-promoted NAu-2 dissolution (abiotic incubations) that was negatively correlated with particle size, bacterial-enhanced dissolution was constant for all size fractions used. We conclude that bio-dissolution of nontronite particles under acidic conditions seems to be controlled by bacterial metabolism rather than by the surface reactivity of mineral.

Estimation of reactive mineral surface area during water–rock interaction using fluid chemical data

Mineral dissolution and precipitation reactions actively participate to control fluid chemistry during water–rock interaction. However, it is difficult to estimate and normalize bulk reaction rates if the mineral surface area effectively participating in the reactions is unknown. In this study, we evaluated the changing of the reactive mineral surface area during the interaction between CO 2-rich fluids and albitite rock reacting under flow-through conditions. Our methodology, adopting an inverse modelling approach, is based on the measured chemical fluid composition as raw data. We estimated the rates of dissolution and the reactive surface areas of the different minerals by reconstructing the chemical evolution of the interacting fluids. This was done by a reaction process schema that was defined by a fractional degree of advance of the irreversible mass-transfer process and by attaining the continuum limit during the water–rock interaction. Calculations were carried out for albite, microcline, biotite and calcite assuming that the ion activity of dissolved silica and aluminium ions was limited by the equilibrium with quartz and kaolinite. We found that the absolute dissolution rate of albite, microcline, biotite and calcite remains essentially constant as a function of time, and the calcite dissolution rate is orders of magnitude higher than silicate minerals. On the contrary, the reactive surface area of the parent minerals varied by more than two orders of magnitude during the observed reaction time, especially for albite. We propose that the reactive surface area depends mainly on the stability of the secondary mineral coating that may passivate the effective reactive surface area of the parent minerals.

Inferring the distribution of iron oxidation species on mineral surfaces during grinding of base metal sulphides

Electrochemistry plays an important role in the flotation of base metal sulphide minerals. During grinding a galvanic interaction occurs between minerals and grinding media and controls the iron contamination on mineral surfaces, which depresses mineral flotation significantly. In this study, the galvanic interaction was quantified by measuring the iron oxidation species originated from grinding media by ethylene diamine-tetra acid (EDTA) extraction in single mineral and mixed mineral systems. It was found that the extent of galvanic interaction between minerals and grinding media was intimately associated with the electrochemical reactivity of minerals. The nobler the mineral, the stronger the galvanic interaction with grinding media, and the higher the amount of iron oxidation species from grinding media. For both galena and chalcopyrite a linear relationship was observed between the amount of iron oxidation species and flotation recovery in single mineral systems. This relationship was able to predict the iron oxidation species on galena and chalcopyrite surfaces when they were mixed with pyrite separately. The distribution of iron oxidation species onto the two minerals in the mixture changed with the ratio of the mineral surface areas and was correlated with mineral flotation recovery. The major cathodic mineral in the mixture was dictated by the combination of mineral surface area and reactivity and drew iron oxidation species from the grinding media.

Measurement of the Reactive Surface Area of Clay Minerals Using Solid-State NMR Studies of a Probe Molecule

Understanding the surface reactivity of clay minerals is necessary for accurate prediction of natural weathering rates due to the ubiquity of clays in the environment as weathering products of primary minerals. However, the reactivity of the heterogeneous surfaces of a clay can be difficult to characterize as clay mineral edge sites often react at different rates or via different mechanisms than sites on the basal planes. Ultimately, a method is needed to probe quantitatively the reactive surface sites in order to predict clay mineral dissolution rates. In this study, solid-state NMR spectroscopy has been utilized to investigate surface hydroxyl species and their relation to clay surface reactivity. The surfaces of two kaolinite samples (KGa-1b and KGa-2) and two montmorillonite samples (STx-1b and SWy-2) were reacted with the probe molecule (3,3,3-trifluoropropyl)dimethylchlorosilane (TFS), which binds selectively to reactive non-hydrogen bonded Q3Si hydroxyl sites. Quantification of 19F spins in the TFS...

Mechanisms for chemostatic behavior in catchments: Implications for CO 2 consumption by mineral weathering

Concentrations of weathering products in streams often show relatively little variation compared to changes in discharge, both at event and annual scales. In this study, several hypothesized mechanisms for this “chemostatic behavior” were evaluated, and the potential for those mechanisms to influence relations between climate, weathering fluxes, and CO 2 consumption via mineral weathering was assessed. Data from Loch Vale, an alpine catchment in the Colorado Rocky Mountains, indicates that cation exchange and seasonal precipitation and dissolution of amorphous or poorly crystalline aluminosilicates are important processes that help regulate solute concentrations in the stream; however, those processes have no direct effect on CO 2 consumption in catchments. Hydrograph separation analyses indicate that old water stored in the subsurface over the winter accounts for about one-quarter of annual streamflow, and almost one-half of annual fluxes of Na and SiO 2 in the stream; thus, flushing of old water by new water (snowmelt) is an important component of chemostatic behavior. Hydrologic flushing of subsurface materials further induces chemostatic behavior by reducing mineral saturation indices and increasing reactive mineral surface area, which stimulate mineral weathering rates. CO 2 consumption by carbonic acid mediated mineral weathering was quantified using mass-balance calculations; results indicated that silicate mineral weathering was responsible for approximately two-thirds of annual CO 2 consumption, and carbonate weathering was responsible for the remaining one-third. CO 2 consumption was strongly dependent on annual precipitation and temperature; these relations were captured in a simple statistical model that accounted for 71% of the annual variation in CO 2 consumption via mineral weathering in Loch Vale.

Feldspar dissolution kinetics and Gibbs free energy dependence in a CO 2-enriched groundwater system, Green River, Utah

Reactions between CO 2-charged brines and reservoir minerals might either enhance the long-term storage of CO 2 in geological reservoirs or facilitate leakage by corroding cap rocks and fault seals. Modelling the progress of such reactions is frustrated by uncertainties in the absolute mineral surface reaction rates and the significance of other rate limiting steps in natural systems. Here we use the chemical evolution of groundwater from the Jurassic Navajo Sandstone, part of a leaking natural accumulation of CO 2 at Green River, Utah, in the Colorado Plateau, USA, to place constraints on the rates and potential controlling mechanisms of the mineral–fluid reactions, under elevated CO 2 pressures, in a natural system. The progress of individual reactions, inferred from changes in groundwater chemistry is modelled using mass balance techniques. The mineral reactions are close to stoichiometric with plagioclase and K-feldspar dissolution largely balanced by precipitation of clay minerals and carbonate. Mineral modes, in conjunction with published surface area measurements and flow rates estimated from hydraulic head measurements, are then used to quantify the kinetics of feldspar dissolution. Maximum estimated dissolution rates for plagioclase and K-feldspar are 2 × 10 − 14 and 4 × 10 − 16 mol m − 2 s − 1 , respectively. Fluid ion-activity products are close to equilibrium (e.g. Δ G r for plagioclase between − 2 and − 10 kJ/mol) and lie in the region in which mineral surface reaction rates show a strong dependence on Δ G r. Local variation in Δ G r is attributed to the injection and disassociation of CO 2 which initially depresses silicate mineral saturation in the fluid, promoting feldspar dissolution. With progressive flow through the aquifer feldspar hydrolysis reactions consume H + and liberate solutes to solution which increase mineral saturation in the fluid and rates slow as a consequence. The measured plagioclase dissolution rates at low Δ G r of 2 × 10 − 14 mol m − 2 s − 1 would be compatible with far-from-equilibrium rates of ~ 1 × 10 − 13 mol m − 2 s − 1 as observed in some experimental studies. This suggests that the discrepancy between field and laboratory reaction rates may in part be explained by the differences in the thermodynamic state of natural and experimental fluids, with field-scale reactions occurring close to equilibrium whereas most laboratory experiments are run far-from-equilibrium.

Biogeochemical weathering in sedimentary chronosequences of the Rhône and Oberaar Glaciers (Swiss Alps): Rates and mechanisms of biotite weathering

We analysed the composition of phyllosilicate minerals in sediments deposited by the Rhône and Oberaar glaciers (Swiss Alps), in order to identify processes and rates of biogeochemical weathering in relation to glacial erosion. The investigated sediments are part of chronosequences consisting of (A) suspended, ”fresh” sediment in melt water; (B) terminal moraines from the Little Ice Age (LIA; approximately 1560–1850); and (C) tills of the Younger Dryas interval (YD; approximately 11'500y BP). Secondary weathering products associated with the suspended sediment have not been observed; we therefore exclude intermittent subglacial storage and weathering of this material and assume that the suspended sediment is directly derived from mechanically abraded bedrock. This implies that biogeochemical weathering processes started once the glacially-derived sediment was deposited in the proglacial area. The combination of a developing vegetation cover, the generally high permeability allowing the percolation of precipitation, and the chemical reactivity related to the dominance of fine-grained material (< 63 μm) drives the weathering process and the initial Umbrepts present in LIA profiles undergo podzolisation and lead to the formation of Humods observed in YD profiles. Systematic XRD analyses of these chronosequences show a progressive decrease in biotite contents and a concomitant increase in pedogenically formed vermiculite with increasing sediment age. Biotite contents decrease by 25–50% in the upper 30 cm of the moraines after 145–275 yr in the proglacial environment. Biotite weathering rates are calculated using the difference in the biotite content between unweathered and weathered glacial sediments within the investigated profiles. The reactive mineral surface area is estimated geometrically, both with regards to the total relative surface (WR T) as well as to the relative edge surface (WR E). WR T Biotite weathering rates are estimated as 10 − 13 –10 − 15 mol biotite m − 2 biotite s − 1 . WR E Biotite weathering rates are on the order of 10 − 13 –10 − 14 mol biotite m − 2 biotite s − 1 . Biotite weathering rates obtained by this study are in the order of one magnitude higher in comparison to other published field-based weathering rates. Using biotite as an indicator, we therefore suggest that glacially-derived material in the area of the Oberaar and Rhône glaciers is generally subjected to enhanced biogeochemical weathering, starting immediately after deposition in the proglacial zone and subsequently continuing for thousands of years after glacier retreat.

The surface chemistry of multi-oxide silicates

The surface chemistry of natural wollastonite, diopside, enstatite, forsterite, and albite in aqueous solutions was characterized using both electrokinetic techniques and surface titrations performed for 20 min in batch reactors. Titrations performed in such reactors allow determination of both proton consumption and metal release from the mineral surface as a function of pH. The compositions, based on aqueous solution analysis, of all investigated surfaces vary dramatically with solution pH. Ca and Mg are preferentially released from the surfaces of all investigated divalent metal silicates at pH less than ∼8.5–10 but preferentially retained relative to silica at higher pH. As such, the surfaces of these minerals are Si-rich and divalent metal poor except in strongly alkaline solutions. The preferential removal of divalent cations from these surfaces is coupled to proton consumption. The number of protons consumed by the preferential removal of each divalent cation is pH independent but depends on the identity of the mineral; ∼1.5 protons are consumed by the preferential removal of each Ca atom from wollastonite, ∼3 protons are consumed by the preferential removal of each Mg or Ca atom from diopside or enstatite, and ∼4 protons are consumed by the preferential removal of each Mg from forsterite. These observations are interpreted to stem from the creation of additional ‘internal’ adsorption sites by the preferential removal of divalent metal cations which can be coupled to the condensation of partially detached Si. Similarly, Na and Al are preferentially removed from the albite surface at 2 > pH > 11; mass balance calculations suggest that three protons are consumed by the preferential removal of each Al atom from this surface over this entire pH range. Electrokinetic measurements on fresh mineral powders yield an isoelectric point (pH IEP) 2.6, 4.4, 3.0, 4.5, and <1, for wollastonite, diopside, enstatite, forsterite, and albite, respectively, consistent with the predominance of SiO 2 in the surface layer of all of these multi-oxide silicates at acidic pH. Taken together, these observations suggest fundamental differences between the surface chemistry of simple versus multi-oxide minerals including (1) a dependency of the number and identity of multi-oxide silicate surface sites on the aqueous solution composition, and (2) the dominant role of metal–proton exchange reactions on the reactivity of multi-oxide mineral surfaces including their dissolution rate variation with aqueous solution composition.

Model system studies of the influence of bacterial biofilm formation on mineral surface reactivity

Biofilm development on mineral surfaces and related changes in surface reactivity were studied using batch and flow through experiments. An artificial groundwater was used as the primary nutrient medium, Pseudomonas aeruginosa (PAO1) was the model microbial organism and ‘mineral’ surfaces were kept as simple as possible by using glass or a polished quartz tile. Experiments were also completed with very low concentrations (100 mg l−1) of iron, Fe2+ , in the solution. In situ confocal laser scanning microscopy of developing colonies during the live growth phase, and of thick, mature biofilms, revealed only sporadic coverage of biofilm cells and associated polymers at the ‘mineral–microbe interface’. Imaging and analysis of biofilm-conditioned surfaces doped with Fe2+ -rich solutions allowed the locus and form of Fe-rich mineral precipitation to be determined and show that biological surface components can cause mineral precipitation from dilute dissolved species which might otherwise remain in solution.

Theoretical investigation of the water/corundum (0001) interface

For the reliable long-term modeling of the actinide migration in geological formations, the adsorption/desorption properties and the reactivity of mineral surfaces must be understood at the molecular level. The adsorption of radioisotopes at mineral surfaces of the aquifer is an important process that leads to the retention of contaminants such as radionuclides. Their transport by the ground water is either retarded or even completely inhibited by the presence of such a surface. Accordingly, this subject is of main importance for the safety assessment of nuclear waste repositories. As part of a joint theoretical/experimental effort, the interaction of water with the corundum (0001) surface is studied using several theoretical methods (Moller-Plesset perturbation theory, coupled cluster singles doubles with triplet corrections, as well as density functional theory). We focus in this study on the determination of the bond lengths and tilt angles of the surface OH species and their respective vibrational frequencies. The theoretical results are confirmed by subsequent simulation of the interface selective nonlinear sum frequency spectra. The excellent agreement of the simulated with the experimental spectra allows an assignment of the observed peaks in the sum frequency spectra of the water/corundum (0001) interface on the basis of our theoretical data. In this theoretical study we are able to give a unique interpretation of the observed sum frequency spectra of the water/corundum (0001) interface.

Biogeochemistry of mineral–organic associations across a long-term mineralogical soil gradient (0.3–4100 kyr), Hawaiian Islands

Organic matter (OM) in mineral–organic associations (MOAs) represents a large fraction of carbon in terrestrial ecosystems which is considered stable against biodegradation. To assess the role of MOAs in carbon cycling, there is a need to better understand (i) the time-dependent biogeochemical evolution of MOAs in soil, (ii) the effect of the mineral composition on the physico-chemical properties of attached OM, and (iii) the resulting consequences for the stabilization of OM. We studied the development of MOAs across a mineralogical soil gradient (0.3–4100 kyr) at the Hawaiian Islands that derived from basaltic tephra under comparable climatic and hydrological regimes. Mineral–organic associations were characterized using biomarker analyses of OM with chemolytic methods (lignin phenols, non-cellulosic carbohydrates) and wet chemical extractions, surface area/porosity measurements (N 2 at 77 K and CO 2 at 273 K), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The results show that in the initial weathering stage (0.3 kyr), MOAs are mainly composed of primary, low-surface area minerals (olivine, pyroxene, feldspar) with small amounts of attached OM and lignin phenols but a large contribution of microbial-derived carbohydrates. As high-surface area, poorly crystalline (PC) minerals increase in abundance during the second weathering stage (20–400 kyr), the content of mineral-associated OM increased sharply, up to 290 mg C/g MOA, with lignin phenols being favored over carbohydrates in the association with minerals. In the third and final weathering stage (1400–4100 kyr), metastable PC phases transformed into well crystalline secondary Fe and Al (hydr)oxides and kaolin minerals that were associated with less OM overall, and depleted in both lignin and carbohydrate as a fraction of total OM. XPS, the N 2 pore volume data and OM–mineral volumetric ratios suggest that, in contrast to the endmember sites where OM accumulated at the surfaces of larger mineral grains, topsoil MOAs of the 20–400-kyr sites are composed of a homogeneous admixture of small-sized PC minerals and OM, which originated from both adsorption and precipitation processes. The chemical composition of OM in surface-horizon MOAs, however, was largely controlled by the uniform source vegetation irrespective of the substrate age whereas in subsoil horizons, aromatic and carboxylic C correlated positively with oxalate-extractable Al and Si and CuCl 2-extractable Al concentrations representing PC aluminosilicates and Al-organic complexes ( r 2 > 0.85). Additionally, XPS depth profiles suggest a zonal structure of sorbed OM with aromatic carbons being enriched in the proximity of mineral surfaces and amide carbons (peptides/proteins) being located in outer regions of MOAs. Albeit the mineralogical and compositional changes of OM, the rigidity of mineral-associated OM as analyzed by DSC changed little over time. A significantly reduced side chain mobility of sorbed OM was, however, observed in subsoil MOAs, which likely arose from stronger mineral–organic bindings. In conclusion, our study shows that the properties of soil MOAs change substantially over time with different mineral assemblages favoring the association of different types of OM, which is further accentuated by a vertical gradient of OM composition on mineral surfaces. Factors supporting the stabilization of sorbed OM were (i) the surface area and reactivity of minerals (primary or secondary crystalline minerals versus PC secondary minerals), (ii) the association of OM with micropores of PC minerals (via ‘sterically’ enhanced adsorption), (iii) the effective embedding of OM in ‘well mixed’ arrays with PC minerals and monomeric/polymeric metal species, (iv) the inherent stability of acidic aromatic OM components, and (iv) an impaired segmental mobility of sorbed OM, which might increase its stability against desorption and microbial utilization.

Combining cosmogenic nuclides and major elements from moraine soil profiles to improve weathering rate estimates

Previous studies of chemical weathering rates for soil developed on glacial moraines generally assumed little or no physical erosion of the soil surface. In this study, we investigate the influence of physical erosion on soil profile weathering rate calculations. The calculation of chemical weathering rates is based on the assumption that soil profiles represent the integrated amount of weathering since the time of moraine deposition. The weathering rate of a surface subjected to denudation is the sum of the weathering loss from the existing soil profile added to the weathering loss in the material removed by denudation, divided by the deposition age. In this study, the amount of weathered material removed since moraine deposition is calculated using the denudation rate estimated from cosmogenic nuclide data and the deposition age of the moraine. Weathering rates accounting for denudation since moraine deposition are compared to weathering rates based on the assumption of no physical erosion and on the assumption of steady-state denudation for the Type Pinedale moraine (∼ 21 ka) and the Bull Lake-age moraine (∼ 140 ka) in the Fremont Lake Area (Wind River Mountains, Wyoming, USA). The total weathering rates accounting for denudation are 8.15 ± 1.05 g (oxide) m − 2 y − 1 for the Type Pinedale moraine and 4.78 ± 0.89 g (oxide) m − 2 y − 1 for the Bull Lake-age moraine, which are ∼ 2 to 4 times higher, respectively, than weathering rates based on the assumption of no physical erosion. The weathering rates based on denudation since moraine deposition are comparable or smaller than weathering rates assuming steady-state denudation. We find the assumption of steady-state denudation is not valid in depositional landscapes with young deposition ages or slow denudation rates. The decrease in weathering rates over time between the Type Pinedale and Bull Lake-age soils that is observed in the case of no physical erosion is decreased when the influence of denudation on the total weathering rates is taken into account. Fresh unweathered material with high reactive mineral surface area is continuously provided to the surface layer by denudation diminishing the effect of decreasing weathering rate over time.

Mineral weathering rates in glacial drift soils (SW Michigan, USA): New constraints from seasonal sampling of waters and gases at soil monoliths

Soil solutions and gases were sampled along 200 cm deep soil profiles from four instrumented soil monoliths in southwest Michigan, established on coarse-grained glacial drift deposits. Seasonal sampling enabled evaluation of thermodynamic versus kinetic controls on carbonate- and silicate-mineral weathering rates, allowing better integration with past field hydrogeochemical studies of Michigan soil and surface water systems. Silicate-weathering products dominate water chemistry in the upper soil zones. Carbonate minerals, comprised of subequal amounts of calcite and dolomite, are only present at depths below 150 cm. When present, carbonate dissolution is rapid and soil water Ca 2+ and Mg 2+ concentrations increase dramatically as observed in other natural soil study sites in southern Michigan. Soil water saturation states are near equilibrium with respect to calcite and slightly less saturated with respect to dolomite. The divalent cations of soil waters and soil CO 2 both show a seasonal trend, with concentration maxima occurring in September and minima in April, suggesting that soil water Ca 2+ and Mg 2+ concentrations are under equilibrium control with carbonate solubility limited by temperature-dependent pCO 2 rather than by direct effects of temperatures. Importantly, monolith soil water Mg 2+/Ca 2+ and calcite and dolomite saturation states are lower than those of streams in the same watershed and also lower than those of soil waters in other Michigan watersheds. Because carbonate weight percentages and chemical compositions in these sites are similar, this difference likely reflects the short exposure path (thus short residence time) of soil waters to carbonate-rich horizons in the monoliths. The dissolution reactions of primary aluminosilicate minerals are incongruent with respect to Al and Si due to kaolinite formation. However, major cations (Ca 2+, Mg 2+, K + and Na +) are stoichiometrically released from silicate dissolution. Na ⁎ (soil water Na + after correction for atmospheric input and derived primarily from plagioclase weathering) exhibits much less seasonality than divalent cations, with only slight elevations observed in the summer months. Soil water H 4SiO 4 0 concentrations show seasonal variations similar to the divalent cations, but are determined by the balance between production (silicate-mineral dissolution) and consumption (kaolinite precipitation). Plagioclase and amphibole are below saturation, and these dissolution reactions must be kinetically controlled. Through a conservative tracer study, about 15% to 45% of applied Br passed out of the monolith profiles in 40–160 days and this long mineral–water contact time is especially important for slow reactions such as silicate dissolution. Based on water chemistry and discharge, bulk reaction rates of calcite, dolomite (Ca 0.5Mg 0.5CO 3), K-feldspar and plagioclase are calculated to be at 3400, 3100, 220, and 320 mol ha − 1 yr − 1 , respectively. Based on mass balance of soil composition, long-term plagioclase-weathering rates (over the past 12,500 years) are calculated at about 2400 mol ha − 1 yr − 1 , much higher than the current rates. This agrees with previous conclusions that weathering rates decrease with time, due to loss of reactive mineral surfaces. Furthermore, both long-term and short-term plagioclase dissolution rates in Michigan are relatively high compared to those in other watersheds with similar age, possibly due to fresh surfaces produced by glaciation, in combination with the high discharge and high plagioclase abundances.

Medical Mineralogy and Geochemistry: An Interfacial Science

Research Article| December 01, 2007 Medical Mineralogy and Geochemistry: An Interfacial Science Nita Sahai Nita Sahai *Dept. of Geology & Geophysics, Dept. of Chemistry University of Wisconsin-Madison 1215 W Dayton St, Madison, WI 53706, USA E-mail: sahai@geology.wisc.edu Search for other works by this author on: GSW Google Scholar Elements (2007) 3 (6): 381–384. https://doi.org/10.2113/GSELEMENTS.3.6.381 Article history first online: 09 Mar 2017 Cite View This Citation Add to Citation Manager Share Icon Share Facebook Twitter LinkedIn MailTo Tools Icon Tools Get Permissions Search Site Citation Nita Sahai; Medical Mineralogy and Geochemistry: An Interfacial Science. Elements 2007;; 3 (6): 381–384. doi: https://doi.org/10.2113/GSELEMENTS.3.6.381 Download citation file: Ris (Zotero) Refmanager EasyBib Bookends Mendeley Papers EndNote RefWorks BibTex toolbar search Search Dropdown Menu toolbar search search input Search input auto suggest filter your search All ContentBy SocietyElements Search Advanced Search Abstract Medical mineralogy and geochemistry is a highly interdisciplinary area of research where the complexity of minerals and mineral surface reactivity in the human body is emphasized. Research in this field will lead to an understanding of the biogeochemical processes responsible for medical conditions, both normal and pathological, that involve the interaction of dissolved inorganic species and bioorganic molecules with minerals. In this article, I highlight some fundamental concepts and challenges in this endeavor, and the subsequent articles provide overviews of specific topics. You do not have access to this content, please speak to your institutional administrator if you feel you should have access.

Controls on major solutes within the drainage network of a rapidly weathering tropical watershed

Surface water chemistry in the main stem and source points of the Rio Icacos basin (Luquillo Experimental Forest, Puerto Rico) was studied to investigate the factors regulating spatial variability in major solutes in a rapidly weathering landscape. We sampled along the main stem as well as at small source points at high elevation where fresh bedrock is frequently exposed, and at low elevation in the floodplain/colluvial plain of the main stem. Concentrations of silicon, alkalinity, and the sum of base cations were lower at the source points than in the main stem, and were lowest in low‐elevation source points. Calcium and sodium were the dominant cations at all sampling points after sea‐salt correction, reflecting the weathering of plagioclase feldspar throughout the basin. The partial pressure of carbon dioxide (pCO2) tended to be higher, and HCO3− concentrations were lower, in the low‐elevation source points than at other positions in the landscape. When coupled with the relatively low concentrations of Si and base cations, this suggests that the availability of primary reactive minerals, rather than carbonic acid concentrations, limits weathering in these low‐elevation sources. Mechanical denudation appears to enhance chemical weathering rates not only by refreshing reactive mineral surfaces but also by contributing carbon dioxide from the decomposition of organic‐rich material in landslides, which occur frequently. The spatial variability of major solutes appears to depend primarily on the availability of fresh primary reactive minerals, carbon dioxide concentrations, and hydrolysis conditions.

“Bioshrouding”—a novel approach for securing reactive mineral tailings

A novel technique ("bioshrouding") for safeguarding highly reactive sulfidic mineral tailings deposits is proposed. In this, freshly milled wastes are colonised with ferric iron-reducing heterotrophic acidophilic bacteria that form biofilms on reactive mineral surfaces, thereby preventing or minimising colonisation by iron sulfide-oxidising chemolithotrophs such as Acidithiobacillus ferrooxidans and Leptospirillum spp. Data from initial experiments showed that dissolution of pyrite could be reduced by between 57 and 75% by "bioshrouding" the mineral with three different species of heterotrophic acidophiles (Acidiphilium, Acidocella and Acidobacterium spp.), under conditions that were conducive to microbial oxidative dissolution of the iron sulfide.