Storage of CO2 as solid Ca, Mg, and Fe carbonates in basaltic rocks may provide a long-lasting solution for reduction of industrial CO2 emissions. Here, we report on the underground stratigraphy of the chemical composition and crystallinity of rocks and their alteration state at a targeted field site for injection of CO2-charged waters, the Hellisheidi area in SW Iceland.

We live at the dynamic interface between the solid Earth and its outer fluid envelopes. This interface, extending from the outer vegetation canopy to the base of active groundwater, was recently named the Critical Zone because it supports life and is increasingly impacted by human actions. Understanding the complex interactions between processes that operate in and shape the Critical Zone requires interdisciplinary approaches that span wide spatial and temporal scales. Tectonic processes, weathering, fluid transport, and biological processes control the function and structure of the Critical Zone. Three Critical Zone Observatories recently established by the U.S. National Science Foundation are designed to integrate studies of process interactions up to the watershed scale. A goal of the program is to build the three independently conceived observatories into a network from which broader understanding — larger spatial scales but also deeper insight — can emerge.

Weathering of terrestrial Ca- and Mg-bearing silicate minerals is an important control on atmospheric CO2 on geological time scales. It has been determined that vascular plants can accelerate mineral weathering as compared to non-vascular plants or non-vegetated surfaces. This indicates that the evolution of vascular plants, particularly the deep-rooted trees, may play a large role in the long-term carbon cycle and its regulation of the atmosphere. The weathering impact of the separate evolutionary appearances of the gymnosperms in the Palaeozoic and the angiosperms in the Mesozoic, and the shifting ecological dominance from the former to the latter, is currently poorly understood. This study aims to contribute to our understanding of the quantitative weathering rates of the angiosperms and gymnosperms by examining plant-mineral interactions of the two tree types in a temperate field setting underlain by granodiorite. Results include determinations of soil element fluxes and etching of minerals. The observed root-mineral interactions resulted in only slightly more weathering of Ca-bearing minerals by the angiosperms. However, we observed significantly more weathering of the Mg-bearing minerals by the gymnosperms. These results suggest that increasing dominance of the angiosperms in forests in the Mesozoic may have had a small or neutral impact on accelerating overall mineral weathering and regulating CO2, but that this impact may be lithology-dependent.

Presented here are quantitative dissolution rate data (volume of pyrite lost/time) for the inorganic oxidation of pyrite in synthetic, anaerobic and acidic (pH 2) hydrothermal vent fluids (HVF) from experiments where the volume loss was measured directly via Vertical Scanning Interferometry (VSI). The VSI-derived reaction rate was 2.12x10-10±1.14x10-1 mol/m2/min, which is ∼2 to 4 orders of magnitude slower than pyrite oxidation rates previously determined using traditional batch experiments where rates are calculated based on changes in solution chemistry. This lower rate stems primarily from differences in experimental conditions (i.e. water to rock ratios, vigorous vs. gentle stir rates, grain-size effects, time), yet the rates derived here are believed to be more representative of pyrite oxidation in natural environments where more static and high solution to solid rate conditions prevail, such as seafloor conditions or acid-mine-drainage environments.

The understanding of biogeochemical processes at the interface between geosphere, hydrosphere and biosphere is of paramount importance for many questions related to global climate and environmental change at very different time and spatial scales. In addition, soils are the principal resource for food production and the understanding of soil formation processes and biological interactions within soils is indispensable for the development of sustainable land-use strategies. In this contribution we present a research initiative, the multidisciplinary ‘BigLink’ Project, aiming at a better understanding of the links between weathering, soil formation and ecosystem evolution and how these biosphere-geosphere interactions are influenced (and themselves influence) climate and environmental change.

Elemental compositions of the <2mm fraction of three sediments sampled along the Kupa River are presented. On plots of log(SiO2/Al2O3) vs. log(CaO+Na2O)/K2O, the sediments plot closest to average sandstone compositions. On plots of weathering indices A vs. B (Kronberg and Nesbitt, 1981) the sediments plot close to basalt, terrestrial crust and granite. X-ray diffraction of the <63 μm fraction suggests chlorite, vermiculite and mica are present as weathering products in the upper, middle and lower stream sediments. Depletion of some elements in the sediments suggests loss of elements from the sediments due to dissolution of minerals.

The kinetics of glauconite dissolution have been determined in the pH range 2—10 (T = 25°C) using flow-batch reactor experiments. Besides the kinetic characteristics, the structural and textural aspects which could influence its long-term reactivity have also been characterized by means of X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM) and BET surface area measurements. The results from these analyses showed that glauconite follows a dual dissolution pathway which is pH-dependent, being more stable at neutral or slightly alkaline pH values. Under acidic conditions, glauconite is slightly more soluble than other ubiquitous silicates present in the marine sediments. The dissolution mechanism is incongruent at very acid pH values and tends to be congruent for intermediate and neutral ones. In addition, the results from the structural analyses suggest that the dissolution is a two-step process: the first one involves the disorder of the octahedral and tetrahedral layers, probably following a turbostratic mechanism which is evident in the XRD spectra as selective broadening of several reflections. In the second step, the dissolution of the cations from interlayer positions takes place and leads to the formation of an amorphous residue which acts as a passivating layer and reduces the reactive surface considerably. The influence of these aspects on CO2 capture via carbonation reactions is discussed.

Minerals are an important component of the soil environment (Dixon et al., 1977). They provide a structural framework which supports plants and contribute to the physical heterogeneity of soil. Minerals also contribute to the fertility of soils. Primary minerals are a source of essential plant nutrients (Harley and Gilkes, 2000). Clay minerals impact on the water-holding capacity of soils, affect the cation exchange capacity of soils (Brown, 1977) and are able to sequester nutrients and contaminants within the soil (Dubbin, 2001).

Earth scientists currently use changes in major and minor elements as an indication of rock alteration. Work on spheroidal weathering has shown an increase in the rare earth element (REE) whole-rock abundancescan accompany minor changes in major elementsand highlights the need for new, more sensitive, geochemical techniques of detecting incipient alteration. Augites from the core and rind of a corestone system from the Tecuamburro complex in SE Guatemala are examined to determine their role in the whole-rock REE increases.

Steady-state dissolution rates of basaltic glass were measured in mixed-flow reactors at 50ºC at pH 3 and 4 as a function of aqueous sulphate concentration. Dissolution rates in the presence of 0.1 moles/kg SO42- were found to be ~3 times greater than those in corresponding SO42- free solutions. This rate increase is found to be approximately consistent with that calculated using a rate equation previously proposed by Gislason and Oelkers (2003). These results suggest that the addition of sulphate to injected CO2 may facilitate CO2 sequestration in basalts by accelerating basaltic glass dissolution rates thus more rapidly releasing aqueous Ca and Mg to solution.

Coal slag and ash, obtained from burning coal in a textile factory in Duga Resa (Croatia) was discharged directly into the Mrežnica River for 110 y (1884–1994), from where it travelled to the Korana River and further to the Kupa River at Karlovac, a total of ~50km from its source. Of 54 elements determined by inductively coupled plasma mass spectrometry (ICP-MS) in the <2 mm sediment fraction, a number of anomalously high levels were recorded. The geoaccumulation index (Igeo) for the anomalous elements were: Hg (1.88), B (4.05), Na (1.44), Al (2.05), V (1.65), Cr (1.20), Fe (1.18), Ni (2.10), Cu (2.37), Sr (0.97), Zr (3.27), Mo (3.34) and U (4.03). Low-field magnetic susceptibility (MS) was measured for each sample. The Igeo for MS in the anomalous region is 5.85. Correlation analysis showed good correlation (>0.90) of MS with: B (0.96), U (0.95), Zr (0.94), Sr (0.93), Na (0.92), Mo (0.92) and Ni (0.90). Cluster analysis of R-modality indicates that MS is linked to B, Mo, Na and U. Low correlation of MS with Fe (0.36) suggests that Fe in stream sediments is not in a ferromagnetic form. Neither maghemite, nor magnetite phases were identified by X-ray diffraction (XRD) in the sediments. Low-field magnetic susceptibility provides an indicator of contamination of river sediments by transported coal slag and ash, although it cannot be prescribed to a single element.

At Niquelândia, Cr extracted from the soil (5,000–9,300 mg.kg-1) is likely the result of the Cr-bearing Fe-oxides compared to the Cr-spinels, showing that low Cr-containing minerals present in the dunite (enstatite, olivine and clay minerals) have been completely dissolved. The chromites, accumulated inside soil profiles, have undergone chemical weathering, leading to a Cr enrichment during soil genesis. Traces of dissolution inside the soil chromites suggest that they can be slowly weathered. In this case chromites could represent a diffuse source of available Cr(III) within the soil profiles.

The effects of CO2 on water-basaltic glass interaction have been simulated at 25ºC. The calculations indicate that addition of CO2 (2—30 bar) to water significantly changes the reaction path. Initially, the pH is buffered between 4 and 6 by CO2 ionization, with dissolution of basaltic glass and the formation of secondary minerals with SiO2, Mg-Fe carbonates and dolomite predominating. Upon the dissolution of additional basaltic glass and mineral fixation of CO2, the pH increases to >8 and (Ca)-Fe-Mg smectites, SiO2, Ca-Na zeolites and calcite become the dominant secondary minerals forming. The overall reaction path depends on the initial water composition, reactive surface area, and the composition of the phyllosilicates and carbonates forming. The key factors are the mobility of Mg2+, Fe2+ and Ca2+ and the competing reactions for these solutes among secondary minerals.

Most fungi synthesize siderophores as chelating agents which form soluble complexes with Fe3+ with very high stability constants, thus solubilizing ferric Fe. Ericoid mycorrhizal fungi release ferricrocin or fusigen as the main siderophores. Ferricrocin was also shown to be produced by the ectomycorrhizal fungi, Cenococcum geophilum and Hebeloma crustuliniforme. Arbuscular mycorrhizal fungi are reported to enhance Fe-uptake rates of associated host plants which can be taken as an indication that mycorrhizal siderophores of a yet unknown structure may be involved. Mycorrhizal fungi of orchids were shown to produce as the main siderophores, both well known ferrichrome-type siderophores or the novel linear trishydroxamate basidiochrome.

Geochemical research on natural weathering has often been directed towards explanations of the chemical composition of surface water and ground water resulting from subsurface water-rock interactions. These interactions are often defined as the incongruent dissolution of primary silicates, such as feldspar, producing secondary weathering products, such as clay minerals and oxyhydroxides, and solute fluxes (Meunier and Velde, 1979). The chemical composition of the clay-mineral product is often ignored. However, in earlier investigations, the saprolitic weathering profile at the South Fork Brokenback Run (SFBR) watershed, Shenandoah National Park, Virginia, was characterized extensively in terms of its mineralogical and chemical composition (Piccoli, 1987; Pochatila et al., 2006; Jones et al., 2007) and its basichydrology. O’Brien et al. (1997) attempted to determine the contribution of primary mineral weathering to observed stream chemistry at SFBR. Mass-balance model results, however, could provide only a rough estimate of the weathering reactions because idealized mineral compositions were utilized in the calculations. Making use of detailed information on the mineral occurrence in the regolith, the objective of the present study was to evaluate the effects of compositional variation on mineral-solute mass-balance modelling and to generate plausible quantitative weathering reactions that support both the chemical evolution of the surface water and ground water in the catchment, as well as the mineralogical evolution of the weathering profile.

Laboratory experiments with two cyanobacterial strains grown on low-nutrient agar media in the presence of biotite flakes were performed in order to reveal possible mechanisms and rates of cyanobacterial bioweathering. Both cyanobacteria colonized the biotite flakes. Leptolyngbya grew mostly in the biotite interlayers, whereas Hassallia colonized the sides and the topmost surface of the biotite flakes. After a 3-month incubation, rounded features including cyanobacterium-shaped pits were observed on the biotite surface cleared of the organic material. No such features were observed on flakes incubated for 1 month.

During chemical weathering and natural hydrothermal reactions, apatite can form by replacing calcium carbonates. In hydrothermal experiments in which aragonite and calcite single crystals have been reacted with phosphate solutions, the carbonates are replaced by polycrystalline hydroxylapatite (HAP). In both cases the crystals have retained their overall morphology while their compositions have changed significantly. The HAP appears to have a crystallographic relationship to the parent carbonate crystals. The textural relationships are consistent with an interface-coupled dissolution-precipitation mechanism. Structural relationships and relative molar volumes and solubilities appear to be factors that greatly affect replacement reactions.

Weathering ofdischarged mine tailings contaminates streams, rivers and floodplains with toxic metals on a vast scale. The magnitude of the problem depends on input tailings mineralogy, storage and dispersal, and climatic conditions. To better understand the mechanisms of long-term tailings weathering, a leaching column study was established, incorporating tailings and soil from Potosí, Bolivia, with the aim of modelling a 25 year field period. The Zn/Cd molar ratio ofthe tailings leachate water, initially 738 for the unaltered tailings, is highly variable over 15 model years of leaching, particularly in the mixed tailings-soil columns. Columns with soil have ratios as high as 2563, while pure tailings columns reach ratios of <376. We employ complementary techniques, involving atomistic computational modelling, leachate analysis and mineralogical characterization, to elucidate the mechanisms governing these incongruent Cd and Zn weathering dynamics.

Biological weathering is a function of biotic energy expenditure. Growth and metabolism of organisms generates acids and chelators, selectively absorbs nutrient ions, and applies turgor pressure and other physical forces which, in concert, chemically and physically alter minerals. In unsaturated soil environments, plant roots normally form symbiotic mycorrhizal associations with fungi. The plants provide photosynthate-carbohydrate-energy to the fungi in return for nutrients absorbed from the soil and released from minerals. In ectomycorrhiza, one of the two major types of mycorrhiza of trees, roots are sheathed in fungus, and 15—30% of the net photosynthate of the plants passes through these fungi into the soil and virtually all of the water and nutrients taken up by the plants are supplied through the fungi. Here we show that ectomycorrhizal fungi actively forage for minerals and act as biosensors that discriminate between different grain sizes (53—90 μm, 500—1000 μm) and different minerals (apatite, biotite, quartz) to favour grains with a high surface-area to volume ratio and minerals with the highest P content. Growth and carbon allocation of the fungi is preferentially directed to intensively interact with these selected minerals to maximize resource foraging.