Kinetics of brucite dissolution at 25°C in the presence of organic and inorganic ligands and divalent metals

Brucite (Mg(OH)₂) dissolution rate was measured at 25°C in a mixed-flow reactor at various pH (5 to 11) and ionic strengths (0.01 to 0.03 M) as a function of the concentration of 15 organic and 5 inorganic ligands and 8 divalent metals. At neutral and weakly alkaline pH, the dissolution is promoted by the addition of the following ligands ranked by decreasing effectiveness: EDTA ≥ H₂PO₄⁻ > catechol ≥ HCO₃⁻ > ascorbate > citrate > oxalate > acetate ∼ lactate and it is inhibited by boric acid. At pH >10.5, it decreases in the presence of PO₄³⁻, CO₃²⁻, F⁻, oxine, salicylate, lactate, acetate, 4-hydroxybenzoate, SO₄²⁻ and B(OH)₄⁻ with orthophosphate and borate being the strongest and the weakest inhibitor, respectively. Xylose (up to 0.1 M), glycine (up to 0.05 M), formate (up to 0.3 M) and fulvic and humic acids (up to 40 mg/L DOC) have no effect on brucite dissolution kinetics. Fluorine inhibits dissolution both in neutral and alkaline solutions. From F sorption experiments in batch and flow-through reactors and the analysis of reacted surfaces using X-ray Photoelectron Spectroscopy (XPS), it is shown that fluorine adsorption is followed by its incorporation in brucite lattice likely via isomorphic substitution with OH. The effect of eight divalent metals (Sr, Ba, Ca, Pb, Mn, Fe, Co and Ni) studied at pH 4.9 and 0.01 M concentration revealed brucite dissolution rates to be correlated with the water molecule exchange rates in the first hydration sphere of the corresponding cation.The effect of investigated ligands on brucite dissolution rate can be modelled within the framework of the surface coordination approach taking into account the adsorption of ligands on dissolution-active sites and the molecular structure of the surface complexes they form. The higher the value of the ligand sorption constant, the stronger will be its catalyzing or inhibiting effect. As for Fe and Al oxides, bi- or multidentate mononuclear surface complexes, that labilize Mg-O bonds and water coordination to Mg atoms at the surface, enhance brucite dissolution whereas bi- or polynuclear surface complexes tend to inhibit dissolution by bridging two or more metal centers and extending the cross-linking at the solid surface. Overall, results of this study demonstrate that very high concentrations of organic ligands (0.01-0.1 M) are necessary to enhance or inhibit brucite dissolution. As a result, the effect of extracellular organic products on the weathering rate of Mg-bearing minerals is expected to be weak.     

Evolution of calc-alkaline to alkaline magmatism through Carboniferous convergence to Permian transcurrent tectonics,western Chinese Tianshan

Continuous magmatic activity occurred in the western Chinese Tianshan, Central Asia, from the Carboniferous to the Permian, i.e. before and after the Late Carboniferous amalgamation of Junggar and the Yili Blocks. Zircon U–Pb LA-ICPMS and Ar–Ar data reveal a coincidence in time between regional wrench faulting and granitoid emplacement. Permian post-collisional granitoids crop out within or at the margins of large-scale dextral strike-slip shear zones, some of them show synkinematic fabrics. The whole rock geochemical features of the Early-Middle Permian granitoids indicate an evolution from high-K calc-alkaline towards alkaline series. In other places of the North Tianshan, alkaline magmatism occurred together with deep marine sedimentation within elongated troughs controlled by wrench faults. Therefore, in contrast with previous interpretations that forwarded continental rift or mantle plume hypotheses, the coexistence of diverse magmatic sources during the same tectonic episode suggests that post-collisional lithosphere-scale transcurrent shearing tightly controlled the magmatic activity during the transition from convergent margin to intraplate anorogenic processes.     

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 SiO₂ 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.     

Mechanism of pyroxene and amphibole weathering—I. Experimental studies of iron-free minerals

The short term (2–40 days) dissolution of enstatite, diopside, and tremolite in aqueous solution at low temperatures (20–60°C) and pH 1–6 has been studied in the laboratory by means of chemical analyses of reacting solutions for Ca²⁺, Mg²⁺, and Si(OH)₄ and by the use of X-ray photoelectron spectroscopy (XPS) for detecting changes in surface chemistry of the minerals. All three minerals were found to release silica at a constant rate (linear kinetics) providing that ultrafine particles, produced by grinding, were removed initially by HF treatment. All three also underwent incongruent dissolution with preferential release of Ca and/or Mg relative to Si from their outermost surfaces. The preferential release of Ca, but not Mg for diopside at pH 6 was found by both XPS and solution chemistry verifying the theoretical prediction of greater mobility of cations located in M₂ structural sites. Loss mainly from M₂ sites also explains the degree of preferential loss of Mg from enstatite at pH 6; similar structural arguments apply to the loss of Ca and Mg from the surface of tremolite. In the case of diopside and tremolite initial incongruency was followed by essentially congruent cation-plus-silica dissolution indicating rapid formation of a constant-thickness, cation-depleted surface layer. Cation depletion at elevated temperature and low pH (~ 1) for enstatite and diopside was much greater than at low temperature and neutral pH, and continued reaction resulted in the formation of a surface precipitate of pure silica as indicated by solubility calculations, XPS analyses, and scanning electron microscopy.From XPS results at pH 6, model calculations indicate a cation-depleted altered surface layer of only a few atoms thickness in all three minerals. Also, lack of shifts in XPS peak energies for Si, Ca, and Mg, along with undersaturation of solutions with respect to all known Mg and Ca silicate minerals, suggest that cation depletion results from the substitution of hydrogen ion for Ca²⁺ and/or Mg²⁺ in a modified silicate structure and not from the precipitation of a new, radically different surface phase. These results, combined with findings of high activation energies for dissolution, a non-linear dependence on a_H⁺ for silica release from enstatite and diopside, and the occurrence of etch pitting, all point to surface chemical reaction and not bulk diffusion (either in solution or through altered surface layers) as the rate controlling mechanism of iron-free pyroxene and amphibole dissolution at earth surface temperatures.     

Morphological evolution of a well‐constrained,subaerial–subaqueous source to sink system: Wabush Lake

Since 1964, the Iron Ore Company of Canada has deposited iron tailings resulting from mining operations into Wabush Lake, Western Labrador, Canada. This activity has resulted in a continuous hyperpycnal flow flowing over the lake floor. Bathymetric surveys were carried out between 1999 and 2008 as part of the overall environmental Iron Ore Company of Canada plans to maintain safe disposal strategies of tailings into the lake. Here, this dataset is used to study the evolution of different channels present in Wabush Lake and their link with knickpoints found at the head of most of these channels. The channels show notable evolution from one survey to the next. Some knickpoints and channels may be followed throughout more than one survey; the evolution of these knickpoints is the process responsible for the creation of erosional channels. The context in which they appear, as well as the evolution of some of the subaqueous channels is analysed. Cyclic steps and sediment waves are also found in the lake. These rhythmic bedforms, also created by the passage of turbidity currents, are analysed. Sediment waves found in Wabush Lake show values for both wavelength and wave height that are approximately one order of magnitude smaller than most of those found in the marine environment.     

Rosia Poieni copper deposit,Apuseni Mountains,Romania: advanced argillic overprint of a porphyry system

The Rosia Poieni deposit is the largest porphyry copper deposit in the Apuseni Mountains, Romania. Hydrothermal alteration and mineralization are related to the Middle Miocene emplacement of a subvolcanic body, the Fundoaia microdiorite. Zonation of the alteration associated with the porphyry copper deposit is recognized from the deep and central part of the porphyritic intrusion towards shallower and outer portions. Four alteration types have been distinguished: potassic, phyllic, advanced argillic, and propylitic. Potassic alteration affects mainly the Fundoaia subvolcanic body. The andesitic host rocks are altered only in the immediate contact zone with the Fundoaia intrusion. Mg-biotite and K-feldspar are the main alteration minerals of the potassic assemblage, accompanied by ubiquitous quartz; chlorite, and anhydrite are also present. Magnetite, pyrite, chalcopyrite and minor bornite, are associated with this alteration. Phyllic alteration has overprinted the margin of the potassic zone, and formed peripheral to it. It is characterized by the replacement of almost all early minerals by abundant quartz, phengite, illite, variable amounts of illite-smectite mixed-layer minerals, minor smectite, and kaolinite. Pyrite is abundant and represents the main sulfide in this alteration zone. Advanced argillic alteration affects the upper part of the volcanic structure. The mineral assemblage comprises alunite, kaolinite, dickite, pyrophyllite, diaspore, aluminium-phosphate-sulphate minerals (woodhouseite-svanbergite series), zunyite, minamyite, pyrite, and enargite (luzonite). Alunite forms well-developed crystals. Veins with enargite (luzonite) and pyrite in a gangue of quartz, pyrophyllite and diaspore, are present within and around the subvolcanic intrusion. This alteration type is partially controlled by fractures. A zonal distribution of alteration minerals is observed from the centre of fractures outwards with: (1) vuggy quartz; (2) quartz + alunite; (3) quartz + kaolinite ± alunite and, in the deeper part of the argillic zone, quartz + pyrophyllite + diaspore; (4) illite + illite-smectite mixed-layer minerals ± kaolinite ± alunite, and e) chlorite + albite + epidote. Propylitic alteration is present distal to all other alteration types and consists of chlorite, epidote, albite, and carbonates. Mineral parageneses, mineral stability fields, and alteration mineral geothermometers indicate that the different alteration assemblages are the result of changes in both fluid composition and temperature of the system. The alteration minerals reflect cooling of the hydrothermal system from >400 °C (biotite), to 300–200 °C (chlorite and illite in veinlets) and to lower temperatures of kaolinite, illite-smectite mixed layers, and smectite crystallization. Hydrothermal alteration started with an extensive potassic zone in the central part of the system that passed laterally to the propylitic zone. It was followed by phyllic overprint of the early-altered rocks. Nearly barren advanced argillic alteration subsequently superimposed the upper levels of the porphyry copper alteration zones. The close spatial association between porphyry mineralization and advanced argillic alteration suggests that they are genetically part of the same magmatic-hydrothermal system that includes a porphyry intrusion at depth and an epithermal environment of the advanced argillic type near the surface.Editorial handling: B. Lehmann     

Denudation rates on cratonic landscapes: comparison between suspended and dissolved fluxes,and 10Be analysis in the Nyong and Sanaga River basins,south Cameroon

South Cameroon is located in a tropical and tectonically quiescent region, with landscapes characterized by thick highly weathered regolith, indicative of the long‐term predominance of chemical weathering over erosion. Currently this region undergoes huge changes due to accelerated mutations related to a growing population and economical developments with associated needs and increasing pressures on land and natural resources. We analysed two of the main south Cameroon rivers: the Nyong River and Sanaga River. The Sanaga catchment undergoes a contrasted tropical climate from sub‐humid mountainous and humid climate and is impacted by deforestation, agriculture, damming, mining and urbanization, especially in the Mbam sub‐basin, draining the highly populated volcanic highlands. By contrast, the Nyong catchment, only under humid tropical climate, is preserved from anthropogenic disturbance with low population except in the region of Yaoundé (Méfou sub‐basin). Moreover the Nyong basin is dam‐free and less impacted by agriculture and logging. We explore both denudation temporal variability and the ratio between chemical and physical denudation through two catchment‐averaged erosion and denudation datasets. The first one consists of an 11‐year long gauging dataset, while the second one comes from cosmogenic radionuclides [CRNs, here beryllium‐10 (¹⁰Be)] from sand sampled in the river mainstreams (timescale of tens to hundreds of thousands of years). Modern fluxes estimated from gauging data range from 5 to 100 m/Ma (10 to 200 t/km²/yr); our calculations indicate that the usual relative contribution of chemical versus physical denudation is 60% and 40%, respectively, of the total denudation. Beryllium‐10 denudation rates and sediment fluxes range from 4.8 to 40.3 m/Ma or 13 to 109 t/km²/yr, respectively, after correction for quartz enrichment. These fluxes are slightly less than the modern fluxes observed in Cameroon and other stable tropical areas. The highest ¹⁰Be‐derived fluxes and the highest physical versus chemical denudation ratios are attributed to anthropogenic impact. Copyright © 2016 John Wiley & Sons, Ltd.     

Late Wisconsinan deglaciation and proglacial lakes development in the Charlevoix region,southeastern Québec,Canada

The Charlevoix region, in southeastern Québec, is characterized by a dramatic landscape formed by the junction of the Laurentian Highlands, the Charlevoix Astrobleme and the St Lawrence Estuary. At the Last Glacial Maximum (LGM), the region was completely covered by the Laurentide Ice Sheet (LIS). The complex topography of the region was the stage of many of the major deglacial events of southern Quebec (e.g. Goldthwait Sea Invasion, St Lawrence Ice‐Stream, Saint‐Narcisse Episode). We present a detailed reconstruction of the pattern of retreat of the LIS in the Charlevoix region based on the interpretation of ice‐marginal features (e.g. moraines, fans) and glaciolacustrine landforms and deposits, two extensive field campaigns, and the interpretation of high‐resolution 3D digital aerial photographs and LiDAR data. Our results indicate five moraine complexes in the region: the Rochette, the Brûlée, the Sainte‐Anne, the Saint‐Narcisse and the Mars‐Batiscan complexes. Deltas, fans, fine‐grained sediments, littoral deposits, drainage breaches and deposits were used to identify 91 palaeo‐proglacial lakes. The identification of these lakes and their relation to moraine complexes enabled the reconstruction of six stages of lake development during the Charlevoix deglaciation. The development of proglacial lakes occurred in all types of terrain (highlands, lowlands, transitory levels above marine limit). We conclude that local topography had a decisive effect on promoting both moraine deposition and lake development. We suggest that similar topographical regions (hilly‐mountainous) that were affected by major ice‐margin stabilizations during glacial retreat should have experience small lakes dominating valleys and topographical lows.     

Some comments on the limb shift of solar lines

It has been suggested that pressure shifts are the sole cause for the systematic blue shift of solar fraunhofer lines (Hart, 1974). To check this we evaluate the significance of pressure shifts for Fe i lines. The observed wavelength shifts of a large number of lines are compared with the shifts calculated for the Lennard-Jones potential following Hindmarsh et al. (1967). The Lennard-Jones potential for the interatomic forces yield pressure shifts caused by neutral hydrogen, which explain only a small fraction of the observed blue shift. It is also shown that the quadratic Stark effect contributes insignificantly to the position of Fe i lines. Table I summarizes the average line shifts for iron lines at the center of the solar disk after correction for pressure shifts.Operated by the Association of Universities for Research in Astronomy, Inc. under contract AST 74-04129 with the National Science Foundation.