X-ray photoelectron spectroscopic studies of dolomite surfaces exposed to undersaturated and supersaturated aqueous solutions

Cleaved surfaces of dolomite were studied using ex-situ X-ray photoelectron spectroscopy (XPS) following exposure of the surfaces to various experimental conditions. Dolomite samples exposed to air, to a highly undersaturated solution (0.1 M NaCl, pH = 9), and to solution with a supersaturation (−Δμ/kT) of 5.5 (pH = 9) were investigated with semiquantitative methods of analysis to ascertain the degree of non-stoichiometry resulting at the dolomite surface from reactive conditions. It was found that the dolomite cleavage surface in undersaturated solution was not altered significantly from the stoichiometric surface termination. The composition of the cleaved surface after exposure to supersaturated solution, a surface known to have self-limiting growth characteristics under similar conditions, was found to be Ca²⁺ rich (Ca_xMg_2 − x(CO₃)₂, 1.7 > x > 1.3). The observations, while underscoring differences in hydration/dehydration kinetics of the two alkaline earth cations, suggest that achievement of equilibrium at dolomite-water interfaces may be subject to significant barriers from both undersaturated and supersaturated solutions.     

Iron isotope fractionation and atom exchange during sorption of ferrous iron to mineral surfaces

The application of stable Fe isotopes as a tracer of the biogeochemical Fe cycle necessitates a mechanistic knowledge of natural fractionation processes. We studied the equilibrium Fe isotope fractionation upon sorption of Fe(II) to aluminum oxide (γ-Al₂O₃), goethite (α-FeOOH), quartz (α-SiO₂), and goethite-loaded quartz in batch experiments, and performed continuous-flow column experiments to study the extent of equilibrium and kinetic Fe isotope fractionation during reactive transport of Fe(II) through pure and goethite-loaded quartz sand. In addition, batch and column experiments were used to quantify the coupled electron transfer-atom exchange between dissolved Fe(II) (Fe(II)_aq) and structural Fe(III) of goethite. All experiments were conducted under strictly anoxic conditions at pH 7.2 in 20 mM MOPS (3-(N-morpholino)-propanesulfonic acid) buffer and 23 °C. Iron isotope ratios were measured by high-resolution MC-ICP-MS. Isotope data were analyzed with isotope fractionation models. In batch systems, we observed significant Fe isotope fractionation upon equilibrium sorption of Fe(II) to all sorbents tested, except for aluminum oxide. The equilibrium enrichment factor, , of the Fe(II)_sorb-Fe(II)_aq couple was 0.85 ± 0.10‰ (±2σ) for quartz and 0.85 ± 0.08‰ (±2σ) for goethite-loaded quartz. In the goethite system, the sorption-induced isotope fractionation was superimposed by atom exchange, leading to a δ^56/54Fe shift in solution towards the isotopic composition of the goethite. Without consideration of atom exchange, the equilibrium enrichment factor was 2.01 ± 0.08‰ (±2σ), but decreased to 0.73 ± 0.24‰ (±2σ) when atom exchange was taken into account. The amount of structural Fe in goethite that equilibrated isotopically with Fe(II)_aq via atom exchange was equivalent to one atomic Fe layer of the mineral surface (∼3% of goethite-Fe). Column experiments showed significant Fe isotope fractionation with δ^56/54Fe(II)_aq spanning a range of 1.00‰ and 1.65‰ for pure and goethite-loaded quartz, respectively. Reactive transport of Fe(II) under non-steady state conditions led to complex, non-monotonous Fe isotope trends that could be explained by a combination of kinetic and equilibrium isotope enrichment factors. Our results demonstrate that in abiotic anoxic systems with near-neutral pH, sorption of Fe(II) to mineral surfaces, even to supposedly non-reactive minerals such as quartz, induces significant Fe isotope fractionation. Therefore we expect Fe isotope signatures in natural systems with changing concentration gradients of Fe(II)_aq to be affected by sorption.     

Metal sorption onto soils loaded with urban particulate matter

The potential effect of urban particulate matter (PM) accumulation on metal sorption onto two contrasting soils (Chernozem and Fluvisol) was investigated in a batch sorption experiment. While the Freundlich isotherms did not indicate any effect of PM addition to the soils, the Langmuir isotherm allowed us to estimate the potential behaviour of the PM in the soil. The PM added to the Chernozem did not lead to substantial changes in sorption of Cd, Cu, Mn, Ni, Pb, and Zn. On the contrary, the presence of PM in the Fluvisol increased the number of potential sorption sites in the soil. However, the results of the approximation showed a lower affinity of Cd, Mn and Ni for the Fluvisol and a better stability and a lower bioavailability of these elements in the Chernozem. In the case of Pb and Cu, no significant changes were observed in PM-enriched soils regardless of the soil properties.     

Study of Ni sorption onto Tio mine waste rock surfaces

Sorption phenomena are known to play significant roles in metal mobility in mine drainage waters. The present study focuses on sorption phenomena controlling Ni concentrations in contaminated neutral drainage issued from the waste rock piles of the Tio mine, a hematite–ilmenite deposit near Havre-Saint-Pierre, Québec, Canada exploited by Rio Tinto Iron and Titanium. Batch sorption tests were conducted on waste rock samples of different composition and degree of alteration, as well as on the main mineral phases purified from the waste rocks. Sorbed phases were submitted to sequential extractions, XPS and DRIFT studies for further interpretation of sorption phenomena. The results from the present study confirm that sorption phenomena play a significant role in the Tio mine waste rocks, and that the main sorbent phases are the residual ilmenite ore in waste rocks, as well as plagioclase, the main gangue mineral. Sequential extractions suggest that most sorption sites are associated with reducible fractions, and XPS results indicate that Ni is sorbed as the hydroxide Ni(OH)₂. The results from the present study provide useful information on sorption phenomena involved in the Tio mine waste rocks and enable further interpretation of Ni geochemistry in contaminated neutral drainage.     

Tentative kinetic model for dolomite precipitation rate and its application to dolomite distribution

The dolomite problem has a long history and remains one of the most intensely studied and debated topics in geology. Major amounts of dolomite are not directly forming today from seawater. This observation has led many investigators to develop geochemical/hydrologic models for dolomite formation in diagenetic environments. A fundamental limitation of the current models for the growth of sedimentary dolomite is the dearth of kinetic information for this phase, in contrast to that available for calcite and aragonite.We present a simple kinetic model describing dolomite growth as a function of supersaturation using data from published high temperature synthesis experiments and our own experimental results. This model is similar in form to empirical models used to describe precipitation and dissolution rates of other carbonate minerals. Despite the considerable uncertainties and assumptions implicit in this approach, the model satisfies a basic expectation of classical precipitation theory, i.e., that the distance from equilibrium is a basic driving force for reaction rate. The calculated reaction order is high (~ 3), and the combined effect of high order and large activation energy produces a very strong dependence of the rate on temperature and the degree of supersaturation of aqueous solutions with respect to this phase.Using the calculated parameters, we applied the model to well-documented case studies of sabkha dolomite at Abu Dhabi (Persian Gulf), and organogenic dolomite from the Gulf of California. Growth rates calculated from the model agree with independent estimates of the age of these dolomites to well within an order of magnitude. A comparison of precipitation rates in seawater also shows the rate of dolomite precipitation to converge strongly with that of calcite with increasing temperature. If correct, this result implies that dolomite may respond to relatively modest warming of surface environments by substantial increases in accumulation rate, and suggests that the distribution of sedimentary dolomite in the rock record may be to some extent a temperature signal.     

Insights for size-dependent reactivity of hematite nanomineral surfaces through Cu sorption

Macroscopic sorption edges for Cu²⁺ were measured on hematite nanoparticles with average diameters of 7 nm, 25 nm, and 88 nm in 0.1 M NaNO₃. The pH edges for the 7 nm hematite were shifted approximately 0.6 pH units lower than that for the 25 nm and 88 nm samples, demonstrating an affinity sequence of 7 nm > 25 nm = 88 nm. Although, zeta potential data suggest increased proton accumulation at the 7 nm hematite surfaces, changes in surface structure are most likely responsible for the preference of Cu²⁺ for the smallest particles. As Cu²⁺ preferentially binds to sites which accommodate the Jahn-Teller distortion of its coordination to oxygen, this indicates the relative importance of distorted binding environments on the 7 nm hematite relative to the 25 nm and 88 nm particles. This work highlights the uniqueness of surface reactivity for crystalline iron oxide particles with decreasing nanoparticle diameter.     

Changes in the sorption capacity of Coastal Plain sediments due to redox alteration of mineral surfaces

Chemical characteristics of grain coatings in a Coastal Plain sandy aquifer on the Eastern Shore of Virginia were investigated where sediments have been exposed to distinct groundwater redox conditions. Dissolved O₂ was 5.0 to 10.6 mg L⁻¹ in the regionally extensive aerobic groundwater, whereas in a narrow leachate plume it was only <0.001 to 0.9 mg L⁻¹. The amount of dissolved Fe in the aerobic groundwater was only 0.005 to 0.01 mg L⁻¹, but it was 12 to 47 mg L⁻¹ in the anaerobic zone. The amount of extractable Fe was an order of magnitude higher for the aerobic sediments than for the anaerobic sediments indicating that reductive dissolution removed the oxide coatings. The capacity for anion sorption on the sediment surfaces, as indicated by the sorption of ³⁵SO₄^2-, was an order of magnitude higher in the aerobic vs. anaerobic sediments. The presence of anaerobic groundwater did not significantly alter the amount of extractable Al oxides on the surface of the sediments, and those coatings helped to maintain a high surface area. The removal of the Fe oxides from the grain surfaces under anaerobic conditions was solely responsible for the significant reduction of SO₄ sorption observed. This loss of capacity for anion sorption could lead to more extensive transport of negatively charged constituents such as some contaminant chemicals or bacteria that may be of concern in groundwater.     

Tentative kinetic model for dolomite precipitation rate and its application to dolomite distribution

The ‘dolomite problem’ has a long history and remains one of the most intensely studied and debated topics in geology. Major amounts of dolomite are not directly forming today from seawater. This observation has led many investigators to develop geochemical/hydrologic models for dolomite formation in diagenetic environments. A fundamental limitation of the current models for the growth of sedimentary dolomite is the dearth of kinetic information for this phase, in contrast to that available for calcite and aragonite. We present a simple kinetic model describing dolomite growth as a function of supersaturation using data from published high temperature synthesis experiments and our own experimental results. This model is similar in form to empirical models used to describe precipitation and dissolution rates of other carbonate minerals. Despite the considerable uncertainties and assumptions implicit in this approach, the model satisfies a basic expectation of classical precipitation theory, i.e., that the distance from equilibrium is a basic driving force for reaction rate. The calculated reaction order is high (~ 3), and the combined effect of high order and large activation energy produces a very strong dependence of the rate on temperature and the degree of supersaturation of aqueous solutions with respect to this phase. Using the calculated parameters, we applied the model to well-documented case studies of sabkha dolomite at Abu Dhabi (Persian Gulf), and organogenic dolomite from the Gulf of California. Growth rates calculated from the model agree with independent estimates of the age of these dolomites to well within an order of magnitude. A comparison of precipitation rates in seawater also shows the rate of dolomite precipitation to converge strongly with that of calcite with increasing temperature. If correct, this result implies that dolomite may respond to relatively modest warming of surface environments by substantial increases in accumulation rate, and suggests that the distribution of sedimentary dolomite in the rock record may be to some extent a temperature signal.     

Metal island growth and dynamics on molybdenite surfaces

In order to understand the adsorption mechanism of metal atoms to semiconducting surfaces, we have studied, as a model system, the vapor phase adsorption of Ag, Au, and Cu on the (001) surface of molybdenite (MoS₂) and the subsequent surface diffusion of these adsorbates. Our scanning tunneling microscopy (STM) images show that, depending on the type of metal atom that is adsorbed, islands of a characteristic size (2 nm for Ag, 8 to 10 nm for Cu, two distinct sizes of 2 nm and 8 to 10 nm for Au), shape (well rounded in the lateral extension) and thickness (one monolayer for Ag, 1 to 1.5 nm for Cu) are formed during the initial stages of deposition. Whole islands are observed to surface diffuse without loss of size or shape. Despite the relatively large size of the copper islands on molybdenite, these islands surface diffuse extensively, suggesting that the Cu-S interaction is weak. Surface diffusion is only hindered once individual islands start to coalesce. As copper islands accumulate, the size and shape of the original islands can still be recognized, supporting the conclusion that these characteristics are constant and that monolayer growth occurs by the aggregation of islands across the surface.The strength and the nature of the Ag-S(MoS₂) bond were further investigated by using molecular orbital calculations, ultraviolet photoelectron spectroscopy (UPS) and scanning tunneling spectroscopy (STS). By applying quantum mechanical approaches using a two-dimensional periodic molybdenite slab and hexagonal MoS₂ clusters of different sizes with metal atoms adsorbed to them, it is possible to calculate the electron transfer between the mineral surface and the metal atom as well as the adsorption energy as a function of surface coverage. In addition, we used the results from the quantum mechanical runs to derive empirical potentials that model the characteristics of the forces within the crystal, within the adsorbed islands, and the metal and mineral surface. The combination of quantum mechanical calculations and empirical force field calculations explain the electronic structure and the highest stability of Ag islands that have seven atoms in diameter, which exactly agrees with the size of experimentally observed islands. UPS results also suggest that a specific new state is formed (approximately 4.5 eV into the valence band) which may describe the Ag-S bond because it does not occur in pure silver or molybdenite.This study shows how the combination of microscopic (STM), spectroscopic (STS, UPS), compositional (X-ray photoelectron spectroscopy, XPS) and molecular modeling (quantum mechanical and empirical) techniques is a useful approach to understand the nature of the metal to sulfide bond. Further insights may be gained concerning the natural association of certain metals with sulfides.     

A radiotracer study on the kinetics of gold sorption by mineral surfaces

Aqueous solutions with about 10 ppt¹⁹⁵Au and [HCl] of 10^–2.3 and 10^–1.3 m were exposed to solid minerals for several months. The gold uptake with time was observed by time-stepped sampling and radiochemical Au analysis. Sorbants were polished thick sections of quartz, pyrite, pyrrhotite and elemental gold, as well as crushed grains and sawed mineral cubes of quartz and pyrite (all randomly oriented). The kinetics of gold sorption strongly varied with the surface area of the sorbents, the type of mineral and the pH of the solution. Mineral-specific differences in reaction rates were observed only at experimental pH values around 2.3, where sorption on pyrrhotite and elemental gold was much more rapid than by quartz and pyrite. At pH around 1.3 gold sorption was rapid on all minerals. This finding is thought to reflect the gold speciation, i.e. neutral hydroxo-gold complexes above pH 1.5, for which only chemisorption is possible, versus dominantly AuCl ₄ ^– below pH 1.5, where unspecific electrostatic interaction enhances reaction rates with all protonated mineral surfaces.     

A performance based approach to dolomite risk management

Urban development commonly disturbs the meta-stable conditions in the dolomite environment which can lead to sinkhole formation. 650 sinkholes, which manifested from 1984 to 2004 in an approximately 3,700 ha urbanized environment, located on dolomite land south of Pretoria in South Africa, was analyzed in the absence of risk mitigation measures. A 4 year period post the implementation of a comprehensive risk management system was also analyzed. This research permitted a timely review of the Buttrick et al. (J South African Inst Civil Eng 43(2):27–36, 2001) methodology for dolomite land hazard identification which is commonly used in stability analysis and the development of risk mitigation strategies in Southern Africa. The research confirmed this methodology and demonstrated that the approach to the mitigation of hazards through risk management can improve the hazard rating of dolomite land. The research provided much needed data and insights to refine and expand upon the current South African methodology to cover the full spectrum of developments in a manner which is capable of being included in legislative frameworks governing the development of dolomite land, both locally and internationally.     

红壤中矿物表面对腐殖质吸附萘的影响

矿物表面可改变土壤腐殖质对疏水性有机污染物的结合能力。采用红壤和高岭石分别与胡敏酸结合制备得到的两种复合体对萘的吸附等温线非线性显著,其n=0.76或0.74,并且有机碳归一化吸附分配系数的实验值Koacds是采用Kow计算得出的理论值Koc的5倍以上,表明红壤、高岭石均对腐殖质吸附萘有强化作用,且红壤较之高岭石对腐殖质吸附萘的影响稍强些。主要原因是,红壤中除了高岭石外,还有与腐殖质结合力很强的铁氧化物,而且很可能是吸附态腐殖质组成结构形态发生了有利于对萘吸附的改变。     

Lithium sorption to Yucca Mountain tuffs

The Li ion has been used as a reactive tracer in field tests performed in the saturated and unsaturated-zone in volcanic tuffs at Yucca Mountain, Nevada. Lithium sorbs weakly by cation exchange and permits field-scale testing of laboratory-based predictions of reactive-solute transport. A series of laboratory studies show that Li sorption is nonlinear and varies with lithology in the different horizons of the tuff. In particular, both Li sorption and Li-specific cation-exchange capacity vary as functions of tuff mineralogy, and can be predicted given quantitative X-ray diffraction data. These results indicate that Li sorption is dominated by clay and zeolite minerals, and that sorption coefficients can be predicted given mineralogic analysis results.     

A urolith of biogenic dolomite—another clue in the dolomite mystery

A male Dalmatian, Canis familiaris, produced uroliths of almost pure dolomite, 3–8 mm across, in his urinary bladder in less than 8 months at 38°C and about 1 atm. The X-ray diffractogram identified the predominant mineral as dolomite, and the sharp (01.5) peak showed it is ordered dolomite, not the disordered form, protodolomite.Geochemically and biologically plausible causes include (1) renal, respiratory, or metabolic alkalosis, (2) infection by urease-producing (urea-splitting) fungi or bacteria and (3) infection by uric acid-fermenting bacteria. Hematological, bacteriological, urological and geochemical considerations most strongly implicate infection by either anaerobic, urease-producing bacteria or anaerobic, uric acid-fermenting bacteria.The physical and chemical conditions of this urinary system more closely approximate modern and inferred ancient carbonate depositional settings than most previous laboratory experiments, especially in terms of temperature, pressure, total salinity and, possibly, biota. The presence of urease-producing and/or uric acid-fermenting bacteria in urea- and/or acid-containing sediment, such as fecal pellets and algal mats, could promote formation of authigenic dolomite or other carbonates.     

A tem microstructural study of dolomite with curved faces (saddle dolomite)

Electron diffraction, analytical electron microscopy, and high voltage, high resolution electron microscopy have been used to investigate crystal defects in calcium-rich saddle dolomites having pronounced curvature of the faces. Results show that branching, ribbon-like defects in these so-called saddle dolomites are thin, coherent laths of calcitic material. The ribbons are profuse and explain the characteristic calcium excess found in most saddle dolomites. Because the lattice spacings of calcite are between 3.8% and 6.7% larger than the corresponding lattice spacings of dolomite, a calcitic ribbon causes local distortion of the host dolomite. The branching ribbons have a predominant {10¯14} orientation and are generally present in high density. They may represent the source of crystal distortion that ultimately manifests itself on the macroscopic scale. The calcitic ribbons form during growth from aqueous solution, although they have features in common with similar defects found in carbonatite carbonates. This fine-scale intergrowth microstructure may be a variant of even finer-scale modulated structures found in other sedimentary calcian dolomites.     

The incongruent solution of dolomite

Two-mineral solubility diagrams are presented for the system calcite: calcium-rich dolomite which show the effect of calcite on the solubility of calcium-rich dolomite and conversely. These diagrams illustrate the incongruent solution of calcium-rich dolomite at low temperatures and the evolution of solutions of calcite and dolomite in a convenient way. They also show how calcium-rich dolomite may appear to be more soluble than calcite under some conditions.     

Construction on dolomite in south Africa

Damage to structures and loss of life have been more severe on dolomite than on any other geological formation in southern Africa. The subsidence that occurs on dolomitic terrain following development or during dewatering has given dolomite a notorious reputation and engineers and geologists became reluctant to recommend development on the material. This has led to the pioneering of founding methods for a wide variety of structures aimed at reducing the risk of severity of damage due to subsidence settlement Structures successfully founded on dolomitic terrane include residential and industrial buildings, gold mine reduction works and shaft structures, tailings dams, water retaining structures, and road and rail links. In this article, various methods of construction, some ot which were developed by the authors, are presented. It commences with a classification of a dolomite site in terms of overburden thickness followed by a discussion of the relevant construction methods The methods include mattresses of compacted soil supported by pinnacles or “floating” in residuum, deep foundations such as caissons, the use of specialized piling techniques, and soil improvement by dynamic consolidation     

Experimentally determined biomediated Sr partition coefficient for dolomite: Significance and implication for natural dolomite

Two strains of moderately halophilic bacteria were grown in aerobic culture experiments containing gel medium to determine the Sr partition coefficient between dolomite and the medium from which it precipitates at 15 to 45 °C. The results demonstrate that Sr incorporation in dolomite does occur not by the substitution of Ca, but rather by Mg. They also suggest that Sr partitioning between the culture medium and the minerals is better described by the Nernst equation (D_Sr^dol = Sr_dol/Sr_bmi), instead of the Henderson and Kracek equation (D_Sr^dol = (Sr/Ca)_dol/(Sr/Ca)_solution. The maximum value for D_Sr^dol occurs at 15 °C in cultures with and without sulfate, while the minimum values occur at 35 °C, where the bacteria exhibit optimal growth. For experiments at 25, 35 and 45 °C, we observed that D_Sr^dol values are greater in cultures with sulfate than in cultures without sulfate, whereas D_Sr^dol values are smaller in cultures with sulfate than in cultures without sulfate at 15 °C.Together, our observations suggest that D_Sr^dol is apparently related to microbial activity, temperature and sulfate concentration, regardless of the convention used to assess the D_Sr^dol. These results have implications for the interpretation of depositional environments of ancient dolomite. The results of our culture experiments show that higher Sr concentrations in ancient dolomite could reflect microbial mediated primary precipitation. In contrast, previous interpretations concluded that high Sr concentrations in ancient dolomites are an indication of secondary replacement of aragonite, which incorporates high Sr concentrations in its crystal lattice, reflecting a diagenetic process.     

Preferred orientation in experimentally deformed dolomite

Fine grained dolomite has been deformed in over twenty compression experiments in a Griggs-type piston-cylinder apparatus at various P and T conditions. Preferred orientation determined quantitatively using X-ray techniques and spherical harmonic analysis of the data is presented in inverse pole-figures of — 2/m symmetry. In most cases specimens display strong preferred orientation which varies mainly as a function of temperature. At all conditions it is very different from calcitic limestone. Although there is no significant grain growth even at 1000 °C the simple c-axes maximum fabric above 700 °C might be the result of recrystallization or translation on c. Below 700 °C, the preferred orientation is much weaker and complex. The primary maximum in the inverse pole-figure is near e, a secondary maximum near a high angle positive rhomb, principal minima are at c and f. This inverse pole-figure is consistent with f-twinning and translation gliding on r (t = a ?), two mechanisms which counteract each other. The latter is a new deformation mechanism for dolomite which we propose in order to explain the pattern of preferred orientation. The minimum at c is less pronounced below 100 ° C suggesting that c-translation may be active, but in these fine-grained aggregates it appears to be less important than is expected from single crystal experiments (Higgs and Handin, 1959), at least at low temperatures.