Specific effects of background electrolytes on the kinetics of step propagation during calcite growth

The mechanisms by which background electrolytes modify the kinetics of non-equivalent step propagation during calcite growth were investigated using Atomic Force Microscopy (AFM), at constant driving force and solution stoichiometry. Our results suggest that the acute step spreading rate is controlled by kink-site nucleation and, ultimately, by the dehydration of surface sites, while the velocity of obtuse step advancement is mainly determined by hydration of calcium ions in solution. According to our results, kink nucleation at acute steps could be promoted by carbonate-assisted calcium attachment. The different sensitivity of obtuse and acute step propagation kinetics to cation and surface hydration could be the origin of the reversed geometries of calcite growth hillocks (i.e., rate of obtuse step spreading < rate of acute step spreading) observed in concentrated (ionic strength, IS = 0.1) KCl and CsCl solutions. At low IS (0.02), ion-specific effects seem to be mainly associated with changes in the solvation environment of calcium ions in solution. With increasing electrolyte concentration, the stabilization of surface water by weakly paired salts appears to become increasingly important in determining step spreading rate. At high ionic strength (IS = 0.1), overall calcite growth rates increased with increasing hydration of calcium in solution (i.e., decreasing ion pairing of background electrolytes for sodium-bearing salts) and with decreasing hydration of the carbonate surface site (i.e., increasing ion pairing for chloride-bearing salts). Changes in growth hillock morphology were observed in the presence of Li⁺, F⁻ and , and can be interpreted as the result of the stabilization of polar surfaces due to increased ion hydration. These results increase our ability to predict crystal reactivity in natural fluids which contain significant amounts of solutes.     

Effects of temperature and transport conditions on calcite growth in the presence of Mg: Implications for paleothermometry

This study links direct measurement of Mg-calcite growth kinetics with high-spatial-resolution analysis of Mg contents in experimental crystals, with particular attention to the effects of temperature on growth rate and reactant transport conditions on Mg distribution. In contrast to previous experiments on Mg partitioning into calcite, here the layer-growth mechanism was observed in situ and step speeds precisely measured with fluid cell atomic force microscopy over a range of temperatures, degrees of supersaturation, and solution Mg concentrations. Data collected from 15° to 30°C yield an activation energy for calcite precipitation of 33 kJ/mol for solutions with [Mg] = 5 × 10⁻⁵ molal. Electron microprobe analyses of large hillocks grown at corresponding conditions demonstrate that Mg has a strong preference for incorporation at negative (acute) step edges, rather than at positive (obtuse) edges when growth rate is limited by surface reactions. This preference is reversed when growth is instead limited by diffusion of reactants through a boundary layer at the mineral-solution interface. These findings show that temperature is not the only strong control on the extent of Mg incorporation and distribution in calcite; transport conditions during mineral growth may also be a first-order factor governing the compositions of natural calcite samples.     

The influence of temperature and seawater composition on calcite crystal growth mechanisms and kinetics: Implications for Mg incorporation in calcite lattice

The composition of carbonate minerals formed in past and present oceans is assumed to be significantly controlled by temperature and seawater composition. To determine if and how temperature is kinetically responsible for the amount of Mg incorporated in calcite, we quantified the influence of temperature and specific dissolved components on the complex mechanism of calcite precipitation in seawater. A kinetic study was carried out in artificial seawater and NaCl-CaCl₂ solutions, each having a total ionic strength of 0.7 M. The constant addition technique was used to maintain [Ca²⁺] at 10.5 mmol kg⁻¹ while [] was varied to isolate the role of this variable on the precipitation rate of calcite.Our results show that the overall reaction of calcite precipitation in both seawater and NaCl-CaCl₂ solutions is dominated by the following reaction:

     

Toward a conceptual model of the calcite surface: hydration,hydrolysis, and surface potential

Because of a recent increase in interest in the properties of the calcite surface, there has also been an increase in activity toward development of mathematical models to describe calcite’s surface behaviour, particularly with respect to adsorption and precipitation. For a mathematical model to be realistic, it must be based on a sound conceptual model of atomic structure at the interface. New observations from high resolution techniques have been combined with previously published data to resolve the apparent conflict with results from electrokinetic studies and to present a picture of what the calcite surface probably looks like at the atomic scale.In ultra-high vacuum (10⁻¹⁰ mbar), a cleaved surface remains unreacted for at least an hour, but the unreacted surface does not remain as a termination of the bulk structure. X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED), and atomic force microscopy (AFM) show that the outer-most atomic layer relaxes and the surface slightly restructures. In air, dangling bonds are satisfied by hydrolysed water. XPS and time-of-flight secondary ion mass spectrometry (TOF-SIMS) reveal the presence of adsorbed OH and H. In AFM images, the features so typical of calcite, namely, alternate-row offset, pairing and height difference, as well as the consistent dependence of these features on the force and direction of tip scanning, are best explained by OH filling of the vacant O sites created during cleavage on the Ca octahedra. Thus there is solid evidence to indicate the presence of OH and H chemi-sorbed at the termination of the bulk calcite structure.Wet chemical studies, however, show that calcite’s pH_pzc (zero point of charge) varies with sample history and solution composition. Electrophoretic mobility measurements indicate that the potential-determining ions are not H⁺ and OH⁻, but rather Ca²⁺ and CO₃²⁻ (or HCO₃⁻ or H₂CO₃⁰). This apparent conflict is resolved by a slight modification of the electrical double layer (EDL) model. At the bulk termination, hydrolysis species are chemi-bonded. At the Stern layer, adsorption attaches Ca²⁺ and CO₃²⁻ (or other carbonate species), but the hydrolysis layer keeps them in outer-sphere coordination to the surface. With dehydration, loss of the hydrolysis species results in direct contact between adsorbed ions and the bulk termination, therefore, inner-sphere sorption is equivalent to extension of the three dimensional bulk network, which is precipitation. Attachment of ions with size and charge compatible with Ca and CO₃ likewise results in coprecipitation and solid–solution formation.     

Rare earth element geochemistry of scleractinian coral skeleton during meteoric diagenesis: a sequence through neomorphism of aragonite to calcite

Rare earth element geochemistry in carbonate rocks is utilized increasingly for studying both modern oceans and palaeoceanography, with additional applications for investigating water–rock interactions in groundwater and carbonate diagenesis. However, the study of rare earth element geochemistry in ancient rocks requires the preservation of their distribution patterns through subsequent diagenesis. The subjects of this study, Pleistocene scleractinian coral skeletons from Windley Key, Florida, have undergone partial to complete neomorphism from aragonite to calcite in a meteoric setting; they allow direct comparison of rare earth element distributions in original coral skeleton and in neomorphic calcite. Neomorphism occurred in a vadose setting along a thin film, with degradation of organic matter playing an initial role in controlling the morphology of the diagenetic front. As expected, minor element concentrations vary significantly between skeletal aragonite and neomorphic calcite, with Sr, Ba and U decreasing in concentration and Mn increasing in concentration in the calcite, suggesting that neomorphism took place in an open system. However, rare earth elements were largely retained during neomorphism, with precipitating cements taking up excess rare earth elements released from dissolved carbonates from higher in the karst system. Preserved rare earth element patterns in the stabilized calcite closely reflect the original rare earth element patterns of the corals and associated reef carbonates. However, minor increases in light rare earth element depletion and negative Ce anomalies may reflect shallow oxidized groundwater processes, whereas decreasing light rare earth element depletion may reflect mixing of rare earth elements from associated microbialites or contamination from insoluble residues. Regardless of these minor disturbances, the results indicate that rare earth elements, unlike many minor elements, behave very conservatively during meteoric diagenesis. As the meteoric transformation of aragonite to calcite is a near worst case scenario for survival of original marine trace element distributions, this study suggests that original rare earth element patterns may commonly be preserved in ancient limestones, thus providing support for the use of ancient marine limestones as proxies for marine rare earth element geochemistry.     

Effect of collector, pH and ionic strength on the cationic flotation of kaolinite

The effect of amine collector type, pH, and ionic strength on the flotation behaviour of kaolinite was investigated in a series of laboratory batch flotation tests. In distilled water, ether diamine, a strong collector for silica, does not induce any flotation or only very weak flotation of kaolinite over a wide pH range from pH 3 to pH 10.5. Ether monoamine causes strong flotation of kaolinite in distilled water, especially in acidic solutions, but high dosages of the collector are required. Such observations are in contrast to the flotation behaviour of oxide minerals such as silica for which ether diamine shows stronger collecting power than ether monoamine. The pH dependence of kaolinite flotation is also opposite to that of oxides, with lower flotation recovery obtained at higher pH. In contrast to oxides, the flotation recovery of kaolinite increases with ionic strength. It was demonstrated that the enhanced flotation of kaolinite in NaCl solutions cannot be attributed to the frothing ability of NaCl or the intercalation of kaolinite by alkylamines. It is proposed that the screened zeta potential of kaolinite particles in a high ionic strength environment causes random aggregation of kaolinite particles exposing hydrophobic (001) silica plane in the presence of ether amines.     

Nanoscale phenomena during the growth of solid solutions on calcite {101¯4} surfaces

This work deals with the growth behaviour of calcite {101¯4} surfaces in contact with multicomponent aqueous solutions containing divalent cations (Ba²⁺, Sr²⁺, Mn²⁺, Cd²⁺, or Mg²⁺). The result is the formation of solid solutions, with calcite or aragonite as one of the end-members. In situ atomic force microscopy has revealed a wide variety of surface phenomena occurring during the formation of these solid solutions. Among them are: (1) the thickening of growth steps and the subsequent dissolution of surfaces followed by the nucleation of secondary three-dimensional nuclei on calcite surfaces, (2) the transition between growth mechanisms, (3) the formation of an epitaxial layer that armours the substrate from further dissolution and (4) the inhibitory effect of the newly formed surface on the subsequent growth (template effect). The two last phenomena can considerably limit coprecipitation as an effective mechanism for divalent metal uptake. All the phenomena described are a consequence of the interplay between thermodynamics, supersaturation of the aqueous solution with respect to the possible solid solutions and the crystallographic control of the surfaces on the cation incorporation, and indicates that there are many differences between the crystal growth of solid solutions and phases with fixed composition.     

Effect of groundwater pH and ionic strength on strontium sorption in aquifer sediments: Implications for Sr mobility at contaminated nuclear sites

Strontium-90 is a beta emitting radionuclide produced during nuclear fission, and is a problem contaminant at many nuclear facilities. Transport of ⁹⁰Sr in groundwaters is primarily controlled by sorption reactions with aquifer sediments. The extent of sorption is controlled by the geochemistry of the groundwater and sediment mineralogy. Here, batch sorption experiments were used to examine the sorption behaviour of ⁹⁰Sr in sediment–water systems representative of the UK Sellafield nuclear site based on groundwater and contaminant fluid compositions. In experiments with low ionic strength groundwaters (<0.01 mol L⁻¹), pH variation is the main control on sorption. The sorption edge for ⁹⁰Sr was observed between pH 4 and 6 with maximum sorption occurring (K_d ∼ 10³ L kg⁻¹) at pH 6–8. At ionic strengths above 10 mmol L⁻¹, and at pH values between 6 and 8, cation exchange processes reduced ⁹⁰Sr uptake to the sediment. This exchange process explains the lower ⁹⁰Sr sorption (K_d ∼ 40 L kg⁻¹) in the presence of artificial Magnox tank liquor (IS = 29 mmol L⁻¹). Strontium K-edge EXAFS spectra collected from sediments incubated with Sr²⁺ in either HCO₃-buffered groundwater or artificial Magnox tank liquor, revealed a coordination environment of ∼9 O atoms at 2.58–2.61 Å after 10 days. This is equivalent to the Sr²⁺ hydration sphere for the aqueous ion and indicates that Sr occurs primarily in outer sphere sorption complexes. No change was observed in the Sr sorption environment with EXAFS analysis after 365 days incubation. Sequential extractions performed on sediments after 365 days also found that ∼80% of solid associated ⁹⁰Sr was exchangeable with 1 M MgCl₂ in all experiments. These results suggest that over long periods, ⁹⁰Sr in contaminated sediments will remain primarily in weakly bound surface complexes. Therefore, if groundwater ionic strength increases (e.g. by saline intrusion related to sea level rise or by design during site remediation) then substantial remobilisation of ⁹⁰Sr is to be expected.     

Experimental investigation of the effects of temperature and ionic strength on Mo isotope fractionation during adsorption to manganese oxides

The Mo stable isotope system is being applied to study changes in ocean redox. Such applications implicitly assume that Mo isotope fractionation in aqueous systems is relatively insensitive to frequently changing environmental variables such as temperature (T) and ionic strength (I). A major driver of fractionation is the adsorption of Mo to Mn oxyhydroxide surfaces [Barling J. and Anbar A. D. (2004) Molybdenum isotope fractionation during adsorption by manganese oxides. Earth Planet. Sci. Lett.217(3-4), 315-329]. Here, we report the results of experiments that determine the extent to which Mo isotope fractionation during adsorption of Mo to the Mn oxyhydroxide mineral birnessite is sensitive to T and I. The results are compared to new predictions from quantum chemical computations. We measured fractionation from 1 to 50 °C at I = 0.1 m and found that Δ^97/95Mo_{dissolved-adsorbed} varies from 1.9‰ to 1.6‰ over this temperature range. Experiments were also performed at 25 °C in synthetic seawater (I = 0.7); fractionation at this condition was the same within analytical error as in low ionic strength experiments. These findings confirm that the Mo isotope fractionation during adsorption to Mn oxyhydroxides is relatively insensitive to variations and T and I over environmentally relevant ranges. To relate these findings to potential mechanisms of Mo isotope fractionation, we also report results for density functional theory computations of the fractionation between and various possible structures of molybdic acid as a function of temperature. Because no plausible species fractionates from with a magnitude matching the experiments, we are left with three possibilities to explain the fractionation: (1) solvation effects on the vibrational frequencies of aqueous species considered thus far are significant, such that our calculations in vacuo yield inaccurate fractionations; (2) a trace aqueous species not yet considered fractionates from and then adsorbs to birnessite; or (3) a surface complex not present in solution forms on birnessite in which Mo is not tetrahedrally coordinated. Our findings help validate assumptions underlying paleoceanographic applications of the Mo isotope system and also lead us closer to understanding the mechanism of isotope fractionation during adsorption of Mo to Mn oxyhydroxides.     

Stability constants for the formation of lead chloride complexes as a function of temperature and ionic strength

The stability constants for the formation of lead (Pb²⁺) with chloride

     

Sorption of Th(IV) on Na-rectorite: Effect of HA, ionic strength, foreign ions and temperature

The sorption of Th(IV) on Na-rectorite as a function of pH, ionic strength, temperature, soil humic acid (HA) and foreign ions was studied by using a batch technique under ambient conditions. The results indicated that the sorption of Th(IV) on Na-rectorite is strongly depended on pH, ionic strength and temperature. The presence of HA enhanced Th(IV) sorption at low pH and had no obvious effect on Th(IV) sorption at high pH. The sorption of Th(IV) decreased with increasing temperature, indicating that the sorption process of Th(IV) on rectorite was exothermic. Sodium-rectorite and HA were characterized by acid–base titration to obtain the pK_a, and the constant capacitance model (CCM) modeled the sorption data very well with the aid of FITEQL 3.2. HA/Th(IV) addition sequences affected Th(IV) sorption in the ternary systems. The sorption of Th(IV) on Na-rectorite may be dominated by surface complexation, while cation exchange also contributes partly to the sorption.     

Effect of pH on boron coprecipitation by calcite: further evidence for nonequilibrium partitioning of trace elements

The influence of pH and concentration on boron coprecipitation by calcite were evaluated under near-equilibrium conditions at 25°C. Calcite was precipitated by adding a metastable polymorph (vaterite or aragonite) to a solution of known boron concentration. This method maintains a nearly constant solution composition during the slow conversion of the metastable polymorph to calcite.Boron uptake in calcite was found to be strongly pH-dependent, increasing two orders of magnitude from pH 8.5 to pH 10.5. Boron incorporation into calcites precipitated from vaterite-saturated solutions was five times greater than in calcites precipitated from aragonite-saturated solutions. Ostensibly, these results suggest that the calcite precipitation rates were not low enough to attain equilibrium partitioning of boron into calcite. However, scanning electron micrograph analyses showed that the prevalent crystal forms of calcite generated from aragonite and those generated from vaterite were distinctly different. The different quantities of boron incorporated into these calcites may reflect different crystal growth mechanisms, consistent with face-dependent, nonequilibrium partitioning of trace elements in calcite.At a constant pH of 9.0, boron uptake increased from less than 15 to over 290 mg/kg CaCO₃ as the solution boron concentration was increased from 5 to 100 mg/kg. Our results agree with those of other investigators, despite differences in solution composition, and calcite precipitation techniques used. The agreement between the studies may be because the crystal growth morphology of the calcite was rhombohedral in both cases.     

Nanoscale effects of strontium on calcite growth: An in situ AFM study in the absence of vital effects

This experimental study presents in situ measurements of step migration rates for layer growth of calcite at various levels of superaturation and fluid Sr concentrations. Our results show that Sr has complex behavior as an impurity. At low concentrations, Sr promotes faster growth. This effect may be associated with slight shifts in calcite solubility when Sr is incorporated or may be due to as yet uncharacterized kinetic effects. At higher concentrations, Sr stops step advancement by pinning kink-sites or step edges. The threshold concentration of Sr needed to halt growth is positively correlated with supersaturation.Addition of Sr to the calcite growth system leads to significant changes in hillock morphology. Hillocks become elongate perpendicular to the projection of the c-glide plane, in contrast to the changes previously reported for Mg. Step edges also become scalloped, and the boundary between the obtuse-stepped flanks disappears and is replaced by a new step direction with edges parallel to [010].Incorporation of Sr was measured at two supersaturation levels and identical fluid [Sr]. The results indicate a strong positive correlation between fluid supersaturation and crystal Sr content. Further, Sr is strongly fractionated between obtuse- and acute-stepped flanks by a factor of approximately two. The sensitivity of Sr uptake to supersaturation may explain apparently contradictory results in the literature regarding whether Sr uptake in the calcite produced by one-celled marine organisms is controlled by temperature. In addition, Sr contents of natural calcite samples may be good indicators of the levels of supersaturation at which the crystals grew.Results of this investigation demonstrate the importance of understanding impurity-specific interactions with calcite growth surfaces at the microscopic scale. Despite similar chemical behavior in some systems, Mg and Sr clearly have very different effects on calcite growth. If Sr and other impurities are to be used as robust indicators of growth conditions in natural calcite samples, well grounded understanding of the mechanisms of recording trace element signatures in calcite is an essential step toward correctly deciphering paleoenvironmental signals from fossil calcite compositions.     

干密度和含水率对稻草加筋土强度与变形的影响

以防腐处理后的稻草加筋滨海盐渍土,完成了三种干密度和三种含水率的稻草加筋土的抗压实验和三轴UU压缩实验。结果表明：干密度较大时,加筋土的抗压强度和抗剪强度较高,达到峰值强度的应变较大,即抗变形能力较强;随含水率的增加,加筋土的强度降低,抗变形能力减弱;加筋稻草增强了土的抗变形能力,提高了土的粘聚力,但对内摩擦角的影响很小;在最优含水率和最大干密度下,加筋效果最优。     

Mathematical approach to calculate indices for depositional environments of pelagic-hemipelagic-terrigenous sediments on the basis of metallic element concentrations

Modern marine sediments can be classified into terrigenous, hemipelagic, and pelagic types according to the distances from the land for the sites recovered and in terms of lithological characteristics of sediments. Ancient cherts are the best sedimentary rocks to reconstruct ancient depositional environments and hemipelagic and pelagic cherts can be identified in terms of lithologic and stratigraphic characteristics. However, geochemical characteristics of modern sediments and ancient cherts can discriminate them into these three types. Particularly, the degree of correlation between Fe and Mg in clay minerals is the most effective criterion for the classification, because the concentration of pelagic clay minerals in which the Fe/Mg ratio is constant may become indices for the classification into the three types. The correlation coefficient and goodness-of-fit to a certain regression line were used as indices of the classification and calculated for several sets of modern sediments and ancient cherts totalling to more than 400 samples. The correlation coefficients and the student-t values for the coefficients become better classification indices than the goodness-of-fit andF-values of the analysis of variance. Goodness-of-fit andF-values can be only used as subsidiary indices for the main classification indices of the correlation coefficients. The classification on the basis of the degree of correlation between Fe and Mg is effective and this approach can be used for other major chemical elements such as Al, K, and Na, if some sequential values of chemical analyses are available.     

Crisis information distribution on Twitter: a content analysis of tweets during Hurricane Sandy

Social media has been widely used for crisis communication during disasters, and its use during extreme events has drawn attention from both researchers and practitioners. Although crisis information coverage and distribution speed are important issues, both have not been studied extensively in the literature. This paper fills this gap by studying information distribution and coverage of social media during disasters. To this end, we searched and analyzed 986,579 tweets posted during Hurricane Sandy (October 22 to November 6, 2012). To learn about responses from official agents, we sampled 163 governmental organizations (GO), 31 non-governmental organizations (NGO) and 276 news agent accounts and their tweets for analysis. Specifically, five social media key performance indicators (KPIs) are studied in this paper, including impression, like, mention, re-tweet, and response time, and other variables such as hashtag, tweet frequency, and information type. We also test whether the five KPIs and other variables are different among different user types. Results show that total impression, re-tweet rate, hashtag, and tweet frequency are significantly \((P<0.05)\) different among different user types. Specifically, although news agent users generate a larger number of total impressions and tweet more frequently than GO and NGO users, their re-tweet rates and number of hashtags are lower than the GO and NGO users. Re-tweet rate based on mentioned users (5%) is significantly higher \((P=0.00)\) than that based on regular followers (0.01%). Nearly 89% of total impressions are generated from regular followers, with impressions from re-tweeting being a minority. This paper provides some new insights into how social media was used for crisis communication during disasters.     

Effect of grossular on garnet-biotite,Fe–Mg exchange reactions: evidence from garnet with mixed growth and diffusion zoning

Garnets that exhibit mixed growth and diffusion zoning are used to evaluate the effect of grossular content on garnet Fe–Mg exchange reactions. These garnets from the uppermost amphibolite-facies to granulite-facies gneiss of the Wissahickon Group, southeastern Pennsylvania, show variation in grossular content (0.035<X _Ca<0.14) but nearly constant Mg? (X _Mg/(X _Mg+X _Fe) and X _Mn through the interior indicating re-equilibration of garnet and matrix minerals with respect to iron, magnesium, and manganese. Mg? is not correlated with calcium content, evidence that the effect of calcium on garnet Fe–Mg exchange reactions is small or is offset by other interactions in almandine-rich garnets. In either case, the data presented here indicate that correction for calcium content of garnets in the application of garnet-biotite geothermometry to high-grade metapelites is unnecessary and may lead to an overestimate of peak temperature.     

The effects of porphyroblast growth on the effective viscosity of metapelitic rocks: implications for the strength of the middle crust

Numerical models are used to examine the effects of porphyroblast growth on the rheology of compositionally layered rocks (metapelites and metapsammites) and by extension the middle crust during prograde metamorphism. As porphyroblast abundance increases during prograde metamorphism, metapelitic layers will strengthen relative to porphyroblast‐free metapelitic units, and potentially relative to quartzofeldspathic metapsammitic units. As metapelitic layers become stronger, the integrated strength of compositionally layered successions increases, potentially causing large volumes of mid‐crustal rock to strengthen, altering the strain‐rate distribution in the middle crust and affecting the geodynamic evolution of an orogenic belt. The growth of effectively rigid porphyroblasts creates strength heterogeneities in the layer undergoing porphyroblast growth, which leads to complex strain‐rate distributions within the layer. At the orogen scale, the strengthening of large crustal volumes (on the order of thousands of cubic kilometres) changes the strain‐rate distribution, which may change exhumation rates of high‐grade metamorphic rocks, the geothermal structure and the topography of the orogen. The presence of a strong zone in the middle crust causes strain‐rate partitioning around the zone, suppressed uplift rates within and above the zone and leads to the development of a basin on the surface.     

Reaction mechanism for the replacement of calcite by dolomite and siderite: implications for geochemistry, microstructure and porosity evolution during hydrothermal mineralisation

Carbonate reactions are common in mineral deposits due to CO₂-rich mineralising fluids. This study presents the first in-depth, integrated analysis of microstructure and microchemistry of fluid-mediated carbonate reaction textures at hydrothermal conditions. In doing so, we describe the mechanisms by which carbonate phases replace one another, and the implications for the evolution of geochemistry, rock microstructures and porosity. The sample from the 1.95 Moz Junction gold deposit, Western Australia, contains calcite derived from carbonation of a metamorphic amphibole—plagioclase assemblage that has further altered to siderite and dolomite. The calcite is porous and contains iron-rich calcite blebs interpreted to have resulted from fluid-mediated replacement of compositionally heterogeneous amphiboles. The siderite is polycrystalline but nucleates topotactically on the calcite. As a result, the boundaries between adjacent grains are low-angle boundaries (<10°), which are geometrically similar to those formed by crystal–plastic deformation and recovery. Growth zoning within individual siderite grains shows that the low-angle boundaries are growth features and not due to deformation. Low-angle boundaries develop due to the propagation of defects at grain faces and zone boundaries and by impingement of grains that nucleated with small misorientations relative to each other during grain growth. The cores of siderite grains are aligned with the twin planes in the parent calcite crystal showing that the reactant Fe entered the crystal along the twin boundaries. Dolomite grains, many of which appear to in-fill space generated by the siderite replacement, also show alignment of cores along the calcite twin planes, suggesting that they did not grow into space but replaced the calcite. Where dolomite is seen directly replacing calcite, it nucleates on the Fe-rich calcite due to the increased compatibility of the Fe-bearing calcite lattice relative to the pure calcite. Both reactions are interpreted as fluid-mediated replacement reactions which use the crystallography and elemental chemistry of the calcite. Experiments of fluid-mediated replacement reactions show that they proceed much faster than diffusion-based reactions. This is important when considering the rates of reactions relative to fluid flow in mineralising systems.     

X-ray absorption spectroscopy study of Cu and Zn adsorption complexes at the calcite surface: Implications for site-specific metal incorporation preferences during calcite crystal growth

We report results from in situ extended X-ray absorption fine structure (EXAFS) spectroscopy studies of Cu(II) and Zn(II) complexes forming at the calcite surface following adsorption from preequilibrated calcite-saturated solutions. Both Cu(II) and Zn(II) coordinate at Ca sites on the calcite surface, forming mononuclear inner-sphere adsorption complexes. The Zn adsorption complexes are in tetrahedral coordination with first-shell O neighbors with R_Zn-O = 1.95 Å, and the Cu complexes are Jahn-Teller distorted, with equatorial R_Cu-O = 1.95 Å. Results from EXAFS data of dilute Cu- and Zn-calcite solid solutions confirm substitution of these metals in the Ca site of the calcite structure as octahedral complexes during coprecipitation. X-ray fluorescence microanalyses of calcite (101?4) hillocks grown in coprecipitation experiments show that divalent Cu and Zn, which have ionic radii smaller than Ca, are preferentially incorporated into the parallel arrays of <4?41>₊ steps that define one pair of symmetrically equivalent vicinal faces on polygonized growth spirals. In contrast, other divalent metals with sixfold ionic radii smaller than Ca (Co, Cd, Mn, Mg) have been shown to be preferentially incorporated into <4?41>₋ growth steps, which define the second pair of vicinal faces on the growth spirals, but which are symmetrically nonequivalent to the steps on the first pair. The distortion from octahedral symmetry observed for the Cu and Zn adsorption complexes likely plays a key role in the observed preference of Cu and Zn for incorporation into the <4?41>₊ steps.