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1.
Yongliang Xiong   《Ore Geology Reviews》2003,23(3-4):259-276
In this study, an attempt has been made to assess aqueous speciation of selenium and solubility product constants of common selenides at elevated temperatures (up to 300 °C) by using various extrapolation methods. This study predicts that reduced selenium species are dominant species in many geological processes even under relatively oxidized conditions such as those dictated by the magnetite–hematite buffer. On the basis of extrapolated equilibrium constants and solubility product constants for common Se-bearing mineral phases, critical ∑Se/∑S ratios (molal ratios) in mineralizing fluids are proposed for independent selenium mineralization. The minimum ∑Se/∑S ratios in mineralizing fluids for independent selenium mineralization should be at least 10−6, 10−5 and 10−4 at 100, 200 and 300 °C, respectively. For giant independent selenium deposits such as the La'erma and Qiongmo Au–Se deposits in the western Qingling mountains, and Yutangba Se deposits in Hubei Province, China, the mineralizing fluids have reached much higher ∑Se/∑S ratios ranging from 10−1 to 10−3 at 200 °C. This study also suggests that the equilibrium assemblage of pyrite–ferroselite among the common ore minerals requires the highest ∑Se/∑S ratios in mineralizing fluids, followed in decreasing order by the assemblages of stibnite–antimonselite, galena–clausthalite, cinnabar–tiemannite, and acanthite/argentite–naumannite. The assemblage of pyrite–ferroselite can also be formed under relatively oxidizing conditions where [∑H2Se]/[∑H2S] ratios can be high enough for the formation of independent ferroselite.  相似文献   

2.
This paper reports a new 1° × 1° global thermal model for the continental lithosphere (TC1). Geotherms for continental terranes of different ages (> 3.6 Ga to present) constrained by reliable data on borehole heat flow measurements (Artemieva, I.M., Mooney, W.D. 2001. Thermal structure and evolution of Precambrian lithosphere: a global study. J. Geophys. Res 106, 16387–16414.), are statistically analyzed as a function of age and are used to estimate lithospheric temperatures in continental regions with no or low-quality heat flow data (ca. 60% of the continents). These data are supplemented by cratonic geotherms based on electromagnetic and xenolith data; the latter indicate the existence of Archean cratons with two characteristic thicknesses, ca. 200 and > 250 km. A map of tectono-thermal ages of lithospheric terranes complied for the continents on a 1° × 1° grid and combined with the statistical age relationship of continental geotherms (z = 0.04  t + 93.6, where z is lithospheric thermal thickness in km and t is age in Ma) formed the basis for a new global thermal model of the continental lithosphere (TC1). The TC1 model is presented by a set of maps, which show significant thermal heterogeneity within continental upper mantle, with the strongest lateral temperature variations (as large as 800 °C) in the shallow mantle. A map of the depth to a 550 °C isotherm (Curie isotherm for magnetite) in continental upper mantle is presented as a proxy to the thickness of the magnetic crust; the same map provides a rough estimate of elastic thickness of old (> 200 Ma) continental lithosphere, in which flexural rigidity is dominated by olivine rheology of the mantle.Statistical analysis of continental geotherms reveals that thick (> 250 km) lithosphere is restricted solely to young Archean terranes (3.0–2.6 Ga), while in old Archean cratons (3.6–3.0 Ga) lithospheric roots do not extend deeper than 200–220 km. It is proposed that the former were formed by tectonic stacking and underplating during paleocollision of continental nuclei; it is likely that such exceptionally thick lithospheric roots have a limited lateral extent and are restricted to paleoterrane boundaries. This conclusion is supported by an analysis of the growth rate of the lithosphere since the Archean, which does not reveal a peak in lithospheric volume at 2.7–2.6 Ga as expected from growth curves for juvenile crust.A pronounced peak in the rate of lithospheric growth (10–18 km3/year) at 2.1–1.7 Ga (as compared to 5–8 km3/year in the Archean) well correlates with a peak in the growth of juvenile crust and with a consequent global extraction of massif-type anorthosites. It is proposed that large-scale variations in lithospheric thickness at cratonic margins and at paleoterrane boundaries controlled anorogenic magmatism. In particular, mid-Proterozoic anorogenic magmatism at the cratonic margins was caused by edge-driven convection triggered by a fast growth of the lithospheric mantle at 2.1–1.7 Ga. Belts of anorogenic magmatism within cratonic interiors can be caused by a deflection of mantle heat by a locally thickened lithosphere at paleosutures and, thus, can be surface manifestations of exceptionally thick lithospheric roots. The present volume of continental lithosphere as estimated from the new global map of lithospheric thermal thickness is 27.8 (± 7.0) × 109 km3 (excluding submerged terranes with continental crust); preserved continental crust comprises ca. 7.7 × 109 km3. About 50% of the present continental lithosphere existed by 1.8 Ga.  相似文献   

3.
Measurements of compressional wave velocity Vp were made in a gas apparatus to 500°C at 10 kbar in three cores of an anisotropic dunite specimen from Twin Sisters Mountain. The axial directions of the three chosen cores coincide with the preferred directions and concentration of olivine crystallographic axes (a [100], b [010], andc [001]).Measured (δVp/δT)p values at 10 kbar in the three cores (−6.7, −5.4 and −6.2 · 10−4 km/sec · deg, respectively), and the mean value for the dunite (−6.1 · 10−4 km/sec · deg) are larger than the Voigt-Reuss-Hill values calculated from single-crystal data. This discrepancy is explained by the presence of internal thermal stresses, due to anisotropic expansion of olivine grains, causing grain boundary cracks to widen.It is concluded that high negative values of (δVp/δT)p for rocks reported in the literature should be carefully evaluated in terms of the formation of new cracks or widening of cracks already present under high pressure-temperature environments.  相似文献   

4.
Study on the kinetics of iron oxide leaching by oxalic acid   总被引：2，自引：0，他引：2  
The presence of iron oxides in clay or silica raw materials is detrimental to the manufacturing of high quality ceramics. Although iron has been traditionally removed by physical mineral processing, acid washing has been tested as it is more effective, especially for extremely low iron (of less than 0.1% w/w). However, inorganic acids such as sulphuric or hydrochloric acids easily contaminate the clay products with SO42− and Cl−, and therefore should be avoided as much as possible. On the other hand, if oxalic acid is used, any acid left behind will be destroyed during the firing of the ceramic products. The characteristics of dissolution of iron oxides were therefore investigated in this study.The dissolution of iron oxides in oxalic acid was found to be very slow at temperatures within the range 25–60 °C, but its rate increases rapidly above 90 °C. The dissolution rate also increases with increasing oxalate concentration at the constant pH values set within the optimum range of pH2.5–3.0. At this optimum pH, the dissolution of fine pure hematite (Fe2O3) (105–140 μm) follows a diffusion-controlled shrinking core model. The rate expression expressed as 1 − (2 / 3)x − (1 − x)2 / 3 where x is a fraction of iron dissolution was found to be proportional to [oxalate]1.5.The addition of magnetite to the leach liquor at 10% w/w hematite was found to enhance the dissolution rate dramatically. Such addition of magnetite allows coarser hematite in the range 0.5–1.4 mm to be leached at a reasonable rate.  相似文献   

5.
We have performed experiments to constrain the effect of sulfur fugacity (fS2) and sulfide saturation on the fractionation and partitioning behavior of Pt, Pd and Au in a silicate melt–sulfide crystal/melt–oxide–supercritical aqueous fluid phase–Pt–Pd–Au system. Experiments were performed at 800 °C, 150 MPa, with oxygen fugacity (fO2) fixed at approximately the nickel–nickel oxide buffer (NNO). Sulfur fugacity in the experiments was varied five orders of magnitude from approximately log fS2 = 0 to log fS2 = −5 by using two different sulfide phase assemblages. Assemblage one consisted initially of chalcopyrite plus pyrrhotite and assemblage two was loaded with chalcopyrite plus bornite. At run conditions pyrrhotite transformed compositionally to monosulfide solid solution (mss), chalcopyrite to intermediate solid solution (iss), and in assemblage two chalcopyrite and bornite formed a sulfide melt. Run-product silicate glass (i.e., quenched silicate melt) and crystalline materials were analyzed by using both electron probe microanalysis and laser ablation inductively coupled plasma mass spectrometry. The measured concentrations of Pt, Pd and Au in quenched silicate melt in runs with log fS2 values ranging from approximately 0.0 to −5.0 do not exhibit any apparent dependence on fS2. The measured Pt, Pd and Au concentrations in mss do vary as a function of fS2. The measured Pt, Pd and Au concentrations in iss do not appear dependent on fS2. The data suggest that fS2, working in concert with fO2, via the determinant role that these variables play in controlling the magmatic sulfide phase assemblage and the solubility of Pt, Pd and Au as lattice bound components in magmatic sulfide phases, is a controlling factor on the budgets of Pt, Pd and Au during the evolution of magmatic systems.  相似文献   

6.
The dissolution rates of natural fluorapatite (FAP), Ca10(PO4)6F2, were measured at 25 °C in mixed-flow reactors as a function of pH from 3.0 to 11.7, and aqueous calcium, phosphorus, and fluoride concentration. After an initial preferential Ca and/or F release, stoichiometric Ca, P, and F release was observed. Measured FAP dissolution rates decrease with increasing pH at 3 ? pH ? 7, FAP dissolution rates are pH independent at 7 ? pH ? 10, and FAP dissolution rates again decrease with increasing pH at pH ? 10. Measured FAP dissolution rates are independent of aqueous Ca, P, and F concentration at pH ≈ 3 and pH ≈ 10.Apatite dissolution appears to be initiated by the relatively rapid removal from the near surface of F and the Ca located in the M1 sites, via proton for Ca exchange reactions. Dissolution rates are controlled by the destruction of this F and Ca depleted surface layer. The destruction of this layer is facilitated by the adsorption/penetration of protons into the surface at acidic conditions, and by surface hydration at neutral and basic conditions. Taking into account these two parallel mechanisms, measured fluorapatite forward dissolution rates can be accurately described using
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7.
The carbonate-hosted Kabwe Pb–Zn deposit, Central Zambia, has produced at least 2.6 Mt of Zn and Pb metal as well as minor amounts of V, Cd, Ag and Cu. The deposit consists of four main epigenetic, pipe-like orebodies, structurally controlled along NE–SW faults. Sphalerite, galena, pyrite, minor chalcopyrite, and accessory Ge-sulphides of briartite and renierite constitute the primary ore mineral assemblage. Cores of massive sulphide orebodies are surrounded by oxide zones of silicate ore (willemite) and mineralized jasperoid that consists largely of quartz, willemite, cerussite, smithsonite, goethite and hematite, as well as numerous other secondary minerals, including vanadates, phosphates and carbonates of Zn, Pb, V and Cu.Galena, sphalerite and pyrite from the Pb–Zn rich massive orebodies have homogeneous, negative sulphur isotope ratios with mean δ34SCDT permil (‰) values of − 17.75 ± 0.28 (1σ), − 16.54 ± 0.0.27 and − 15.82 ± 0.25, respectively. The Zn-rich and Pb-poor No. 2 orebody shows slightly heavier ratios of − 11.70 ± 0.5‰ δ34S for sphalerite and of − 11.91 ± 0.71‰ δ34S for pyrite. The negative sulphur isotope ratios are considered to be typical of sedimentary sulphides produced through bacterial reduction of seawater sulphate and suggest a sedimentary source for the sulphur.Carbon and oxygen isotope ratios of the host dolomite have mean δ13CPDB and δ18OSMOW values of 2.89‰ and 27.68‰, respectively, which are typical of marine carbonates. The oxygen isotope ratios of dolomite correlate negatively to the SiO2 content introduced during silicification of the host dolomite. The depletion in 18O in dolomite indicates high temperature fluid/rock interaction, involving a silica- and 18O-rich hydrothermal solution.Two types of secondary fluid inclusions in dolomite, both of which are thought to be related to ore deposition, indicate temperatures of ore deposition in the range of 257 to 385 and 98 to 178 °C, respectively. The high temperature fluid inclusions contain liquid + vapour + solid phases and have salinities of 15 to 31 eq. wt.% NaCl, whereas the low temperature inclusions consist of liquid + vapour with a salinity of 11.5 eq. wt.% NaCl.Fluid transport may have been caused by tectonic movements associated with the early stages of the Pan-African Lufilian orogeny, whereas ore deposition within favourable structures occurred due to changes in pressure, temperature and pH in the ore solution during metasomatic replacement of the host dolomite. The termination of the Kabwe orebodies at the Mine Club fault zone and observed deformation textures of the ore sulphides as well as analysis of joint structures in the host dolomite, indicate that ore emplacement occurred prior to the latest deformation phase of the Neoproterozoic Lufilian orogeny.  相似文献   

8.
The 1.27 Ga old Ivigtut (Ivittuut) intrusion in South Greenland is world-famous for its hydrothermal cryolite deposit [Na3AlF6] situated within a strongly metasomatised A-type granite stock. This detailed fluid inclusion study characterises the fluid present during the formation of the cryolite deposit and thermodynamic modelling allows to constrain its formation conditions.Microthermometry revealed three different types of inclusions: (1) pure CO2, (2) aqueous-carbonic and (3) saline-aqueous inclusions. Melting temperatures range between − 23 and − 15 °C for type 2 and from − 15 to − 10 °C for type 3 inclusions. Most inclusions homogenise between 110 and 150 °C into the liquid.Stable isotope compositions of CO2 and H2O were measured from crushed inclusions in quartz, cryolite, fluorite and siderite. The δ13C values of about − 5‰ PDB are typical of mantle-derived magmas. The differences between δ18O of CO2 (+ 21 to + 42‰ VSMOW) and δ18O of H2O (− 1 to − 21.7‰ VSMOW) suggest low-temperature isotope exchange. δD (H2O) ranges from − 19 to − 144‰ VSMOW. The isotopic composition of inclusion water closely follows the meteoric water line and is comparable to Canadian Shield brines. Ion chromatography revealed the fluid's predominance in Na, Cl and F. Cl/Br ratios range between 56 and 110 and may imply intensive fluid–rock interaction with the host granite.Isochores deduced from microthermometry in conjunction with estimates for the solidification of the Ivigtut granite suggest a formation pressure of approximately 1–1.5 kbar for the fluid inclusions. Formation temperatures of different types of fluid inclusions vary between 100 and 400 °C. Thermodynamic modelling of phase assemblages and the extraordinary high concentration in F (and Na) may indicate that the cryolite body and its associated fluid inclusions could have formed during the continuous transition from a volatile-rich melt to a solute-rich fluid.  相似文献   

9.
Small grains of Ru–Os–Ir sulfides or alloys that formed in the early stages of the crystallization of basaltic magmas occur as inclusions in chromitites from many ophiolite complexes, Ural/Alaskan-type and layered intrusions. The nature of platinum-group elements is debated, i.e., whether they originally occurred in a metallic state or bonded with sulfur or other ligands. The application of kinetics and suggestions regarding the mechanisms of PGE formation may contribute to a better understanding of the genetic processes for platinum-group mineral (PGM) formation. The aim of the present study is to investigate the type of mechanism (associative, dissociative or interchange) and the possibility of direct formation of PGM from the reaction of free metals with sulfur, defining also the structure of possible intermediate species.The literature on the grain sizes (r) of platinum-group minerals (PGM) and their formation temperatures (range between 700 and 1100 °C) reveals an Arrhenius temperature dependence. The activation energy was estimated to be 450 ± 45 kJ mol−1. Applying the Eyring equation to the same data, a linear relationship between 2.5ln(r) + ln(T) versus 1/T was obtained, leading to an estimation of the free energy of activation, ΔG≠ = 440 ± 43 kJ mol−1. The thermodynamic relation ΔG≠ = ΔH≠ − TΔS≠, used together with the relation ΔΗ≠ = Eact − RT leads to the calculation of ΔS≠ at various temperatures. The estimated entropy of activation at various temperatures being almost zero, we suggest an interchange mechanism for PGM formation.The possibility of PGM formation from the direct reaction of free metals with sulfur would be inconsistent with the estimated entropy of activation values (ΔS≠  0) at various temperatures. In the cases of PGMs of known r, the formation temperatures can be estimated, and then the free energy of activation obtained, applying 2.5ln(r) + ln(T) versus 1/T (straight line). From that value, the entropy of activation can be calculated [ΔS≠ = −R + (Eact − ΔG≠)/T], and an interchange mechanism is proposed. Furthermore, applying the relation of 2.5ln(r) + ln(T) versus 1/T on PGM grains of known r and T, an interchange mechanism for their formation can be suggested if they fit the above line.  相似文献   

10.
The Late Precambrian–Early Paleozoic metamorphic basement forms a volumetrically important part of the Andean crust. We investigated its evolution in order to subdivide the area between 18 and 26°S into crustal domains by means of petrological and age data (Sm–Nd isochrons, K–Ar). The metamorphic crystallization ages and tDM ages are not consistent with growth of the Pacific margin north of the Argentine Precordillera by accretion of exotic terranes, but favor a model of a mobile belt of the Pampean Cycle. Peak metamorphic conditions in all scattered outcrop areas between 18 and 26°S are similar and reached the upper amphibolite facies conditions indicated by mineral paragensis and the occurrence of migmatite. Sm–Nd mineral isochrons yielded 525±10, 505±6 and 509±1 Ma for the Chilean Coast Range, the Chilean Precordillera and the Argentine Puna, and 442±9 and 412±18 Ma for the Sierras Pampeanas. Conventional K–Ar cooling age data of amphibole and mica cluster around 400 Ma, but are frequently reset by Late Paleozoic and Jurassic magmatism. Final exhumation of the Early Paleozoic orogen is confirmed by Devonian erosional unconformities. Sm–Nd depleted mantle model ages of felsic rocks from the metamorphic basement range from 1.4 to 2.2 Ga, in northern Chile the average is 1.65±0.16 Ga (1σ; n=12), average tDM of both gneiss and metabasite in NW Argentina is 1.76±0.4 Ga (1σ; n=22), and the isotopic composition excludes major addition of juvenile mantle derived material during the Early Paleozoic metamorphic and magmatic cycle. These new data indicate a largely similar development of the metamorphic basement south of the Arequipa Massif at 18°S and north of the Argentine Precordillera at 28°S. Variations of metamorphic grade and of ages of peak metamorphism are of local importance. The protolith was derived from Early to Middle Proterozoic cratonic areas, similar to the Proterozoic rocks from the Arequipa Massif, which had undergone Grenvillian metamorphism at ca. 1.0 Ga.  相似文献   

11.
Talc is one of the weakest minerals that is associated with fault zones. Triaxial friction experiments conducted on water-saturated talc gouge at room temperature yield values of the coefficient of friction, μ (shear stress, τ/effective normal stress, σ′N) in the range 0.16–0.23, and μ increases with increasing σ′N. Talc gouge heated to temperatures of 100°–400 °C is consistently weaker than at room temperature, and μ < 0.1 at slow strain rates in some heated experiments. Talc also is characterized by inherently stable, velocity-strengthening behavior (strength increases with increasing shear rate) at all conditions tested. The low strength of talc is a consequence of its layered crystal structure and, in particular, its very weak interlayer bond. Its hydrophobic character may be responsible for the relatively small increase in μ with increasing σ′N at room temperature compared to other sheet silicates.Talc has a temperature–pressure range of stability that extends from surficial to eclogite-facies conditions, making it of potential significance in a variety of faulting environments. Talc has been identified in exhumed subduction zone thrusts, in fault gouge collected from oceanic transform and detachment faults associated with rift systems, and recently in serpentinite from the central creeping section of the San Andreas fault. Typically, talc crystallized in the active fault zones as a result of the reaction of ultramafic rocks with silica-saturated hydrothermal fluids. This mode of formation of talc is a prime example of a fault-zone weakening process. Because of its velocity-strengthening behavior, talc may play a role in stabilizing slip at depth in subduction zones and in the creeping faults of central and northern California that are associated with ophiolitic rocks.  相似文献   

12.
The isotopic composition of Fe was determined in water, Fe-oxides and sulfides from the Tinto and Odiel Basins (South West Spain). As a consequence of sulfide oxidation in mine tailings both rivers are acidic (1.45 < pH < 3.85) and display high concentrations of dissolved Fe (up to 420 mmol l− 1) and sulphates (up to 1190 mmol l− 1).The δ56Fe of pyrite-rich samples from the Rio Tinto and from the Tharsis mine ranged from − 0.56 ± 0.08‰ to + 0.25 ± 0.1‰. δ56Fe values for Fe-oxides precipitates that currently form in the riverbed varied from − 1.98 ± 0.10‰ to 1.57 ± 0.08‰. Comparatively narrower ranges of values (− 0.18 ± 0.08‰ and + 0.21 ± 0.14‰) were observed in their fossil analogues from the Pliocene–Pleistocene and in samples from the Gossan (the oxidized layer that formed through exposure to oxygen of the massive sulfide deposits) (− 0.36 ± 0.12‰ to 0.82 ± 0.07‰). In water, δ56Fe values ranged from − 1.76 ± 0.10‰ to + 0.43 ± 0.05‰.At the source of the Tinto River, fractionation between aqueous Fe(III) and pyrite from the tailings was less than would be expected from a simple pyrite oxidation process. Similarly, the isotopic composition of Gossan oxides and that of pyrite was different from what would be expected from pyrite oxidation. In rivers, the precipitation of Fe-oxides (mainly jarosite and schwertmannite and lesser amounts of goethite) from water containing mainly (more than 99%) Fe(III) with concentrations up to 372 mmol l− 1 causes variable fractionation between the solid and the aqueous phase (− 0.98‰ < Δ56Fesolid–water < 2.25‰). The significant magnitude of the positive fractionation factor observed in several Fe(III) dominated water may be related to the precipitation of Fe(III) sulphates containing phases.  相似文献   

13.
Simultaneous measurements of compressional and shear wave velocities, Vp and Vs, in acidic and basic igneous rocks and volcanic glasses, were made up to 900°C and at 10–20 kbar.The effects of pressure and temperature on Vp and Vs in glasses and glassy rocks change at about 600°C, presumably the glass transition temperature. These effects are directly related to the silica content in the samples. and for obsidian are negative at room temperature and 245°C, but are positive at 655°C. The velocity—pressure relations for obsidian display an obvious hysteresis phenomena. for basalt glass is slightly negative, but is positive for usual substances at room temperature, and for obsidian and glassy andesite are positive up to about 600°C but are negative above that temperature. However, for basalt glass as well as other crystalline rocks, and are negative at all temperatures. Glass once heated above the glass transition temperature Tg under pressure P1 retains the memory of pressure P1 after it is cooled down below Tg and while subjected to another pressure P2. An abrupt shift of the velocities correlating to pressure P2 occurs when the glass is again heated to Tg. Vp−T and Vs−T relations for obsidian, glassy andesite, and basalt glass clearly exhibit this pressure memory.  相似文献   

14.
We have analysed the halogen concentrations and chlorine stable isotope composition of fluid inclusion leachates from three spatially associated Fe-oxide ± Cu ± Au mineralising systems in Norrbotten, Sweden. Fluid inclusions in late-stage veins in Fe-oxide–apatite deposits contain saline brines and have a wide range of Br/Cl molar ratios, from 0.2 to 1.1 × 10−3 and δ37Cl values from −3.1‰ to −1.0‰. Leachates from saline fluid inclusions from the Greenstone and Porphyry hosted Cu–Au prospects have Br/Cl ratios that range from 0.2 to 0.5 × 10−3 and δ37Cl values from −5.6‰ to −1.3‰. Finally, the Cu–Au deposits hosted by the Nautanen Deformation Zone (NDZ) have Br/Cl molar ratios from 0.4 to 1.1 × 10−3 and δ37Cl values that range from −2.4‰ to +0.5‰, although the bulk of the data fall within 0‰ ± 0.5‰.The Br/Cl ratios of leachates are consistent with the derivation of salinity from magmatic sources or from the dissolution of halite. Most of the isotopic data from the Fe-oxide–apatite and Greenstone deposits are consistent with a mantle derived source of the chlorine, with the exception of the four samples with the most negative values. The origin of the low δ37Cl values in these samples is unknown but we suggest that there may have been some modification of the Cl-isotope signature due to fractionation between the mineralising fluids and Cl-rich silicate assemblages found in the alteration haloes around the deposits. If such a process has occurred then a modified crustal source of the chlorine for all the samples cannot be ruled out although the amount of fractionation necessary to generate the low δ37Cl values would be significantly larger.The source of Cl in the NDZ deposits has a crustal signature, which suggests the Cl in this system may be derived from (meta-) evaporites or from input from crustal melts such as granitic pegmatites of the Lina Suite.  相似文献   

15.
Apatite dissolution experiments were conducted using both a fluidized bed and stirred tank reactor over a range of pH, temperature, solution saturation state, and on non-carbonated and carbonated apatite compositions: igneous fluorapatite (FAP) and sedimentary carbonate fluorapatite (CFA), respectively. From 2 <pH <6, the rate of release from dissolution of all apatite components [calcium (Ca), phosphorus (P), and fluoride (F)] increased with decreasing pH for FAP. From 6 < pH < 8.5, the FAP dissolution rate is pH independent. Measuring apatite dissolution rates at pH > 8.5 were not possible due to detection limits of the analytical techniques used in this study and the high insolubility of FAP. For the CFA compositions studied, the dissolution rate decreased with increasing pH from 4 < pH < 7. During early stages of the dissolution reaction for both FAP and CFA, mineral components were released in non-stoichiometric ratios with reacted solution ratios of dissolved Ca:P and Ca:F being greater than mineral stoichiometric ratios, suggesting that Ca was preferentially released compared to P and F from the mineral structure during the early stages of dissolution. An increase in reacted solution pH accompanies this early elevated release of Ca. As the dissolution reaction proceeded to steady state, dissolution became congruent. When normalized to BET measured surface area, FAP dissolved faster from 4 < pH < 7 compared to CFA. The apparent Arrhenius activation energy (Ea) of FAP dissolution over the temperature range of 25-55°C at pH = 3.0, I = 0.1, and pCO2 = 0 is 8.3 ± 0.2 kcal mol−1. Both the apparent exchange of solution H+ for solid-bound Ca at low pH in the early stage of dissolution and the Ea of dissolution suggest a surface and not a diffusion controlled dissolution reaction for FAP and CFA. The degree of undersaturation of the solution, ΔGR, with respect to FAP was important in determining the dissolution rate. At pH = 3.0, I = 0.1, and pCO2 = 0, the dissolution rate of FAP was ∼ 5× greater in the far-from-equilibrium region compared to the near-equilibrium slope region.A simple apatite weathering model incorporating the experimental results from this study was constructed, and numerical calculations suggest that during the Phanerozoic both the surface area of igneous rock available for weathering and the average global temperature were important factors in determining the P weathering flux from apatite dissolution. It is possible that elevated global temperatures coupled with relatively high surface area of igneous rock during the early- to mid-Paleozoic resulted in elevated P weathering fluxes, which along with climatic evolutionary pressures of the Neoproterozoic, facilitated the radiation of multicellular organisms, large-scale phosphorite deposition, and abundance of calcium phosphate shelled organisms during the early Cambrian.  相似文献   

16.
A novel one-step hydrothermal synthesis of 11 Å tobermorite, a cation exchanger, from a unique combination of waste materials is reported. 11 Å tobermorite was prepared from stoicheiometric quantities of cement bypass dust and waste container glass at 100 °C in water. The product also comprised 10 wt.% calcite and trace quartz as residual parent phases from the cement bypass dust. In a batch sorption study at 20 °C the uptakes of Cd2+ and Pb2+ by the waste-derived tobermorite product were found to be 171 mg g− 1 and 467 mg g− 1, respectively, and in both cases the removal process could be described using a simple pseudo-second-order rate model (k2 = 2.30 × 10− 5 g mg− 1 min− 1 and 5.09 × 10− 5 g mg− 1 min− 1, respectively). The sorption characteristics of the 11 Å tobermorite are compared with those of other waste-derived sorbents and potential applications are discussed.  相似文献   

17.
The intrinsic room temperature magnetic properties of pure calcite were determined from a series of natural crystals, and they were found to be highly dependent on the chemical composition. In general, dia-, para-, and ferromagnetic components contribute to the magnetic susceptibility and the anisotropy of magnetic susceptibility (AMS). With a combination of magnetic measurements and chemical analysis these three contributions were determined and related to their mineralogical sources. The intrinsic diamagnetic susceptibility of pure calcite is − 4.46 ± 0.16 × 10− 9 m3/kg (− 12.09 ± 0.5 × 10− 6 SI) and the susceptibility difference is 4.06 ± 0.03 × 10− 10 m3/kg (1.10 ± 0.01 × 10− 6 SI). These diamagnetic properties are easily dominated by other components. The paramagnetic contribution is due to paramagnetic ions in the crystal lattice that substitute for calcium; these are mainly iron and manganese. The measured paramagnetic susceptibility agrees with the values calculated from the known concentration of paramagnetic ions in the crystals according to the Curie law of paramagnetic susceptibility. Substituted iron leads to an increase in the AMS. The paramagnetic susceptibility difference was found to correlate linearly with the iron content for concentrations between 500 and 10,000 ppm. An empirical relation was determined: (k1 − k3)para (kg/m3) = Fe-content (ppm) × (1 ± 0.1) × 10− 12 (kg/m3/ppm). The maximum susceptibility difference (Δk = k1 − k3) was found to be unaffected by iron contents below 100 ppm. Ferromagnetic contributions due to inclusions of ferromagnetic minerals can dominate the susceptibility. They were detected by acquisition of isothermal remanent magnetization (IRM) and their contribution to the AMS was separated by high-field measurements.  相似文献   

18.
Homogeneous 129I / 127I ratios from 6.51 ± 1.36 × 10− 14 to 12.6 ± 1.49 × 10− 14 were measured in formation brine at the Pol-Chuc, Abkatún, Taratunich–Batab off-shore oil reservoirs, Bay of Campeche in S-Mexico. Cosmogenic production could account for a homogeneous, Late Cretaceous/Paleocene time period (71.3 ± 5.3 to 56.3 ± 2.9 Ma) for the sedimentation and burial of organic material in the source formation. As the actual reservoir column is formed by Paleocene to Kimmeridgian sediments, the lower part of the lithological column must have received hydrocarbons that migrated downward from an initial source rock (Upper Cretaceous?) during a post-Paleocene event, probably during Miocene. Cosmogenic production from Tithonian shales can be excluded, as 129I would have been decayed. As an alternative or complementary process, the subsurface, radiogenic production of 129I / 127I by 238U-fission in Uranium-enriched sediments should also be considered to explain the present, low 129I / 127I ratios.  相似文献   

19.
Cementitious materials used for radioactive waste repository construction complicate the performance assessment of radioactive waste systems because the use of cement may greatly alter the pH (8–13) of groundwater and release constituents such as calcium ions. Under such conditions, it is important to clarify also the dynamic behavior of silica (silicic acid), in order to evaluate the alteration in the chemical and physical properties of the fractured layer or the host rock surrounding the repository. Since silica undergoes polymerization, precipitation or dissolution depending on the pH and/or temperature, the behavior of silica would be greatly complicated in the presence of other ions. This study is focused on the deposition rates of polysilicic acid and soluble silicic acid with up to 10−3 M Ca ions. In the experiment, Na2SiO3 solution (250 mL, pH > 10, 298 K) was poured into a polyethylene vessel containing amorphous silica powder (0.5 g), and a buffer solution, HNO3, and CaNO3 as Ca ions were sequentially added into the vessel. The pH of the solution was set to 8. The silica, initially in a soluble form at pH > 10 (1.4 × 10−2 M), became supersaturated and either deposited on the solid surface or changed into the polymeric form. Then the concentrations of both poly- and soluble silicic acid were monitored over a 40-day period. The decrease of polysilicic acid became slow with an increase in the concentration of Ca ions in the range of up to 10−3 M. In general, the addition of electrolytes to a supersaturated solution accelerates the aggregation and precipitation of polymeric species. However, the experimental result showed that polysilicic acid in the presence of Ca ions is apparently stable in solution, compared with that under a Ca-free condition. On the other hand, the concentration of soluble silicic acid in the presence of Ca ions immediately became metastable, that is, slightly higher than the solubility of soluble silicic acid. Its dynamic behavior was similar to that in the Ca-free condition.  相似文献   

20.
Bacterial metal reduction is an important biogeochemical process in anaerobic environments. An understanding of electron transfer pathways from dissimilatory metal-reducing bacteria (DMRB) to solid phase metal (hydr)oxides is important for understanding metal redox cycling in soils and sediments, for utilizing DMRB in bioremedation, and for developing technologies such as microbial fuel cells. Here we hypothesize that the outer membrane cytochromes OmcA and MtrC from Shewanella oneidensis MR-1 are the only terminal reductases capable of direct electron transfer to a hematite working electrode. Cyclic voltammetry (CV) was used to study electron transfer between hematite electrodes and protein films, S. oneidensis MR-1 wild-type cell suspensions, and cytochrome deletion mutants. After controlling for hematite electrode dissolution at negative potential, the midpoint potentials of adsorbed OmcA and MtrC were measured (−201 mV and −163 mV vs. Ag/AgCl, respectively). Cell suspensions of wild-type MR-1, deletion mutants deficient in OmcA (ΔomcA), MtrC (ΔmtrC), and both OmcA and MtrC (ΔmtrC–ΔomcA) were also studied; voltammograms for ΔmtrC–ΔomcA were indistinguishable from the control. When the control was subtracted from the single deletion mutant voltammograms, redox peaks were consistent with the present cytochrome (i.e., ΔomcA consistent with MtrC and ΔmtrC consistent with OmcA). The results indicate that OmcA and MtrC are capable of direct electron exchange with hematite electrodes, consistent with a role as terminal reductases in the S. oneidensis MR-1 anaerobic respiratory pathway involving ferric minerals. There was no evidence for other terminal reductases operating under the conditions investigated. A Marcus-based approach to electron transfer kinetics indicated that the rate constant for electron transfer ket varies from 0.025 s−1 in the absence of a barrier to 63.5 s−1 with a 0.2 eV barrier.  相似文献   

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