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1.
Problems of dissolution of the so-called secondary copper sulphides are very important for dynamic as well as percolation leaching of ores. This paper deals with dissolution kinetics of sulphides in an alkaline medium, using complex-forming agents in connection with possibility to leach basic, partially oxidized ores. Natural minerals and their polydispersions were investigated and the so-called geometrical model was used for evaluation. Basic dependences of the dissolution rate on the reagent concentration and pH value of the leaching solution were found and an attempt at their mathematical expression and physical interpretation was made. The first part of this work refers to the systems of covellite-ethylene diamine tetra-acetic acid (EDTA) and covellite-ethylene diamine (EDA). The established dependences are not only of theoretical but also of practical importance.  相似文献   

2.
Ferrihydrite (Fh) coprecipitated with exopolymers of plants and microbes may differ in its geochemical reactivity from its abiotic counterpart. We synthesized Fh in the presence and absence of acid polysaccharides (polygalacturonic acid (PGA), alginate, xanthan) and characterized the physical and structural properties of the precipitates formed [Mikutta C., Mikutta R., Bonneville S., Wagner F., Voegelin A., Christl I. and Kretzschmar R. (2008) Synthetic coprecipitates of exopolysaccharides and ferrihydrite. Part I: Characterization. Geochim. Cosmochim. Acta]. In this paper, we focus on the reactivity of PGA and alginate coprecipitates and pure Fh, and studied their interaction with the microbial siderophore desferrioxamine B (DFOB) in the presence and absence of low molecular weight organic (LMWO) acid anions (malate, citrate). Batch adsorption and dissolution experiments were performed in the dark at pH 7 in 10 mM NaClO4 background electrolyte. In the dissolution experiments, different modes of ligand addition were applied (single, simultaneous, stepwise). With an estimated Langmuir sorption maximum of 15 mmol/mol Fe, a PGA coprecipitate with 11% Corg sorbed about four times as much DFOB as pure Fh, and the amount of DFOB sorbed was ∼4-fold larger than estimated from the sum of DFOB sorption to pure Fh and PGA alone. The apparent initial dissolution rates, Rapp-initial, and pseudo-first order rate coefficients, k, of the coprecipitates exceeded those of pure Fh by up to two orders of magnitude. Citrate and malate exerted a strong synergistic effect on the DFOB-promoted dissolution of pure Fh, whereas synergistic effects of both anions were absent or negligible for the coprecipitates. Rapp-initial of the citrate and DFOB-promoted dissolution of PGA coprecipitates increased with increasing molar C/Fe ratio of the coprecipitates, independent of the charge of the LMWO ligand. Our results indicate that polyuronates stabilize Fh particles sterically and /or electrostatically, thus increasing the mineral surface area accessible to LMWO ligands. In contrast, pure Fh was coagulated at pH 7 (pHiep of Fh = 7.1), and hence only a small fraction of the Fh surface underwent dissolution. The increase in ligand-accessible surface area of Fh upon coprecipitation with acid polysaccharides seems to primarily control the kinetics of the ligand-promoted dissolution at neutral pH. In pH environments where the solubility of Fe(III) is very low, dissolution rates of Fe(III) (hydr)oxides in such coprecipitates may therefore exceed those of pure minerals by several orders of magnitude, despite a similar crystallinity of the minerals.  相似文献   

3.
《Geochimica et cosmochimica acta》1999,63(19-20):3261-3275
Studies on the dissolution kinetics of kaolinite were performed using batch reactors at 25°C and in the pH range from 1 to 13. A rapid initial dissolution step was first observed, followed by a linear kinetic stage reached after approximately 600 hr of reaction during which the kaolinite dissolves congruently at pH < 4 and pH > 11. The apparent incongruency between pH 5 and 10 was due to the precipitation of an Al–hydroxide phase. The true dissolution rates were computed from the amount of Si released into solution. The rate dependence on pH can be described by: r = 10−12.19aH+0.55 + 10−14.36 + 10−10.71aOH0.75Between pH 5 and 10, the rate is approximately constant, although a smooth minimum was observed at pH close to 9. mAn attempt was made to obtain a general rate law based on the coordination theory, which was first applied to the mineral dissolution studies by Stumm and co-workers. The kinetic data were combined with the results obtained for the surface speciation by Huertas et al. (1998). It is possible to express the linear dissolution rate as a simple power function of the concentration of the surface sites active in various pH ranges: r = 10−8.25 [>Al2OH2+] + 10−10.82 [>AlOH2+]0.5 + 10−9.1 [>Al2OH + >AlOH + >SiOH] + 103.78 [>Al2O + >AlO]3This equation assumes that the dissolution mechanism is mainly controlled by the two Al surface sites (external and internal structural hydroxyls, and aluminol at the crystal edges) under both acidic and alkaline conditions. The model reflects well the important contribution of the crystal basal planes to the dissolution of kaolinite.  相似文献   

4.
Experiments with both iron sulphide and copper sulphide precipitates in aqueous solution show that oxygen is significant in determining the mineral phases resulting after heating up to 180 °C. Tetragonal FeS converts to FeS2 and Fe3O4 in the presence of oxygen, while in the absence of oxygen under the same conditions it converts to hexagonal FeS. Suspensions of covellite and of chalcocite under the same conditions convert to digenite in the presence of oxygen, but remain unchanged when oxygen is absent. Experimental evidence is advanced to support structure determinations that CuS contains disulphide ions.
Zusammenfassung Experimente mit in wässrigen Lösungen ausgefällten Eisen- und Kupfersulfiden dokumentieren die außerordentliche Bedeutung des Sauerstoffes auf die Bildungs- und Verhaltensweise von Mineralphasen, beobachtet nach dem Aufheizen auf 180 °C. So bildet sich aus ursprünglich tetragonalem FeS letzten Endes Pyrit und Magnetit, wenn Sauerstoff zugegen war, während bei dessen Abwesenheit, aber sonst gleichen Versuchsbedingungen, die Umwandlung in hexagonales FeS erfolgte. Suspensionen von Covellin und Chalkosin wurden, unter analogen Versuchsbedingungen und in Gegenwart von Sauerstoff, in Digenit überführt, während sonst, wenn keine Sauerstoffeinwirkung stattfand, die Mineralphasen keinerlei Veränderungen erkennen ließen. Mittels solcher experimenteller Methoden lassen sich bei der Strukturbestimmung des CuS offenbar Merkmale des Vorhandenseins von Disulfidionen erkennen.


Published by permission of the Director, Bureau of Mineral Resources, Canberra A. C. T., Australia.

Temporary Address: Mineralog.-Petrograph. Inst. Univ. Heidelberg, Berliner Str. 19, 69 Heidelberg, Germany  相似文献   

5.
Summary The Abakaliki lead-zinc deposit in the lower Benue Trough (Nigeria) represents the largest of a series of fracture controlled base metal deposits within the Lower Cretaceous (Albian) Asu River Group shales. Field evidence, ore microscopy and electron microprobe analysis of the lodes, suggest that the vein mineralization commenced with pre-ore precipitation of diagenetic marcasite, pyrite and minor gel-like colloform textured schalenblende and galena especially at the vein/wall rock contacts. This was succeeded by an ore stage consisting mainly of sphalerite, galena, chalcopyrite and pyrite. Accessories include bournonite and boulangerite. There was also a later introduction of complex intergrowths comprising bornite, chalcocite, enargite, and tennantite. In addition a lead/iron bearing copper sulphide and a copper bismuth sulphide of wittichenite composition (Cu6Bi2SO6), the optical parameters of which do not agree with those of wittichenite, were also introduced. The late stage copper sulphides and sulphosalts were formed as replacements of earlier lower temperature (ca. 170°C) main phase mineralization, when temperature rose in minimum up to 230°C.
Koexistierende Kupfer-Sulfide und Sulfosalze in der Blei-Zink-Iagerstätte Abakaliki, Unterer Benue-Graben (Nigeria) und ihre genetische Bedeutung
Zusammenfassung Die Blei-Zink-Lagerstätte Abakaliki im Unteren Benue-Graben (Nigeria) ist die größte einer Reihe von durch Bruchstrukturen bestimmten Buntmetallagerstätten innerhalb der unterkretazischen (Albian) Asu River Group Shales. Geländebeobachtungen, Erzmi-kroskopie undzeigen, Mikrosondenanalysen zeigen, daß die Gangmineralisation mit der Ablagerung von diagenetischem Markasit, Pyrit und, in kleinerem Ausmaß gel-ähnlicher kolloformer Schalenblende und Bleiglanz, besonders an den Kontaktzonen zwischen Gängen und Nebengestein begonnen hat. Darauf folgte ein Stadium der Erzablagerung, wobei es hauptsächlich zur Bildung von Zinkblende, Bleiglanz, Kupferkies und Pyrit kam. Bournonit und Boulangerit kommen als Nebengemengteile vor. Schließlich gab es eine spätere Bildung von komplexen Verwachsungen, die aus Bornit, Kupferglanz, Enargit und Tennantit bestehen. Außerdem kam es zum Absatz eines Blei-Eisenführenden Kupfersulfids und eines Kupfer-Wismut-Sulfids, dessen Zusammensetzung mit der von Wittichenit (Cu6B22S6) übereinstimmt, dessen optische Parameter jedoch anders sind. Die späten Kupfersulfide und Sulfosalze wurden durch Verdrängung von früheren Tieftemperaturerzen (ca. 170°C) der Hauptphase gebildet, wo die Temperaturen mindestens bis auf 230°C anstiegen.


With 4 Figures  相似文献   

6.
Galvanic currents were measured by short circuiting two half cells; PbS  N2 (g)  KNO3 | KNO3  O2 (g) or H2O2  PbS, and then after adding xanthate to the l.h.s. cell. Such addition of xanthate resulted in a 10 fold (with O2 in the r.h.s. cell) and 100 fold (with H2O2 in r.h.s. cell) increase in the short circuit and steady state currents and also lead to bubble attachment on galena in the l.h.s. cell, in nitrogen atmosphere. The results indicated a heterogeneous, two site electrochemical mechanism for the reduction of oxygen and oxidative adsorption of xanthate on galena.  相似文献   

7.
Scanning Force Microscopy (SFM) was used to develop a method which can provide quantitative kinetic data of crystal growth and dissolution. Based on observations of single crystal faces in monolayer resolution, morphology and temperature dependent growth and dissolution rates can be obtained. From these kinetic data activation energies can be calculated and compared with existing theories. The experimental method works by extracting grown or dissolved terrace areas and step densities from image sequences taken at different temperatures. As an example, the method is applied for dissolution on the brucite (001) surface in acidic water (pH 2.7) within the temperature range of 21 to 35°C. At these conditions the dissolution rate depends nonlinearly on the step density and gives evidence for interstep interaction. The calculated activation energy for dissolution is 60 ± 12 kJ mol−1. With this high activation energy, dissolution cannot be regarded as a transport-controlled process, and is therefore surface controlled.  相似文献   

8.
The removal of Cd from aqueous solutions by hydroxyapatite (HAP) was investigated with and without EDTA being present. Batch experiments were carried out using synthetic hydroxyapatite with Ca/P 1.57 and a specific surface area of 37.5 m2/g in the pH range 4–9 (25 °C; 0.1 M KNO3). The surface composition of the solid phases were analysed by X-ray Photoelectron Spectroscopy (XPS). The surface layer of HAP was found to undergo a phase transformation with a (Ca + Cd)/P atomic ratio of 1.4 and the involvement of an ion exchange process (Ca2+ ↔ Cd2+). The amount of Cd removed from the solution increased with increasing pH, reaching ≈100% at pH 9. In the presence of EDTA Cd removal was reduced due to the formation of [CdEDTA]2− in solution. The solubility of HAP increases in the presence of EDTA at pH values above 5, mainly due to the formation of [CaEDTA]2−. In contrast to this, the solubility was found to decrease in the presence of Cd2+ and CdEDTA2−. Using XPS the formation of a Cd-enriched HAP surface was found, which was interpreted as the formation of a solid solution of the general composition: Ca8.4-xCdx(HPO4)1.6(PO4)4.4(OH)0.4Ca8.4-xCdx(HPO4)1.6(PO4)4.4(OH)0.4.  相似文献   

9.
Pb2+, like Cu2+, forms strong complexes with fulvic acids (Cd2+-fulvate complexes are much weaker), but Pb-fulvate precipitates at a much lower mole ratio of metal ion to fulvic acid than either Cu-fulvate or Cd-fulvate does. Physical association of Pb2+ with Pb-fulvate solids as well as complexation by sites still available in the precipitates probably causes the increased removal of free Pb2+ from solution after precipitation begins.  相似文献   

10.
11.
通过白云岩化鲕粒灰岩与0.1 mol/L乙酸的旋转盘溶解动力学实验,研究了深埋藏中有机质热演化过程中伴生的有机酸对鲕粒灰岩储层的改造作用机理.结果显示,白云岩化鲕粒灰岩溶解反应的速率在3.26×10-7~6.66×10-7 mol/(cm2·s)之间,并且溶蚀速率随温度和转速的增加而增大.反应前后样品表面的扫描电子显微...  相似文献   

12.
Magnesite (104) dissolution kinetics were studied in acidic aqueous solutions (2.0 < pH < 4.2) at temperatures between 60 and 90°C by atomic force microscopy (AFM). Comparison of dissolution fluxes obtained by AFM and chemical methods revealed six to seven times larger dissolution fluxes obtained by chemical analysis. Corresponding empirical activation energies were found to be 74 ±22 kJ/mol and 41 ± 4 kJ/mol (at pH 4.2) for the AFM and chemical methods, respectively. The empirical reaction order with respect to proton concentration was 0.36 ± 0.13 and 0.47 ± 0.03 for AFM and chemical methods, respectively. These comparisons suggest that the two experimental measurement methods differ as a result of the different sampling length scales associated with the methods. Negligible changes in step dissolution velocity with changes in bulk pH were found, suggesting that the principal source of increasing dissolution flux with decreasing pH is an increase in step density. However, the observed stable step orientation, which is dependent on pH, suggests that more than one proton adsorption equilibrium should be used to describe the surface chemistry of magnesite in acidic solution.  相似文献   

13.
14.
Fifty scapolites have been analysed spectrographically for numerouselements. Average concentrations (p.p.m.) were as follows: B25, Be 9–3, Ga 33, Ti 82, Li 56, Cu 4–4, Zr 59,Mn 57, Sr 1,800, Pb 45, Ba 120, Rb 20. The following were seldomor never detected: Cr, Ni, Co, Mo, Sn, V, Sc, Ag, Y, La. Themajor elements Ca, Na, K were also determined. The distributionof the trace elements can be explained by isomorphous substitution,but no detailed correlation of trace elements with each otheror with major elements was found. Refractive indices were determined and the relation betweenaverage index and per cent Me was examined: correlation waspoor, which may in part be attributed to analytical error. Examination of scapolite parageneses shows that scapolite characteristicallyoccurs in the upper amphibolite facies or the pyroxene hornfelsfacies: it is not restricted to these and may occur in any faciesfrom zeolitic to granulitic and in any hornfels facies. Theelements generally concentrated in scapolite include Ca, Na,C, Cl, S, H, B, Be, Li, Sr, Pb. The presence of C, Cl, S, Htestify to genesis in the presence of high partial pressureof CO2, Cl2, SO3, H2O (or related compounds), that is in pneumatolytic,pegmatitic, or hydrothermal environments. The concentrationof B, Be, Li can also be attributed to these conditions. The source of the elements concentrated in scapolite must inpart be common rocks. In a limited contact zone, the nearbymagma supplied some elements, but where regional scapolitizationhas taken place the presence of magma is less clear. Many commonrocks or rock series contain all the necessary constituents,but some particular conjunction of conditions is necessary forscapolite to form, or it would be more common.  相似文献   

15.
This paper explores how dissolution and precipitation reactions are coupled in batch reactor experimental systems at elevated temperatures. This is the fifth paper in our series of ‘‘Coupled Alkali Feldspar Dissolution and Secondary Mineral Precipitation in Batch Systems.’’ In the previous four papers we presented batch experiments of alkali-feldspar hydrolysis and explored the coupling of dissolution and precipitation reactions(Fu et al. in Chem Geol91:955–964, 2009; Zhu and Lu in Geochim Cosmochim Acta 73:3171–3200, 2009; Zhu et al.in Geochim Cosmochim Acta 74:3963–3983, 2010; Lu et al. in Appl Geochem30:75–90, 2013). Here, we present the results of additionalK-rich feldspar hydrolysis experiments at 150 °C. Our solution chemistry measurements have constrained feldspar dissolution rates, and our high resolution transmission electron microscopy work has identified boehmite precipitation. Reaction path modeling of K-feldspar dissolution and boehmite precipitation simulated the coupled reactions, but only with forced changes of boehmite rate law in the middle of experimental duration. The results which are reported in this article lend further support to our hypothesis that slow secondary mineral precipitation explains part of the wellknown apparent discrepancy between lab measured and field estimated feldspar dissolution rates(Zhu et al. in Water–rock interaction, 2004).  相似文献   

16.
This paper explores how dissolution and precipitation reactions are coupled in batch reactor experimental systems at elevated temperatures. This is the fourth paper in our series of “Coupled Alkali Feldspar Dissolution and Secondary Mineral Precipitation in Batch Systems”. In our third paper, we demonstrated via speciation-solubility modeling that partial equilibrium between secondary minerals and aqueous solutions was not attained in feldspar hydrolysis batch reactors at 90-300 °C and that a strong coupling between dissolution and precipitation reactions follows as a consequence of the slower precipitation of secondary minerals (Zhu and Lu, 2009). Here, we develop this concept further by using numerical reaction path models to elucidate how the dissolution and precipitation reactions are coupled. Modeling results show that a quasi-steady state was reached. At the quasi-steady state, dissolution reactions proceeded at rates that are orders of magnitude slower than the rates measured at far from equilibrium. The quasi-steady state is determined by the relative rate constants, and strongly influenced by the function of Gibbs free energy of reaction (ΔGr) in the rate laws.To explore the potential effects of fluid flow rates on the coupling of reactions, we extrapolate a batch system (Ganor et al., 2007) to open systems and simulated one-dimensional reactive mass transport for oligoclase dissolution and kaolinite precipitation in homogeneous porous media. Different steady states were achieved at different locations along the one-dimensional domain. The time-space distribution and saturation indices (SI) at the steady states were a function of flow rates for a given kinetic model. Regardless of the differences in SI, the ratio between oligoclase dissolution rates and kaolinite precipitation rates remained 1.626, as in the batch system case (Ganor et al., 2007). Therefore, our simulation results demonstrated coupling among dissolution, precipitation, and flow rates.Results reported in this communication lend support to our hypothesis that slow secondary mineral precipitation explains part of the well-known apparent discrepancy between lab measured and field estimated feldspar dissolution rates (Zhu et al., 2004). Here we show how the slow secondary mineral precipitation provides a regulator to explain why the systems are held close to equilibrium and show how the most often-quoted “near equilibrium” explanation for an apparent field-lab discrepancy can work quantitatively. The substantiated hypothesis now offers the promise of reconciling part of the apparent field-lab discrepancy.  相似文献   

17.
In order to evaluate the complex interplay between dissolution and precipitation reaction kinetics, we examined the hypothesis of partial equilibria between secondary mineral products and aqueous solutions in feldspar-water systems. Speciation and solubility geochemical modeling was used to compute the saturation indices (SI) for product minerals in batch feldspar dissolution experiments at elevated temperatures and pressures and to trace the reaction paths on activity-activity diagrams. The modeling results demonstrated: (1) the experimental aqueous solutions were supersaturated with respect to product minerals for almost the entire duration of the experiments; (2) the aqueous solution chemistry did not evolve along the phase boundaries but crossed the phase boundaries at oblique angles; and (3) the earlier precipitated product minerals did not dissolve but continued to precipitate even after the solution chemistry had evolved into the stability fields of minerals lower in the paragenesis sequence. These three lines of evidence signify that product mineral precipitation is a slow kinetic process and partial equilibria between aqueous solution and product minerals were not held. In contrast, the experimental evidences are consistent with the hypothesis of strong coupling of mineral dissolution/precipitation kinetics [e.g., Zhu C., Blum A. E. and Veblen D. R. (2004a) Feldspar dissolution rates and clay precipitation in the Navajo aquifer at Black Mesa, Arizona, USA. In Water-Rock Interaction (eds. R. B. Wanty and R. R. I. Seal). A.A. Balkema, Saratoga Springs, New York. pp. 895-899]. In all batch experiments examined, the time of congruent feldspar dissolution was short and supersaturation with respect to the product minerals was reached within a short period of time. The experimental system progressed from a dissolution driven regime to a precipitation limited regime in a short order. The results of this study suggest a complex feedback between dissolution and precipitation reaction kinetics, which needs to be considered in the interpretation of field based dissolution rates.  相似文献   

18.
Metal cycling via physical and chemical weathering of discrete sources (copper mines) and regional (non-point) sources (sulfide-rich shale) is evaluated by examining the mineralogy and chemistry of weathering products in Great Smoky Mountains National Park, Tennessee, and North Carolina, USA. The elements in copper mine waste, secondary minerals, stream sediments, and waters that are most likely to have negative impacts on aquatic ecosystems are aluminum, copper, zinc, and arsenic because these elements locally exceed toxicity guidelines for surface waters or for stream sediments. Acid-mine drainage has not developed in streams draining inactive copper mines. Acid-rock drainage and chemical weathering processes that accompany debris flows or human disturbances of sulfidic rocks are comparable to processes that develop acid-mine drainage elsewhere. Despite the high rainfall in the mountain range, sheltered areas and intermittent dry spells provide local venues for development of secondary weathering products that can impact aquatic ecosystems.Electronic Supplementary Material  Supplementary material is available for this article if you access the article at . A link in the frame on the left on that page takes you directly to the supplementary material.
Jane M. HammarstromEmail: Phone: +1-703-6486165Fax: +1-703-6486252
  相似文献   

19.
The leaching of major species from fly ash is a function of the pH of the solution in contact with the fly ash. The aim of this study was to determine the effect of the pH of the leachant on the leaching of species from the ash residues recovered after the long-term fly ash–brine interactions. Acid neutralization capacity (ANC) tests using solutions of different pH values ranging from the initial pH of the ash residues (11–12) to pH 4 were employed in the leaching experiments. The ANC tests revealed that the release of major species from the ash residues depended on the pH of the leachants except for Na and Cl, where the significant concentrations leached were independent of the solution pH. The concentrations of Al and Si in the ANC leachates were very high at pH below 6 while Ca, K, Sr, Mg and B were immediately mobilized from the brine impacted fly ash when in contact with de-ionized water, and leaching increased as the pH decreased. The concentration of SO4 leached from the brine impacted ash residues at high pH was high, and the leaching increased with decrease in the pH of the leachant. This study shows that most of the major elements captured in the ash residues could be mobilized when in contact with aqueous solutions of various pH. This reveals that the co-disposal of fly ash and brine may not be the best practice as the major elements captured in the ash residues could leach over time.  相似文献   

20.
In the present study, stabilization treatment using waste resource stabilizers was performed for soil contaminated with As and heavy metals (Pb and Cu). Calcined oyster shell (COS) and coal mine drainage sludge (CMDS) were used as a mixed stabilizing agent for a wet-curing duration of 28 days. After the stabilization treatment, the treatment process efficiency was evaluated by the results of various batch- and column-leaching tests. Neutral and weak acid extraction methods, such as water-soluble extraction and SPLP, did not exhibit satisfactory results for heavy metal stabilization, even if they showed very low leachability. On the other hand, TCLP and 0.1 M HCl extraction showed that the stabilizers significantly reduced the amount of heavy metals leached from the soil, which strongly supports the thesis that the stabilization treatment is efficient in the acidic leaching conditions that were explored. Specifically, in the 0.1 M HCl extraction, the reduction efficiencies of As, Pb, and Cu leachings were more than 90 %, compared with control experiments. This study demonstrates that the application of waste resources for the stabilization of As and heavy metals is feasible. However, some limitations observed in the experiments should be considered in future studies, such as the mobilization of alkali-soluble elements, and in particular, exchangeable fractions of Cu. In addition, the treatment efficiency can be evaluated by different leaching methods, which suggests that multidirectional approaches are required for the proper evaluation of stabilization treatment.  相似文献   

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