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Int. J. Miner. Process. 72 (2003) 373 – 386 www.elsevier.


Pyrite oxidation in alkaline solutions: nature of the product layer
C.L. Caldeira a, V.S.T. Ciminelli a,1, A. Dias a, K. Osseo-Asare b,*

Metallurgical and Materials Engineering Department-UFMG, Rua Espirito Santo 35, Belo Horizonte, MG 30160-030, Brazil b Department of Materials Science and Engineering, The Pennsylvania State University, University Park, PA 16802, USA Received 20 February 2003; received in revised form 5 June 2003; accepted 1 July 2003

Abstract The nature of the oxides formed during pyrite oxidation by molecular oxygen in alkaline solutions has been investigated with the aid of Eh – pH diagrams and direct analysis of the solid products. X-ray diffraction (XRD) and infrared analyses indicate that the products formed are determined by solution composition. In hydroxide medium, hematite, as the main phase, and small amounts of ferrihydrite are identified. In contrast, in carbonate medium, the main constituent is ferrihydrite, with some iron hydroxide carbonate phase also present. In calcium hydroxide medium, only calcium carbonate was detected on the surface of oxidized pyrite in an amount that increased when the system was opened to the atmosphere. Only by diffuse reflectance infrared spectroscopy (IR) was it possible to identify carbonate compounds among the products formed during pyrite oxidation in aqueous solutions. The morphology of the product layers was also affected by solution composition. In NaOH solutions, the particles are initially covered by a thin oxide layer that fractures after longer reaction times. Most of the oxide reports to the solution, where it remains as a stable suspension. Pyrite oxidation in Na2CO3/NaHCO3 solutions results in particles that are initially covered by a discontinuous oxide coating that grows with reaction time, thus increasing the overall pyrite surface coverage. In this case, a precipitation confined to the solid/liquid interface is favored by the higher ionic strength of the sodium carbonate solutions. D 2003 Elsevier B.V. All rights reserved.
Keywords: pyrite; alkaline solution; oxide

1. Introduction The kinetics and mechanisms of pyrite oxidation have been extensively studied in order to understand and control the reaction in mineral processing, metal extraction, and acid mine drainage (AMD), among other processes (Brown and Jurinak, 1989; Nicholson et al., 1988, 1990; Hood, 1991; Moses and Herman,
* Corresponding author. Fax: +1-814-863-4718. E-mail addresses: (V.S.T. Ciminelli), (K. Osseo-Asare). 1 Fax: +55-31-238-1815. 0301-7516/$ - see front matter D 2003 Elsevier B.V. All rights reserved. doi:10.1016/S0301-7516(03)00112-1

1991; Ciminelli and Osseo-Asare, 1995a,b). Pyrite decomposition in alkaline solutions allows the neutralization of the acid formed during the oxidation reaction and maintains a favorable pH condition for the precipitation of iron. The rate of pyrite oxidation has been found to be affected by the nature of the reagent used to control the pH. Among these reagents, sodium carbonate/bicarbonate is claimed to be particularly effective in enhancing the decomposition of pyrite in aerated solutions (Wheelock, 1981; Guay, 1981a; Souza and Ciminelli, 1992). Higher oxidation levels of pyrite and arsenopyrite as well as higher gold recoveries, in comparison with those observed in

i. In solutions with pH>3. 1995a.g. 1992). 1989. 2. Nicholson et al.374 C.b. with respect to their composition and morphology. Based on these results. and a shaft at the center connected to a constant speed motor. dried with acetone. reagent concentration. Lowson. 1995a. 72 (2003) 373–386 NaOH solutions. Peru. produces insoluble iron oxides that precipitate in the bulk aqueous phase or on the surface of the parent mineral. Preparation of pyrite samples The sample used in the leaching experiments consisted of large pieces (50 –100 mm) of pyrite from Huanzala. This material was ground to À 0.b) suggested that sodium carbonate enhances the oxidation of pyrite by favoring the removal of the oxide coating.. Miner. e. Ciminelli and Osseo-Asare. 1980. this presaturation treatment served to minimize further reagent absorption by the gas stream passing through the reactor. scanning electron microscopy (SEM)..e. The above works. Unreacted and oxidized pyrite samples were analyzed with techniques such as optical microscopy. small samples of the ground material were soaked in 3 M hydrochloric acid solution for 36 h. The material below 38 Am was further separated into two fractions. The pyrite oxidation is a surfacecontrolled reaction (Lowson. The acid solution dissolved oxides and other soluble compounds already present in the raw material or oxides formed during grinding. and thickness. the physicochemical nature and the morphological differences of the solids obtained in NaOH. Variants of Fourier transform infrared spectros- copy (FTIR). 1956. Na2CO3. Gases feeding the reactor were first purified through columns containing DrieriteR (dehumidifier) and AscariteR (for CO2 removal). 1963. Guay (1981a.L. Ciminelli and Osseo-Asare. grain size.30 mm and classified into various size fractions by wet – dry screening. and infrared spectroscopy (IR). 1991. Rochester. and CaO systems are discussed. a condenser. have been reported for the pressure oxidation of a refractory gold concentrate (Souza and Ciminelli. Koslides and Ciminelli. 1982. Evangelou et al. 1982). The leaching experiments were performed in a baffled 2-l glass reaction vessel immersed in a controlled temperature bath. above and below 10 Am. 1981. and temperature (Burkin and Edwards.b). and kept under vacuum in a desiccator.b. Chuang et al. 1981a. 1992. rinsed with double-distilled water. however. The total gas flow rate was fixed at 180 cm3/min. At the start of the run. Wheelock. purchased from Ward’s Natural Science Establishment. 1990. Nitrogen was additionally passed through copper coils heated at about 400 jC. and diffuse reflectance (DRIFT) analyses were used to determine the vibrational modes of the oxidation products of pyrite. Many authors observed an increase in the rate of pyrite oxidation with the increase of pH. The four-hole cover was fitted with a thermometer. Caldeira et al. porosity. For instance.. Some characteristics of the coating formed in systems containing CaO are also presented. the oxidative leaching of iron-containing sulfide minerals.0. 1963). Guay. 1989. Warren (1956) found that the increase of pH caused by addition of small amounts of calcium carbonate resulted in drastic reduction of pyrite decomposition. a fritted glass gas inlet. filtered. Brown and Jurinak. The kinetics of pyrite oxidation in alkaline solutions has been correlated with the properties of the oxide coating (Warren. transmission (FTTIR)... like pyrite. depend on the experimental conditions and on the characteristics of the reacting phase (Burkin and Edwards. 1982. the gases were bubbled through a sample of the leach solution. / Int. Following the purification. 1998). The precipitate often forms a coating. NY. the rate then becoming controlled by diffusion in the product layer. thus increasing the exposure of fresh surfaces to oxidation.1. Hiskey and Schlitt. Process. whose properties. Experimental procedures 2. The present investigation is aimed at characterizing the solid products of pyrite oxidation by molecular oxygen in NaOH and Na2CO3 solutions. Hood. Warren (1956) explained the reduction as a consequence of the formation of a growing film of iron oxide. X-ray diffraction (XRD). 1988. 1 g of pyrite was added to 1 l of solution that had been . The solution chemical conditions that constrain the solid product formation are also examined with the aid of Eh – pH diagrams developed for the Fe – S– CO3 –H2O system. Brown and Jurinak. Prior to the leaching experiments. did not show direct experimental evidence of chemical or morphological differences to support the proposed hypotheses. J. with a Donaldson Accucut Classifier.

1 (right). 2. It can be seen that the product layer appears more discontinuous in the case of the carbonate solution. In these measurements. MCT detector. thus allowing a direct measure of the reacted fraction.0 (Roine. J. For the transmittance measurements. the samples were mixed with KBr powder in very low concentrations (1 wt. CsI beam splitter). The IR measurements occurred under vacuum. Therefore. 1952). Analytical techniques The samples prepared by the aforementioned procedures (prior to and after leaching) were characterized by wet chemical analysis. 1c (left). 72 (2003) 373–386 375 previously thermally equilibrated to the desired temperature and saturated for at least 1 h with the gas mixture. 2. version 4. and sharp edges. e. The Correspondence Principle of Criss and Cobble (1964) was used by the HSC program to estimate heat capacities at 100 jC. The oxidation of pyrite was followed by two different analytical techniques. 3. left). when necessary. The first consisted of washing the solid residues with a hot solution of 3 M HCl in order to remove oxides produced during the reaction. The mixture was pressed under vacuum into disks of 13-mm diameter. but maintains the coarse granulation identified at the beginning of the reaction (Fig. smooth surfaces. A Perkin Elmer infrared spectrometer model Spectrum 1000 was used for the transmission analysis (under the following conditions: 64 scans of accumulation. adjusted with the addition of drops of 1 M sodium hydroxide solution. and optical microscopy (Wild Heerbrugg optical microscope). a pure KBr disk was used for the reference spectrum. 1974) and the HSC Chemistry software data base. the corresponding micrographs for the sodium hydroxide system are also provided in Fig. using a gold mirror as a reference spectrum. at an applied pressure of 750 MPa. This became quite evident from optical microscope observations (not shown here). 1999). and weighed. 1 (left) show the morphology of pyrite particles after oxidation in sodium carbonate solution. 1a. Diffuse reflectance analyses were undertaken with a BOMEM DA8 FTIR spectrometer (under the following conditions: 64 scans of accumulation. unreacted pyrite was then filtered. Caldeira et al. under the experimental conditions used in the present study. 2 cmÀ 1 resolution. The potential (Eh) is based on the standard hydrogen electrode and has the units of volts. 1b (left). The red color that characterizes the oxide product contrasted with the metallic luster of clean spots of pyrite surface. X-ray diffraction (Philips model PW1710). operating at 25 kV and with a Noran energy-dispersive spectrometer (ZAF corrections)). / Int. 2 cmÀ 1 resolution.8-Am membrane filter. dried with acetone. pH diagrams for the Fe – S – CO3 – H2O system at 25 and 100 jC were constructed with thermodynamic data taken from the literature (Naumov et al. The pH was checked periodically and. this procedure was adopted only for experiments of relatively long duration. in the spectral range of 400– 4000 cmÀ 1. Results and discussion 3. Morphology analysis The SEM micrographs presented in Fig. which characterize the unreacted particles. At the end of a test..C. The second technique consisted in analyzing the soluble sulfur species produced during the oxidation of pyrite by precipitation with barium chloride (Kolthoff and Sandell.1.. Thermodynamic analysis Potential (Eh) vs. The thickness of the oxide layer and details of the oxide – pyrite contact are better illustrated in Fig. Process.L. metallic luster. For purposes of comparison. Globar source). scanning electron microscopy (SEM) (JSM 35C. the solid residues were separated from the solution with a 0. KBr beam splitter.% sample). The overall appearance contrasts with the typical features.2. The technique is not recommended for samples containing less than 5 mg of sulfate.3. Morphologies of particles reacted for longer times (24 h) in carbonate solution are presented in Fig. Miner. which corresponds to a pyrite conversion of 10%. DTGS detector.g. The method was modified to include the oxidation of all soluble sulfur species to sulfate with bromine water or hydrogen peroxide. in the spectral range of 600– 4000 cmÀ 1. A gap between the external oxide layer and the internal pyrite phase may have been formed during drying . The product layer grows with time. The insoluble.

Rela- . Scanning electron microscope micrographs of reacted pyrite at 80 jC in 0. The nature of the contact between the unreacted core and the product layer is highlighted in Fig. Caldeira et al.4 mmol/l NaOH (right). Compared to the carbonate system (Fig.4.376 C. 1a (right) one can observe that with longer treatment time. and metallization required for SEM sample preparation.1 mol/l Na2CO3 and NaHCO3 (left) and in 0. Conditions: (a) pH 10 and t = 60 min. 1b (right) shows a particle with a partially detached product layer.L. like an extension of the internal phase. the product layer becomes highly fragmented. Fig. 1b (right). t = 24 h. the product layer appears denser. 1. J. Morphologies of pyrite particles obtained after 24 h of oxidation in NaOH solution are presented in Fig. left). S and Si have been indicated in the oxide layer by semi-quantitative microprobe analysis. Miner. / Int. Comparing this latter result with Fig. Process. (b) and (c) pH 11. 72 (2003) 373–386 Fig. 1. 1c (right).

Process. / Int. 2a also indicates that at pH < 4 and mild oxidizing conditions (Eh f 0. The above results illustrate the distinct morphology of the oxide coatings formed during pyrite oxidation in NaOH and Na2CO3 solutions. Fig. 1999). experimental conditions maintained in the present investigation. 2a.b. e. Thermodynamic analysis The thermodynamics of the Fe – S – CO3 – H2O system was studied with the help of Eh – pH diagrams. J. [CO3] = 0. Eq. 2b indicates that. 72 (2003) 373–386 377 tively high iron (low sulfur) content in the apparently unreacted internal core compared to concentrations typical of the original pyrite sample. Under an oxygen partial pressure of 1 atm and at pH 10– 11. This compound would be subsequently transformed to the more stable ferric hydroxide in contact with fresh oxygen and . Fig. ferrous carbonate. it can be argued that oxidation of pyrite consumes oxygen and produces acid: FeS2ðSÞ þ 15 7 O2ðgÞ þ H2 O Z FeðOHÞ3 þ 2H2 SO4ðaqÞ : 4 2 ð1Þ Fe(OH)3 represents generic Fe3 + precipitates.b.1.2.. 2. 2a). The standard free energies of formation for both 25 and 100 jC are presented in Table 1.e. According to Fig. 2b). Two possible reasons for the differences caused by the addition of carbonate ions will be considered: (a) alteration of the chemical nature of the product layer through precipitation of iron carbonate and (b) modification of the oxide precipitation conditions through the formation of soluble iron carbonate complexes and increase of ionic strength..5. 3. [Fe] = 0. 1995a.5% Fe and 53. and soluble ferrous sulfate are reduced with respect to the hematite stability field.017 M. 46. Fig. Caldeira et al. siderite (FeCO3). Nevertheless. 2a. the areas occupied by pyrite.C. (1974) and the HSC database (Roine. according to Fig. pyrite would decompose to soluble ferrous or ferrous sulfate ions.g. oxidizing conditions and pH = 10 – 12). under the same pH. Eh – pH diagram for the Fe – S – CO3 – H2O system at (a) 25 jC and (b) 100 jC. a high-temperature Eh – pH diagram has been developed (Fig. and temperature conditions.033 M. should favor the formation of FeCO3.5% S. as temperature increases to 100 jC. To be consistent with the temperature (50 –95 jC) maintained in the oxidation experiments (Ciminelli and Osseo-Asare. The dissolved ferric iron region also disappears. is formed around neutral pH and relatively lower Eh. Iron carbonate. has been detected through microprobe analyses. This may indicate the presence of a thin oxide layer covering the sulfide grain. hematite (Fig. (1) implies a lower oxygen concentration and a lower pH at the reaction front compared to the conditions prevailing in the bulk. iron carbonate is unstable under the experimental conditions prevailing in this study (i. the main product of pyrite decomposition is a-Fe2O3.2. The thermodynamic data were mostly based on the compilation of Naumov et al. [S] = 0. as observed at the beginning of reaction. Stronger oxidation conditions (higher Eh) would lead to ferric ion (pH < 1) or hematite formation.4 M.L.b). Miner.5 V). pO2. and this. Nature of the solid products 3.

887 À 128. b Taken from Naumov et al.658 À 62.510 À 157.948 À 140.000 0. 3b) that could be associated with the presence of y-FeOOH (feroxyhite.467 a Data from HSC Chemistry software database. the authors only reported the formation of Fe(II) – CO3 complexes and carboxylic groups on the surface of pyrite samples exposed to atmospheric oxidation (Evangelou and Huang.405 À 122.488 À 158.000 À 116.611 20.288 À 177. however.401 24.087 À 184.259 À 197.688 À 106.000 À 126.081 4.830 À 536. Evangelou et al. sulfur.174 À 133.516 2.547 19. 3).104 À 180. The identification of the solid products was complemented by infrared spectroscopy and the results will be described below.600 À 58. indicating that oxidation was incomplete.791 À 192.845 À 111.830 À 65.173 À 4. Ciminelli (1987).487 À 126.000 À 162.697 À 57. the products of pyrite oxidation consisted of a series of iron oxide hydroxide phases. Carbonate compounds such as ferrous hydroxy carbonate (Fe2(OH)2CO3) and siderite (FeCO3) may also be present. using diffuse reflectance spectroscopy.383 À 252.645 À 116.403 À 37. but none was able to identify the characteristic bands of carbonate species.897 À 521. kcal/mola 25 jC C Fe FeCO3b FeO Fe2O3 Fe3O4 Fe(OH)2 Fe(OH)3 FeO*OH FeS FeS2 FeSO4 Fe2(SO4)3 H2SO4 S À CO2 3 (aq) Fe3 +(aq) Fe2 +(aq) FeO(aq) FeO+(aq) FeOH2 +(aq) FeOH+(aq) + Fe2(OH)4 2 (aq) FeSO4(aq)b Fe2(SO4)3(aq) FeSO+ 4(aq) H2CO3(aq) HCOÀ 3 (aq) H2S(aq) HSÀ(aq) H2SO3(aq) H2SO4(aq) H2S2O3(aq) H2S2O4(aq) H2S2O8(aq) HSOÀ 3 (aq) HSOÀ 4 (aq) S2 À(aq) À S2 2 (aq) À SO2 3 (aq) À SO2 4 (aq) 2À S2O3 (aq) 0.378 C.615 À 167. Process.464 À 116.416 À 144.715 À 53.875 À 50. . and Ciminelli et al. Caldeira et al.550 À 190. 72 (2003) 373–386 Table 1 Selected standard free energies of formation (DGjf) for iron.264 À 6. Miner.053 À 116. The oxidation products exhibit peaks with relatively lower intensities.863 À 124..107 À 21.806 À 103. In previous transmission infrared spectroscopy studies. The formation of FeCO3 is demonstrated by the results shown in the following section.260 À 119.137 À 500.269 À 115. synthetic).8 and 35.614 À 2. J.657 À 148.947 À 128.080 À 167.350 À 140. The diffractograms for oxidized pyrite in carbonate and hydroxide media show that the most intense and well-defined peaks are attributable to pyrite.489 0. A comparison between the XRD patterns obtained in different alkaline media clearly shows distinguishable oxidation products (Fig.844 À 112. hydroxide ions that become available at the product/ solution interface.839 À 6. 1999).484 À 24. 1994.730 À 177.743 À 202.000 0. Hood (1991). A direct experimental evidence for the proposed role of carbonate in pyrite oxidation is not yet available. / Int.0 (Roine.451 À 175.050 À 21. 3.215 22.008 À 147.885 0. (1994) attempted to identify iron carbonate complexes in the products of pyrite aqueous oxidation.970 À 172.2. our pyrite samples were subjected to both DRIFT and FTTIR analyses.9j2h (Fig.811 À 164. In an attempt to understand and explain these results. 1998). (1998) have also investigated the aqueous oxidation of pyrite in bicarbonate media. In sodium carbonate/bicarbonate solution.962 100 jC 0. Only the hematite phase was identified as an oxidation product in sodium hydroxide solution.243 À 24.093 À 57. However. and carbonate species Species Standard free energy (DGjf).908 À 123.370 À 38. Evangelou et al. (1974).2.L. Products analyses by X-ray diffraction and infrared spectroscopy X-ray diffraction (XRD) patterns of unreacted pyrite and oxidized pyrite in alkaline media are displayed in Fig. although there is an inversion of the peak intensities at 53.575 À 50. The broad background at 35j is characteristic of amorphous hydrated iron oxide phases.387 À 266. The identified ferrihydrite (Fe5HO8Á4H2O) peaks indicate this phase as the main constituent.494 À 111.711 À 54.455 À 172. 3.553 À 177. it is not evident when oxidation is carried out in the absence of carbonate.413 À 242.000 À 157.390 À 166.784 À 47.514 À 236. no carbonate phase matches the peaks completely.154 À 540. version 4.

Diffuse reflectance (DRIFT) and transmittance (FTTIR) spectra of unreacted and oxidized pyrite in carbonate and hydroxide media are shown in Fig. and 1070 cmÀ 1 would correspond to the splitting of the asymmetric triply degenerate S – O stretching. S—Siderite (ICDD 29-0696). of the sulfate species. The splitting of degenerate m3 vibration and the formerly forbidden m1 band indicates that the sulfate symmetry is lowered by coordination with .1 mM NaOH. Process. y-FeOOH (ICDD 13-0087). P—Pyrite (ICDD 06-0710). 72 (2003) 373–386 379 Fig.L. XRD patterns for (a) unreacted pyrite. 4. characteristic bands of the sulfide. Miner. Caldeira et al.C. sulfate compounds. For unreacted pyrite. / Int. C—iron carbonate hydroxide (ICDD 33-0650). 1976). 1130.1 M (Na2CO3 + NaHCO3). (b) pyrite oxidized in 0. H—Hematite (ICDD 33-0664). Fx—Feroxyhite. A strong infrared absorption band at around 420 cmÀ 1 is assigned to the disulfide (S– S) group in pyrite lattice (van der Marel and Beutelspacher. The multiple absorption bands observed in the DRIFT and FTTIR spectra at 1230. m3 vibration. and absorbed water can be identified in both the DRIFT and FTTIR spectra. Fh—Ferrihydrite (ICDD 29-0712). 3. and (c) pyrite oxidized in 0. J.

1 mol/l (Na2CO3 + NaHCO3). J. pH = 10.380 C. cations (Nakamoto.L. 72 (2003) 373–386 Fig. Pyrite samples oxidized for 60 min.1 mmol/l NaOH. Hug. The broad . Infrared spectra obtained by diffuse reflectance (a) and transmittance (b).. Caldeira et al. Miner. Concentrations: 0. 1997). 1978. T = 80 jC. 1999). / Int. 0. Peak et al. The number of splits suggests that sulfate is mainly bidentate in its coordination with Fe(III) (Hug. 1997. 4. In addition to the m3 vibration of sulfate. Process. the transmission spectra exhibit bands that can be attributed to sulfate bending mode (m2) at 610 cmÀ 1 and the band characteristic of symmetric S –O stretching vibration (m1 sulfate mode) at 1000 cmÀ 1.

. 1996). The amplitude of this splitting characterizes a carboxylate bidentate complex on pyrite surface (Nakamoto. which can be assigned to iron oxyhydroxides. In carbonate medium. respectively. 1978).. iron (III) hydroxycarbonates (Markov et al. Thus. these bands have higher intensities than in hydroxide medium. the regions below 1000 cmÀ 1 show well-defined bands (FTTIR spectra. Legrand et al. 4) is due to the OH stretching vibration mode of iron oxyhydroxides. thus showing up much more prominently in the transmission than in the DRIFT technique. It is important to point out that typical carbonate vibrational modes did not appear in the FTTIR spectra. 4b). could carbonate species be identified on pyrite surface... 1992. while higher frequencies arise from Si – O – Si bonds (Parfitt et al. 1995. In both alkaline media. by infrared techniques. the band at 3420 cmÀ 1 (Fig. and ferrous – ferric . 4b). This may explain why carbonate species were not reported in previous works (Ciminelli.. The well-defined peaks at 1615 and 1640 cmÀ 1 are attributed to water bending mode and Fe –OH bending mode. the band at 3630 cmÀ 1 (DRIFT spectrum) can be attributed to the hydroxyl stretching vibration of iron oxyhydroxide. these being more intense in carbonate medium. in hydroxide medium. J. Natural and synthetic ferrihydrite samples containing traces of Si show a broad. Cornell and Schwertmann. Miner. and 917 cmÀ 1 that can be assigned to ferrihydrite. These bands. the peaks are less intense and are ill defined (Fig. 4a) show two well-defined peaks near 1430 and 1530 cmÀ 1. the FTTIR spectra retain the peaks at 1615 and 1640 cmÀ 1 even after pyrite oxidation. 1978). Fig. Blengino et al. while the peak at 1640 cmÀ 1 (OH bending) almost completely disappears after oxidation. 72 (2003) 373–386 381 band centered about 3420 cmÀ 1 and the band at 1630 cmÀ 1 are assigned to O – H stretching and bending modes of water. In addition to these. Cornell and Schwertmann. such as ferrihydrite (Cornell and Schwertmann. as a product of pyrite oxidation in aqueous solutions. lower frequencies correspond to silicate forming Fe– O – Si bonds.. the transmission spectra exhibit well-defined bands at 917 cmÀ 1. 1987. intense band around 940 cmÀ 1. assigned to ‘‘C – O’’ symmetric and ‘‘C – O’’ asymmetric stretching vibrational modes. Baes and Bloom (1989) and Evangelou and Wang (1993) have shown that DRIFT spectroscopy is one of the most sensitive infrared techniques for surface analyses. produced by CO2 reacting with pyrite surface. A comparison of the DRIFT and FTTIR spectra of oxidized pyrite samples in both carbonate and hydroxide media indicates two main differences: the DRIFT spectra (Fig. The 1430 and 1530 cmÀ 1 bands (DRIFT) can be attributed to the presence carbonate on the oxidized pyrite surface (Fig. In both alkaline media. its intensity being higher in carbonate than in hydroxide medium. Caldeira et al. only with the use of a surface sensitive technique. 1996). the results reported here represent the first time that carbonate species have been identified. but different from a typical free carbonate molecule with a single band at 1430 cmÀ 1. The water bands in the FTTIR spectra may be explained by the residual water present inside the particles. mainly in carbonate media. The band at 480 cmÀ 1 was assigned to the Fe –O stretching mode in the Fe –O(OH) group. residual water is still present on the surface of the unreacted pyrite. As far as the authors are aware. Therefore. In hydroxide medium. 1990. 2À CO3 . In carbonate medium. such as DRIFT. respectively (van der Marel and Beutelspacher. Conversely. at 1430 cmÀ 1 (Nakamoto.C. though. The peak at 917 cmÀ 1 can be associated with the presence of ferrihydrite (Music et al. this peak is also seen in the DRIFT spectra. 1995. which is present in ferrihydrite. 2000). / Int. Drissi et al.L. 1990). the presence of carbonate bands may be explained by reagent or air contamination. the spectrum exhibits bands at 480. 1996). Hood. which are assigned to the splitting of the m3 vibrational mode of carbonate ion. 700. 1993. though less intense. Nakamoto. the presence of Si is attributed to the dissolution of the glass apparatus. This complex may involve carbonate coordination with iron in com(II) pounds such as siderite and green rust-1 (Fe4 (III) Fe2 (OH)12CO3Á2H2O) or carbonate adsorbed on the amorphous iron oxyhydroxides (Markov et al. 580. 4). The absence of the HOH bending vibration mode around 1600 cmÀ 1 in the DRIFT spectra indicates that water is not present on pyrite surface after oxidation.. Process. 1991). 1976. are similar to those of bicarbonate À ion. 1978). HCO3 or carboxylate ion (COOÀ). In carbonate medium. which is consistent with the results obtained by XRD. CO2 from air contamination may explain the bands at 1430 cmÀ 1. In our experiments.

3. In hydroxide medium.. 1995). goethite being the end product. thus confirming the XRD pattern shown in Fig. 3. Infrared spectra of reagent grade CaO (a). . 1996). compared to 14% in sodium carbonate solutions) and no oxides were identified as oxidation products. ferrihydrite and iron carbonate compounds were identified in sodium carbonate solutions. The solid green rusts are double-layer hydroxide salts in which positively charged octahedral Fe hydroxyl layers are 2À 2À linked by interlayer anions (ClÀ. the small bands at 550. The results obtained by XRD and infrared analysis indicate that there are significant differences in the solid products formed on oxidized pyrite surface in the different alkaline media: sodium hydroxide. In contrast. sodium carbonate. / Int. Miner. 5. Cornell and Schwertmann. and 650 cmÀ 1 are attributable to hematite (van der Marel and Beutelspacher.L. 1995. CO3 ) that are stable only at low redox potential. The precipitation of calcium carbonate and the consequent passivation of the sulfide surface may explain the low oxidation yield. 5a) used in the experiments reported here and in the solid residues of repeated tests with pyrite. 1996). 72 (2003) 373–386 hydroxide carbonate (Blengino et al.382 C. FTTIR spectra for oxidized pyrite in CaO solutions (Fig. 1978). Process. van der Marel and Beutelspacher. This indicates that the iron carbonate species acted as a precursor of ferrihydrite formation. and 1125 cmÀ 1. Caldeira et al. 700. ferrihydrite (Fe5HO8Á4H2O) was the only oxide phase identified by XRD. Nucleation and growth of hematite involve a combination of dehydration and rearrangement processes. and 1430 cmÀ 1. 3b. After oxidation. In carbonate/bicarbonate media. 1992) may also be associated with this phenomenon. Upon oxidation. J. Very low oxidation of pyrite was obtained in the presence of lime (2% conversion after 10 h. The industrial procedure of adding lime or cement to the ore pulp during pre-aeration for the combined effect of pH increase and passivation of sulfide surface (Marsden and House. Drissi et al. y-FeOOH can also be implicated due to the bands at 650. Ferrihydrite can be transformed to the more stable hematite or goethite phases (Cornell and Schwertmann. (2001) as a metastable product of the oxidation of (II) (III) the green rust-1 (GR1 – CO3) (Fe4 Fe2 (OH) 12 CO3Á2H2O). Ferrihydrite was reported by Benali et al. 5) exhibit the main absorption bands of calcium carbonate (330. pyrite sample oxidized in CaO solutions in closed (b) and open systems (c). The intensity of the main absorption band of the calcium carbonate (at 1430 cmÀ 1) was significantly increased when the reactor was opened to the atmosphere (Fig. Oxide precipitation and morphology The observed formation of different solid products is most likely the result of differences in the mechanisms of pyrite oxidation in carbonate and hydroxide solutions. leaving only a very weak peak at 1125 cmÀ 1 (coincident peak). Calcium carbonate was detected in the reagent grade CaO (Fig. 870. 935. Hematite was the main product detected in hydroxide solutions. the split bands assigned to sulfate vibrations (1000 – 1200 cmÀ 1 range) disappeared.. 5c). 1976. while calcium carbonate was the main product in the presence of lime. SO4 . and calcium hydroxide solutions. 1976). 600. the green rusts are transformed to goethite or lepidocrocite. This characteristic band can be assigned to the m3 vibrational mode of free sulfate ion (Nakamoto. which are facilitated by the Fig.

Process. and by lowering water activity. hematite and y-FeOOH (feroxyhite) were identified by XRD and IR analyses. J. the end product is hematite. 1991). In order for iron oxide to form.b) and King (1998). Whether dehydroxylation of y-FeOOH takes place in the dry state or in solution. as an end product. thereby decreasing supersaturation.1 mol/l). This phenomenon is suggested by the micrograph shown in Fig. In addition to that. The reaction of pyrite oxidation in alkaline solutions can be decomposed into a two-step process involving oxidative dissolution. which depicts an oxide coating comprising a denser outer texture in contrast to a more granular inner . Bruno and Duro.C. that is finally transformed to hematite. The presence of silica was claimed to promote the formation of ferrihydrite on the pyrite surface over the formation of other iron oxyhydroxides (Hood. This precipitate may act as a seed for further precipitation. Hematite and goethite were not identified in the bicarbonate/carbonate media. further aging and recrystallization may occur. solid green rust. Another relevant factor to be considered is the higher ionic strength of the carbonate system due to higher Na2CO3 concentration (0. silica retards the transformation of ferrihydrite to more crystalline iron oxyhydroxides by stabilizing its structure (Cornell and Schwertmann. Ferrihydrite transformation is favored by increasing pH and temperature. In hydroxide media. values for the Fe(III) carbonate complexation constants are poorly defined (Hummel. At pH 12. y-FeOOH is formed over a wide pH range if the rate of oxidation is extremely high—as a result of addition of H2O2 or exposure of Fe(OH)2 to air. compared with the hydroxide system. The integrity of the coating is maintained even at 50% conversion. as compared to NaOH concentration ( f 0. The latter is converted to the oxides either by a solid state or via a solution (reconstructive) transformation. but as pH drops. the necessary supersaturation ratio must be attained.1 – 1 mmol/l). The carbonate ion can influence the rate of oxide precipitation through its ability to form metastable complexes with ferric and ferrous ions. 72 (2003) 373–386 383 structural resemblance between ferrihydrite and hematite. While the presence of CO2/carbonate in solution favors the conversion of ferrihydrite to goethite. (1992a. It can however exist as a metastable phase for short periods of time (Cornell and Schwertmann. thus favoring the growth of the oxide layer. thereby favoring coagulation at the pyrite surface. as well as their equilibrium constants. Bruno et al. the wellcrystallized y-FeOOH is formed. Possible origins of these morphological differences include carbonate complexation and ionic strength effects. Compared to Fe(II). 1996). This may explain the fact that neither hematite nor goethite was identified by XRD and infrared analyses. As yFeOOH and hematite have a similar anionic framework (hcp). 1996). compared with the oxide formed in sodium hydroxide solution. leading to the formation of feroxyhite (y-FeOOH). In contrast to hematite. the product becomes increasingly less ordered. the conversion proceeds relatively easily. Thus. By complexing the Fe(II) and Fe(III) ions.b) found that the presence of CO2 significantly increased the solubility of ferric hydroxide. It is possible that Fe(OH)2 is formed initially. the Fe2 + released from pyrite surface during its oxidation undergoes different chemical reactions until the oxide phase arises. 1996). / Int. 2000).L. Fe(OH)2 is thermodynamically unstable with respect to magnetite and other Fe3 + compounds. the formation of goethite from ferrihydrite in both acid and alkaline media involves dissolution of ferrihydrite followed by nucleation and growth of goethite in solution. The formation of these species. It is known that the oxidation and hydrolysis of Fe2 + leads to Fe(III)-oxides either directly or via soluble green rust complexes. (1992a. It was mentioned in the previous section that the oxide formed in the carbonate system appears to be coarser grained and preferentially attached to the pyrite particles. A lower nucleation rate will result in larger particles. Thus. Poorly crystalline y-FeOOH transforms di- rectly to hematite under vacuum and in air at 150 jC (Cornell and Schwertmann. As reported by Cornell and Schwertmann (1996). Miner. The higher ionic strength of the carbonate system decreases the thickness of the electrical double layer. or Fe(OH)2. it is to be expected that the rate of oxide nucleation will be lower in the carbonate system. followed by oxidation/precipitation. 2000. pH 10 and temperatures of 80jC promote the formation of hematite. Caldeira et al. 1c (left). followed by y-FeOOH. in spite of the high stirring rates maintained during the experiments. has been reported by Bruno et al. the concentration of free iron ions is reduced. Given longer reaction times and relatively high temperatures.

it is concluded that solution composition has a significant influence on the nature of the products of pyrite oxidation in alkaline solutions.. Brown.. High-temperature potential/pH diagrams for the iron – water and iron – water – sulphur systems.L. It is suggested that the formation of a stable nucleus occurs far from the interface and does not coagulate to give larger agglomerates due to the low ionic strength of the hydroxide system.-M. finer granulation. resulting in pyrite particles uniformly covered by a thin. In Baes. i... R. O. 72 (2003) 373–386 texture. Soil Science Society of America Journal 53. .. and small amounts of feroxyhite are identified. Abdelmoula. J. V. Labbe. 1715 – 1726.. J. Biernat. suggest a precipitation mechanism different from that occurring in the carbonate system. W. Capes.S. Process. Bruno. in sodium hydroxide solutions. a discontinuous and coarse granular oxide coating initially covers the particles. 1989. L.T. Ge Effect of orthophosphate on the oxidation products of Fe(II) – Fe(III) hydroxycarbonate: the transformation of green rust to ferrihydrite... In hydroxide medium. Corrosion Science 37 (4).. Mechanism of pyrite oxidation in aqueous mixtures. the main constituent is ferrihydrite. 2001.384 C. Reply to W. The coating breaks down after some time. Jurinak. Diffuse reflectance and transmission Fourier transform infrared (DRIFT) spectroscopy of humic and fulvic acids. M. hematite is the main phase. the precipitation seems to occur mainly in the bulk solution. A further question to be addressed is the extent to which the different morphologies affect the rate of pyrite oxidation. thus increasing oxide coverage on the pyrite surface. The thermodynamics and kinetics of hematite dissolution in bicarbonate solutions at T = 25 jC’’ by J. M. A. fine texture oxide layer and a stable colloidal suspension. In contrast.P. which report to the bulk. in carbonate medium. and fragmentation after a certain period of time. Caldeira et al. R. were also in the form of relatively coarse grains (of about 1 Am) that could be easily separated by filtration.. J.R. Robbiola. Journal of Environmental Quality 18.M. / Int. smaller and more uniform thickness. The morphological differences observed in the iron oxide produced during pyrite oxidation in the carbonate and hydroxide media are related to a distinct chemical nature of the solid product and to the kinetics of iron precipitation. the infrared results indicated that calcium carbonate precipitated on the surface of the oxidized pyrite in an amount that increased when the system was opened to the atmosphere.. P. Duro... Benali. The distinctive characteristics of the oxide formed in NaOH solutions. By using the diffuse reflectance technique. The coating grows with further oxide precipitation on the existing nuclei. some iron hydroxide carbonate phase may also be present. The morphology of the solid products of pyrite oxidation was also found to be different in alkaline sodium hydroxide and sodium carbonate solutions. Roberto L. Refait.U. Bruno. 1995. 1989. Precipitation at the pyrite surface is favored by the high ionic strength of the sodium carbonate solutions.e. 695 – 700. 2000.J.G. ´ nin. and Finep/PADCT. 1 (right) shows that pyrite particles were initially fully covered by a thin oxide layer.. Acknowledgements The authors are thankful to Prof. The oxide precipitates.. Geochimica et Cosmochimica Acta 65 (11). Fig. L. Conclusions Based on the above discussion. carbonate compounds were identified for the first time among the products formed during pyrite oxidation in aqueous solutions.R. Keddam. Moreira for providing the facilities for the IR analyses. Electrochimica Acta 17. J. Iron oxides appear to precipitate (or re-precipitate) mainly in the bulk as very fine particles (below 0.. J. References 4. 545 – 550. which fragmented at longer reaction times.5 Am) that remain in suspension for several days with no significant sedimentation. Robins. 621 – 643.J. Blengino. sodium carbonate solutions. J. A. Ciminelli gratefully acknowledges the research support and sponsorship of the following Brazilian agencies: CNPq. Hummel’s comment on and correction to ‘‘On the influence of carbonate in mineral dissolution: 1. P.B. Physico-chemical characterization of corrosion layers formed on iron in a sodium carbonate – bicarbonate containing environment. In the presence of calcium ions. Miner. Bloom.. 1261 – 1283. 1972. The support of the Millennium Science Initiative: ‘‘Water—A Mineral Approach’’ is also appreciated.

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