Synthesis, characterization, and thermochemistry of K-Na-H3O jarosites

Drouet, Christophe; Navrotsky, Alexandra

doi:10.1016/s0016-7037(02)01299-1

Cited by 168 publications

(139 citation statements)

References 26 publications

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“…2a) are similar to those previously reported (Powers et al, 1975;Serna et al, 1986;Baron and Palmer, 1996;Sasaki et al, 1998;Drouet and Navrotsky, 2003). The intense absorption observed in the region 2900 to 3700 cm -1 can be attributed to O-H stretching (v OH ).…”

Section: Characterisation Of Synthetic Jarositesupporting

confidence: 89%

Dissolution of jarosite [KFe3(SO4)2(OH)6] at pH 2 and 8: Insights from batch experiments and computational modelling

Smith

Hudson‐Edwards

Dubbin

et al. 2006

Geochimica et Cosmochimica Acta

128

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Jarosite [KFe 3 (SO 4 ) 2 (OH) 6 ] is a mineral that is common in acidic, sulphate-rich environments, such as acid sulphate soils derived from pyrite-bearing sediments, weathering zones of sulphide ore deposits and acid mine or acid rock drainage (ARD/AMD) sites. The structure of jarosite is based on linear tetrahedral-octahedral-tetrahedral (T-O-T) sheets, made up from slightly distorted FeO 6 octahedra and SO 4 tetrahedra. Batch dissolution experiments carried out on synthetic jarosite at pH 2, to mimic environments affected by ARD/AMD, and at pH 8, to simulate ARD/AMD environments recently remediated with slaked lime (Ca(OH) 2 ), suggest first order dissolution kinetics. Both dissolution reactions are incongruent as revealed by non-ideal dissolution of the parent solids and, in the case of the pH 8 dissolution, because of a secondary goethite precipitate on the surface of the dissolving jarosite grains. The pH 2 dissolution yields only aqueous K, Fe and SO 4 . Aqueous, residual solid and computational modelling of the jarosite structure and surfaces using the GULP and MARVIN codes, respectively, show for the first time that there is selective dissolution of the A-and T-sites, which contain K and SO 4 , respectively, relative to Fe, which is located deep within the T-O-T jarosite structure. These results have implications for the chemistry of ARD/AMD waters, and for understanding reaction pathways of ARD/AMD mineral dissolution.

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Section: Characterisation Of Synthetic Jarositesupporting

confidence: 89%

Dissolution of jarosite [KFe3(SO4)2(OH)6] at pH 2 and 8: Insights from batch experiments and computational modelling

Smith

Hudson‐Edwards

Dubbin

et al. 2006

Geochimica et Cosmochimica Acta

128

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show abstract

“…2a-c) with those previously reported confirm that the phases synthesised are jarosite analogues and that no other phases have been detected (Baron and Palmer, 1996;Drouet and Navrotsky, 2003;Powers et al, 1975;Serna et al, 1986). The O-H stretching (v OH ) band in the region 2900 to 3700 cm -1 shifts toward lower frequencies for the synthetic Pb-As (3343 cm -1 ), Pb-Cu (3362 cm -1 ) and Pb-Zn jarosites (3357 cm -1 ), compared with end-member synthetic K-jarosite (3385 cm -1 ) (Smith et al, 2006).…”

Section: Fourier Transform Infrared Spectroscopy (Ftir)supporting

confidence: 85%

“…c !H ds (SO 3(g) ) as determined by Majzlan et al (2002). Forray et al (2010)., b Drouet and Navrotsky (2003)., c Robie and Hemingway (1995). d Majzlan et al (2002), e SGTE (1999), f Nordstrom and Archer (2003).…”

Section: Discussionmentioning

confidence: 99%

“…4MoO 3 of the SO 3 , dissolved Pb 2+ , Zn 2+ , As 5+ and Fe 3+ oxides and gaseous H 2 O, all at 700°C. Previous studies on simple sulphates and jarosite phases (Majzlan et al, 2002;Drouet and Navrotsky, 2003;Forray et al, 2005) have shown that all the sulphur is retained in the melt as SO 4 2-, rather than emitted in the gas phase.…”

Section: Calorimetrymentioning

confidence: 97%

“…These cycles involves the enthalpy of drop solution of lead carbonate PbCO 3 (Forray et al, 2010), ZnO, and CuO as well as other thermodynamic data taken from the literature (Robie and Hemingway, 1995;SGTE, 1999;Majzlan et al, 2002;Drouet and Navrotsky, 2003;Nordstrom and Archer, 2003) and listed in Table 5. Application of these thermodynamic cycles leads to the heat of formation, from the elements (!Hº f ) -3691.2 ± 8.6 kJ/mol for the synthetic Pb-As jarosite, -3653.6 ± 8.2 kJ/mol for the synthetic Pb-Cu jarosite and -3669.4 ± 8.4 kJ/mol for the synthetic Pb-Zn jarosite.…”

Section: Calorimetric Datamentioning

confidence: 99%

See 2 more Smart Citations

Synthesis, characterization and thermochemistry of synthetic Pb–As, Pb–Cu and Pb–Zn jarosites

Forray

Smith

Navrotsky

et al. 2014

Geochimica et Cosmochimica Acta

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The enthalpy of formation from the elements of well characterized Pb-As, Pb-Cu, measured by high temperature oxide melt solution calorimetry and gave !Hº f = -3691.2 ± 8.6 kJ/mol, !Hº f = -3653.6 ± 8.2 kJ/mol, and !Hº f = -3669.4 ± 8.4 kJ/mol, respectively. Using estimated entropies, the standard Gibbs free energy of formation from elements at 298 K !Gº f of the three compounds were calculated to be -3164.8 ± 9.1 kJ/mol, -3131.4 ± 8.7 kJ/mol, and -3153.6 ± 8.9 kJ/mol, respectively. Based on these free energies, their logK sp values are -13.94 ± 1.89, -4.38 ± 1.81 and -3.75 ± 1.80, respectively. For tis compounds, a log 10 {Pb 2+ } -pH diagram is presented. The diagram shows that the formation of Pb-As jarosite may decrease aqueous arsenic and lead concentrations to meet drinking water standards. The new thermodynamic data confirm that transformation of Pb-As jarosite to plumbojarosite is thermodynamically possible.

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Laboratory simulations of acid‐sulfate weathering under volcanic hydrothermal conditions: Implications for early Mars

Marcucci

Hynek

2014

JGR Planets

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We have completed laboratory experiments and thermochemical equilibrium models to investigate secondary mineral formation under conditions akin to volcanic, hydrothermal acid-sulfate weathering systems. Our research used the basaltic mineralogy at Cerro Negro Volcano, Nicaragua, characterized by plagioclase, pyroxene, olivine, and volcanic glass. These individual minerals and whole-rock field samples were reacted in the laboratory with 1 molal sulfuric acid at varying temperatures (65, 150, and 200°C), fluid:rock weight ratios (1:1, 4:1, and 10:1), and durations (1–60 days). Thermochemical equilibrium models were developed using Geochemist's Workbench. To understand the reaction products and fluids, we employed scanning electron microscopy/energy dispersive spectroscopy, X-ray diffraction, and inductively coupled plasma-atomic emission spectroscopy. The results of our experiments and models yielded major alteration minerals that include anhydrite, natroalunite, minor iron oxide, and amorphous Al-Si gel. We found that variations in experimental parameters did not drastically change the suite of minerals produced; instead, abundance, size, and crystallographic shape changed. Our results also suggest that it is essential to separate phases formed during experiments from those formed during fluid evaporation to fully understand the reaction processes. Our laboratory reacted and model predicted products are consistent with the mineralogy observed at places on Mars. However, our results indicate that determination of the formation conditions requires microscopic imagery and regional context, as well as a thorough understanding of contributions from both experiment precipitation and fluid evaporation minerals.

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Synthesis, characterization, and thermochemistry of K-Na-H3O jarosites

Cited by 168 publications

References 26 publications

Dissolution of jarosite [KFe3(SO4)2(OH)6] at pH 2 and 8: Insights from batch experiments and computational modelling

Dissolution of jarosite [KFe3(SO4)2(OH)6] at pH 2 and 8: Insights from batch experiments and computational modelling

Synthesis, characterization and thermochemistry of synthetic Pb–As, Pb–Cu and Pb–Zn jarosites

Laboratory simulations of acid‐sulfate weathering under volcanic hydrothermal conditions: Implications for early Mars

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