The Crystal Chemistry of Sulfate Minerals

Hawthorne, Frank C.; Krivovichev, Sergey V.; Burns, Peter C.

doi:10.2138/rmg.2000.40.1

Cited by 277 publications

(180 citation statements)

References 200 publications

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“…The clusters may polymerize in the following ways: (1) unconnected polyhedra; (2) finite clusters; (3) infinite chains; (4) infinite sheets; (5) infinite frameworks. This approach has been used extensively to develop hierarchical classifications for a range of oxysalt minerals, for example, phosphates, arsenates and vanadates (Kostov and Breskovska 1989), phosphates (Huminicki and Hawthorne 2002), sulphates (Sabelli and Trosti-Ferroni 1985;Hawthorne et al 2000a), borates Hawthorne et al 1996a;Grice et al 1999). In addition, other approaches have attempted to span several traditional chemical groups of minerals (e.g., Lima-de-Faria 1978, 1994Hawthorne 1985Hawthorne , 1986Hawthorne , 1990Hawthorne , 1997aBurns 1999Burns , 2005Burns et al 1996;Filatov et al 1992;Krivovichev 2008;Krivovichev et al 1998).…”

Section: The Structure Hierarchy Hypothesismentioning

confidence: 99%

“…at the linking anion; as interstitial cations in the structure can provide additional bond-valence to the linking anions, the valence-sum rule (Brown 2002) may be satisfied, and such polymerization is common in borate minerals. Early classifications were reviewed by Christ and Clark (1977) who produced a scheme in general use for 20 years, until superseded by the scheme of Burns et al (1995), Hawthorne et al (1996a) and Grice et al (1999).…”

Section: The Structure Hierarchy Hypothesismentioning

confidence: 99%

“…15. We may use bondvalence theory to calculate the Lewis basicity of these clusters (Hawthorne et al 1996a). As is apparent in Fig.…”

Section: Physical Aspects Of the Structure Hierarchy Hypothesismentioning

confidence: 99%

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A bond-topological approach to theoretical mineralogy: crystal structure, chemical composition and chemical reactions

Hawthorne

2012

Phys Chem Minerals

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Here, I describe a theoretical approach to the structure and chemical composition of minerals based on their bond topology. This approach allows consideration of many aspects of minerals and mineral behaviour that cannot be addressed by current theoretical methods. It consists of combining the bond topology of the structure with aspects of graph theory and bond-valence theory (both long range and short range), and using the moments approach to the electronic energy density-of-states to interpret topological aspects of crystal structures. The structure hierarchy hypothesis states that higher bond-valence polyhedra polymerize to form the (usually anionic) structural unit, the excess charge of which is balanced by the interstitial complex (usually consisting of large low-valence cations and (H 2 O) groups). This hypothesis may be justified within the framework of bond topology and bond-valence theory, and may be used to hierarchically classify oxysalt minerals. It is the weak interaction between the structural unit and the interstitial complex that controls the stability of the structural arrangement. The principle of correspondence of Lewis acidity-basicity states that stable structures will form when the Lewis-acid strength of the interstitial complex closely matches the Lewis-base strength of the structural unit, and allows us to examine the factors that control the chemical composition and aspects of the structural arrangements of minerals. It also provides a connection between a structure, the speciation of its constituents in aqueous solution and its mechanism of crystallization. The moments approach to the electronic energy densityof-states provides a link between the bond topology of a structure and its thermodynamic properties, as indicated by correlations between average anion coordination number and reduced enthalpy of formation from the oxides for [6]

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Section: The Structure Hierarchy Hypothesismentioning

confidence: 99%

Section: The Structure Hierarchy Hypothesismentioning

confidence: 99%

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A bond-topological approach to theoretical mineralogy: crystal structure, chemical composition and chemical reactions

Hawthorne

2012

Phys Chem Minerals

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“…Jarosite is a member of the isostructural jarosite -alunite group of minerals that has a general formula AB 3 (TO 4 ) 2 (OH) 6 , where A represents cations with a coordination number # 9, and B and T represent cations with octahedral (O) and tetrahedral (T) coordination, respectively (Jambor, 1999;Hawthorne et al, 2000). In an ideal jarosite [KFe 3 (SO 4 ) 2 (OH) 6 ], the B site cation is Fe(III), the A site is occupied by a cation (mainly K + , but also H 3 O + , hydronium; Brophy and Sheridan, 1965;Kubisz, 1970;Dutrizac and Kaiman, 1976;Ripmeester et al, 1986) in 12-fold coordination, and the T site is filled by sulphate (SO 4 2-) (Brophy and Sheridan, 1965;Kubisz, 1964).…”

Section: Introductionmentioning

confidence: 99%

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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“…Jarosite is a member of the isostructural jarosite-alunite group of minerals that has a general formula of AB 3 (TO 4 ) 2 (OH) 6 , where A represents cations with a coordination number ≥ 9, and B and T represent cation sites with octahedral (O) and tetrahedral (T) coordination, respectively (Jambor, 1999;Hawthorne et al, 2000). In ideal jarosite [KFe 3 (SO 4 ) 2 (OH) 6 ], the B site cation is Fe(III), the A site is occupied by a cation (mainly K + , but also H 3 O + , hydronium; Brophy and Sheridan, 1965;Kubisz, 1970;Dutrizac and Kaiman, 1976;Ripmeester et al, 1986) in 12-fold coordination, and the T site is filled by sulphate (SO 4 2-) (Kubisz, 1964;Brophy and Sheridan, 1965).…”

Section: Introductionmentioning

confidence: 99%

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

129

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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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The Crystal Chemistry of Sulfate Minerals

Cited by 277 publications

References 200 publications

A bond-topological approach to theoretical mineralogy: crystal structure, chemical composition and chemical reactions

A bond-topological approach to theoretical mineralogy: crystal structure, chemical composition and chemical reactions

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

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

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