Vanadium(V) adsorption onto goethite (α-FeOOH) at pH 1.5 to 12: a surface complexation model based on ab initio molecular geometries and EXAFS spectroscopy

We measured the adsorption of V(V) onto goethite (α-FeOOH) under oxic (P_O2 = 0.2 bar) atmospheric conditions. EXAFS spectra show that V(V) adsorbs by forming inner-sphere complexes as VO₂(OH)₂ and VO₃(OH). We predicted the relative energies and geometries of VO₂(O, OH)₂-FeOOH surface complexes using ab initio calculations of the geometries and energetics of analogue Fe₂(OH)₂(H₂O)₆O₂VO₂(O, OH)₂ clusters. The bidentate corner-sharing complex is predicted to be substantially (57 kJ/mol) favoured energetically over the hypothetical edge-sharing bidentate complex. Fitting the EXAFS spectra using multiple scattering shows that only the bidentate corner-sharing complex is present with Fe-V and V-O distances in good agreement with those predicted. We find it important to include multiple scattering in the fits of our EXAFS data otherwise spurious V-Fe distances near 2.8 Å result which may be incorrectly attributed to edge-sharing complexes. We find no evidence for monodentate complexes; this agrees with predicted high energies of such complexes. Having identified the Fe₂O₂V(OH)₂⁺ and Fe₂O₂VO(OH)⁰ surface complexes, we are able to fit the experimental vanadium(V) adsorption data to the reactions

     

Surface complexation model for multisite adsorption of copper(II) onto kaolinite

We measured the adsorption of Cu(II) onto kaolinite from pH 3-7 at constant ionic strength. EXAFS spectra show that Cu(II) adsorbs as (CuO₄H_n)ⁿ⁻⁶ and binuclear (Cu₂O₆H_n)ⁿ⁻⁸ inner-sphere complexes on variable-charge ≡AlOH sites and as Cu²⁺ on ion exchangeable ≡X--H⁺ sites. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed at least up to pH 6.5. Inner-sphere complexes are bound to the kaolinite surface by corner-sharing with two or three edge-sharing Al(O,OH)₆ polyhedra. Our interpretation of the EXAFS data are supported by ab initio (density functional theory) geometries of analog clusters simulating Cu complexes on the {110} and {010} crystal edges and at the ditrigonal cavity sites on the {001}. Having identified the bidentate (≡AlOH)₂Cu(OH)₂⁰, tridentate (≡Al₃O(OH)₂)Cu₂(OH)₃⁰ and ≡X--Cu²⁺ surface complexes, the experimental copper(II) adsorption data can be fit to the reactions

     

Surface complexation of arsenic(V) to iron(III) (hydr)oxides: structural mechanism from ab initio molecular geometries and EXAFS spectroscopy

Arsenic(V), as the arsenate (AsO₄)³⁻ ion and its conjugate acids, is strongly sorbed to iron(III) oxides (α-Fe₂O₃), oxide hydroxides (α-,γ-FeOOH) and poorly crystalline ferrihydrite (hydrous ferric oxide). The mechanism by which arsenate complexes with iron oxide hydroxide surfaces is not fully understood. There is clear evidence for inner sphere complexation but the nature of the surface complexes is controversial. Possible surface complexes between AsO₄ tetrahedra and surface FeO₆ polyhedra include bidentate corner-sharing (²C), bidentate edge-sharing (²E) and monodentate corner-sharing (¹V). We predicted the relative energies and geometries of AsO₄-FeOOH surface complexes using density functional theory calculations on analogue Fe₂(OH)₂(H₂O)_nAsO₂(OH)₂³⁺ and Fe₂(OH)₂(H₂O)_nAsO₄⁺ clusters. The bidentate corner-sharing complex is predicted to be substantially (55 kJ/mole) more favored energetically over the hypothetical edge-sharing bidentate complex. The monodentate corner-sharing (¹V) complex is very unstable. We measured EXAFS spectra of 0.3 wt. % (AsO₄)³⁻ sorbed to hematite (α-Fe₂O₃), goethite(α-FeOOH), lepidocrocite(γ-FeOOH) and ferrihydrite and fit the EXAFS directly with multiple scattering. The phase-shift-corrected Fourier transforms of the EXAFS spectra show peaks near 2.85 and 3.26 Å that have been attributed by previous investigators to result from ²E and ²C complexes. However, we show that the peak near 2.85 Å appears to result from As-O-O-As multiple scattering and not from As-Fe backscatter. The observed 3.26 Å As-Fe distance agrees with that predicted for the bidentate corner-sharing surface (²C) complex. We find no evidence for monodentate (¹V) complexes; this agrees with the predicted high energies of such complexes.     

Sigioite : The oxidation mechanism in [M 2 3 + (PO4)2(OH)2(H2O)2]2 - structures

Summary The crystal structure of sigloite, Fe³ [(H₂O)₃OH] [Al₂(PO₄)₂(OH)₂(H₂O)₂]- 2 H₂O, triclinic, a 5.190 (2), b 10.419 (4), c 7.033 (3) Å, 105.00 (3), 111.31(3), 70.87 (3)°, V 330.5 (2) Å3, Z = 1, space group P , has been refined to anR index of 5.3% using 1713 observed (I > 2.5 1) reflections collected with graphite-monochromated MoK X-rays. Sigloite is isostructural with the laueite-group minerals. Corner-linked [A1₅] chains (: unspecified ligand) are cross-linked by (PO₄) tetrahedra to form a mixed corner-linked tetrahedral-octahedral sheet of composition [A1₂(PO₄)₂(OH)₂(H₂O)₂]²-. These sheets are linked by (Fe³⁺O₂(OH, H₂O)₄) octahedra and two (H₂O) groups that participate in a hydrogen-bonding network. Sigloite is the oxidized equivalent of paravauxite, Fe²⁺(H₂O)4[Al₂(PO₄)₂(OH)₂(H₂O)₂]-² H₂O, and detailed comparison of the two structures shows that the oxidation mechanism involves loss of hydrogen from one of the (H₂O) groups coordinating the Fe³⁺, and positional disorder of both the Fe³⁺ and (OH) and (H₂O) ligands.

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Siggloit: Der Oxidationsmechanismus in (M ₂ ³ ₊ (PO₄)₂(OH)₂(H2O)₂]²- Strukturen

Zusammenfassung Die Kristallstruktur von Sigloit, Fe³⁺ [(H₂O)₃OH] [Al₂(PO₄)₂(OH)₂(H₂O)₂].2 H₂O, triklin, a 5,190 (2), b 10,419 (4), c 7,033 (3) Å, 105,00 (3), 111,31 (3), 70,87 (3)°, V 330,5 (2) ų,Z = 1, Raumgruppe P , wurdefür 1713 beobachtete Reflexe (I > 2,5 I), die mit MoKa-Röntgenstrahlung (Graphit-Monochromator) gesammelt wurden, auf einen R-Wert von 5,3% verfeinert. Sigloit ist isotyp mit den Mineralen deer Laueit-Gruppe. Über Ecken verknüpfte [A1₅]-Ketten (: nicht spezifizierter Ligand) werden über (P0₄)-Tetraeder zu ebenfalls über Ecken verknüpfte Tetraeder-OktaederSchichten der Zusammensetzung [A1₂(PO₄)₂(OH)₂(H₂O)₂]²- verbunden. Diese Schichten werden über (Fe³⁺O₂(OH, H2O)₄)-Oktaeder und zwei (H₂O)-Gruppen, die amWasserstoffbrücken-Netzwerk beteiligt sind, verbunden. Sigloit ist das oxidierte Analogon zu Paravauxit, Fe²⁺(H₂O)₄[A1₂(PO₄)₂(OH)₂(H₂O)₂] - 2 H₂O; ein detaillierter Vergleich dieser beiden Strukturen zeigt, daß der Oxidationsmechanismus sowohl den Verlust eines Wasserstoffatoms (H₂O)-Gruppe, welche ein Fe³⁺-Atom koordiniert, als auch eine Fehlordnung der Punktlagen von Fe³⁺ und von den (OH) und (H₂O) Liganden bedingt.

     

Sideronatrite: A mineral with a {Fe2(SO4)4(OH)2} guildite type chain?

Summary Recently several natural and artificial ferric iron sulphate crystal structures have been solved. Sideronatrite, Na₂Fe³⁺(SO₄)₂(OH)·3H₂O, does not provide good crystals for structural purposes. However if we examine crystallographic, chemical and physical data some useful information about the ...Fe–O–S... structural topology can be inferred. In fact this analysis strengthens the hypothesis that there is a {Fe ₂ ³⁺ (SO₄)₄(OH)₂} chain in sideronatrite like that found in guildite, Cu²⁺Fe³⁺(SO₄)₂(OH)·4H₂O.

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Sideronatrit: Ein Mineral mit einer {Fe₂(SO₄)₄(OH)₂}-Kette vom Typ Guildit?

Zusammenfassung Kürzlich wurden die Kristallstrukturen mehrerer natürlicher und künstlicher Ferrisulfate gelöst. Sideronatrit, Na₂Fe³⁺(SO₄)₂(OH)·3H₂O, liefert keine für die Strukturuntersuchung gut geeigneten Kristalle. Dennoch erhält man aus der Untersuchung der kristallographischen, chemischen und physikalischen Daten nützliche Information über die ...Fe–O–S...-Topologie der Struktur. Eine solche Analyse spricht für die Hypothese, daß der Sideronatrit eine {Fe ₂ ³⁺ (SO₄)₄(OH₂)}-Kette enthält, wie sie im Guildit, Cu²⁺Fe³⁺(SO₄)₂(OH)·4H₂O, gefunden wurde.

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With 1 Figure

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Paper presented at the Sixth European Crystallographic Meeting. Barcelona, Spain 1980.     

Surface complexation of U(VI) on goethite (α-FeOOH)

Sorption of U(VI) to goethite is a fundamental control on the mobility of uranium in soil and groundwater. Here, we investigated the sorption of U on goethite using EXAFS spectroscopy, batch sorption experiments and DFT calculations of the energetics and structures of possible surface complexes. Based on EXAFS spectra, it has previously been proposed that U(VI), as the uranyl cation , sorbs to Fe oxide hydroxide phases by forming a bidentate edge-sharing (E2) surface complex, >Fe(OH)₂UO₂(H₂O)_n. Here, we argue that this complex alone cannot account for the sorption capacity of goethite (α-FeOOH). Moreover, we show that all of the EXAFS signal attributed to the E2 complex can be accounted for by multiple scattering. We propose that the dominant surface complex in CO₂-free systems is a bidentate corner-sharing (C2) complex, (>FeOH)₂UO₂(H₂O)₃ which can form on the dominant {101} surface. However, in the presence of CO₂, we find an enhancement of UO₂ sorption at low pH and attribute this to a (>FeO)CO₂UO₂ ternary complex. With increasing pH, U(VI) desorbs by the formation of aqueous carbonate and hydroxyl complexes. However, this desorption is preceded by the formation of a second ternary surface complex (>FeOH)₂UO₂CO₃. The three proposed surface complexes, (>FeOH)₂UO₂(H₂O)₃, >FeOCO₂UO₂, and (>FeOH)₂UO₂CO₃ are consistent with EXAFS spectra. Using these complexes, we developed a surface complexation model for U on goethite with a 1-pK model for surface protonation, an extended Stern model for surface electrostatics and inclusion of all known UO₂-OH-CO₃ aqueous complexes in the current thermodynamic database. The model gives an excellent fit to our sorption experiments done in both ambient and reduced CO₂ environments at surface loadings of 0.02-2.0 wt% U.     

Corrosion of brass in a marine environment: mineral products and their relationship to variable oxidation and reduction conditions

Minerals coating brass ammunition shells that rested at the bottom of Halifax Harbour, Nova Scotia, for 52 a have been identified by X-ray diffraction and analytical scanning electron microscopy. The admiralty brass shells, partially buried in anoxic muds, straddle a strong Eh gradient ranging from 0 mV to values characteristic of oxygenated seawater. Whereas the brass surface in contact with the sediment has been preserved, parts of the shells exposed to seawater have corroded throughout their thickness. The corrosion products identified include metallic Cu, djurleite (Cu_1.96S), cuprite (Cu₂O), atacamite (Cu₂Cl(OH)₃), spertiniite (Cu(OH)₂) and hydrozincite (Zn₅(CO₃)₂(OH)₆). These products are those predicted thermodynamically on the basis of ambient Eh and pH. However, this study also revealed the presence of a mineral not previously known to exist and tentatively identified as Cu₁₄Zn₁₄Cl₅(SO₄)₅(OH)₄₁.H₂O. This “new” mineral seems to have a stability field in Eh–pH diagrams similar to that of connellite (Cu₁₉Cl₄SO₄(OH)₃₂.2H₂O).     

The crystal structure of arsentsumebite, Pb2Cu[(As, S)O4]2(OH)

Summary The crystal structure of arsentsumebite, ideally, Pb₂Cu[(As, S)O₄]₂(OH), monoclinic, space group P2₁/m, a = 7.804(8), b = 5.890(6), c = 8.964(8) ?, β = 112.29(6)°, V = 381.2 ?³, Z = 2, d_calc. = 6.481 has been refined to R = 0.053 for 898 unique reflections with I> 2σ(I). Arsentsumebite belongs to the brackebuschite group of lead minerals with the general formula Pb₂ Me(XO₄)₂(Z) where Me = Cu²⁺, Mn²⁺, Zn²⁺, Fe²⁺, Fe³⁺; X = S, Cr, V, As, P; Z = OH, H₂O. Members of this group include tsumebite, Pb₂Cu(SO₄)(PO₄)(OH), vauquelinite, Pb₂Cu(CrO₄)(PO₄)(OH), brackebuschite, Pb₂ (Mn, Fe)(VO₄)₂(OH), arsenbracke buschite, Pb₂(Fe, Zn)(AsO₄)₂(OH, H₂O), fornacite, Pb₂Cu(AsO₄)(CrO₄)(OH), and feinglosite, Pb₂(Zn, Fe)[(As, S)O₄]₂(H₂O). Arsentsumebite and all other group members contain M = M–T chains where M = M means edge-sharing between MO₆ octahedra and M–T represents corner sharing between octahedra and XO₄ tetrahedra. A structural relationship exists to tsumcorite, Pb(Zn, Fe)₂(AsO₄)₂ (OH, H₂O)₂ and tsumcorite-group minerals Me(1)Me(2)₂(XO₄)₂(OH, H₂O)₂. Received June 24, 2000; revised version accepted February 8, 2001     

Minerals with Brackebuschite-Like Structures: A Novel Solid Solution System Involving Cr<Superscript>6+</Superscript> and V<Superscript>5+</Superscript>

A novel complex continuous system of solid solutions involving vauquelinite Pb₂Cu(CrO₄)(PO₄)(OH), bushmakinite Pb₂Al(VO₄)(PO₄)(OH), ferribushmakinite Pb2Fe³⁺(VO₄)(PO₄)(OH), and a phase with the endmember formula Pb₂Cu(VO₄)(PO₄)(H₂O) or Pb₂Cu(VO₄)(РО₃ОН)(ОН) is studied based on samples from the oxidation zone of the Berezovskoe, Trebiat, and Pervomaisko-Zverevsky deposits in the Urals, Russia. This is the first natural system in which chromate and vanadate anions show a wide range of substitutions and the most extensive solid solution system involving (CrO₄)^2– found in nature. The major couple substitution is Cr⁶⁺ + Cu²⁺ ? V⁵⁺ + M³⁺, where M = Fe, Al. The correlation coefficients calculated from 125 point analyses are: 0.96 between V and (Fe + Al), 0.96 between Cr and (Cu + Zn),–0.96 between V and (Cu + Zn),–0.97 between Cr and (Fe + Al), and–0.97 between (Fe + Al) and (Cu + Zn). The substitutions V⁵⁺ ? Cr⁶⁺ (correlation coefficient–0.98) and to a lesser extent P⁵⁺ ? As⁵⁺ (correlation coefficient–0.86) occur at two types of tetrahedral sites, whereas the metal–nonmetal/metalloid substitutions, i.e., V or Cr for P or As, are minor. The substitution Fe³⁺ ? Al³⁺ is also negligible in this solid solution system.     

Ferrotochilinite, 6FeS · 5Fe(OH)2, a new mineral from the Oktyabr’sky deposit, Noril’sk district, Siberia, Russia

A new mineral, ferrotochilinite, ideally 6FeS · 5Fe(OH)₂, was found at the Oktyabr’sky Mine, Oktyabr’skoe Cu-Ni deposit, Noril’sk, Krasnoyarsk krai, Siberia, Russia. It is associated with ferrovalleriite, magnetite and Fe-rich, chlorite-like phyllosilicate in the cavities of pentlandite-mooihoekite-cubanite ore with subordinate magnetite and chalcopyrite. Ferrotochilinite occurs as flattened on [001], prismatic to elongated lamellar crystals up to 0.1 × 0.5 × 3.2 mm, typically split and curved. Aggregates (up to 6.5 mm in size) are fanlike, rosette-like, or chaotic. Ferrotochilinite is dark bronze. The streak is black. The luster is moderately metallic. The Mohs’ hardness is ca. 1; VHN is 13 kg/mm². Cleavage is {001} perfect, micalike. Individuals are flexible, inelastic. D(calc) = 3.467 g/cm³. In reflected light, ferrotochilinite is gray, with the hue changing from pale beige to bluish; bireflectance is distinct. Anisotropy is distinct, with gray bluish to yellowish beige rotation colors. No internal reflections. Reflectance values [R _min-R _max, % (λ, nm)] are: 11.6–11.4 (470), 11.2–12.4 (546), 11.1–13.6 (589), 11.0–15.5 (650). The IR spectrum shows the presence of (OH) groups bonded with Fe cations and the absence of H₂O molecules. Chemical composition (wt %; electron probe; H content is calculated) is as follows: 0.02 Mg, 61.92 Fe, 0.03 Ni, 0.09 Cu, 19.45 S, 16.3 O, 1.03 H _calc; the total is 98.84. The empirical formula calculated on the basis of 6 S atoms is: Mg_0.01Fe_10.96Ni_0.005Cu_0.015S₆(OH)_10.07 = (Fe_5.98Cu_0.0015Ni_0.005)_Σ6S₆(OH)_9.80(Fe _4.89 ²⁺ Mg_0.01)_Σ4.90(OH)_9.80Fe _0.09 ³⁺ (OH)_0.27. Ferrotochilinite is monoclinic, space group is C2/m, Cm or C2, the unit-cell dimensions are: a = 5.463(5), b = 15.865(17), c = 10.825(12) Å, β = 93.7(1)°, V = 936(3) ų, Z = 2. The strongest reflections in the X-ray powder diffraction pattern (d, Å-I[hkl]) are: 10.83-13[001], 5.392-100[002], 3.281-7[023], 2.777-7[150], 2.696-12[004, $20\bar 1$ ], 2.524-12[ $22\bar 1$ , $20\bar 2$ ], 2.152-8[134, 153], 1.837-11[135, $17\bar 3$ ]. Ferrotochilinite is a structural analog of tochilinite, with Fe²⁺ instead of Mg in the hydroxide part. The type specimen is deposited in Fersman Mineralogical Museum of Russian Academy of Sciences, Moscow.     

Geochemical models of the impact of acidic groundwater and evaporative sulfate salts on Boulder Creek at Iron Mountain,California

During dry season baseflow conditions approximately 20% of the flow in Boulder Creek is comprised of acidic metals-bearing groundwater. Significant amounts of efflorescent salts accumulate around intermittent seeps and surface streams as a result of evaporation of acid rock drainage. Those salts include the Fe-sulfates — rhomboclase ((H₃O)Fe³⁺(SO₄)₂·3H₂O), ferricopiapite (Fe³⁺₅(SO₄)₆O(OH)·20H₂O), and bilinite (Fe²⁺Fe₂³⁺(SO₄)₄·22H₂O); Al-sulfates — alunogen (Al₂(SO₄)₃·17H₂O) and kalinite (KAl(SO₄)₂·11H₂O); and Ca- and Mg-sulfates — gypsum (CaSO₄·2H₂O), and hexahydrite (MgSO₄·6H₂O). The dissolution of evaporative sulfate salt accumulations during the first major storm of the wet season at Iron Mountain produces a characteristic hydrogeochemical response (so-called “rinse-out”) in surface waters that is subdued in later storms. Geochemical modeling shows that the solutes from relatively minor amounts of dissolved sulfate salts will maintain the pH of surface streams near 3.0 during a rainstorm. On a weight basis, Fe-sulfate salts are capable of producing more acidity than Al- or Mg-sulfate salts. The primary mechanism for the production of acidity from salts involves the hydrolysis of the dissolved dissolved metals, especially Fe³⁺. In addition to the lowering of pH values and providing dissolved Fe and Al to surface streams, the soluble salts appear to be a significant source of dissolved Cu, Zn, and other metals during the first significant storm of the season.     

Niedermayrite, Cu4Cd(SO4)2(OH)6 · 4H2O, a new mineral from the Lavrion Mining District, Greece

Summary Niedermayrite, Cu₄Cd(SO₄)₂(OH)₆ · 4H₂O, is a new mineral discovered in 1995 in the Km3-area of the Lavrion mining district, Greece. It forms tiny euhedral plates, commonly intergrown as green crusts up to several cm² in size on a matrix consisting of a brecciated marble with sphalerite, chalcopyrite, galena, greenockite, hawleyite and pyrite. Associated secondary minerals are gypsum, malachite, chalcanthite, brochantite, hemimorphite, hydrozincite, aurichalcite, one unknown Cd-sulfate, monteponite and otavite. Niedermayrite is non-fluorescent and has a bluish-green colour with vitreous lustre, the streak is white. The crystals are brittle with perfect cleavage parallel {010}. Optics: biaxial (–) with n(calc.), n, and n =1.609, 1.642(2), and 1.661(2), respectively; orientation n//b. The calculated density is 3.292 gcm^–3. The most prominent form is {010}. Analysis by electron microprobe gives CdO 16.5, CuO 45.7, SO₃ 21.6, H₂O 16.2 wt.% (calc. to 100% sum) and the empirical formula Cu_4.29Cd_0.96S_2.01O_11.28 · 6.71 H₂O (based on 18 oxygens p.f.u.). By TGA an H₂O content of 18.9 wt.% was obtained. The ideal formula (confirmed by the crystal structure refinement) is Cu₄Cd(SO₄)₂(OH)₆ · 4H₂O with a theoretical H₂O content of 17.2 wt.%. The strongest lines in the X-ray powder diffraction pattern (Gandolfi camera, visually estimated I, refined lattice parameters a = 5.535(2), b = 21.947(9), c = 6.085(2) Å, = 91.98(3)°) are: (d_obs[Å]/I_obs/hkl) (11.02/90/0 2 0), (5.874/20/0 1 1), (5.496/100/0 4 0), (5.322/25/0 2 1), (4.079/50/0 4 1), (3.660/20/0 6 0), (3. 437/30/1 5 0), (3.243/40/1 4 1), (2.470/30/2 4 0), (2.425/20/1 4 –2), (2.205/20/2 6 0) and (1.897/20/1 8 2). The mineral is monoclinic, P2₁/m, Z = 2, a = 5.543(1) Å, b = 21.995(4) Å, c = 6.079(1) Å, = 92.04(3)°, V = 740.7(2) ų. The crystal structure was determined by single crystal X-ray methods and was refined to R1= 0.026, wR2 = 0.056. The structure of niedermayrite is characterized by ² [Cu₄(OH)₆O₂]^2– sheets of edgesharing Cu coordination octahedra parallel to (010) with attached SO₄ tetrahedra, and intercalated CdO₂(H₂O)₄ octahedra with a system of hydrogen bonds. Close relationships to the crystal structures of christelite and campigliaite exist. The new mineral is named for Dr. Gerhard Niedermayr, Naturhistorisches Museum Wien, Austria.

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Niedermayrit, Cu₄Cd(SO₄)₂(OH)₆ · 4H₂O, ein neues Mineral aus dem Bergbaugebiet Lavrion, Griechenland

Zusammenfassung Niedermayrit, Cu₄Cd(SO₄)₂(OH)₆ · 4H₂O, ist ein neues Mineral, das 1995 im Km3-Bereich des Bergbaugebietes Lavrion, Griechenland, gefunden wurde. Es bildet winzige gut ausgebildete Plättchen, häufig miteinander verwachsen in grünen Krusten bis zu mehreren cm² Größe. Die Matrix besteht aus brecciösem Marmor mit Sphalerit, Chalcopyrit, Galenit, Greenockit, Hawleyit und Pyrit. Sekundäre Begleitminerale sind Gips, Malachit, Chalcanthit, Brochantit, Hemimorphit, Hydrozincit, Aurichalcit, ein unbekanntes Cd-Sulfat, Monteponit und Otavit. Niedermayrit fluoresziert nicht, besitzt blaugrüne Farbe mit Glasglanz, der Strich ist weiß. Die Kristalle sind spröd mit perfekter Spaltbarkeit parallel {010}. Optik: biaxial (–) mit n(ber.), n, und n=1.609, 1.642(2), und 1.661(2); Orientierung n//b. Die berechnete Dichte beträgt 3.292 gcm^–3. Die auffallendste Flächenform ist {010}. Die chemische Analyse mittels Mikrosonde ergibt CdO 16.5, CuO 45.7, SO₃ 21.6, H₂O 16.2wt.% (ber. auf 100% Summe) und die empirische Formel Cu_4.29Cd_0.96S_2.01O_11.28 · 6.71 H₂O (basierend auf 18 Sauerstoffatomen pro Formeleinheit). Aus der TGA wurde ein H₂O Gehalt von 18.9 Gew.% erhalten. Die Idealformel (bestätigt durch die Kristallstrukturverfeinerung) ist Cu₄Cd(SO₄)₂(OH)₆ · 4H₂O bei einem theoretischen H₂O-Gehalt von 17.2 Gew.%. Die stärksten Linien im Pulverdiffraktogramm (Gandolfi Kamera, visuell geschätzte I, verfeinerte Gitterkonstanten a = 5.535(2), b = 21.947(9), c = 6.085(2) Å, = 91.98(3)°) sind: (d_obs[Å]/I_obs/hkl) (11.02/90/0 2 0), (5.874/20/0 1 1), (5.496/100/0 4 0), (5.322/25/0 2 1), (4.079/50/0 4 1), (3.660/20/0 6 0), (3.437/30/1 5 0), (3.243/40/1 4 1), (2.470/30/2 4 0), (2.425/20/1 4 –2), (2.205/20/2 6 0) und (1.897/20/1 8 2). Das Mineral ist monoklin, P2₁/m, Z = 2, a = 5.543(1) Å, b = 21.995(4) Å, c = 6.079(1) Å, = 92.04(3)°, V = 740.7(2) ų Die Kristallstruktur wurde mittels Einkristallröntgenmethoden bestimmt und zu R1 = 0.026, wR2 = 0.056 verfeinert. Die Struktur von Niedermayrit ist durch ² [Cu₄(OH)₆O₂]^2– Schichten von kantenverknüpften Cu-Koordinationsoktaedern parallel (010) gekennzeichnet mit damit verbundenen SO₄ Tetraedern und dazwischen befindlichen CdO₂(H₂O)₄ Oktaedem mit einem Wasserstoffbrückensystem. Es bestehen enge Beziehungen mit den Kristallstrukturen von Christelit und Campigliait. Das neue Mineral ist nach Dr. Gerhard Niedermayr, Naturhistorisches Museum Wien, Österreich, benannt.

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With 7 Figures     

Oxidation modes and thermodynamics of Fe oxyhydroxycarbonate green rust: Dissolution-precipitation versus in situ deprotonation

Fe^II-III hydroxycarbonate green rust GR(CO₃²⁻), Fe^II₄ Fe^III₂ (OH)₁₂ CO₃·3H₂O, is oxidized in aqueous solutions with varying reaction kinetics. Rapid oxidation with either H₂O₂ or dissolved oxygen under neutral and alkaline conditions leads to the formation of ferric oxyhydroxycarbonate GR(CO₃²⁻)∗, Fe^III₆ O₁₂ H₈ CO₃·3H₂O, via a solid-state reaction. By decreasing the flow of oxygen bubbled in the solution, goethite α-FeOOH forms by dissolution-precipitation mechanism whereas a mixture of non-stoichiometric magnetite Fe_(3−x)O₄ and goethite is observed for lower oxidation rates. The intermediate Fe^II-III oxyhydroxycarbonate of formula Fe^II_6(1−x) Fe^III_6x O₁₂ H_2(7−3x) CO₃·3H₂O, i.e. GR(x)∗ for which x ? [1/3, 1], is the synthetic compound that is homologous to the fougerite mineral present in hydromorphic gleysol; in situ oxidation accounts for the variation of ferric molar fraction x = [Fe^III]/{[Fe^II]+[Fe^III]} observed in the field as a function of depth and season but limited to the range [1/3, 2/3]. The domain of stability for partially oxidized green rust is observed in the E_h-pH Pourbaix diagrams if thermodynamic properties of GR(x)∗ is compared with those of lepidocrocite, γ-FeOOH, and goethite, α-FeOOH. Electrochemical equilibrium between GR(x)∗ and Fe^II in solution corresponds to E_h-pH conditions close to those measured in the field. Therefore, the reductive dissolution of GR(x)∗ can explain the relatively large concentration of Fe^II measured in aqueous medium of hydromorphic soils containing fougerite.     

Kobyashevite, Cu5(SO4)2(OH)6·4H2O, a new devilline-group mineral from the Vishnevye Mountains, South Urals, Russia

A new mineral kobyashevite, Cu₅(SO₄)₂(OH)₆·4H₂O (IMA 2011–066), was found at the Kapital’naya mine, Vishnevye Mountains, South Urals, Russia. It is a supergene mineral that occurs in cavities of a calcite-quartz vein with pyrite and chalcopyrite. Kobyashevite forms elongated crystals up to 0.2 mm typically curved or split and combined into thin crusts up to 1?×?2 mm. Kobyashevite is bluish-green to turquoise-coloured. Lustre is vitreous. Mohs hardness is 2½. Cleavage is {010} distinct. D(calc.) is 3.16 g/cm³. Kobyashevite is optically biaxial (?), α 1.602(4), β 1.666(5), γ 1.679(5), 2 V(meas.) 50(10)°. The chemical composition (wt%, electron-microprobe data) is: CuO 57.72, ZnO 0.09, FeO 0.28, SO₃ 23.52, H₂O(calc.) 18.39, total 100.00. The empirical formula, calculated based on 18 O, is: Cu_4.96Fe_0.03Zn_0.01S_2.01O_8.04(OH)_5.96·4H₂O. Kobyashevite is triclinic, $ P\overline{\,1 } $ , a 6.0731(6), b 11.0597(13), c 5.5094(6)?Å, α 102.883(9)°, β 92.348(8)°, γ 92.597(9)°, V 359.87(7)?ų, Z?=?1. Strong reflections of the X-ray powder pattern [d,Å-I(hkl)] are: 10.84–100(010); 5.399–40(020); 5.178–12(110); 3.590–16(030); 2.691–16(20–1, 040, 002), 2.653–12(04–1, 02–2), 2.583–12(2–11, 201, 2–1–1), 2.425–12(03–2, 211, 131). The crystal structure (single-crystal X-ray data, R?=?0.0399) сontains [Cu₄(SO₄)₂(OH)₆] corrugated layers linked via isolated [CuO₂(H₂O)₄] octahedra; the structural formula is CuCu₄(SO₄)₂(OH)₆·4H₂O. Kobyashevite is a devilline-group member. It is named in memory of the Russian mineralogist Yuriy Stepanovich Kobyashev (1935–2009), a specialist on mineralogy of the Urals.     

Die Kristallstruktur des Johannits,Cu(UO2)2(OH)2(SO4)2·8H2O

Zusammenfassung Die Kristallstruktur des Johannits wurde anhand eines verzwillingten Kristalls von Joachimsthal, Böhmen, mit dreidimensionalen Röntgendaten bestimmt und für 2005 unabhängige Reflexe aufR=0,039 verfeinert. Johannit kristallisiert triklin, RaumgruppeP1, mita=8,903 (2),b=9,499 (2),c=6,812 (2) Å, =109,87 (1) =112,01 (1), =100,40 (1)° undV=469,9 ų. Chemische Formel und Zellinhalt lauten Cu(UO₂)₂(OH)₂(SO₄)₂·8H₂O, das ist um zwei H₂O-Moleküle mehr als bisher angenommen. In der Struktur sind pentagonal dipyramidale (UO₂)(OH)₂O₃-Polyeder paarweise über eine von zwei OH-Gruppen gebildete Kante zu Doppelpolyedern und diese wiederum durch SO₄-Gruppen zu (UO₂)₂(OH)₂(SO₄)₂-Schichten parallel (100) verknüpft. Die Schichten sind parallel über gestreckte Cu(H₂O)₄O₂-Oktaeder und Wassermoleküle miteinander verbunden. Folgende Bindungslängen wurden gefunden: U–O=1,78 Å (2x) und 2,34–2,39 Å (5x); Cu–O=1,97 Å (4x) und 2,40 Å (2x); =1,47 Å; O–O in Wasserstoffbrücken 2,71–2,91 Å (8x) und 3,30 Å.

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The crystal structure of johannite, Cu(UO₂)₂(OH)₂(SO₄)₂·8H₂O

Summary The crystal structure of johannite has been determined from threedimensional X-ray data measured on a twinned crystal from Joachimsthal, Böhmen, and has been refined toR=0.039 for 2005 independent reflections. Johannite crystallizes triclinic, space groupP1, witha=8.903 (2),b=9.499 (2),c=6.812 (2) Å, =109.87(1), =112.01(1), =100.40 (1)° andV=469.9 ų. Chemical formula and cell content are Cu(UO₂)₂(OH)₂(SO₄)₂·8H₂O, by two H₂O molecules more than previously assumed. Pairs of pentagonal dipyramidal (UO₂) (OH)₂O₃ polyhedra form double polyhedra by edgesharing via two OH groups. The double polyhedra are linked by the SO₄ tetrahedra to form layers (UO₂)₂(OH)₂(SO₄)₂ parallel zu (100). These layers are interconnected parallel toa by elongated Cu(H₂O)₄O₂ octahedra and water molecules. Following bond lengths have been observed: U–O=1.78 Å (2x) and 2.34–2.39 Å (5x); Cu–O=1.97 Å (4x) and 2.40 Å (2x); =1.47 Å; O–O for hydrogen bonds 2.71–2.91 Å (8x) and 3.30 Å.

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Mit 2 Abbildungen     

Heat capacity, entropy, and magnetic properties of jarosite-group compounds

Jarosite phases are common minerals in acidic, sulfate-rich environments. Here, we report heat capacities (C _p) and standard entropies (S°) for a number of jarosite samples. Most samples are close to the nominal composition AFe₃(SO₄)₂(OH)₆, where A = K, Na, Rb, and NH₄. One of the samples has a significant number of defects on the Fe sites and is called the defect jarosite; others are referred to as A-jarosite. The samples, their compositions, and the entropies at T = 298.15 K are:

Crystal structure and refined formula of garyansellite Mg<Subscript>2</Subscript>Fe<Superscript>3+</Superscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH) · 2H<Subscript>2</Subscript>O

Single-crystal study of the structure (R = 0.0268) was performed for garyansellite from Rapid Creek, Yukon, Canada. The mineral is orthorhombic, Pbna, a = 9.44738(18), b = 9.85976(19), c = 8.14154(18) Å, V = 758.38(3) ų, Z = 4. An idealized formula of garyansellite is Mg₂Fe³⁺(PO₄)₂(OH) · 2H₂O. Structurally the mineral is close to other members of the phosphoferrite–reddingite group. The structure contains layers of chains of M(2)O₄(OH)(H₂O) octahedra which share edges to form dimers and connected by common edges with isolated from each other M(1)O₄(H₂O)₂ octahedra. The neighboring chains are connected to the layer through the common vertices of M(2) octahedra and octaahedral layers are linked through PO₄ tetrahedra.     

Avdoninite: New data,crystal structure and refined formula K<Subscript>2</Subscript>Cu<Subscript>5</Subscript>Cl<Subscript>8</Subscript>(OH)<Subscript>4</Subscript> · 2H<Subscript>2</Subscript>O

The paper reports new findings of avdoninite from deposits of active fumaroles in the Second Scoria Cone at the Northern Breach of the Great Fissure Tolbachik Eruption, Tolbachik Volcano, Kamchatka Peninsula, Russia. The crystal structure of the mineral has been determined for the first time, which has allowed reliable determination of its space group and unit cell dimensions, refinement of its formula K₂Cu₅-Cl₈(OH)₄ · 2H₂O, and correct indexing of its X-ray powder diffraction pattern. Avdoninite is monoclinic, space group P2₁/c, a = 11.592(2), b = 6.5509(11), c = 11.745(2) Å, β = 91.104(6)°, V = 891.8(3) ų, Z = 2. The crystal structure of this mineral has been determined on a single crystal R ₁ [F > 4σ (F)] = 0.063. It is based on sheets of copper–oxo-chloride complexes [Cu₅Cl₈(OH)₄]^2– parallel to (100). The K⁺ cation and H₂O molecules are interlayers.     

Arsenate and arsenite adsorption onto Al-containing ferrihydrites. Implications for arsenic immobilization after neutralization of acid mine drainage

Natural ferrihydrites (Fh) often contain impurities such as aluminum, especially in acid mine drainage, and these impurities can potentially impact the chemical reactivity of Fh with respect to metal (loid) adsorption. In the present study, we have investigated the influence of aluminum on the sorption properties of ferrihydrite with respect to environmentally relevant aqueous arsenic species, arsenite and arsenate. We have conducted sorption experiments by reacting aqueous As(III) and As(V) with synthetic Al-free and Al-bearing ferrihydrite at pH 6.5. Our results reveal that, when increasing the Al:Fe molar ratio in Fh, the sorption density dramatically decreased for As(III), whereas it increased for As(V). Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy analysis at the As K-edge indicated that the As^IIIO₃ pyramid binds to FeO₆ octahedra on both Al-free Fh and Al-bearing Fh, by forming bidentate mononuclear edge-sharing (²E) and bidentate binuclear corner-sharing (²C) surface complexes characterized by As–Fe distances of 2.9 Å and 3.4 Å, respectively. The decrease in As(III) sorption density with increasing Al:Fe ratio in Fh could thus be explained by a low affinity of the As(OH)₃ molecule for Al surface sites compared to Fe ones. In contrast, on the basis of available literature on As(V) adsorption mechanisms, we suggest that, in addition to inner-sphere ²C arsenate surface complexes, outer-sphere arsenate surface complexes forming hydrogen bonds with both Al–OH and Fe–OH surface sites could explain the enhancement of As(V) sorption onto aluminous Fh relative to Al-free Fh, as observed in the present study. The presence of aluminum in Fh may thus enhance the mobility of arsenite with respect to arsenate in Acid Mine Drainage impacted systems, while mixed Al:Fe systems could present an alternative for arsenic removal from impacted waters, provided that As(III) would be oxidized to As(V).     

Crystal chemistry of a natural schorlomite and Ti-andradites synthesized at different oxygen fugacities

Ti-andradites were synthesized at a pressure of P(H₂O)=3 kbar and temperatures of 700–800° C. Oxygen fugacities were controlled by solid state buffers (Ni/NiO; SiO₂ + Fe/Fe₂SiO₄). The Fe²⁺-and Fe³⁺-distribution was determined by low temperature Mössbauer spectroscopy. The water content was measured by a solid's moisture analyzer. The chemical composition of the synthetic and the natural sample has been determined by electron microprobe. Ti-andradites from runs at high oxygen fugacities have Fe³⁺ on octahedral and tetrahedral sites; Ti-andradites from runs at low oxygen fugacities have tetrahedrally and octahedrally coordinated Fe²⁺ as well. These “reduced” garnets must also contain Ti³⁺ on octahedral sites. Charge balance is maintained due to substitution of O^2? by (OH)^? by two mechanisms: (SiO₄)^4? ? (O₄H₄)^4? and (Fe³⁺O₆)^9? ? (Fe²⁺O₅OH)^9?. FTIR spectra of the synthetic samples do show the presence of structurally bound (OH)^?. In a natural sample tetrahedrally and octahedrally coordinated Fe³⁺ are observed together with Fe²⁺ on all three cation sites of the garnet structure.