Crystal chemistry of selenates with mineral-like structures. VI. Hydrogen bonds in the crystal structure of [(H5O2)(H3O)(H2O)][(UO2)(SeO4)2]

The crystal structure of a new compound, [(H₅O₂)(H₃O)(H₂O)][(UO₂)(SeO₄)₂] (monoclinic, P2₁/n a = 8.3105(15), b = 11.0799(14), c = 13.227(2) Å, β = 103.880(13)°, V = 1182.4(3) ų), has been solved by direct methods and refined to R ₁ = 0.036. The structure is based on [(UO₂)(SeO₄)₂]^2? sheet complexes formed by corner-shared UO₇ pentagonal bipyramids and SeO₄ tetrahedrons. The sheets are parallel to the ( $ \bar 1 The crystal structure of a new compound, [(H₅O₂)(H₃O)(H₂O)][(UO₂)(SeO₄)₂] (monoclinic, P2₁/n a = 8.3105(15), b = 11.0799(14), c = 13.227(2) ?, β = 103.880(13)°, V = 1182.4(3) ?³), has been solved by direct methods and refined to R ₁ = 0.036. The structure is based on [(UO₂)(SeO₄)₂]²⁻ sheet complexes formed by corner-shared UO₇ pentagonal bipyramids and SeO₄ tetrahedrons. The sheets are parallel to the (01) plane. Oxonium ions and water molecules forming [(H₃O)·(H₂O)·(H₅O₂)]²⁺ complexes are interlayer. Among minerals, the existence of (H₅O₂)⁺ has been unambiguously confirmed only in rhomboclase, (H₅O₂)⁺[Fe₂(SO₄)₂(H₂O)₂]. Original Russian Text ? S.V. Krivovichev, 2008, published in Zapiski Rossiiskogo Mineralogicheskogo Obshchestva, 2008, No. 2, pp. 123–130.     

Five-coordinate Cd in the crystal structure of triploidite-type Cd2(AsO4)(OH)

This paper reports on hydrothermal synthesis and crystal structure refinement of dicadmium arsenate hydroxide, Cd₂(AsO₄)(OH), obtained at 220 °C and autogenous pressure. Its crystal structure is monoclinic, space group P2₁/a, with a = 13.097(3), b = 14.089(3), c = 10.566(2) Å, β = 108.38(3)°, V = 1850.2(6) ų (Z = 16). It is isotypic with the members of the triploidite group of minerals and synthetic compounds, and thus shows a close topological relationship with the triplite group. The complex framework contains edge- and corner-sharing CdO₄(OH) and CdO₄(OH)₂ polyhedra, linked via corner-sharing to AsO₄ tetrahedra (average As—O distances range between 1.682 and 1.688 Å). Four five-coordinated Cd sites are at the centers of distorted trigonal bipyramids (average Cd—O distances are between 2.225 and 2.251 Å), whereas the remaining four Cd sites have a distorted octahedral coordination environment (average Cd—O distances are between 2.297 and 2.320 Å). The positions of all the hydrogen atoms were located in a difference-Fourier map and refined with an isotropic displacement parameter. The hydrogen-bonds are weak to very weak. The unusual five-coordination of Cd is briefly discussed in relation to comparable minerals and compounds. Among triploidite-type compounds, Cd₂(AsO₄)(OH) is the member with the largest unit cell reported so far, and the second known arsenate member.     

Crystal chemistry of selenates with mineral-like structures: V. Crystal structures of (H3O)2[(UO2)(SeO4)2(H2O)](H2O)2 and (H3O)2[(UO2)(SeO4)2(H2O)](H2O), new compounds with rhomboclase and goldichite topology

The crystal structures of two new compounds (H₃O)₂[(UO₂)(SeO₄)₂(H₂O)](H₂O)₂ (1, orthorhombic, Pnma, a = 14.0328(18), b = 11.6412(13), c = 8.2146(13) Å, V = 134.9(3) ų) and (H₃O)₂[(UO₂)(SeO₄)₂(H₂O)](H₂O) (2, monoclinic, P2₁/c, a = 7.8670(12), b = 7.5357(7), c = 21.386(3) Å, β = 101.484(12)°, V = 1242.5(3) ų) have been solved by direct methods and refined to R ₁ = 0.076 and 0.080, respectively. The structures of both compounds contain sheet complexes [(UO₂)(SeO₄)₂]^2? formed by cornershared [(UO₂)O₄(H₂O)] bipyramids and SeO₄ tetrahedrons. The sheets are parallel to the (100) plane in structure 1 and to (?102) in structure 2. The [(UO₂)(SeO₄)₂(H₂O)]^2? layers are linked by hydrogen bonds via interlayer groups H₂O and H₃O⁺. The sheet topologies in structures 1 and 2 are different and correspond to the topologies of octahedral and tetrahedral complexes in rhomboclase (H₂O₂)⁺[Fe(SO₄)₂(H₂O)₂] and goldichite K[Fe(SO₄)₂(H₂O)₂](H₂O)₂, respectively.     

Vanadio-pargasite NaCa2(Mg4V)(Si6Al2)O22(OH)2: a New Mineral of the Amphibole Supergroup

Geology of Ore Deposits - A new mineral was discovered in Cr–V-bearing marbles of the Sludyanka Complex from the Pereval marble quarry, Sludyanka district, southern Baikal region, Russia. It...     

The stability of primary alluaudites in granitic pegmatites: an experimental investigation of the Na2(Mn2−2x Fe1+2x )(PO4)3 system

In order to assess the geothermometric potential of the Na₂(Mn_2−2x Fe_1+2x )(PO₄)₃ system (x = 0–1), which represents the compositions of natural weakly oxidized alluaudites, we performed hydrothermal experiments between 400 and 800°C, at 1 kbar, under an oxygen fugacity (f(O₂)) controlled by the Ni–NiO (NNO), Fe₂O₃–Fe₃O₄ (HM), Cu₂O–CuO (CT), and Fe–Fe₃O₄ (MI) buffers. When f(O₂) is controlled by NNO, single-phase alluaudites crystallize at 400 and 500°C, whereas the association alluaudite + marićite appears between 500 and 700°C. The limit between these two fields corresponds to the maximum temperature that can be reached by alluaudites in granitic pegmatites, because marićite has never been observed in these geological environments. Because alluaudites are very sensitive to variations of oxygen fugacity, the field of hagendorfite, Na₂MnFe²⁺Fe³⁺(PO₄)₃, has been positioned in the f(O₂)–T diagram, and provides a tool that can be used to estimate the oxygen fugacity conditions that prevailed in granitic pegmatites during the crystallization of this phosphate.     

新矿物（1995．1—2000．12）（补遗）

本文以表格的形式补充列举了经国际矿物学协会(IMA)新矿物与矿物命名委员会(CNMMN)批准、并于1995年至2000年期间在各国有关刊物上正式发表的、以前在本刊公布的新矿物中被遗漏的58个新矿物，这58个新矿物包括硅酸盐、硫酸盐、硫化物类、硫盐、碳酸盐、草酸盐、卤化物类(包括氯化物、氟化物)、磷酸盐、砷酸盐、硼酸盐、碲酸盐、硒酸盐、锑酸盐、铬酸盐、钼酸盐、复杂氧化物和单质互化物。其表格列举方式依次为：矿物的中外文名称及化学式、晶系及晶胞参数、主要粉晶数据、物理性质、光学性质、产状及共生(伴生)组合等。     

High-pressure phase transformation of carbonate malachite Cu2(CO3)(OH)2 driven by [CuO6] regularization and [CO3] rotation

High-pressure synchrotron X-ray diffraction and infrared absorption spectroscopy have been employed to study the crystal chemistry and phase transitions in an[OH]-bearing carbonate,malachite Cu2(CO₃)(OH)₂,to determine the effect of[OH]on the stability of carbonate.We found that the crystal structure of malachite is stabilized by a high degree of[CuO₆]-octahedron distortion,as is manifested by large variations in Cu–O bond lengths resulting from oxygen atoms that connect to hydrogen at crystallographically different sites.External pressure offsets the effect of hydrogen bond,promotes[CuO₆]compression and regularization and accordingly[CO₃]rotation.Rotation of[CO₃]-triangles,in turn,assists in a conversion in the crystal orientation of the[CuO₆]structural unit.During compression to above~6 GPa,malachite begins to turn into the rosasite lattice,accompanied with a jump in density of 3.3%.Rosasite is characterized with a hardened lattice and preserves to the maximum pressure(18.2 GPa)of the present study.Phase transformation mechanism of malachite to rosasite is different from that of carbonates,with the latter being driven by an almost uniform compression of[MO₆]-octahedron(M=Ca,Cd,Mn,Fe,Zn,Mg,etc.)and rotation/translation of[CO₃]-triangle under pressure.     

A modern, guano-related occurrence of foggite, CaAl(PO4)(OH)2 · H2O and churchite-(Y), YPO4 · 2H2O in Cioclovina Cave, Romania

Summary This study reports foggite and churchite-(Y) from two spatially separate locations in the guano-related phosphate deposit from the Cioclovina Cave, Romania. Optical microscope observations, powder X-ray diffraction, electron microprobe analyses, and FTIR were used in the analysis of the two minerals. The chemical composition of foggite was determined to be Ca_0.925(Al_0.91Fe²⁺_0.016)_Σ0.926(P_0.991Si_0.043)_Σ1.034O_3.74(OH)_2.26 · H₂O and churchite-(Y) [(Y_0.830Dy_0.043Er_0.033Gd_0.029Yb_0.022)_Σ0.957Ca_0.009]P_1.023O_4.00 · 2H₂O. Chemical analyses of Cioclovina churchite-(Y) clearly revealed enrichment in lanthanides of even atomic number. The refined unit-cell parameters are for foggite (orthorhombic) a = 9.264(1) ?, b = 21.334(8) ?, c = 5.197(7) ?, and V = 1027.13(8) ?³ (Z = 8); for churchite-(Y) (monoclinic): a = 5.578(8) ?, b = 15.013(6) ?, c = 6.277(8) ?, β = 117.94(4)°, and V = 464.38(5) ?³ (Z = 4). FTIR spectrum of churchite-(Y) exhibits all the bands assigned to the vibrations of PO₄, OH, and water groups. Unlike other documented occurrences of foggite and churchite-(Y), in Cioclovina Cave, the occurrence of these minerals are related to a process that phosphatized subjacent limestone and various cave sediments (sand, clay, and limy mud) to form a complex phosphate assemblage. The minerals are presumably derived from phosphate-rich solutions that reacted with clay earth while moving downward through the sediments. Foggite was formed at the expense of the originally precipitated crandallite. Locally concentrated yttrium, REE, and dissolved phosphate are probably responsible for the precipitation of churchite-(Y). Present address: Department of Geology, University of South Florida, Tampa, FL, USA     

Experimental and theoretical study of (Fe2+, Mg)(Al,Fe3+)2O4 spinels: Activity-composition relationships,miscibility gaps,vacancy contents

The compositions of (Fe²⁺, Mg)(Al, Fe³⁺)₂O₄ spinels equilibrated with a l M (Fe²⁺, Mg)Cl₂ aqueous solution at 800°C, 4 kbars were determined. General considerations of reciprocal systems allow derivation of the exchange isotherm between a chloride aqueous solution and (Mg, Fe²⁺)Al₂O₄ spinels. They enable calculation of ΔG of the reaction: FeCl₂ + MgAl₂O₄ = MgCl₂ + FeAl₂O₄ΔG = 2.9 kcal at 800°C, 4 kbars and provide the activity-composition relationships for the binary join FeAl₂O₄-MgAl₂O₄, which shows a substantial positive deviation from ideality. Some tie-lines between coexisting aluminous and ferric spinels were also obtained in the (Fe²⁺, Mg)(Al, Fe³⁺)₂O₄ system.These experimental data are modeled by a Gibbs free energy formulation of the spinel solid solution (Lehmann and Roux, 1984), where the corrective function g₂, necessary to reproduce the deviations from ideality, is artificially split into two parts:

• 1.(1) A homogeneous second degree polynomial in the composition variables, containing only the terms specific to the reciprocal nature of the system, whose coefficients are deduced from ΔG of the exchange reaction: MgAl₂O₄ + FeFe₂O₄ = MgFe₂O₄ + FeAl₂O₄ΔG = 4.5 kcal at 800°C, 4 kbars
• 2.(2) A homogeneous second degree polynomial in the site occupancy fractions, to model the non-ideal behavior of the (Fe²⁺, Mg)Al₂O₄ and (Fe₂₊, Mg)Fe₂O₄ spinels and the miscibility gap along the Fe(Al, Fe³⁺)₂O₄ join.

A model of reciprocal spinel solution involving defect end-members is used to estimate the vacancy contents of the spinels in equilibrium with sesquioxides. In this case, the corrective function necessary to take into account the reciprocal nature of the system is no longer a second degree polynomial, but a rational fraction.     

南华砷铊矿床铊黄铁矿的发现和研究

铊黄铁矿产在云南省南华砷铊矿床中,是钻的主要工业矿物。矿物是浅黄白色,金属光泽,条痕黑褐色。呈微粒和结核状分散在砷铝矿石中。矿物粒径0．001～0．028mm,HM＝5．4,VHN100＝514kg／mm2,D＝5．2。共生矿物有雄黄、方铅矿、闪锌矿、白云石、石英和流砷铊铅矿等。矿相显微镜下反射色呈灰白色,均质性。电子探针分析平均化学成分及其变化范围（％）：S48．64（45．58～50．12）,As5．31（3．80～6．96）,Fe38．63（37．65～40．50）,T16．96（514～865）,总计99．56。按（Fe,T1）／（S,As）原子数1：2计算,钻黄铁矿理论式为（Fe,Tl）（S,As）2。X射线粉晶分析属等轴晶系,空间群Pa3,Z＝4,a＝0．5442±0．02nm,略大于黄铁矿。从矿物化学式中可看出铊和砷分别替代铁和硫,它们的含量已超出通常黄铁矿中杂质含量范围,放将其定为铊黄铁矿。矿物存放在中国科学院地球化学研究所陈列馆。     

Crystal structure and chemical formula of schmiederite,Pb2Cu2(OH)4(SeO3)(SeO4), with a comparison to linarite,PbCu(OH)2(SO4)

Summary Based on a X-ray structure analysis it was proved that the mineral schmiederite contains both selenite and selenate groups [a = 9.922(3)Å,b = 5.712(2)Å,c = 9.396(3)Å, = 101.96(3)°, space group P2₁/m,Z = 2 {Pb₂Cu₂(OH)₄(SeO₃)(SeO₄)},R _w = 0.055 for 1131 reflections up to sin / = 0.65 Å^–1]. The crystal structure is closely related to that of linarite [a = 9.701(2) Å,b = 5.650(2) Å,c= 4.690(2)Å, = 102.65(2)°, space group P2₁/m,Z = 2 {PbCu(OH)₂(SO₄)},R _w = 0.034 for 1991 reflections up to sin / = 1.0 Å^–1].The Pb atom in linarite and the Pb(1) atom in schmiederite have each three Pb-O bonds < 2.45 Å with trigonal pyramidal arranged ligands; the Pb(2) atom in schmiederite has only one such near O atom. The Cu atoms are approximately square planar coordinated by hydroxil groups. In addition two further O atoms complete the coordination figure to a strongly distorted octahedron. All the anion groups have the usual geometry.

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Kristallstruktur und chemische Formel von Schmiederit, Pb₂Cu₂(OH)₄(SeO₃)(SeO₄), mit einem Vergleich zu Linarit, PbCu(OH)₂(SO₄)

Zusammenfassung Basierend auf einer Röntgen-Strukturuntersuchung konnte das Vorliegen von Selenit-und Selenatgruppen im Mineral Schmiederit belegt werden [a=9,922(3) Å,b = 5,712(2) Å,c = 9,396(3) Å, = 101,96(3)°, Raumgruppe P2₁/m,Z=2 {Pb₂Cu₂(OH)₄(SeO₃)(SeO₄)},R _w = 0,055 für 1131 Reflexe bis sin /, = 0,65 Å^–1]. Die Kristallstruktur weist enge Beziehungen zu jener des Linarits auf [a = 9,701(2) Å,b = 5,650(2) Å,c = 4,690(2) Å, = 102,65(2)°, Raumgruppe P2₁/m,Z=2 {PbCu(OH)₂(SO₄)},R _w = 0,034 für 1991 Reflexe bis sin / = 1,0 Å^–1].Das Pb-Atom im Linarit sowie das Pb(1)-Atom im Schmiederit haben jeweils drei Pb-O-Bindungen <,45 Å, wobei die Liganden trigonal pyramidal angeordnet sind; das Pb(2)-Atom im Schmiederit hat hingegen nur ein derart nahes O-Atom. Die Cu-Atome sind etwa quatratisch planar von Hydroxilgruppen koordiniert; zwei weitere O-Atome ergänzen die Koordinationsfigur zur einem stark verzerrten Oktaeder. Die Aniongruppen haben die üblichen Dimensionen.

     

(Na,Ca)(Ti3+,Mg)Si2O6-clinopyroxenes at high pressure: influence of cation substitution on elastic behavior and phase transition

A compressional study of (Na,Ca)(Ti³⁺,Mg)Si₂O₆-clinopyroxenes was carried out at high pressures between 10⁻⁴ and 10.2 GPa using in situ single-crystal X-ray diffraction, Raman spectroscopy and optical absorption spectroscopy. Compressional discontinuities accompanied by structural changes, in particular, the appearance of two distinct Ti³⁺–Ti³⁺ distances within the octahedral chains at 4.37 GPa, provide evidence for the occurrence of a phase transition in NaTi³⁺Si₂O₆. Equation-of-state parameters are K ₀ = 115.9(7) GPa with K′ = −0.9(3) and K ₀ = 102.7(8) GPa with K′ = 4.08(5) for the low- and high-pressure range, respectively. The transition involves a C2/c–P [`1] \overline{1} symmetry change, which can be confirmed by the occurrence of new modes in Raman spectra. Since no significant discontinuity in the evolution of the unit-cell volume with pressure has been observed, the transition appears to be second-order in character. The influence of the coupled substitution Na⁺Ti³⁺↔Ca²⁺Mg²⁺ on the static compression behavior and the structural stability has been investigated using a sample of the intermediate composition (Na_0.54Ca_0.46)(Mg_0.46Ti_0.54)Si₂O₆. No evidence for a deviation from continuous compression behavior has been found, neither in lattice parameter nor in structural data and the fit of a third-order Birch–Murnaghan equation-of-state to the pressure–volume data yields a bulk modulus of K ₀ = 109.1(5) GPa and K′ = 5.02(13). Raman and polarized absorption spectra have been compared to NaTiSi₂O₆ and reveal major similarities. The main driving force for the phase transition in NaTi³⁺Si₂O₆ is the localization of the Ti³⁺ d-electron and the accompanying distortion, which is suppressed in the (Na,Ca)(Ti³⁺,Mg)Si₂O₆-clinopyroxene.     

Perrierite-(La), (La,Ce,Ca)4(Fe2+,Mn)(Ti,Fe3+,Al)4(Si2O7)2O8, a new mineral species from the Eifel volcanic district, Germany

Non-metamict perrierite-(La) discovered in the Dellen pumice quarry, near Mendig, in the Eifel volcanic district, Rheinland-Pfalz, Germany has been approved as a new mineral species (IMA no. 2010-089). The mineral was found in the late assemblage of sanidine, phlogopite, pyrophanite, zirconolite, members of the jacobsite-magnetite series, fluorcalciopyrochlore, and zircon. Perrierite-(La) occurs as isolated prismatic crystals up to 0.5 × 1 mm in size within cavities in sanidinite. The new mineral is black with brown streak; it is brittle, with the Mohs hardness of 6 and distinct cleavage parallel to (001). The calculated density is 4.791 g/cm³. The IR spectrum does not contain absorption bands that correspond to H₂O and OH groups. Perrierite-(La) is biaxial (-), α = 1.94(1), β = 2.020(15), γ = 2.040(15), 2V _meas = 50(10)°, 2V _calc = 51°. The chemical composition (electron microprobe, average of seven point analyses, the Fe²⁺/Fe³⁺ ratio determined from the X-ray structural data, wt %) is as follows: 3.26 CaO, 22.92 La₂O₃, 19.64 Ce₂O₃, 0.83 Pr₂O₂, 2.09 Nd₂O₃, 0.25 MgO, 2.25 MnO, 3.16 FeO, 5.28 Fe₂O₃, 2.59 Al₂O₃, 16.13 TiO₂, 0.75 Nb₂O₅, and 20.06 SiO₂, total is 99.21. The empirical formula is (La_1.70Ce_1.45Nd_0.15Pr_0.06Ca_0.70)_Σ4.06(Fe _0.53 ²⁺ Mn_0.38Mg_0.08)_Σ0.99(Ti_2.44Fe _0.80 ³⁺ Al_0.62Nb_0.07)_Σ3.93Si_4.04O₂₂. The simplified formula is (La,Ce,Ca)₄(Fe²⁺,Mn)(Ti,Fe³⁺,Al)₄(Si₂O₇)₂O₈. The crystal structure was determined by a single crystal. Perrierite-(La) is monoclinic, space group P2₁/a, and the unit-cell dimensions are as follows: a =13.668(1), b = 5.6601(6), c = 11.743(1) Å, β = 113.64(1)°; V = 832.2(2) ų, Z = 2. The strong reflections in the X-ray powder diffraction pattern are [d, Å (I, %) (hkl)]: 5.19 (40) (110), 3.53 (40) ( $\overline 3 $ 11), 2.96 (100) ( $\overline 3 $ 13, 311), 2.80 (50) (020), 2.14 (50) ( $\overline 4 $ 22, $\overline 3 $ 15, 313), 1.947 (50) (024, 223), 1.657 (40) ( $\overline 4 $ 07, $\overline 4 $ 33, 331). The holotype specimen of perrierite-(La) is deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow, Russia, with the registration number 4059/1.     

Ni isotope fractionation during coprecipitation of Fe(III)(oxyhydr)oxides in Si solutions

The dramatic decline in aqueous Ni concentrations in the Archean oceans during the Great Oxygenation Event is evident in declining solid phase Ni concentrations in Banded Iron Formations (BIFs) at the time. Several experiments have been performed to identify the main removal mechanisms of Ni from seawater into BIFs, whereby adsorption of Ni onto ferrihydrites has shown to be an efficient process. Ni isotopic measurements have shown limited isotopic fraction during this process, however, most experiments have been conducted in simple solutions containing varying proportions of dissolved Fe and Ni as NO₃ salts, as opposed to Cl salts which are dominant in seawater. Further, Archean oceans were, before the advent of siliceous eukaryotes, likely saturated with amorphous Si as seen in the interlayered chert layers within BIFs. Despite Si being shown to greatly affect the Ni elemental partitioning onto ferrihydrite solids, no studies have been made on the effects of Si on the Ni isotope fractionation. Here we report results of multiple coprecipitation experiments where ferrihydrite precipitated in mixed solutions with Ni and Si. Ni concentrations in the experiments ranged between 200 and 4000 nM for fixed concentrations of Si at either 0, 0.67 or 2.2 mM. The results show that Si at these concentrations has a limited effect on the Ni isotope fractionation during coprecipitation of ferrihydrite. At 0.67 mM, the saturation concentration of cristobalite, the isotopic fractionation factors between the precipitating solid and experimental fluid are identical to experiments not containing Si (0.34 ± 0.17‰). At 2.2 mM Si, and the saturation concentration of amorphous silica, however, the Ni isotopic composition of the ferrihydrite solids deviate to more negative values and show a larger variation than at low or no Si, and some samples show fractionation of up to 0.5‰. Despite this seemingly more unstable fractionation behaviour, the combined results indicate that even at as high concentrations of Si as 2.2 mM, the δ⁶⁰Ni values of the forming ferrihydrites does not change much. The results of our study implicate that Si may not be a major factor in fractionating stable Ni isotopes, which would make it easier to interpret future BIF record and reconstruct Archean ocean chemistry.     

A geochemical model for removal of iron(II)(aq) from mine water discharges

A steady state geochemical model has been developed to assist in understanding surface-catalysed oxidation of aqueous Fe(II) by O₂(aq), which occurs rapidly at circumneutral pH. The model has been applied to assess the possible abiotic removal of Fe(II)(aq) from alkaline ferruginous mine water discharges using engineered reactors with high specific-surface area filter media. The model includes solution and surface speciation equilibrium, oxidation kinetics of dissolved and adsorbed Fe(II) species and mass transfer of O₂(g). Limited field data for such treatment of a mine water discharge were available for model development and assessment of possible parameter values. Model results indicate that an adsorption capacity between 10⁻⁶ and 10⁻⁵ mol l⁻¹ is sufficient for complete removal, by oxidation, of the Fe(II)(aq) load at the discharge. This capacity corresponds approximately to that afforded by surface precipitation of Fe(III) oxide onto plastic trickling filter media typically used for biological treatment of wastewater. Extrapolated literature values for microbial oxidation of Fe(II)(aq) by neutrophilic microbial populations to the simulated reactor conditions suggested that the microbially-mediated rate may be several orders-of-magnitude slower than the surface-catalysed oxidation. Application of the model across a range of mine water discharge qualities shows that high Fe(II)(aq) loadings can be removed if the discharge is sufficiently alkaline. Additional reactor simulations indicate that reactor efficiency decreases dramatically with pH in the near acid region, coinciding with the adsorption edge for Fe²⁺ on Fe oxyhydroxide. Alkaline discharges thus buffer pH within the range where Fe(II)(aq) adsorbs onto the accreting Fe hydroxide mineral surface, and undergoes rapid catalytic oxidation. The results suggest that the proposed treatment technology may be appropriate for highly ferruginous alkaline discharges, typically associated with abandoned deep coal mines.     

Summary findings of the fourth international radiocarbon intercomparison (FIRI)(1998–2001)

Interlaboratory comparisons have been widely used in applied radiocarbon science. These are an important part of ongoing quality assurance (QA) programmes, which are vital to the appropriate interpretation of the evidence provided by the ¹⁴C record in Quaternary applications (including climate change and environmental reconstruction). International comparisons of laboratory performance are an essential component of the quality assurance process in radiocarbon dating. If the user community is to have confidence in radiocarbon results, it needs to be assured that laboratories world wide are producing measurements that are reliable and in accordance with ‘good practice’. The findings from the most recent (completed in 2001) and extensive (more than 90 participating laboratories) radiocarbon intercomparison (FIRI) are reported here. This study was designed (i) to assess comparability, or otherwise, of the results from different laboratories and (ii) to quantify the extent and possible causes of any interlaboratory variation. The results demonstrate that there are no significant differences amongst the main measurement techniques (gas proportional counting, liquid scintillation counting and accelerator mass spectrometry (AMS)) but there is evidence of small laboratory offsets relative to known age samples for some laboratories. There is also evidence in some cases of underestimation of measurement precision. Approximately 10% of all results were classified as extreme (outliers) and these results were generated by 14% of the laboratories. Overall, the evidence supports the fact that radiocarbon laboratories are generally accurate and precise but that, notwithstanding internal QA procedures, some problems still occur, which can best be detected by participation in independent intercomparisons such as FIRI, where the results allow individual laboratories to assess their performance and to take remedial measures where necessary. The results from FIRI are significant in that they show a broad measure of agreement between measurements made in different laboratories on a wide range of materials and they also demonstrate no statistically significant difference between measurements made by radiometric or AMS techniques. Copyright © 2002 John Wiley & Sons, Ltd.     

Refinement of the crystal structure of bonshtedtite, Na3Fe(PO4)(CO3)

The crystal structure of bonshtedtite, Na₃Fe(PO₄)(CO₃) (monoclinic, P2₁/m, a = 5.137(4), b = 6.644(4), c = 8.908(6) Å, β = 90.554(14)°, V = 304.0(4) ų, Z = 2) has been refined to R ₁ = 0.041 on the basis of 1314 unique reflections. The structure is similar to that of other minerals of the bradleyite group. It is based on the [Fe(PO₄)(CO₃)]^3? layers oriented parallel to (001). The layers are formed by corner-sharing PO₄ tetrahedra and FeO₄(CO₃) complexes, where FeO₆ tetrahedra and CO₃ triangles are edge-shared. The topology of the octa-tetrahedral layer in bonshtedtite is similar to that of the autunite-group minerals, but it differs from the latter in terms of local topological properties.