Single/multiple input-single output transfer function with noise models for constituents of iron ores of Northern Goa, India

Parametric time domain time series models for different chemical constituents such as SiO ₂,Fe ₂ O ₃,TiO ₂,MnO, and P ₂ O ₅ of iron ores belonging to banded hematite quartzites in Bicholim Mine (Goa) have been utilized for forecasting Fe ₂ O ₃ assay values through single/multiple input—single output (Fe ₂ O ₃ ) transfer function with noise methodology. Statistically significant correlated chemical constituent inputs (say, SiO ₂,TiO ₂,MnO, P ₂ O ₅ ) along lateral (horizontal strike direction) and vertical (perpendicular to bedding planes) sections in this mine are useful in modeling as well as forecasting assay values of blocks of ore to be exploited. Parameters of transfer function—noise models are estimated by utilizing time domain methodology, and the usefulness of these models for optimization of mining operations is discussed.     

The crystal structure of scotlandite,PbSO3

Summary The crystal structure of scotlandite —a=4.505(2),b=5.333(2),c=6.405(6) Å, =106.24(3)^o; space groupP2₁/m; cell content 2 {PbSO₃} — was determined from singlecrystal X-ray diffractometer data. Scotlandite is isotypic with molybdomenite, PbSeO₃. Lead is coordinated to nine oxygen atoms with Pb-O_av=2.75 Å, and possibly further to one sulphur atom with Pb–S=3.46 Å. The average S–O distance in the pyramidal SO₃ group is 1.52 Å. The structural relationships to cerussite, PbCO₃, are discussed.

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Die Kristallstruktur des Scotlandits, PbSO₃

Zusammenfassung Die Kristallstruktur des Scotlandits —a=4,505(2),b=5,333(2),c=6,405(6) Å, =106,24(3)^o; RaumgruppeP2₁/m; Zellinhalt 2 {PbSO₃} — wurde aus Einkristall-Röntgendiffraktometerdaten bestimmt. Scotlandit ist mit Molybdomenit, PbSeO₃, isotyp. Blei wird von neun Sauerstoffatomen mit Pb–O_av=2,75 Å und möglicherweise zusätzlich von einem Schwefelatom mit Pb–S=3,46 Å koordiniert. Der durchschnittliche S–O-Abstand in der pyramidalen SO₃-Gruppe mißt 1,52 Å. Die strukturellen Beziehungen zu Cerussit, PbCO₃, werden diskutiert.

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With 2 Figures     

Petrochemical and thermodynamic evidence on the origin of kimberlites

The petrochemistry of kimberlites from Yakutia and Lesotho has been studied using a silicate melt model with the SiO₂, CO₂ and H₂O derivatives as the main anions.A model has been developed, according to which the dissolution of H₂O in an ultramafic melt results in orthosilicates (H₂SiC ₄ ^-2 , H₃SiO ₄ ^– , H₄SiO₄ etc.) rather than metasilicates, while the dissolution of CO₂ produces additional hydrocarbonate complexes. It suggests that at high PCO ₂ ¹ , and where the orthosilicic calcium salt clusters are likely to be present in the magma, the kimberlite melt can break down into carbonate and silicate liquids. Therefore, the composition of kimberlite magma will be determined by the H₂O/CO₂ ratio under the relatively constant fluid pressure. This can be seen from the distinct fluidrs trend in the H₂O-CO₂-SiO₂ diagram for the Yakutia and Lesotho diamond-bearing kimberlites. The H₂O/CO₂ ratio changes with the liquidus temperature along this trend (Perchuk and Vaganov 1977) which suggests that liquid immiscibility predominates over the simple CO₂ solubility in the melts of kimberlite composition. The well-known Boyd's diagrams for the equilibrium PT-conditions in peridotites have been applied along with new experimental data to natural Cpx and Opx, and the PT-parameters were correlated for peridotite inclusions in kimberlite pipes in Yakutia and Lesotho. The liquidus temperatures for the extrapolated area of these correlations gave depths (pressures) at which kimberlite magmas are formed (200–250 km).The hypothesis on SiO₂ partitioning between the melt and the fluid was used to calculate the composition of dry initial kimberlite which characterised the average mantle composition: SiO₂ — 45.12; TiO₂ — 2.49; Al₂O₃ — 3.58; Cr₂O₃ — 0.12; FeO — 9.32; MnO — 0.16; CoO — 0.11; MgO — 23.47; CaO — 13.44; Na₂O — 0.20; K₂O — 1.12; P₂O₅ — 0.69; S — 0.18; sum — 100 wt.%. This kimberlite is close to wehrlite in composition.     

Glassy orthopyroxene granodiorites of the Pannonian Basin: tracers of ultra-high-temperature deep-crustal anatexis triggered by Tertiary basaltic volcanism

Glassy orthopyroxene granodiorite-tonalite (named pincinite after type locality) was described from basaltic lapilli tuffs of the Pliocene maar near Pinciná village in the Slovakian part of the Pannonian Basin. Two pincinite types exhibit a qualitatively similar mineral composition (quartz, An_20–55 plagioclase, intergranular silicic glass with orthopyroxene and ilmenite, ±K-feldspar), but strongly different redox potential and formation PT conditions. Peraluminous pincinite is reduced (6–7% of total iron as Fe³⁺ in corundum-normative intergranular dacitic glass) and contains ilmenite with 8–10 mol% Fe₂O₃ and orthopyroxene dominated by ferrosilite. High-density (up to 0.85 g/cm³) primary CO₂ inclusions with minor H₂, CH₄, H₂S, CO and N₂ (<2 mol% total) are present in Qtz and Plg. Equilibrium PT conditions inferred from the intergranular Opx–Ilm–Glass assemblage and fluid density correspond to 1,170±50°C, 5.6±0.4 kbar, respectively. Metaluminous pincinite is more oxidised (25–27% of total iron as Fe³⁺ in diopside-normative intergranular glass of rhyolite–trachyte–dacite composition) and contains Fe₂O₃-rich ilmenite (17–29 mol%) associated with enstatite. Fluid inclusions are composed of CO₂–H₂O mixtures with up to 38 mol% H₂O. Raman spectroscopy revealed H₂S along with dominant CO₂ in the carbonic phase. Equilibrium PT parameters for the intergranular Opx–Ilm–Glass assemblage correspond to 740±15°C, 2.8±0.1 kbar, respectively. Reducing gas species (<2 mol% total) in the CO₂-inclusions of the peraluminous pincinite resulted from hydrogen diffusion due to fH₂ gradient imposed during decrease of redox potential from the log fO₂ values near QFM during Qtz + Plg growth, to QFM-2 incidental to the superimposed Opx + Ilm assemblage in the intergranular melt. The decrease in oxygen fugacity was recorded also in the metaluminous pincinite, where log fO₂ values changed from ~QFM + 2.6 to QFM + 0.4, but hydrogen diffusion did not occur. Absence of OH-bearing minerals, major and trace element abundances (e.g. REE 300–320, Nb 55–57, Th 4–31, Zr 240–300 ppm, FeO_tot/MgO up to 11), and Sr–O isotope ratios in the pincinites are diagnostic of high-temperature anorogenic magmas originated by dehydration melting of biotite in quartz-feldspathoid crust (⁸⁷Sr/⁸⁶Sr>0.705–0.706, ¹⁸O>9 V-SMOW) around alkali basalt reservoir in depths between 17 and 20 km, and around late stage derivatives of the basalt fractionation, intruding the crust up to depths of 10–11 km. Low water activity in the pincinite parental melt was caused by CO₂-flux from the Tertiary basaltic reservoirs and intrusions. The anatexis leads to generation of a melt-depleted granulitic crust beneath the Pannonian Basin, and the pincinites are interpreted as equivalents of igneous charnockites and enderbites quenched at temperatures above solidus and unaffected by sub-solidus re-equilibration and metamorphic overprint.     

1Tc-Strontiohilgardit (Ca,Sr)2[B5O8(OH)2Cl] und seine Stellung in der Hilgarditgruppe X2/II[B5O8(OH)2Cl]

Zusammenfassung 1Tc-Strontiohilgardit (Ca, Sr)₂ [B₅O₈(OH)₂,Cl] mit Ca : Sr etwa 1 : 1 ist ein neues Mineral der Hilgarditgruppe. Fundpunkt: Reyersbausen (9° 59,7 E, 51° 36,6 N), Grube Königshall-Hindenburg, Flöz Staßfurt in sylvinitischer Ausbildung.Konstanten : triklin-pedial,a ₀=6,38 Å,b ₀=6,480 Å,c ₀=6,608 Å, =75,4°,=61,2°, =60,5°; tafelige-gestreckte Links- und Re chtskristalle, farblos, wasserunlöslich, piezoelektrisch. Härte 5–7, Dichte 2,99 g cm^–3;n =1,638,n =1,639,n =1,670; 2V =19°.Neue Daten für die Hilgarditgruppe : 2 M (Cc)-Calciumhilgardit (=Hilgardit) =4 Ca₂[B₅O₃(OH)₂Cl], Raumgruppe Cc.3Tc-Calciumhilgardit (=Parahilgardit) = 3 Ca₂[B₅O₃(OH)₂Cl]; trinklin-pedial, ₀=6,31 Å,b =6,484 Å,c ₀=17,50 Å; =84,0°,=79,6°, =60,9°.Die Polymorphiebeziehungen sind geometrisch deutbar durch eine spezielle Art der Polytropie (Stapelung von Links- und Rechtskristallen im Elementarbereich).     

Equation of state,structural behaviour and phase diagram of synthetic MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript>, as a function of pressure and temperature

The behaviour of synthetic Mg-ferrite (MgFe₂O₄) has been investigated at high pressure (in situ high-pressure synchrotron radiation powder diffraction at ESRF) and at high temperature (in situ high-temperature X-ray powder diffraction) conditions. The elastic properties determined by the third-order Birch–Murnaghan equation of state result in K₀=181.5(± 1.3) GPa, K=6.32(± 0.14) and K= –0.0638 GPa^–1. The symmetry-independent coordinate of oxygen does not show significant sensitivity to pressure, and the structure shrinking is mainly attributable to the shortening of the cell edge (homogeneous strain). The lattice parameter thermal expansion is described by _a0+_a1*(T–298)+_a2/(T–298)², where _a0=9.1(1) 10^–6 K^–1, _a1=4.9(2) 10^–9 K^–2 and _a2= 5.1(5) 10^–2 K. The high-temperature cation-ordering reaction which MgFe-spinel undergoes has been interpreted by the ONeill model, whose parameters are = 22.2(± 1.8) kJ mol^–1 and =–17.6(± 1.2) kJ mol^–1. The elastic and thermal properties measured have then been used to model the phase diagram of MgFe₂O₄, which shows that the high-pressure transition from spinel to orthorombic CaMn₂O₄-like structure at T < 1700 K is preceded by a decomposition into MgO and Fe₂O₃.     

The crystal structure of sarcolite

Summary The crystal structure of sarcolite from Monte Somma (Vesuvius), Na(Na, K, Fe, Mg)<1 Ca₆[Al₄Si₆O₂₃](OH, H₂O)<2 [(Si,P)O₄]_0.5[(CO₃, Cl)]_0.5, space groupI4/m witha=12,343(5)Å,c=15,463(5)Å andZ=4, has been determined from X-ray data collected on an automatic diffractometer. The 1637 independent reflections withI>2 (I) converged to a conventionalR value of 0.054 with partially anisotropic factors.The tetrahedral framework in sarcolite has a sharing coefficient of 1.85. Mean Si–O and Al–O distances are 1.616 and 1.763 Å, respectively. Isolated (Si, P)O₄, CO₃, OH, H₂O and Cl species occupy cavities in the tetrahedral framework in a partially disordered way. The two crystallographically different Ca atoms coordinate respectively with 5 and 6 framework oxygens; further contacts occur with available anions. Ca–O distances range from 2.34 to 2.69 Å. Na atoms coordinate with 4 oxygens of the tetrahedral frame and one from the CO₃ groups.A structure analysis of a sarcolite crystal baked out at 1100°C confirmed some structural details involving atoms occupying cavities in the tetrahedral framework.

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Die Kristallstruktur des Sarkoliths

Zusammenfassung Die Kristallstruktur des Sarkoliths vom Monte Somma (Vesuv), Na(Na, K, Fe, Mg)<1 Ca₆[Al₄Si₆O₂₃](OH, H₂O)<2[(Si, P)O₄]_0,5[(CO₃, Cl)]_0,5, RaumgruppeI4/m,a ₀=12,343(5)Å,c ₀=15,463(5)Å,Z=4, wurde aus Röntgendaten, die auf einem automatischen Diffraktometer gesammelt worden waren, bestimmt. Der konventionelleR-Wert für 1637 kristallographisch unabhängige Reflexe mitI>2 (I) konvergierte mit partiell anisotropen Temperaturfaktoren auf 0.054.Der Verknüpfungskoeffizient des Tetraedergerüstes in Sarkolith ist 1,85. Die mittleren Si–O-bzw. Al–O-Abstände sind 1,616Å und 1,763 Å. Isolierte Strukturbestandteile (Si, P)O₄, CO₃, OH, H₂O und Cl besetzen zum Teil ungeordnet die Hohlräume des Tetraedergerüstes. Die beiden kristallographisch verschiedenen Ca-Atome werden von funf bzw. sechs Sauerstoffen des Gerüstes koordiniert, weitere Kontakte bestehen zu verfügbaren Anionen. Die Ca–O-Abstände variieren von 2,34 bis 2,69 Å. Die Na–Atome sind von vier Sauerstoffen des Tetraedergerüstes und von einem weiteren der CO₃-Gruppen koordiniert. Die Strukturanalyse eines bei 1100°C getemperten Sarkolithkristalls bestätigte einige Details über die Atome, welche die Hohlräume des Tetraedergerüstes besetzen.

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With 4 Figures     

Heat capacities and entropies of silicate liquids and glasses

The heat capacities of several dozen silicate glasses and liquids composed of SiO₂, TiO₂, Al₂O₃, Fe₂O₃, FeO, MgO, CaO, BaO, Li₂O, Na₂O, K₂O, and Rb₂O have been measured by differential scanning and drop calorimetry. These results have been combined with data from the literature to fit C _pas a function of composition. A model assuming ideal mixing (linear combination) of partial molar heat capacities of oxide components (each of which is independent of composition), reproduces the glass data within error. The assumption of constancy of ¯C _p,iis less accurate for the liquids, but data are not sufficient to adequately constrain a more complex model. For liquids containing alkali metal and alkaline earth oxides, heat capacities are systematically greater in liquids with high field strength network modifying cations. Entropies of fusion (per g-atom) and changes of configurational entropy with temperature, are similarly affected by composition. Both smaller cation size and greater charge are therefore inferred to lead to greater development of new structural configurations with increasing temperature in silicate liquids.     

Hydrometallurgical processing and recovery of molybdenum trioxide from spent catalyst

Hydrometallurgical processing of spent hydrodesulphurisation (HDS) catalyst for the recovery of molybdenum using sodium carbonate and hydrogen peroxide mixtures was investigated. The results indicated that the recovery of molybdenum was largely dependent on the concentrations of Na₂CO₃ and H₂O₂ in the reaction medium, which controls the acidity of the leach liquor and carry over of impurities such as Al, Ni, P, Si and V. Leaching process was exothermic and leaching efficiency of molybdenum decreased with increasing solid to liquid ratio. Large scale leaching of spent catalyst, under optimum conditions: 20% pulp density, 85 g/L Na₂CO₃, 10 vol.% H₂O₂ and 1 h reaction, resulted a leaching efficiency of 84% Mo. The obtained leach liquor contained (g/L): Mo — 22.0, Ni — 0.015 and Al — 0.82, P — 1.1, Si — 0.094 and minor quantities of V — 8 mg/L, As and Co — < 1 mg/L. Recovery of Mo from leach solution as MoO₃ of 97.30% purity was achieved by ammonium molybdate precipitation method.     

The upper stability limit of the assemblage paragonite + quartz and its natural occurrences

The assemblage paragonite + quartz is encountered frequently in low- to medium-grade metamorphic rocks. With rising grade of metamorphism they react mutually to yield the condensed assemblage albite + Al₂SiO₅.The univariant curve pertaining to the equilibrium paragonite + quartz=albite + andalusite + H₂O has been located experimentally. The reversed P _{H 2 O}-T data are: 1 kb: 470–490° C 2 kb: 510–530° C 3 kb: 540–560° C 4 kb: 560–580° C 5 kb: 590–600° C The univariant curve pertaining to the equilibrium paragonite + quartz=albite + kyanite + H₂O runs through the following P _{H 2 O}-T-intervals: 5 kb: 570–625° C 6 kb: 600–630° C 7 kb: 620–640° C Thermodynamic calculations of S ₂₉₈ ⁰ , H _f,298 ⁰ and G _f,298 ⁰ of the phase paragonite from the experimental data presented above and those obtained from the equilibria of the reaction paragonite=albite + corundum + H₂O (Chatterjee, 1970), agree within the limits of uncertainty. This prompts the idea that Zen's (1969) suggestion of a possible error of approximately 7 kcal in G _f,298 ⁰ of the Al₂SiO₅ polymorphs may in fact be due to an error of similar magnitude in G _f,298 ⁰ of corundum.A best estimate of S ₂₉₈ ⁰ , H _f,298 ⁰ and G _f,298 ⁰ of paragonite based on these considerations yield: S ₂₉₈ ⁰ : 67.61±3.9 cal deg^–1 gfw^–1 H _f,298 ⁰ : –1411.4±2.7 kcal gfw^–1 G _f,298 ⁰ : –1320.9±4.0 kcal gfw^–1 These numbers will be subject to change when better thermochemical data on corundum and albite are available.In medium-grade metamorphic rocks the assemblage paragonite + quartz is commonly found in stable coexistence with such other phases as muscovite, staurolite, andalusite, kyanite, but not with cordierite or sillimanite. However, the assemblage paragonite-sillimanite has been reported to be stable in the absence of quartz. All these petrologic observations can be explained on the basis of the stability data of the phases and phase assemblages concerned.     

Refinement of the crystal structure of papagoite,CaCuAlSi2O6(OH)3

Summary The crystal structure of papagoite, CaCuAlSi₂O₆(OH)₃, monoclinic,a = 2.926 (3),b = 11.496 (3),c = 4.696 (1) Å, = 100.81 (2)°, V = 685.4 (3) ų, space groupC 2/m,Z = 4, has been refined to anR index of 3.4% for 913 observed reflections measured with MoK X-radiation. The single unique Cu cation is surrounded by six anions in a pseudo-octahedral arrangement showing strong Jahn-Teller distortion. Edge-sharing rutile-like chains of pseudo-octahedrally coordinated Cu and Al extend in the Y direction, and are cross-linked into an octahedral sheet by Ca₂Ø₁₀ (O = unspecified ligand, O or OH) dimers. These sheets are linked by (Si₄O₁₂) rings to form a mixed tetrahedral-octahedral framework.

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Verfeinerung der Kristallstruktur von Papagoit, CaCuAlSi₂O₆(OH)₃

Zusammenfassung Die Kristallstruktur von Papagoit, CaCuAlSi₂O₆(OH)₃, monoklina = 12,926 (3),b = 11.496 (3),c = 4.696 (1) Å, = 100.81 (2)°,V = 685.4 (3) ų, RaumgruppeC2/m,Z = 4, wurde für 913 beobachtete, MoK-Röntgenstrahlung gemessene Reflexe aufR = 3,4% verfeinert. Das eine symmetrieunabhängige Kupfer-Kation ist pseudooktaedrisch von sechs Anionen mit einer starken Jahn-Teller-Verzerrung umgeben. Die pseudo-oktaedrisch koordinierten Cu- und Al-Atome werden über Kanten zu parallel zur y-Achse verlaufenden rutil-ähnlichen Ketten verbunden, die zusammen mit den Ca₂Ø₁₀-Gruppen (Ø = nicht spezifsierter Ligand, O bzw. OH) Oktaederschichten bilden. Diese Schichten werden durch (Si₄O₁₂)-Ringe zu einem aus Tetraedern und Oktaedern bestehenden Netzwerk verknüpft.

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With 4 Figures     

Crystallization of apatite in natural magmas under high pressure,hydrous conditions,with particular reference to ‘Orogenic’ rock series

Two separate series of hydrous experiments involving (1) imposing apatite saturation on a series of igneous rock compositions from basanite to rhyolite, and (2) crystallizing similar natural rock compositions progressively until apatite appears, demonstrate a close dependence between apatite saturation and silica content of the magma, and determine P₂O₅ levels at a given silica value and temperature at which that composition may be expected to crystallize apatite. The effect of pressure on apatite solubility is not great, and is most significant for silicic compositions.P₂O₅ vs SiO₂ relationships of the low-K island arc suite, calcalkaline suite and high-K calc-alkaline suite, appear regular and characteristic for each suite, and when linked with the experimental work on apatite solubility, indicate the following: (1) the low-K and calc-alkaline series have low P₂O₅ contents (0.1–0.2 wt.%) and relatively flat P₂O₅-SiO₂ patterns; they do not show evidence of reaching apatite saturation until rhyodacite-rhyolite compositions are obtained for the low-K suite, and andesite-dacite compositions for the calc-alkaline suite; (2) the high-K calc-alkaline series has higher P₂O₅ contents (0.4–0.6 wt.%) in mafic compositions, and achieves apatite saturation over a wide compositional range for the series; (3) the calc-alkaline and high-K calc-alkaline series are probably lower temperature, and more hydrous than the low-K series; (4) anomalous P₂O₅-SiO₂ distributions may indicate non-equilibrium crystallization of apatite, magma-mixing and crystal accumulation processes active in generation of the orogenic volcanic series.     

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     

The use of tourmaline in geochemical prospecting for gold and copper mineralization

Chemical composition, unit cell parameters, and trace elements of tourmalines from Mesozoic gold-quartz-sulphide and gold-bearing copper-porphyry ore-magmatic systems of the Trans-Baikal area and Mongolia show that they belong to the specific schorl-dravite highly ferruginous oxytourmaline series. They are low in alumina (Al₂O₃ = 16–33%) and have MgO contents (up to 10%) and Fe₂O₃ (1%). There is a direct correlation of unit cell parameters (a,c,V) with total iron, which permits composition estimates from X-ray diffraction analyses. As a rule, these tourmalines contain high concentrations of Au, Pb and Cu, which are mainly hosted by inclusions of native gold and ore minerals. The highest As abundances are contained in the tourmalines of the copper-porphyry field.Two trends of isomorphic replacement are related to increasing Fe content of oxyferruginous tourmalines:(1) “Acid leaching” trend (less ferruginous part of the series) Mg + Fe²⁺ + 4Al + 40 4Fe³⁺ + 2 + 4(OH,F); and (2) “conjugate deposition” trend Mg + 1.5Fe²⁺ + 1.5Al + 4(OH,F) 4Fe³⁺ + 4O.These features distinguish tourmalines from gold-bearing systems from schorl-dravites of tin and rare-metal deposits. They may be used in metallogenic analyses, interpretation of the origin of primary and secondary anomalies, and assessment of the type and zonation of ore fields.     

Refinement of the crystal structure of wöhlerite

Summary The crystal structure of wöhlerite (monoclinicP2₁,a=10.823(3,b=10.244(3),c=7.290(2) Å, =109.00(4)^o) was refined using 2343 independent diffractions toR ₁=0.019 andR ₂=0.025.The refinement confirms the main features of the structure model proposed byShibayeva andBelov (1962), namely the walls of large cation polyhedra interconnected as in cuspidine, with Si₂O₇ groups linked to the polyhedra. At difference from the structure proposed by the quoted authors, both the Si₂O₇ groups are clinging to edges of calcium polyhedra.The cation distribution in the polyhedral walls and the location of fluorine anions are clarified and discussed, resulting in the following crystal chemical formula Na₄(Ca_7.48Mn_0.20Fe_0.32)Zr₂(Nb_1.6Ti_0.4) (Si₂O₇)₄O₄F₂(O_1.6F_0.4).

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Verfeinerung der Kristallstruktur des Wöhlerits

Zusammenfassung Die Kristallstruktur des Wöhlerits (monoklinP2₁,a ₀=10,823(3),b ₀=10,244(3),c ₀=7,290(2) Å, =109,00(4)^o) wurde mit 2343 unabhängigen Reflexen aufR ₁=0,019 undR ₂=0,025 verfeinert.Die Verfeinerung bestätigt im wesentlichen Züge des vonShibayeva undBelov (1962) vorgeschlagenen Strukturmodells, nämlich Bänder aus den Polyedern um die großen Kationen, die — wie im Cuspidin — durch an den Polyedern hängenden Si₂O₇-Gruppen verknüpft sind.Die Kationenverteilung in den Polyederbändern und die Lokalisation der Fluor-Anionen wurden aufgeklärt und werden diskutiert; es ergibt sich folgende kristallchemische Formel Na₄(Ca_7,48 Mn_0,20Fe_0,32)(Zr₂(Nb_1,6 Ti_0,4) (Si₂O₇)₄O₄F₂(O_1,6F_0,4).

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With 3 Figures     

Calcite dissolution kinetics in saline waters

The effect of ionic strength (I), pCO₂, and temperature on the dissolution rate of calcite was investigated in magnesium-free, phosphate-free, low calcium (m_Ca2+ ≈ 0.01 m) simple KCl and NaCl solutions over the undersaturation range of 0.4 ≤ Ω_calcite ≤ 0.8. First-order kinetics were found sufficient to describe the rate data where the rate constant (k) is dependent on the solution composition. Rates decreased with increasing I and were faster in KCl than NaCl solutions at the same I indicating that Na⁺ interacts more strongly with the calcite surface than K⁺ or that water is less available in NaCl solutions. Rates increased with increasing pCO₂ and temperature, and their influences diminished at high I. Arrhenius plots yielded a relatively high activation energy (E_a ≈ 20 ± 2 kJ mol^− 1) which indicated that dissolution was dominated by surface-controlled processes. The multiple regression model (MR) of Gledhill and Morse (2006a) was found to adequately describe the results at high I in NaCl solutions, but caution must be used when extrapolating to low I or pCO₂ values. These results are consistent with the hypothesis that the mole fraction of “free” solvent (X_{“free”H2O}) plays a significant role in the dissolution kinetics of calcite with a minimum value of  45–55% required for dissolution to proceed in undersaturated solutions at 25–55 °C and pCO₂ = 0.1–1 atm. This hypothesis has been incorporated into a modified version of the MR model of Gledhill and Morse (2006a) where X_{“free”H2O} has replaced I and the Ca²⁺ and Mg²⁺ terms have been dropped:

     

Metamorphic evolution of the Maud Belt: P–T–t path for high-grade gneisses in Gjelsvikfjella, Dronning Maud Land, East Antarctica

A metamorphic petrological study, in conjunction with recent precise geochronometric data, revealed a complex P–T–t path for high-grade gneisses in a hitherto poorly understood sector of the Mesoproterozoic Maud Belt in East Antarctica. The Maud Belt is an extensive high-grade, polydeformed, metamorphic belt, which records two significant tectono-thermal episodes, once towards the end of the Mesoproterozoic and again towards the late Neoproterozoic/Cambrian. In contrast to previous models, most of the metamorphic mineral assemblages are related to a Pan-African tectono-thermal overprint, with only very few relics of late Mesoproterozoic granulite-facies mineral assemblages (M₁) left in strain-protected domains. Petrological and mineral chemical evidence indicates a clockwise P–T–t path for the Pan-African orogeny. Peak metamorphic (M_2b) conditions recorded by most rocks in the area (T = 709–785 °C and P = 7.0–9.5 kbar) during the Pan-African orogeny were attained subsequent to decompression from probably eclogite-facies metamorphic conditions (M_2a).The new data acquired in this study, together with recent geochronological and geochemical data, permit the development of a geodynamic model for the Maud Belt that involves volcanic arc formation during the late Mesoproterozoic followed by extension at 1100 Ma and subsequent high-grade tectono-thermal reworking once during continent–continent collision at the end of the Mesoproterozoic (M₁; 1090–1030 Ma) and again during the Pan-African orogeny (M_2a, M_2b) between 565 and 530 Ma. Post-peak metamorphic K-metasomatism under amphibolite-facies conditions (M_2c) followed and is ascribed to post-orogenic bimodal magmatism between 500 and 480 Ma.     

Critical state behaviour of weakly bonded soil in drained state

A series of consolidated drained triaxial test was performed on weakly bonded soils that were artificially prepared by mixing sand (87%) and kaolin (13%). To create weakly bond strength, samples were fired at 500°C for 5 h. A critical state (CS) concept was used to interpret the results in order to describe the behaviour of the studied soil. Defining the CS is not always straightforward. Several tests showed changing in deviator stress q and volumetric strain ε_v up to the end of tests. Hence, defining the CS requires careful assessments on q–ε_a, Δu–ε_a, q–p′ and v–ln p′ spaces which were performed. A ‘discontinuity’ approach was applied to position the CS on dilatant path in v–ln p′ spaces after considering stress-strain and volumetric strain curves. The critical state line in a v–ln p? space from bonded samples exhibited differences to the destructured samples. This suggests that the influence of cementation bond is substantially clear at lower stresses but as stresses increase beyond the stress yield, cementation degradation becomes more significant. The effect of bonding can be clearly visualised from the normalisation of the stress paths of destructured and bonded samples.     

Voluminous granitic magmas from common basaltic sources

Granitic—rhyolitic liquids were produced experimentally from moderately hydrous (1.7–2.3 wt% H₂O) medium-to-high K basaltic compositions at 700 MPa and fO₂ controlled from Ni-NiO –1.3 to +4. Amount and composition of evolved liquids and coexisting mineral assemblages vary with fO₂ and temperature, with melt being more evolved at higher fO₂s, where coexisting mineral assemblages are more plagioclase- and Fe–Ti oxide-rich and amphibole-poor. At fO₂ of Ni–NiO +1, typical for many silicic magmas, the samples produce 12–25 wt% granitic–rhyolitic liquid, amounts varying with bulk composition. Medium-to-high K basalts are common in subduction-related magmatic arcs, and near-solidus true granite or rhyolite liquids can form widely, and in geologically significant quantities, by advanced crystallization–differentiation or by low-degree partial remelting of mantle-derived basaltic sources. Previously differentiated or weathered materials may be involved in generating specific felsic magmas, but are not required for such magmas to be voluminous or to have the K-rich granitic compositions typical of the upper continental crust.     

Amphibole-plagioclase equilibria: An empirical model for the relation albite+tremolite=edenite+4 quartz

Equilibria between plagioclase, calcic amphibole and quartz can be described, in part, by the relation among mineral components: NaAlSi₃O₈+Ca₂Mg₅Si₈O₂₂(OH)₂ = NaCa₂Mg₅AlSi₇O₂₂(OH)₂+4SiO₂; this relation governs the partitioning of Na between plagioclase and the A-site of coexisting amphibole. Data from natural amphibolites reveal that this partitioning is systematic and sensitive to metamorphic grade. The ideal portion of the equilibrium constant (K _id = X _{Na, A}/X_{, A} · X _Ab) derived from natural samples is sensitive to bulk composition, inasmuch as both plagioclase and amphibole are highly non-ideal. Samples from a single outcrop have values ranging from 0.5 (X _Ab=0.74) to 4.1 (X _Ab=0.10). The continuous reaction, NaAlSi₃O₈+Ca₂Mg₅Si₈O₂₂(OH)₂ = NaCa₂Mg₅AlSi₇O₂₂(OH)₂+4SiO₂, proceeds to the right with increasing grade of metamorphism and for a given bulk composition, K _id increases with increasing temperature. Two related discontinuous reactions, actinolite+albite=hornblende+oligoclase+quartz and actinolite+oligoclase=hornblende+anorthite+quartz, also proceed to the right with increasing metamorphic grade and result in changes in the topology of a phase diagram that describes the partitioning of Na between plagioclase and amphibole A-site. A Schreinemakers' net is presented that is consistent with natural occurrences. The results of this study should aid in the delineation of metamorphic facies within amphibolites.