Field setting,mineralogy, chemistry,and genesis of arc picrites,New Georgia,Solomon Islands

The field setting, petrography, mineralogy, and geochemistry of a suite of picrite basalts and related magnesian olivine tholeiites (New Georgia arc picrites) from the New Georgia Volcanics, Kolo caldera in the active ensimatic Solomon Islands arc are presented. These lavas, with an areal extent in the order of 100² km and almost 1 km thick in places, are located close to the intersection of the Woodlark spreading zone with the Pacific plate margin. They contain abundant olivine (Fo_94-75) and diopside (Cr₂O₃ 1.1-0.4%, Al₂O₃ 1–3%), and spinels characterised by a large range in Cr/(Cr+Al) (0.85–0.46) and Mg/(Mg+ Fe⁺⁺) (0.65–0.1). The spinels are Fe⁺⁺⁺ rich, with Fe⁺⁺⁺/ (Fe⁺⁺⁺+Cr+Al) varying from 0.06 to 1.0. A discrete group of spinels with the highest Cr/(Cr+Al) (0.83–0.86) and lowest Fe⁺⁺⁺ contents are included in the most Mg-rich olivine (Fo_91–94) and both may be xenocrystal in origin.The lavas, which range between 10–28% MgO, define linear trends on oxide (element) — MgO diagrams and these trends are interpreted as olivine (0.9) clinopyroxene (0.1) control lines. For the reconstructed parent magma composition of these arc picrites, ratios involving CaO, Al₂O₃, TiO₂, Zr, V and Sc are very close to chondritic. REE patterns are slightly LREE — enriched ((La/Sm)^N 1.3–1.43) and HREE are flat. All lavas show marked enrichments in K, Rb, Sr, Ba, and LREE relative to MORB with similar MgO contents, but the TiO₂ content of the proposed parent magma is close to those of postulated primary MORB liquids. It is proposed that the arc parent magma was produced by partial melting of sub-oceanic upper mantle induced by the introduction of LILE — enriched hydrous fluids derived by dehydration and/or partial melting of subducted ocean crust and possibly minor sediments.     

The Nature and Origin of Ultramafic Lamprophyres: Aln?ites and Allied Rocks

Ultramafic lamprophyres (UML) are rare but widespread, hypabyssalrocks, rich in K, Mg, Cr, Ni, Sr, Ba, REE, and volatiles, containingless Si and more Ca than other silicate igneous rocks, and gradinginto carbonatites. They carry phenocryst combinations of olivine(Fo_92–72), phlogopite (rich in Ti, Fe³⁺ , Ba or F), Al-Ti-(Fe³⁺and richteritic to eckermannitic amphiboles. Groundmasses includeCa-Fe-Mg-carbonates (?partly primary), feldspathoids, Ca-Fe-Ti-Zr-garnets,soda-melilite, monti cellite, Mg-Mn-ilmenite, perovskite, serpentine,Fe- Mg-Ti-Mn-Cr-Al-spinels ? glass. Megacrysts include (?cognate)salitic pyroxenes, phiogopites or Ti-hastingsites, and morerarely, xenocrystic Cr-Ti-pyrope, orthopyroxenes and diopsides.Xenoliths include spinel and/or garnet-lherzolites, dunites,and phlogopite?amphibole-bearing pendotites. UML are readilydistinguished from kimberlites by petrological association (e.g.with ijolites), geochemistry (e.g. lower Mg, higher Ca, P),texture (e.g. lack of two olivine generations) and mineralogy(e.g. presence of groundmass feldspathoids ? melilite). UMLare distinguished also from melilitites by lower Si, Al, Na,higher Ca, K, P; more abundant primary carbonate, phiogopiteand amphibole; and by lack of groundmass olivine and phenocrystmelilite. Closer extrusive equivalents of UML may however occuramong ankaratrites. The most common UML types are aln?ite (melilite-rich)and aillikite (melilite-free, carbonate-rich). Aillikites arecompositionally closer to carbonatites than alnOites. Rarertypes include poizenite (melilite + feldspathoids), ouachitite(feldspathoids + carbonates) and damkjernite (feldspathoids+ carbonates+ < 10 per cent alkali feldspars). UML form localizeddyke-swarms or diatreme-clusters, mainly related to continentalrifting, and may represent parent magmas for coeval carbonatitecomplexes. Their additional occurrence in an oceanic setting,their mantle xenolith content, and their high mg, Cr and Ni,together suggest that many of them are primary, mantle-derivedmagmas, generated at depths between those of melilitites andkimberlites (c. 100–150 km), but at higher CO₂ pressuresthan melilitites. Other UML, however, have been extensivelymodified from primary compositions by fractionation, accumulation,or interaction with alkali+volatile-rich fluids.     

Mineralogy,petrology, and phase relations of glaucophane-lawsonite zone blueschists from the Tavşanli Region,Northwest Turkey

Glaucophane-lawsonite facies blueschists representing a metamorphosed sequence of basic igneous rocks, cherts and shales have been investigated northeast of the district of Tav?anli in Northwest Turkey. Sodic amphiboles are rich in magnesium reflecting the generally high oxidation states of the blueschists. Lawsonite has a very uniform composition with up to 2.5 wt.% Fe₂O₃. Sodic pyroxenes show an extensive range of compositions with all the end-members represented. Chlorites are uniform in their Al/(Al+Fe+Mg) ratio but show variable Fe/ (Fe+Mg) ratios. Garnets from metacherts are rich in spessartine (>50%) whereas those from metabasites are largely almandine. Pistacite rich epidote is found in metacherts coexisting with lawsonite. Phengites are distinctly higher in their Fe, Mg and Si contents than those from greenschist facies. Hematites with low TiO₂ are ubiquitous in metacherts. Fe²⁺/Mg partitioning between chlorite and sodic amphibole is strongly controlled by the calcium content of the sodic amphibole and ranges from 1.1 for low calcium substitution to 0.8 for higher calcium substitution. The Al/Fe³⁺ partition coefficient between sodic amphibole and sodic pyroxene is 2.1. A model system has been constructed involving projections from lawsonite, iron-oxide and quartz onto a tetrahedron with Na, Al, Fe²⁺ and Mg at its apices. Calcite is treated as an indifferent phase. The model system illustrates the incompatibility of the sodic pyroxene with chlorite in the glaucophanelawsonite facies; this assemblage is represented by sodic amphibole. Sodic amphibole compositions are plotted in terms of coexisting ferromagnesian minerals. Five major areas on the sodic amphibole compositional field are delineated, each associated with one of the following minerals: chlorite, stilpnomelane, talc, almandine, deerite.     

Petrogenesis of extension-related alkaline volcanism in Karaburhan (Sivrihisar–Eskisehir), NW Anatolia, Turkey

Alkaline lavas were erupted as phonolites and trachytes around Karaburhan (Sivrihisar–Eskisehir, NW Anatolia) within the Izmir–Ankara–Erzincan suture zone. These volcanic rocks were emplaced as domes, close and parallel to the ophiolite thrust line. According to ⁴⁰Ar/³⁹Ar geochronological analyses of sanidine crystals from the phonolites, the age of the alkaline volcanics is 25 Ma (Late Oligocene–Early Miocene).The flow-textured phonolites are porphyritic and consist mainly of sanidine, clinopyroxene, and feldspathoid crystals. The clinopyroxenes show compositional zoning, with aegirine (Na_0.82–0.96Fe⁺³_0.68–0.83) rims and aegirine–augite cores (containing calcium, magnesium, and Fe⁺²). Some aegirine–augites are replaced with sodium-, calcium-, and magnesium-rich amphibole (hastingsite). Feldspathoid (hauyne) crystals enriched with elemental Na and Ca have been almost completely altered to zeolite and carbonate minerals. The fine-grained trachytes with a trachytic texture consist of feldspar (oligoclase and sanidine) phenocrystals and clinopyroxene microphenocrystals within a groundmass made up largely of alkali feldspar microlites.Although there are some differences in their element patterns, the phonolites and trachytes exhibit enrichment in LILEs (Sr, K, Rb, Ba, Th) and LREEs (La, Ce, Pr, Nd) and negative anomalies in Nb and Ta. These geochemical characteristics indicate a lithospheric mantle enriched by fluids extracted from the subduction component. In addition, the high ⁸⁷Sr/⁸⁶Sr (0.706358–0.708052) and low ¹⁴³Nd/¹⁴⁴Nd (0.512546–0.512646) isotope concentrations of the alkaline lavas reflect a mantle source that has undergone metasomatism by subduction-derived fluids. Petrogenetic modeling indicates that the alkaline lavas generated from the subduction-modified lithospheric mantle have undergone assimilation, fractional crystallization, and crustal contamination, acquiring high Pb, Ba, Rb, and Sr contents and Pb isotopic compositions during their ascent through the thickened crust in an extensional setting.     

Some petrological aspects of the Prairie Creek diamond-bearing kimberlite diatreme,Arkansas

Based on modal and chemical composition, the rocks of the Prairie Creek diatreme situated 4 km SSE of Murfreesboro, Pike County, Arkansas, are classified as micaceous kimberlite. The K-Ar isotopic analysis of phlogopite from this diatreme yielded an age of 106 ± 3 m.y. (Albian) which is in agreement with stratigraphic relations. Electron beam probe data on minerals from kimberlite breccia, one of the three textural types, are presented. The breccia is considered as the potential source of the diamonds that have been mined at the diatreme. It contains phenocrysts of olivine (Fo_90–92) and serpentine pseudomorphs after olivine embedded in a groundmass of serpentine, minor calcite, chrome-diopside, phlogopite (Mg/Mg+Fe = 84.15%), perovskite, spinels, and pentlandite. Xenoliths of shales, sandstones, and mantle-derived ultramafic material are also present. Spinels are rich in Cr, Ti, and Fe and generally low in Al. Zoned spinels show enrichments in Ti and Fe towards their rims. A positive correlation between 100(Fe³⁺+Ti)/(Cr+Al+Fe³⁺+Ti) and 100 Mg/(Mg+Fe²⁺) ratios exists in these spinels and probably reflects an oxygen fugacity increase during magma crystallization. Occluded gases in diamonds and kimberlites corroborate the hypothesis that the parent magma of the Prairie Creek kimberlite was derived by partial melting of upper-mantle garnet lherzolite under volatile-rich conditions, primarily enriched in H₂O and CO₂.     

Konvergenzerscheinungen der Mineralbildung einiger sedimentärer deutscher Eisenerze

Zusammenfassung Sedimentäre Eisenerze können durch Ausflocken von Fe⁺⁺⁺haltigen Solen und durch Ausfällen von Fe⁺⁺haltigen Lösungen gebildet werden. Aus Solen gebildete Erze werden als Begleitelemente Kieselsäure und Aluminium anreichern, während aus Lösungen gebildete Erze manganreicher sind und Kieselsäure und Aluminium zurücktreten.     

The cumulus and post-cumulus evolution of chrome-spinels in ultrabasic layered intrusions: evidence from the Cuillin Igneous Complex,Isle of Skye,Scotland

Chrome-spinels from the layered Peridotilte Series of the unmetamorphosed, anorogenic 60 Ma Cuillin Igneous Complex, Isle of Skye, display a wide variety of compositions. Cumulus (within seams) chrome-spinels from the lowest exposed portion of the Peridotite Series exhibit features indicative of textural equilibrium, are rich in Al and Mg, and have low values of the ratio Cr/(Cr+Al). Cumulus chrome-spinels from higher up in the series are different from these: particularly, textural disequilibrium is evident, intercumulus plagioclase and olivine are present, and the chrome-spinels are rich in Cr, Fe and Ti, with high values of the ratio Cr/(Cr+Al). Intercumulus (dispersed) chrome-spinels tend towards anhedral forms and define enrichment trends towards Fe (both Fe²⁺ and Fe³⁺) with decreasing Mg, Cr and Al, and towards Al, with decreasing Fe²⁺ and Cr (and increasing Mg). Individual crystals are completely homogeneous and are devoid of reaction rims. The observed textural characteristics and compositional data of the chrome-spinels documented here suggest that the semi-quantitative peritectic reaction: aluminous chrome-spinel + meltplagioclase + olivine + chromian chrome-spinel, is responsible for the observed parageneses, and that both the environment of crystallization (eumulus or intercumulus) and the role of plagioclase ±olivine crystallization are critical parameters for this geochemical trend in spinels within upper crustal magmatic systems. The effects of pyroxene crystallization on the development of this geochemical trend are also considered. This investigation highlights the need to consider the role of post-cumulus mineral-melt reactions and their influences upon the final compositions of major oxide and silicate phases within layered intrusions.     

Experimental tests of the effects of Al substitution on the goethite-water D/H fractionation factor

Twelve goethite samples with different degrees of substitution of Al for Fe were synthesized at 22-48 °C and pH values of 1.5-14 under closed system conditions and used to study the effects of Al substitution on the hydrogen isotopic fractionation between goethite and its ambient water. The syntheses followed two pathways: (1) Fe³⁺ hydrolysis in high pH aqueous solutions; (2) oxidation of Fe²⁺ to Fe³⁺ in mid to low pH solutions. XRD and SEM analyses indicated that, irrespective of temperature and pH, goethite was the predominant product of the syntheses in all of the experiments (with degrees of Al substitution as high as ∼13 mol %). “High temperature nonstoichiometric” (HTN) water is present in all of the samples and rapidly exchanges D/H with ambient vapor at room temperature. Uncertainties in the value of the apparent D/H fractionation factor (α_e-v) between HTN water and ambient exchange water at 22 °C lead to significant uncertainties in determinations of the δD values of structural hydrogen (δD_s) in goethites which contain high proportions of HTN water. As determined for the samples of this study, α_e-v has a nominal value of 0.942 (±0.02). δD_s values determined using an α_e-v value of 0.942 indicate that Al substitution increases the δD value of structural hydrogen in goethite by about 1.4 (±0.4)‰ for each increase in Al of 1 mol %. This dependence on Al is of the same sign as, but somewhat larger in magnitude than, the effect of Al predicted by a published model (∼0.7‰ per mol % Al). The overall uncertainties in the current results suggest that an increase of ∼1‰ per mol % Al, as adopted by previous studies, may be a reasonable estimate with which to adjust δ D_s values of natural goethites to those of the pure FeOOH endmember and could be valid for degrees of Al substitution of up to at least 15 mol %. These synthesis experiments also yield a hydrogen isotopic fractionation factor (^Dα_G-W) between pure goethite (α-FeOOH) and liquid water of 0.900 (±0.006), which is analytically indistinguishable from the published value of 0.905 (±0.004). Thus, use of an ^Dα_G-W value of 0.905 in applications to the FeOOH component of natural goethites is supported by the current study.     

Tourmaline from deposits of the Birgil’da-Tomino ore cluster, South Urals

Tourmalines from the Kalinovka porphyry copper deposit with epithermal bismuth-gold-basemetal mineralization and the Michurino gold-silver-base-metal prospect have been studied in the South Urals. Tourmaline from the Kalinovka deposit occurs as pockets and veinlets in quartz-sericite metasomatic rock and propylite. The early schorl-“oxy-schorl” [Fe_tot/(Fe_tot + Mg) = 0.66?0.81] enriched in Fe³⁺ is characterized by the homovalent isomorphic substitution of Fe³⁺ for Al typical of propylites at porphyry copper deposits. The overgrowing tourmalines of the second and third generations from propylite and quartz-sericite metasomatic rock are intermediate members of the dravite-magnesio-foitite solid solution series [Fe_tot/(Fe_tot + Mg) = 0.05?0.46] with homovalent substitution of Mg for Fe²⁺ and coupled substitution of ^X _? + ^YAl for ^XNa + ^YMg. These substitutions differ from the coupled substitution of ^YAl + ^WO^2? for ^YFe²⁺ + ^WOH^? in tourmaline from quartz-sericite rocks at porphyry copper deposits. At the Michurino prospect, the tourmaline hosted in the chlorite-pyrite-quartz veins and veinlets with Ag-Au-Cu-Pb-Zn mineralization is an intermediate member of the dravite-magnesio-foitite solid solution series [Fe_tot/(Fe_tot + Mg) = 0.20?0.31] with homovalent substitution of Mg for Fe²⁺ and coupled substitutions of ^X _? + ^YAl for ^XNa + ^YMg identical to that of late tourmaline at the Kalinovka deposit. Thus, tourmalines of the porphyry and epithermal stages are different in isomorphic substitutions, which allow us to consider tourmaline as an indicator of super- or juxtaposed mineralization.     

57Fe mössbauer study of clinopyroxenes in the join CaFe3+ AlSiO6 - CaTiAl2O6

Synthetic clinopyroxenes of compositions between CaFe³⁺AlSiO₆ and CaFe _0.85 ³⁺ Ti_0.15Al_1.15Si_0.85O₆ have been studied by ⁵⁷Fe Mössbauer spectroscopy. The spectra consist of two doublets assigned to Fe³⁺ in M1 and T sites. From the area ratios of the doublets the site occupancies of Fe³⁺ and Al were determined. Si decreases from 1.00 to 0.85 and Al+Fe³⁺ increases from 1.00 to 1.15 per formula unit with increasing CaTiAl₂O₆ component of the clinopyroxene. The atomic ratio of Fe³⁺(T)/Fe³⁺(total) is 0.11–0.16; 4.5–7.5 percent of the T sites are occupied by Fe³⁺. Thus the presence of Si-O-Fe³⁺, Al-O-Fe³⁺, and Fe³⁺-O-Fe³⁺ bonds is expected in addition to Si-O-Si, Si-O-Al and Al-O-Al bonds. However, the possibility of the former bonds being present would be small, because the amount of Fe³⁺(T) is far less than that of Si and Al. The isomer shift of Fe³⁺(T) is one of the largest in the values found previously for Fe³⁺(T) in silicates. It increases with increasing CaTiAl₂O₆ component and seems to be correlated to the ionic character of the cation — anion bonds calculated from electronegativity. The quadrupole splittings of Fe³⁺(M1) and Fe³⁺(T) decrease with the substitution of Fe³⁺?Ti⁴⁺ in the M1 and of Si?Al in the T sites.     

Postcumulus modification of magnetite grains in the upper zone of the Bushveld Complex,South Africa

A detailed electron microprobe study has been made of magnetite grains from magnetitite layer 1 of the upper zone of the Bushveld Complex, in order to establish if there is any evidence for postcumulus processes having affected magnetite compositions. Representative composition profiles obtained from detailed step traverses are presented for touching magnetite grains and where magnetite is in contact with either ilmenite or plagioclase.Magnetite grains in all textural settings are compositionally heterogeneous. Touching magnetite grains display systematic compositional zonations: the rims of grains show a marked decrease in Al and Mg towards the grain boundary; the cores are characterised by a distinctive peak and trough pattern for these elements. These variations can be related to the positions of exsolved phases. Exsolutions in the cores are either pleonaste or an Fe³⁺ bearing AlMg spinel, whereas those at the grain boundaries are generally more Al-rich and include corundum. Similar exsolution related compositional variations for Mg and Al were found in magnetites in contact with ilmenite and plagioclase.A model has been developed which illustrates the possible sequence of postcumulus events during the interval between accumulation of the magnetite and the cessation of subsolidus reactions. The essential feature of the model is the delicate interplay between depletion of the host magnetite by corundum, pleonaste and the Fe³⁺ bearing AlMg spinel exsolutions, and diffusion of Al and Mg into the depleted areas from the surrounding magnetite.Data for Cr contents in magnetites show that although this particular trace element is apparently resistant to redistribution by exsolution processes, it is affected by subsolidus re-equilibration between magnetite and ilmenite, or magnetite and intercumulus liquid.     

NMR and EPR studies of the chemically intermediate plagioclase feldspars

The NMR spectra of ²⁷Al and ²³Na and the EPR spectra of Fe³⁺ and Mn²⁺ have been studied in a range of plagioclase feldspars, of intermediate composition. Many of these crystals have previously been investigated by TEM methods (McLaren and Marshall, 1974). The broad, central ²⁷Al signals observed in labradorites have been interpreted in terms of an overall order/disorder of the Al/Si distribution. Spin Hamiltonian parameters have been determined for the Fe³⁺ spectra observed in labradorites and bytownites; these spectra were similar and yielded evidence of disordering of the Al/Si distribution. The severe limitations imposed by the variety of sites, the complex microstructures and the disordering, limit the structural information available from the resonance methods.     

Effects of hydrothermal alteration on the compositions of chromian spinels

Chromite spinels in hydrothermally altered rocks from fracture-zone ultramafic rocks and from both ultramafic cumulate pods and sheeted dikes in the Josephine ophiolite, California, display a wide variety of compositions. Alteration of the spinel may not be visible in thin section. The primary composition changes accompanying hydrothermal alteration are increase in Cr/(Cr+Al) and/or Fe²⁺/(Fe²⁺+Mg). In general, altered spinel grains associated with hornblende and chlorite show an increase in Cr/(Cr+Al) from core to rim. Altered spinel grains associated with serpentine show an increase in Fe²⁺/(Fe²⁺+Mg) from core to rim but may not show an increase in Cr/(Cr+Al). The compositional zoning in some altered spinel grains appears to result both from reaction of clinopyroxene plus spinel to form hornblende, and from reaction of hornblende to form chlorite. These observations suggest that subsolidus hydrothermal metamorphic effects need to be considered when interpreting spinel compositions and the compositions should not be interpreted solely in terms of igneous processes. Further, the presence of highly altered spinels may be indicative of hydrothermal alteration in rocks where other evidence of such alteration is absent.     

Mössbauer and ELNES spectroscopy of (Mg,Fe)(Si,Al)O3 perovskite: a highly oxidised component of the lower mantle

(Mg,Fe)(Si,Al)O₃ perovskite samples with varying Fe and Al concentration were synthesised at high pressure and temperature at varying conditions of oxygen fugacity using a multianvil press, and were characterised using ex?situ X-ray diffraction, electron microprobe, Mössbauer spectroscopy and analytical transmission electron microscopy. The Fe³⁺/ΣFe ratio was determined from Mössbauer spectra recorded at 293 and 80?K, and shows a nearly linear dependence of Fe³⁺/ΣFe with Al composition of (Mg,Fe)(Si,Al)O₃ perovskite. The Fe³⁺/ΣFe values were obtained for selected samples of (Mg,Fe)(Si,Al)O₃ perovskite using electron energy-loss near-edge structure (ELNES) spectroscopy, and are in excellent agreement with Mössbauer data, demonstrating that Fe³⁺/ΣFe can be determined with a spatial resolution on the order of nm. Oxygen concentrations were determined by combining bulk chemical data with Fe³⁺/ΣFe data determined by Mössbauer spectroscopy, and show a significant concentration of oxygen vacancies in (Mg,Fe)(Si,Al)O₃ perovskite.     

Clinoenstatite in volcanic rocks from the Bonin Islands

Multiply-twinned clinoenstatite has been found in andesitic rocks from Chichi-jima and Mukojima in the Bonin Islands.The clinoenstatite occurs as (1) reaction rims around olivine, (2) composite crystals with bronzite, and (3) anhedral phenocrysts rimmed or included by bronzite.The clinoenstatite is chemically characterized by low contents of Ca (less than 0.5 wt.% oxide), Fs (9.2–11.5) and Al (less than 0.6 wt.% oxide) relative to the coexisting bronzite. The partition coefficient, K _{D op} ^cp =(Mg/Fe²⁺)^cp/(Mg/Fe²⁺)^op between coexisting clinoenstatite and bronzite, ranges from 1.02 to 1.32 (average 1.17). The Fe²⁺/Mg+Fe²⁺ ratios of coexisting clinoenstatite and bronzite are different in different rock types, which suggests variable inversion temperatures of protoenstatite to orthopyroxene in boninite.Bronzite phenocrysts in a specimen, ranging from Fs15 to Fs30, coexist with augite phenocrysts, whereas those in the other specimens, ranging from Fs12 to Fs18, do not coexist with augite phenocrysts. These differences in petrographical nature and mineral chemistry among the specimens examined may be due to variations in their quenching stages.The boninite clinoenstatite and bronzite are relatively rich in Ca and Mg, compared with the Papuan and Mariana pyroxenes, which seems to depend upon the rock chemistry.     

Organic complexation and translocation of ferric iron in podzols of the Negro River watershed. Separation of secondary Fe species from Al species

The development of podzols in lateritic landscapes of the upper Amazon basin contributes to the exportation of organic carbon and associated metals in the black waters of the Negro River watershed. We have investigated the distribution of Fe^III in the clay-size fraction of eight organic-rich horizons of waterlogged plateau podzols, to unravel the weathering conditions and mechanisms that control its transfer to the rivers. The speciation and amount of Fe^III stored in residual mineral phases of laterites, or bound to organic compounds of weakly and well-expressed podzols, were determined by electron paramagnetic resonance spectroscopy combined with chemical analyses.Reducing conditions restrict the production of organo-Fe complexes in the subsoil B-horizons of waterlogged podzols and most of the Fe²⁺ released from the dissolution of Fe-oxides is exported to the rivers via the perched groundwater. However, significant amounts of diluted Fe^III bound to organic ligands (Fe^III_OM) and nano Fe-oxides are produced at the margin of the depression in the topsoil A horizons of weakly expressed podzols due to shorter periods of anoxia. The downward translocation of organically bound metals from topsoil A to subsoil B-horizons of podzols occurs in shorter distances for Fe than it does for Al. This separation of secondary Fe species from Al species is attributed to the physical fractionation of their organic carriers in texture contrasted B-horizons of podzols, as well as to the effect of pH on metal speciation in soil solutions and metal binding onto soil organic ligands (mostly for Al). This leads us to consider the topsoil A horizons of weakly expressed podzols, as well as the subsoil Bh horizon of better-expressed ones, as the main sources for the transfer of Fe^III_OM to the rivers. The concentration of Fe^III_OM rises from soil sources to river colloids, suggesting drastic biogeochemical changes in more oxygenated black waters of the Negro River watershed. The contribution of soil organic matter to the transfer of Fe to rivers is likely at the origin of the peculiar Fe isotope pattern recently recognized in podzolic environments.     

Iron sulfide oxidation and the chemistry of acid generation

Acid mine drainage, produced from the oxidation of iron sulfides, often contains elevated levels of dissolved aluminum (AI), iron (Fe), and sulfate (SO₄) and low pH. Understanding the interactions of these elements associated with acid mine drainage is necessary for proper solid waste management planning. Two eastern oil shales were leached using humidity cell methods. This study used a New Albany Shale (4.6 percent pyrite) and a Chattanooga Shale (1.5 percent pyrite). The leachates from the humidity cells were filtered, and the filtrates were analyzed for total concentrations of cations and anions. After correcting for significant solution species and complexes, ion activities were calculated from total concentrations. The results show that the activities of Fe³⁺, Fe²⁺, Al³⁺, and SO₄ ²⁻ increased due to the oxidation of pyrite. Furthermore, the oxidation of pyrite resulted in a decreased pH and an increased pe+pH (redox-potential). The Fe³⁺ and Fe²⁺ activities appeared to be controlled by amorphous Fe(OH)₃ solid phase above a pH of 6.0 and below pe+pH 11.0. The Fe³⁺, Fe²⁺, and SO₄ ²⁻ activities reached saturation with respect to FeOHSO₄ solid phase between pH 3.0 and 6.0 and below pe+pH 11.0 Below a pH of 3.0 and above a pe+pH of 11.0, Fe²⁺, Fe³⁺, and SO₄ ²⁻ activities are supported by FeSO₄·7H₂O solid phase. Above a pH of 6.0, the Al³⁺ activity showed an equilibrium with amorphous Al(OH)₃ solid phase. Below pH 6.0, Al³⁺ and SO₄ ²⁻ activities are regulated by the AlOHSO₄ solid phase, irrespective of pe+pH. The results of this study suggest that under oxidizing conditions with low to high leaching potential, activities of Al and Fe can be predicted on the basis of secondary mineral formation over a wide range of pH and redox. As a result, the long-term chemistry associated with disposal environments can be largely predicted (including trace elements).     

Variation of infrared absorption spectra in the system Bi2Al4−x Fe x O9 (x = 0–4), structurally related to mullite

The crystal structure of Bi₂Al_4−x Fe _x O₉ compounds (x = 0–4) has striking similarities with the crystal structure of mullite. A complete substitution of Al by Fe³⁺ in both octahedral and tetrahedral sites is a particular structural feature. The infrared (IR) spectra of the Bi₂M₄O₉ compounds (M = Al, Fe³⁺) are characterised by three band groups with band maxima in the 900–800, 800–600 and 600–400 cm⁻¹ region. Based on the spectroscopic results obtained from mullite-type phases, the present study focuses on the composition-dependent analysis of the 900–800 cm⁻¹ band group, which is assigned to Al(Fe³⁺)–O stretching vibrations of the corner-sharing MO₄ tetrahedra. The Bi₂Al₄O₉ and Bi₂Fe₄O₉ endmembers display single bands with maxima centred at 922 and 812 cm⁻¹, respectively. Intermediate Bi₂Al_4−x Fe _x O₉ compounds exhibit a distinct splitting into three relatively sharp bands, which is interpreted in terms of ordering effects within the tetrahedral pairs. Thereby the high-energy component band of the band triplet relates to Al–O–Al conjunctions and the low-energy component band to Fe–O–Fe conjunctions. The intermediate band is assigned to stretching vibrations of Al–O–Fe or Fe–O–Al configurations of the corner-sharing tetrahedral pairs. Bands in the 800–600 cm⁻¹ range are assigned to low-energy stretching vibrations of the MO₄ tetrahedra and to M–O–M bending vibrations of the tetrahedral pairs. Absorptions in the 600–400 cm⁻¹ range are essentially determined by M–O stretching modes of the M cations in octahedral coordination.     

Thermodynamics of multicomponent pyroxenes: III. Calibration of Fe2+(Mg)-1, TiAl2(MgSi2)-1, TiFe 2 3+ (MgSi2)-1, AlFe3+(MgSi)-1, NaAl(CaMg)-1, Al2(MgSi)-1 and Ca(Mg)-1 exchange reactions between pyroxenes and silicate melts

A thermodynamic model for the Gibbs free energy of igneous pyroxenes with the general formula [Na, Ca, Fe²⁺, Mg]^M2[Fe²⁺, Mg, Ti, Al, Fe³⁺]^M1[Al, Fe³⁺, Si]^TetSiO₆ is calibrated from experimentally determined compositions of coexisting pyroxene and silicate melt. The model is based upon the general formulation, and relies upon the calibration of the “quadrilateral” subsystem, previously published by the present authors. The calibration database of pyroxene-liquid equilibria spans a broad spectrum of temperature, pressure and oxygen fugacity conditions, ranging from 1000°–1600°C, 0.001–30 kbar and iron-wüstite to air. Chemical potentials of endmember pyroxene components as well as exchange potentials between pyroxenes and coexisting liquids are defined utilizing the present authors' thermodynamic melt model. Model parameters are extracted from these relations by regression analysis. The resulting model and derivative endmember properties are internally consistent with an existing standard state thermodynamic database. The success of the model and its applicability to igneous petrogenesis are demonstrated by comparing calculated and experimentally determined liquidus compositions, temperatures and symmetry states for pyroxenes crystallizing from a variety of silicate melts, ranging in composition from tholeiites and angrites through rhyolites to potash ankaratrites.     

Micas from the Khaluta carbonatite deposit,western Transbaikal region

The Khaluta carbonatite deposit located in the western Transbaikal region was formed during the Late Mesozoic rifting in the southern framework of the Siberian Craton. Carbonatite is associated with shonkinite and syenite and is accompanied by fenitization. The composition of mica in more than 160 samples of country rocks, carbonatites, silicate rocks, and fenites was studied. The Fe³⁺ and Fe²⁺ contents, as well as oxygen isotopic composition, were determined. The Mg and Fe contents increase, whereas the Ti and Al contents decrease in micas when passing from silicate rocks and fenites to carbonatites. Micas from carbonatites are depleted in Al, enriched in Fe³⁺, and distinguished by high Si and F contents. According to our calculations, in some cases Al replaces Si in the tetrahedral site instead of replacement of Fe³⁺ as is characteristic of tetraferriphlogopite. Formally, the mica from carbonatites falls within the tetraferriphlogopite field, but typical inverse pleochroism is not always observable. The δ¹⁸O values of micas from carbonatite, shonkinite, syenite, and fenite are similar to those of mantle-derived silicate minerals. The δ¹⁸O values in the minerals coexisting with phlogopite testify to their isotopic equilibrium and make it possible to calculate the crystallization temperature of carbonatite.