Stable carbon isotopic compositions of individual aromatic hydrocarbons as source and age indicators in oils from western Australian basins

The present study aims to establish the factors controlling the stable carbon isotopic compositions (δ¹³C) of individual aromatic hydrocarbons analysed by compound specific isotope analysis (CSIA) in crude oils from western Australian petroleum basins of varying age and facies type. This paper reports δ¹³C values of individual aromatic hydrocarbons, like alkylbenzenes, alkylnaphthalenes, alkylphenanthrenes and methylated biphenyls. The main aims are to confirm the origin (source) and age of these oils based on CSIA of selected aromatic compounds and to understand why the Sofer plot is ineffective in establishing the source of western Australian petroleum systems. The bulk δ¹³C of saturated and aromatic hydrocarbon fractions of crude oils have been previously used to differentiate sources, however, many Australian crude oils are not classified correctly using this method. The oils were classified as marine by the δ¹³C values of individual aromatic compounds and as terrigenous based on the bulk δ¹³C data (Sofer plot).The oils where the δ¹³C values of 1,6-DMN and 1,2,5-TMN isomers are most negative are indicative of a marine source, whereas oils with a less negative values for the 1,6-DMN and 1,2,5-TMN isomers are derived from marine source rocks that contain a significant terrigenous component. Similarly, oils with the least negative δ¹³C values for the 1-MP and 1,9-DMP isomers reflect varying inputs of terrigenous organic matter to the their marine source rocks. Plots of P/DBT and Pr/Ph concentration ratios versus δ¹³C values of DMP, 1,6-DMN, 1,2,5-TMN, 1-MP and 1,9-MP are constructed to establish the relative amount of terrigenous organic matter contributing to the source rock of a series of marine oils. The ratios of P/DBT and Pr/Ph plotted against the δ¹³C values of the aromatic isomers (such as 1,6-DMN, 1,2,5-TMN, 1-MP and 1,9-MP) provide a novel and convenient way to discriminate crude oils derived from different source rocks that contain varying amounts of marine and terrigenous organic matter.     

Thermodynamics of arsenates,selenites, and sulfates in the oxidation zone of sulfide ores: Part III: Eh-pH diagrams of the Me-As-H<Subscript>2</Subscript>O systems (Me = Co,Ni, Fe,Cu, Zn,Pb) at 25°C

The behavior of arsenic at the Earth’s surface and nearby at low temperatures and pressures depends mainly on the redox potential and the acidity-alkalinity of the crystallization media. These parameters determine the migration of arsenic compounds and their precipitation as various solid phases. Understanding the mechanism of arsenic’s behavior under surface conditions, which is important for solving environmental problems, is an urgent task of contemporary mineralogy and geochemistry. The activities of the components in natural waters beyond the zones of natural (oxidation zones) and man-made contamination with arsenic (a _ΣAs = 3 × 10⁻⁸, a _ΣFe = 10⁻⁵, a _ΣCu = 10⁻⁷, a _ΣZn = 5 × 10⁻⁷, a _ΣCo = 10⁻⁸, a _ΣNi = 6 × 10⁻⁸, a _ΣPb = 10⁻⁸) and in waters formed in the oxidation zone (a _ΣSe = 10⁻³, a _ΣFe = 10⁻², a _ΣCu = 10⁻², a _ΣZn = 5 × 10⁻², a _ΣCo = 10⁻³, a _ΣNi = 10⁻², a _ΣPb = 10⁻⁴) have been estimated. Eh-pH diagrams were calculated and plotted using the Geochemist’s Workbench (GMB 7.0) software package. The database comprises the thermodynamic parameters of 46 elements, 47 main particles, 48 redox pairs, 551 particles in solution, 624 solid phases, and 10 gases. The Eh-pH diagrams of the Me-As-H₂O systems (Me = Co, Ni, Fe, Cu, Zn, Pb) were plotted for the average contents of these elements in the underground water and for their higher contents in the oxidation zones of sulfide deposits. The formation of Co, Ni, Fe, Cu, Zn, and Pb arsenates at the surface is discussed.     

Thermodynamics of arsenates,selenites, and sulfates in the oxidation zone of sulfide ores: IV. Eh-pH diagrams of the Me-Se-H<Subscript>2</Subscript>O systems (Me = Co,Ni, Fe,Cu, Zn,Pb) at 25°C

The behavior of selenium at the Earth’s surface and nearby at low temperatures and pressures is controlled by variations of the redox potential and the acidity of solutions. These parameters determine the migration of selenium and its precipitation as various solid phases. Understanding the mechanism of selenium’s behavior under surface conditions, which is important for solving environmental problems, is an urgent task of contemporary mineralogy and geochemistry. The activities of components in natural waters beyond the zones of natural (oxidation zones) and man-made contamination with selenium (a _ΣSe = 10⁻⁹, a _ΣFe = 10⁻⁵, a _ΣCu = 10⁻⁷, a _ΣZn = 5 × 10⁻⁷, a _ΣCo = 10⁻⁸, a _ΣNi = 6 × 10⁻⁸, a _ΣPb = 10⁻⁸) and in waters formed in the oxidation zone (a _ΣSe = 10⁻⁵–10⁻⁴, a _ΣFe = 10⁻², a _ΣCu = 10⁻², a _ΣZn = 5 × 10⁻², a _ΣCo = 10⁻³, a _ΣNi = 10⁻², a _ΣPb = 10⁻⁴) have been estimated. Eh-pH diagrams were calculated and plotted using the Geochemist’s Workbench (GMB 7.0) software package. The database comprises the thermodynamic parameters of 46 elements, 47 main particles, 48 redox pairs, 551 particles in solution, 624 solid phases, and 10 gases. The Eh-pH diagrams of the Me-Se-H₂O systems (Me = Co, Ni, Fe, Cu, Zn, Pb) were plotted for the average contents of these elements in underground water and for their contents in oxidation zones of sulfide deposits. The formation of Co, Ni, Fe, Cu, Zn, and Pb selenites and selenates at the surface is discussed.     

Alkyl Naphthalenes and Phenanthrenes: Molecular Markers for Tracing Filling Pathways of Light Oil and Condensate Reservoirs

<正>Condensates and light oils are generally characterized by high maturity,low concentration of sterane and terpane biomarkers and low content of non-hydrocarbon fraction.As a result,some commonly-used sterane,terpane and carbazole migration parameters in conventional oil reservoirs may have a certain limitation in condensate and light oil reservoirs for their poor signal-noise ratios in the gas chromatography-mass spectrometry(GC-MS).Naphthalene,phenanthrene and their methylated substituents,however,are present in significant concentrations in condensates and light oils.Taking the Fushan depression(in the Beibuwan Basin,Northern South China Sea) as an example, this paper attempts for the first time to use polycyclic aromatic hydrocarbon(PAH)-related parameters to trace migration directions and filling pathways for condensate and light oil reservoirs.The result shows that TMNr(i.e.1,3,7-TMN/(1,3,7-TMN + 1,2,5-TMN),TMN:trimethylnaphthalene)),MPI-1 (i.e.1.5×(2-MP + 3-MP)/(P + 1-MP + 9-MP),P:phenanthrene MP:methylphenanthrene),MN/DMN (Σmethylnaphthalene/Σdimethylnaphthalene,%) and MN/TMN(Σmethylnaphthalene/Σtrimethylnaphthalene, %) can be used to trace the filling pathways of condensate and light oil reservoirs.These parameters,together with geological consideration and other bulk oil properties(e.g.the gas to oil ratio and density),suggest that the condensates and light oils in the Huachang oil and gas field are mainly sourced from the Bailian sag that is located to the northeast of the Huachang uplift in the Fushan depression.     

New data on associations of platinum-group minerals in placer deposits of British Columbia, Canada

Summary We have conducted electron microprobe (EMP) analysis of 158 grains of platinum-group minerals (PGM; 0.1–1 mm in size) from 11 placer samples collected from Holocene fluvial placers and buried paleochannel placers at various localities in British Columbia. These grains principally comprise Pt-Fe-(Cu) alloy minerals: Fe-rich platinum [ΣPGE:(Fe + Cu + Ni) = 3.6–7.6], Pt₃Fe-type alloy (isoferroplatinum or Fe-rich platinum), subordinate “Pt₂Fe”-type alloy (probably, a compositional variant of Fe-rich platinum) and the tulameenite-tetraferroplatinum series. Less-abundant are iridium [Ir-dominant Ir-Os-(Pt) alloy] and osmium [Os-dominant Os-Ir-(Pt) alloy]. Ruthenium [Ru-dominant Ru-Ir-Os alloy] occurs as a single grain. One of these Pt-Fe alloy grains is unusually zoned; its core zone is: Pt_74.0Fe_20.4Cu_1.9Ir_1.5Rh_1.1Pd_1.0Os_0.08Ru_0.01Ni_0.01 (in at%) [ΣPGE:(Fe + Cu + Ni) = 3.5], and its rim zone is: Pt_78.5Fe_15.5Cu_1.7Ir_1.5Rh_1.4 Pd_1.2Ni_0.15Os_0.06Ru_<0.01 [ΣPGE:(Fe + Cu + Ni) = 4.8]. This zoning indicates late-stage removal of Fe and corresponding addition of Pt, probably as a result of interaction with a late fluid phase. Various combinations of minor elements: Ir-Rh, Rh-Pd, and Ir-Rh-Pd are observed in the analysed Pt-Fe-Cu alloys. However, the Ir-Pd pair appears to be prohibited because of crystallochemical factors. Minute PGM inclusions in Pt-Fe alloy grains, likely derived from the Tulameen complex, comprise: hongshiite (Pt_1.04Pd_0.02 Cu_0.93), sperrylite (Pt_0.93Ir_0.03)_Σ0.96(As_2.02Sb_0.01)_Σ2.03, hollingworthite-platarsite (Rh_0.74 Pt_0.21Fe_0.02Pd_0.02Ir_0.01)_Σ1.00S_0.91As_1.10, cuprorhodsite-malanite (Cu_0.91Fe_0.03Ni_<0.01)_Σ0.95 (Rh_1.06Pt_0.89Ir_<0.01)_Σ1.95S_4.10, a rare Te-rich isomertieite (Pd_10.96Fe_0.03)_Σ10.99(Sb_1.13 Te_0.94)_Σ2.07As_1.93, and an unusual Pt-Pd-Rh antimonide [(Pt + Pd + Rh):(Sb + As) = 1.2–1.25], related to genkinite. This antimonide may exhibit a minor solid solution extending from genkinite toward stumpflite. In addition, 20 grains of diopside [Ca_46.4–49.1Mg_42.8–48.2Fe_3.1–8.1; ≤0.59 wt% Cr₂O₃] and 20 grains of olivine [Fo_86.8–91.5 Fa_7.9–12.5], from a PGM-bearing placer located in the vicinity of the Tulameen complex, were analysed. The compositional ranges of these placer silicates are comparable to those of clinopyroxene and olivine in the olivine clinopyroxenite and dunite units of the Tulameen complex. The majority of the analysed placer PGM grains were probably derived from Alaskan-type source rocks, whereas an ophiolitic source, associated with the Atlin ophiolite complex, is suggested for the placer PGM deposits in the Atlin area, northern British Columbia. Authors’ addresses: Andrei Y. Barkov, Robert F. Martin, Department of Earth and Planetary Sciences, McGill University, 3450 University Street, Montreal, Quebec H3A 2A7, Canada; Michael E. Fleet, Department of Earth Sciences, University of Western Ontario, London, Ontario, N6A 5B7, Canada; Graham T. Nixon and Victor M. Levson, B.C. Geological Survey, Ministry of Energy, Mines and Petroleum Resources, PO Box 9320 Stn. Prov. Govt., Victoria, British Columbia V8W 9N3, Canada     

A Raman spectroscopic study of arsenite and thioarsenite species in aqueous solution at 25°C

The Raman spectra of thioarsenite and arsenite species in aqueous solution were obtained at room temperature. Solutions at constant ΣAs + ΣS of 0.1 and 0.5 mol kg^-1 were prepared with various ΣS/ΣAs ratios (0.1–9.0) and pH values (~7–13.2). Our data suggest that the speciation of As under the conditions investigated is more complicated than previously thought. The Raman measurements offer evidence for at least six separate S-bearing As species whose principal bands are centered near 365, 385, 390, 400, 415 and 420 cm^-1. The data suggest that at least two different species may give rise to bands at 385 cm^-1, bringing the probable minimum number of species to seven. Several additional species are possible but could not be resolved definitively. In general, the relative proportions of these species are dependent on total As concentration, ΣS/ΣAs ratio and pH. At very low ΣS/ΣAs ratios we also observe Raman bands attributable to the dissociation products of H₃AsO₃(aq). Although we were unable to assign precise stoichiometries for the various thioarsenite species, we were able to map out general pH and ΣS/ΣAs conditions under which the various thioarsenite and arsenite species are predominant. This study provides a basis for more detailed Raman spectroscopic and other types of investigations of the nature of thioarsenite species.     

REE-, Zr-, and Th-rich titanite and associated accessory minerals from a kersantite in the Frankenwald, Germany

Summary The mineral chemistry of a Variscan lamprophyre (kersantite) from the Frankenwald, Germany, has been investigated by electron microprobe. This potassic, Si-saturated, mafic rock contains an assemblage of different generations of titanite and allanite-(Ce), Th-rich zircon, and metamict REE–Ti–Zr–Th silicates. The primary ferroan-ceroan titanite contains unusually high contents of REE₂O₃ (max. (ΣLa to Sm)+Y = 36.8 oxide wt.%), ZrO₂ (max. 5.4 wt.%), and ThO₂ (max. 3.1 wt.%). Its empirical formula averages to (Ca_0.31 La_0.17 Ce_0.30 Pr_0.03 Nd_0.08 Sm_0.01 Y_0.01 Fe²⁺_0.06 Th_0.02 Mn_0.01)_Σ1.00 (Ti_0.60 Fe²⁺_0.22 Al_0.06 Zr_0.07 Mg_0.04 Nb_0.01)_Σ1.00 O_1.00(Si_0.93 Al_0.07)_Σ1.00 O₄. Element correlations reveal operation of the complex substitution Ca²⁺+Ti⁴⁺+Th⁴⁺ ⇔ REE³⁺+Al³⁺+Zr⁴⁺. In comparison to allanite-(Ce), ferroan-ceroan titanite preferentially incorporated the LREE and Th. This finding is inconsistent with previous experimental studies and suggests that both minerals are not cogenetic. High Zr contents in titanite, usually known only from Si-undersaturated alkaline rocks, and the predominance of Fe²⁺ suggest that the ferroan-ceroan titanite crystallized from an alkali-rich, low-fO₂ residual melt.     

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     

Geochemical study of peridotites from the Manipur Ophiolite Complex,Northeast India with special reference to their PGE concentration

The peridotites of the Manipur Ophiolite Complex (MOC) have been examined based on mineral chemistry, major elements and PGE contents. They represent high-magnesian cumulates with Mg# > 0.90 (Mg/Mg+Fe) in olivine and Cr# > 0.12 (Cr/Cr+Al) in spinel. High Mg* contents of the olivine show that these rocks are most likely derived from partial melting of the residual upper mantle. The peridotites contain higher concentration of Palladium Group PGE (PPGE) (Rh=4.4−6.6ppb; Pd=336−458ppb and Pt=14.6−36.4ppb) than the Iridium Group PGE (IPGE) (Os=2.4−5.8ppb; Ir=3.2−4.16ppb and Ru=5.2−7ppb). These are characterized by overall enrichment of PGE concentration (σPGE=365.8 − 516.6 ppb) and high ratio of (Pt+Pd)/(Os+Ir+Ru). This suggests that the rocks are formed by partial melting and crystal fractionation of olivine-rich (picritic) magma.     

Terpenoid biomarker distributions in low maturity crude oils

Twenty-seven heavy crude oils of diverse origin were geochemically assessed with respect to both bulk and mlecular composition for the purpose of identifying and quanttfying valid biomarker parameters for low maturity oils. The low thermal maturity level of many of these oils is evident from the bulk and alipathic chromatographic data, and oil sourced from both marine and terrigenous organic matter are represented. Selective metastable ion monitoring (SMIM) was employed to measure separately the distribution of C₂₇, C₂₈, and C₂₉ sterane isomers. The useful maturity indicators include the C₂₉ 5α(H) 20S/20R ratio, the relative quantity of the biological sterane configuration in each of the total normal C₂₇, C₂₈, and C₂₉ steranes, and the rearranged to normal sterane ratio. In addition, C₂₇ rearranged steran es appear to form at a faster rate than C₂₈ or C₂₉ rearranged steranes. However, the isomerization of the C₂₇ biological component appears to occur at a slower rate than the C₂₉ counterpart suggesting that the former may be used as a maturity parameter at higher levels of thermal maturation. In the triterpane distributions, the C₂₇ trisnorhopane isomers and the moretane to hopane ratios appear to be both source and maturity related and cannot be used as successful maturity parameters in oils unless they share a common source. The C₃₁₊ hopane 22S/22R equilibrium ratio appears to increase with increasing molecular weight (C₃₁–C₃₄).     

Dualite, Na30(Ca,Na,Ce,Sr)12(Na,Mn,Fe,Ti)6Zr3Ti3MnSi51O144(OH,H2O,Cl)9, a new zircono-titanosilicate with a modular eudialyte-like structure from the Lovozero alkaline Pluton, Kola Peninsula, Russia

Dualite has been found at Mount Alluaiv, the Lovozero Pluton, the Kola Peninsula in peralkaline pegmatoid as sporadic, irregularly shaped grains up to 0.3–0.5 mm across. K-Na feldspar, nepheline, sodalite, cancrinite, aegirine, alkaline amphibole, eudialyte, lovozerite, lomonosovite, vuonnemite, lamprophyllite, sphalerite, and villiaumite are associated minerals. Dualite is yellow, transparent or translucent, with conchoidal fracture. The new mineral is brittle, with vitreous luster and white streaks. The Mohs hardness is 5. The measured density is 2.84(3) g/cm₃ (volumetric method); the calculated density is 2.814 g/cm₃. Dualite dissolves and gelates in acid at room temperature. It is nonfluorescent. The new mineral is optically uniaxial and positive; ω = 1.610(1), ɛ = 1.613(1). Dualite is trigonal, space group R3m. The unit cell dimensions are a = 14.153(9), c = 60.72(5) ?, V = 10533(22) ?, Z = 3. The strongest reflections in the X-ray powder pattern [d, ? (I,%)(hkl)] are as follows: 7.11(40)(110), 4.31(50)(0.2.10), 2.964(100)(1.3.10), 2.839(90)(048), 2.159(60)(2.4.10, 0.4.20), 1.770(60)(2.4.22, 4.0.28, 440), 1362(50)(5.5.12, 3.0.42). The chemical composition (electron microprobe, H₂O calculated from X-ray diffraction data) is as follows, wt %: 17.74 Na₂O, 0.08 K₂O, 8.03 CaO, 1.37 SrO, 0.29 BaO, 2.58 MnO, 1.04 FeO, 0.79 La₂O₃, 1.84 C₂O₃, 0.88 Nd₂O₃, 0.20 Al₂O₃, 51.26 SiO₂, 4.40 TiO₂, 5.39 ZrO₂, 1.94 Nb₂O₅, 0.58 Cl, 1.39 H₂O,-O = 0.13 Cl₂; they total is 99.67. The empirical formula calculated on the basis of 106 cations as determined by crystal structure is (Na_29.79Ba_0.1K_0.10)_Σ30(Ca_8.55Na_1.39REE_1.27Sr_0.79)_Σ12 · (Na_3.01Mn_1.35Fe_0.87²⁺Ti_0.77)_Σ6(Zr_2.61Nb_0.39)_Σ3 (Ti_2.52Nb_0.48)_Σ3(Mn_0.82Si_0.18)_Σ1(Si_50.77Al_0.23)_Σ51 O₁₄₄[(OH)_6.54(H₂O)_1.34·Cl_0.98]_Σ8.86). The simplified formula is Na₃₀(Ca,Na,Ce,Sr)₁₂(Na,Mn,Fe,Ti)₆Zr₃Ti₃ MnSi₅₁O₁₄₄ (OH,H₂O,Cl)₉). The name dualite is derived from Latin dualis (dual) alluding to the dual taxonomic membership of this mineral, which is at the same time zirconosilicate and titanosilicate. The crystal structure is characterized by two module types (alluivite-like and eudialyte-like) alternating along a threefold axis with a doubled c period relative to eudialyte and close chemical affinity to rastsvetaevite (Khomyakov et al., 2006a) and labyrynthite (Khomyakov et al., 2006b). According to the authors’ crystal chemical taxonomy of the eudialyte group, the new mineral belongs to one of three subgroups characterized by a 24-layered structural framework. Dualite is a mineral formed during the final stages of peralkaline pegmatite formation. The type material of dualite is deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow. Original Russian Text ? A.P. Khomyakov, G.N. Nechelyustov, R.K. Rastsvetaeva, 2007, published in Zapiski Rossiiskogo Mineralogicheskogo Obshchestva, 2007, Pt CXXXVI, No. 4, pp. 68–73. Approved by the Commission on New Minerals and Mineral Names, International Mineralogical Association, July 8, 2005.     

The gold–vanadium–tellurium association at the Tuvatu gold–silver prospect, Fiji: conditions of ore deposition

Summary The Tuvatu gold–telluride prospect is one of several epithermal gold systems along the >250 km northeast trending Viti Levu lineament, Fiji, which are genetically associated with alkalic magmatism. Vein structures contain a variety of sulfides, native elements, sulfosalts, and tellurides. Calaverite is intimately associated with various vanadium-bearing minerals: roscoelite, karelianite, vanadian muscovite, Ti-free nolanite, vanadian rutile, schreyerite, and an unnamed vanadium silicate. Thermodynamic calculations for the systems V–Al–K–Si–O–H (Cameron, 1998) and Au–Te–Cl–S–O–H at estimated conditions of formation of the telluride-native gold stage at Tuvatu (∼250 °C, ΣAu = 1 ppb, ΣTe = 1 ppb, ΣS = 0.001 m, ΣV = 0.0001 m, and a_K = 0.01), show that the stability fields of calaverite, roscoelite, and karelianite converge in pH-fO₂ space near the hematite–magnetite buffer and at neutral to slightly acid conditions. Thermodynamic and textural data suggest that these minerals were deposited together at Tuvatu and likely explain the common coexistence of roscoelite and calaverite in epithermal gold systems elsewhere. The presence of magnetite with up to 0.7 wt.% V₂O₃ in the Navilawa Monzonite is consistent with the derivation of V from the alkalic intrusive rocks, which are also considered to be the source of Au and Te in the Tuvatu deposit.     

Evolution and REE geochemistry of Huangsha-Tieshanlong ore-bearing granite

Our studies show that the granite bodies (γ ₅ ^{2 − 1} and γ ₅ ³ ) which constitute the Huangsha-Tieshanlong composite granitic intrusion in Jiangxi are characterized by their similarities in mineral assemblage, petrochemistry, trace element and REE distribution pattern. The values of ΣREE, ΣLREE, ΣHREE, ΣCe/ΣY, δEu and La/Yb apparently decrease from γ ₅ ^{2 − 1a} to γ ₅ ^{2 − 1b} , γ ₅ ³ and γ ₅ ³ . It is shown that the early Yenshanian W(Ta, Nb)-bearing granite (γ ₅ ^{2 − 1} ) and late Yenshanian Ta, Nb-bearing granite (γ ₅ ³ ) may have been derived from the differentiation and evolution of granitic magmas due to repeated remelting of the crust and their earlier and later intrusion. Although the earlier (γ ₅ ^{2 − 1b} and later (γ ₅ ³ ) albitized Ta, Nb-bearing granites show some obvious differences in REE content, their δEu values and La/Yb ratios are similar to each other. Therefore, it may be concluded that the early and late Ta, Nb-bearing granites were derived from a congenetic magma.     

Metasomatism of sub-arc mantle peridotites below southernmost South America: reduction of<Emphasis Type="Italic"> f</Emphasis>O<Subscript>2</Subscript> by slab-melt

Quaternary basalts in the Cerro del Fraile area contain two types of mantle xenoliths; coarse-grained (2–5 mm) C-type spinel harzburgites and lherzolites, and fine-grained (0.5–2 mm) intensely metasomatized F-type spinel lherzolites. C-type xenoliths have high Mg in olivine (Fo = 90–91) and a range in Cr# [Cr/ (Cr + Al) = 0.17–0.34] in spinel. Two C-type samples contain websterite veinlets and solidified patches of melt that is now composed of minute quenched grains of plagioclase + Cr-spinel + clinopyroxene + olivine. These patches of quenched melts are formed by decompression melting of pargasitic amphibole. High Ti contents and common occurrence of relic Cr-spinel in the quenched melts indicate that the amphibole is formed from spinel by interaction with the Ti-rich parental magma of the websterite veinlets. The fO₂ values of these two C-type xenoliths range from ΔFMQ −0.2 to −0.4, which is consistent with their metasomatism by an asthenospheric mantle-derived melt. The rest of the C-type samples are free of “melt,” but show cryptic metasomatism by slab-derived aqueous fluids, which produced high concentrations of fluid-mobile elements in clinopyroxenes, and higher fO₂ ranging from ΔFMQ +0.1 to +0.3. F-type lherzolites are intensely metasomatized to form spinel with low Cr# (∼0.13) and silicate minerals with low MgO, olivine (Fo = ∼84), orthpyroxene [Mg# = Mg/(Mg + ΣFe) = ∼0.86] and clinopyroxene (Mg# = ∼0.88). Patches of “melt” are common in all F-type samples and their compositions are similar to pargasitic amphibole with low TiO₂ (<0.56 wt%), Cr₂O₃ (<0.55 wt%) and MgO (<16.3 wt%). Low Mg# values of silicate minerals, including the amphibole, suggest that the metasomatic agent is most likely a slab melt. This is supported by high ratios of Sr/Y and light rare earth elements (REE)/heavy REE in clinopyroxenes. F-type xenoliths show relatively low fO₂ (ΔFMQ −0.9 to −1.1) compared to C-type xenoliths and this is explained by the fusion of organic-rich sediments overlying the slab during the slab melt. Trench-fill sediments in the area are high in organic matter. The fusion of such wet sediments likely produced CH₄-rich fluids and reduced melts that mixed with the slab melt. High U and Th in bulk rocks and clinopyroxene in F-type xenoliths support the proposed interpretation.     

Microanalysis of Fe3+/ΣFe in oxide and silicate minerals by investigation of electron energy-loss near-edge structures (ELNES) at the Fe M 2,3 edge

The Fe M _2,3-edge spectra of solid solutions of garnets (almandine-skiagite Fe₃(Al_1–xFe_x)₂[SiO₄]₃ and andradite-skiagite (Fe_1–xCa_x)₃Fe₂[SiO₄]₃), pyroxenes (acmite-hedenbergite (Ca_1–xNa_x)(Fe²⁺ _1−xFe³⁺ _x)Si₂O₆), and spinels (magnetite-hercynite Fe(Al_1–xFe_x)₂O₄) have been measured using the technique of parallel electron energy-loss spectroscopy (EELS) conducted in a transmission electron microscope (TEM). The Fe M _2,3 electron energy-loss near-edge structures (ELNES) of the minerals exhibit a characteristic peak located at 4.2 eV and 2.2 eV for trivalent and divalent iron, respectively, prior to the main maximum at about 57 eV. The intensity and energy of the pre-edge feature varies depending on Fe³⁺/ΣFe. We demonstrate a new quantitative method to extract the ferrous/ferric ratio in minerals. A systematic relationship between Fe³⁺/ΣFe and the integral intensity ratio of the main maximum and the pre-edge peak of the Fe M _2,3 edge is observed. Since the partial cross sections of the Fe M _2,3 edges are some orders of magnitude higher than those of the Fe L _2,3 edges, the Fe M _2,3 edges are interesting for valence-specific imaging of Fe. The possibility of iron valence-specific imaging is illustrated by Fe M _2,3-ELNES investigations with high lateral resolution from a sample of ilmenite containing hematite exsolution lamellae that shows different edge shapes consistent with variations in the Fe³⁺/ΣFe ratio over distances on the order of 100 nm. Received: 14 April 1998 / Revised, accepted: 8 March 1999     

Near surface manifestation of hydrocarbons in Proterozoic Bhima and Kaladgi Basins: Implications to hydrocarbon resource potential

Reconnaissance surface geochemical survey for adsorbed soil gas analysis conducted in Proterozoic Bhima and Kaladgi Basins, have revealed occurrence of anomalous concentrations of light gaseous hydrocarbons i.e. C₁ to C₄ (CH₄, C₂H₆, C₃H₈, i-C₄H₁₀ and n-C₄H₁₀) in the near surface soils. The concentrations of C₁ and ΣC₂₊(C₂H₆+C₃H₈+ i-C₄H₁₀+ n-C₄H₁₀) in Bhima and Kaladgi Basins are in the range of 1–2594 ppb and 1 to 57 ppb and 1–1142 ppb and 1–490 ppb, respectively. The carbon isotopic data of adsorbed soil gas methane in few selected samples are in the range of −29.9 to −39‰ (PDB). The evaluation of adsorbed soil gas data indicates that all the gas components are cogenetic and hydrocarbon ratios of C₁/(C₂+C₃) < 10 and C₃/C₁*1000 between 60–500 and 20–60 suggest that the adsorbed gases are derived from oil and gas-condensate zones. The carbon isotopic values of methane further support thermogenic origin of these migrated gases. The concentration distribution of C₁ and ΣC₂₊ in the study areas illustrate C₁ and ΣC₂₊ anomalies near Katamadevarhalli, Andola and Talikota in Bhima Basin and near Kaladgi, Lokapur and north of Mudhol in Kaladgi Basin. The hydrocarbon anomalies near the surface coincide with the favourable subsurface structural features and correlate with existing geochemical and geophysical data in these basins suggesting seepage related anomalies.     

A crystallographic and m?ssbauer spectroscopy study of Fe

The crystal chemistry of garnet solid solutions on the Fe ₃ ²⁺ Al₂Si₃O₁₂-Fe ₃ ²⁺ Fe ₂ ³⁺ Si₃O₁₂ (almandine-“skiagite”) and Ca₃Fe ₂ ³⁺ Si₃O₁₂-Fe ₃ ²⁺ Fe ₂ ³⁺ Si₃O₁₂ (andradite-“skiagite”) joins have been investigated by single-crystal X-ray structure refinements and M?ssbauer spectroscopy. Together, these two solid solution series encompass the complete range in Fe³⁺/ΣFe from 0.0 to 1.0. All garnets are isotropic and were re0fined in the Ia d space group. Small excess volumes of mixing are observed in andradite-“skiagite” solid solutions (W _v =1.0±0.2 cm³ mol^-1) and along the almandine-“skiagite” join (W _v =-0.77±0.17cm³ mol^-1). The octahedral (Al, Fe³⁺)-O bond lengths show a much greater variation across the almandine-skiagite join compared to the andradite-skiagite garnets. The dodecahedral (X)-O bond lengths show the opposite behaviour. In andradite-“skiagite” solid solutions, the octahedral site passes from being flattened to elongated parallel to the 3 axis of symmetry with increasing “skiagite” content. A perfect octahedron occurs in a composition of ≈35 mol% “skiagite”. The occupancy of the neighboring dodecahedral sites has the greatest effect on octahedral distortion and vice versa. The M?ssbauer hyperfine parameters of Fe²⁺remain constant in both solid solutions. The hyperfine parameters of Fe³⁺ (at room temperature: centre shift=0.32–0.40 mm/sec, quadrupole splitting (QS)≈0.21–0.55 mm/ sec) indicate that all Fe³⁺ is in octahedral coordination. The Fe³⁺ parameters are nearly constant in almandine-“skiagite” solid solutions, but vary significantly across the andradite-“skiagite” join. The structural unit that contributes to the electric field gradient of the octahedral site is different from that of the coordinating oxygen polyhedron, probably involving the neighboring dodeca-hedral sites.     

REE Geochemical Evolution and Its Significance of Early Precambrian Metamorphic Terrain,Wuyang,Henan

The supracrustal rocks of the Wuyang metamorphic terrain are divided into the Zhao anzhuang,Tieshanmiao and Yangshuwan Formations.These three Formations were dated at 3000-2550Ma,2550-2300Ma and 2300-2200Ma,respectively.∑REE and La/Yb)n of the Zhao anzhuang Formation volcanic rocks are obviously higher than those of the Tiesanmiao Formation equivalents,suggesting a sedimentary gap(2550 Ma boundary)between these two formations,The Zhao‘anzhuang Formation is older than the Tieshanmiao Formation.The sediments of these two Formations show no obvious differences in REE and are generally characterized by low ∑REE and positive Eu anomalies.On the contrary,the sediments of the Yangshuwan Formation are characterized by high ∑REE and negative Eu anomalies.Detailed discussions demonstrate that the Yangshuwan Formation was deposited in an oxidizing environment whereas the other two formations were formed in a reducing environment.At the end of the evolution of the Tieshanmiao Formation about 2300 Ma ago,the sedimentary environment was transformed from reducing to oxidizing .On the basis of the SHAB (soft/hard acid and base)theory,an oxidation-reduction model for sedimentary REE evolution has been established .It is proposed that the mantle tends to become gradually depleted in REE.especially in LREE,and the indices ∑REE and La/Yb) n of mantle-dervived volcanic rocks also tend to become lower and lower.     

Factors Controlling Sulfide Geochemistry in Sub-tropical Estuarine and Bay Sediments

The primary factors that control the concentration of total reduced (inorganic) sulfide in coastal sediments are believed to be the availability of reactive iron, dissolved sulfate and metabolizable organic carbon. We selected nine sites in shallow (<3 m), close to sub-tropical, estuaries and bays along the central Texas coast that represented a range in sediment grain size (a proxy for reactive iron), salinity (a proxy for dissolved sulfate), and total organic carbon (a proxy for metabolizable organic carbon). Based on these parameters a prediction was made of which factor was likely to control total reduced sulfide at each site and what the relative total reduced sulfide concentration was likely to be. To test the prediction, the sediments were analyzed for total reduced sulfide, acid volatile sulfide, and citrate dithionate-extractable, HCl-extractable and total Fe in the solid phase. Using solid-state gold–mercury amalgam microelectrodes and voltammetry, we determined pore water depth profiles of Fe(II) and ΣH₂S and presence or absence of FeS_(aq). At five of the nine sites the calculated degree of sufildization of citrate dithionite-reactive-iron was close to or greater than 1 indicating that rapidly reactive iron was probably the limiting factor for iron sulfide mineral formation. At one site (salinity = 0.9) dissolved Fe(II) was high, ΣH₂S was undetectable and the total reduced sulfide concentration was low indicating sulfate limitation. At the last three sites a low degree of sulfidization and modest total reduced (inorganic) sulfide concentrations appeared to be the result of a limited supply of metabolizable organic carbon. Fe(II)–S(-II) clusters (FeS_(aq)) were undetectable in 10 out of 12 bay sediment profiles where ΣH₂S was close to or below detection limits, but was observed in all other porewater profiles. Acid volatile sulfide, but not total reduced sulfide, was well correlated with total organic carbon and ranged from being undetectable in some cores to representing a major portion of total reduced sulfide in other cores. Although predicted controls on total reduced sulfide were good for very low salinity water or sandy sediments, they were only right about half the time for the other sediments. The likely reasons for the wrong predictions are the poor correlation of total organic carbon with grain size and differing fractions of metabolizable organic carbon in different sedimentary environments. Differences in sediment accumulation rates may also play a role, but these are difficult to determine in this region where hurricanes often resuspend and move sediments. This study demonstrates the need to examine more complex and often difficult to determine parameters in anoxic “normal marine” sediments if we are to understand what controls the concentration and distribution of sulfides.