Trace element crystal chemistry of mantle eclogites

Rare earth element (REE) concentrations have been measured using instrumental neutron activation analysis on clean separates of primary minerals from 11 eclogite samples from the Bobbejaan and Roberts Victor kimberlites, South Africa. Samples were selected to reflect minimal secondary alteration and represent a broad range of eclogite compositions from coesiteand corundum-grospydites through magnesian bimineralic eclogites. Correlations between REE concentrations and major-element compositions suggest that garnet and clinopyroxene crystal chemistry are the dominant control on REE distribution and that these approach solidstate equilibrium distributions. Reconstructed wholerock REE concentration variation with whole-rock major-element compositions are consistent with an origin by high-pressure igneous fractionation followed by reequilibration to lower temperatures at pressures in excess of three GPa.     

Physicochemical conditions of deposition and origin of carbonate-hosted base metal sulfide mineralization, Thermes ore-field, Rhodope Massif, northeastern Greece

Vein and stratabound base metal sulfide mineralization of the Thermes ore-field, Rhodope Massif, NE Greece, is hosted in marbles. The Thermes area is a structurally complex, E-W-trending zone consisting of felsic gneisses alternating with amphibolites, amphibole-biotite, and biotite gneisses, and marbles. These rocks have undergone amphibolite facies metamorphism (5–7 kbar, 580°–620°C), in Upper Cretaceous to Eocene times, and were subsequently retrograded to greenschist facies metamorphism of Miocene age. Granitoids of Oligocene age, and volcanic rocks of Eocene-Oligocene age, crosscut the metamorphic rocks. Two major base metal sulfide ore varieties occur in the Thermes ore-field. The first comprises brecciated vein Pb-Zn mineralization, related to NNWand NNE-trending faults. The second comprises stratabound (manto) polymetallic, and Pb-Zn replacement ores with associated veins. On the basis of ore geochemistry, as well as field and textural evidence, these two ore varieties form part of a vein associated skarnreplacement base metal sulfide ore system. Based on fluid inclusion data in quartz, together with the iron content of sphalerites and existing lead and sulfur isotope data, it is suggested that after the cessation of the regional amphibolite facies metamorphism circulating evolved meteoric waters, probably with magmatic fluid contributions, deposited sulfide ores at temperatures of 200°2-400°C, and pressures of less than 300 bar. Ore was deposited as a result of increase in pH of the mineralizing fluids due to fluid-rock interaction, and adiabatic cooling and/or simple cooling accompanying fluid boiling. Thermochemical considerations indicate a pH increase from about 4 to 7 and a decrease in and .     

Rajkonkoski gold-telluride ore occurrence: A new high prospective type of complex noble metal mineralization in the Karelian Proterozoic

The Rajkonkoski ore occurrence is located within the region of the Karelian craton (AR₂) and the Svecofennian folded belt (PR₁) conjugation. It is presented by quartz-carbonate veins in metadoleriles and a zone of brecciation, crumple, and silification of carbonaceous shales within the volcanites of the Soanlakhtinsky suite (PR₁). Ore mineralization in black shales and quartz veins has features of genetic similarity presenting different levels of the ore system controlled by different range strike-slip fault dislocations. At the Rajkonkoski ore occurrence, 41 ore minerals have been identified: 12 tellurides (native tellurium, hedleyite, pilsenite, tsumoite, tellurobismuthite, hessite, stuetzite, radclidzhite, joseite-B, altaite, volynskite, petzite); 4 bismuth-tellurides of the following compositions Bi₃Te, Bi₃Te₂, BiTe₄, PbBiTe; 3 selenides (clausthalite, tellurolaitakarite, native selenium); and 12 native metals (gold, silver, electrum, copper, iron, lead, tin, bismuth, osmiridium). The contents of the main ore minerals in places exceed 10%, and the concentrations of elements reach as follows: Cu and Pb, 5%; Zn, Bi, 1%; Se, 219 ppm; Te, 171 ppm; Sb, 3 ppm; As, 5 ppm; Ag, >0.1%; Au, 35.28 ppm. Ore mineralization is formed during the temperature interval from 550°C up to <170oC in the conditions of high activity of Se and Te, and beginning from medium temperatures (>300°C) complete miscibilities galenite-clausthalite and galenite-altaite are observed. In aggregate with a wide temperature interval (>400°C) of ore process evolution and mineral specia variety of telluride and native metal mineralizations, the original “torsion” of different temperature mineralizations makes it possible to determine the affiliation of the Rajkonkoski ore occurrence to the xenothermal type deposits or epithermal “alkaline,” gold-telluride A-type characterized by a close connection with magmatism of increased alkalinity and the original geochemical (Te-V-F) and mineral (tellurides of gold, silver and other metals, fluorite, roscoelite, vanadium-containing sulfides) associations. Taking into consideration that many of the xenothermal and epithermal A-type gold and silver deposits are large commercial objects, the prospects of the Rajkonkoski ore occurrence and the region of the Karelian craton and Svecofennian folded belt conjugation seem to be significant for noble metal mineralization.     

Trace element chemistry of lithium-rich micas from rare-element granitic pegmatites

Summary Granitic pegmatites characterized by advanced accumulation and fractionation of incompatible rare lithophile elements (Li, Rb, Cs, Be, Ta Nb, B, P and F), often contain mineral assemblages which host lithium-rich micas. Lepidolite and lithian muscovite occur in high-pressure spodumene, low-pressure petalite, phosphorus-enriched amblygonite and fluorine-rich lepidolite subtypes of orogenic affiliated complex type granitic pegmatites and rarely in anorogenic affiliated amazonite-bearingTrace element data determined by X-ray fluorescence for lepidolite of various pegmatite subtypes, morphology (book, scaly, fine-grained), position within the pegmatite (primary zones, replacement units, pockets), mineral assemblages and tectonic affinity (orogenic vs anorogenic) show extreme fractionation of Rb and Cs; modest levels of T1, Ga, Nb, Ta, Sn and Zn; and typically low abundances of Ba, Sr, Ni, Pb, Y, V, W and Zr. Extreme fractionation is indicated by low values of K/Rb, K/Cs and Nb/Ta which are lowest in lepidolite from petalite subtype pegmatites.No systematic differences in trace element content is evident among the different lepidolite morphologies or paragenetic position. Lepidolite from spodumene subtype pegmatites are generally slightly less fractionated than those from petalite or lepidolite subtype pegmatites.

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Spurenelement-Chemie von Lithium-reichen Glimmern aus granitischen Pegmatiten

Zusammenfassung Granitische Pegmatite, die durch fortgeschrittene Anreicherung und Fraktionierung von inkompatiblen, seltenen, lithophilen Elementen (Li, Rb, Cs, Be, Ta Nb, B, P und F) charakterisiert sind, enthalten häufig Mineralparagenesen mit Lithium-reichen Glimmern. Lepidolith und Li-Muskowit treten in Hochdruck-Spodumen, in Niedrigdruck-Petalit, in mit Phosphor angereichertem Amblygonit und in Fluor-reichen Lepidolith-Unterarten aus komplexen orogenen granitischen Pegmatiten und selten auch aus anorogenen, Amazonit-führenden Pegmatiten, auf.Spurenelement-Daten aus der Röntgenfluoreszenzanalyse von Lepidolith aus verschiedenen Pegmatit-Untertypen, die Morphologie (tafelig, schuppig, feinkörnig), die Position innerhalb des Pegmatits (primäre Zonen, verdrängte Einheiten, Taschen), Mineralbestände und tektonische Affinität (orogen gegen anorogen) zeigen eine extreme Fraktionierung von Rb und Cs, bescheidene Gehalte an TI, Ga, Nb, Ta, Sn und Zn; und typischerweise geringe Häufigkeiten von Ba, Sr, Ni, Pb, Y, V, W und Zr. Die extreme Fraktionierung wird durch niedrige Werte von K/Rb, K/Cs und Nb/Ta angezeigt, die in Lepidolith von Pegmatiten des Petalit-Subtyps am niedrigsten sind.Aus den verschiedenen Morphologien oder paragenetischen Positionen von Lepidolith sind keine systematischen Unterschiede im Spurenelementgehalt ersichtlich. Lepidolith aus Pegmatiten des Spodumen-Subtyps sind generell etwas weniger fraktioniert als jene von Pegmatiten des Petalit- oder Lepidolith-Subtyps.

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With 4 Figures     

安徽铜陵矿集区铜官山矿田胶状黄铁矿矿物学特征及其对成矿作用的制约

铜官山矿田是铜陵矿集区内五大矿田之一,矿田内顺层产出的层状硫化物矿体是铜金矿床的主矿体,矿体内含有较多的胶状黄铁矿,其成因的争议制约了对铜金矿床成矿作用的解析。本文主要利用场发射扫描电镜(FE-SEM)等纳米矿物学手段,并结合光学显微镜、粉晶X射线衍射(XRD)、微区激光拉曼光谱分析等方法,对矿田内铜官山矿床及天马山矿床内层状硫化物矿体中胶状黄铁矿矿石的矿物组成、微形貌、微结构等特征进行系统研究,结果表明胶状黄铁矿矿石多呈胶状、鲕状结构,具有同心环状构造,同心环被赤铁矿、菱铁矿与黄铜矿脉穿切。同心环主要由白铁矿+有机质与胶状黄铁矿交替组成。胶状黄铁矿的黄铁矿颗粒粒径从纳米至亚微米均有分布,以自形-半自形立方体为主,少数呈他形,脉体边部胶状黄铁矿颗粒较大,自形程度较高,重结晶显著。矿石中含有少量白云石、伊利石微晶体,与胶状黄铁矿紧密共存,显示典型沉积特征。共存石英磨圆度较高,存在次生加大现象,表面存在胶状黄铁矿印模,显示为碎屑成因。这些综合信息表明胶状黄铁矿非岩浆热液成因,而是与石炭系地层同沉积成岩成因,并可能有微生物作用参与。高孔隙率、高化学活性及较高有机质含量的胶状黄铁矿可能为燕山期岩浆热液演化的含铜成矿流体提供了沉淀剂,对矿田内铜金硫化物矿体的层控性发挥了重要的控制作用。     

葡萄牙NeVes COrVO块状硫化物矿床锡石的微量元素地球化学

对葡萄牙Neves Corvo Cu.Sn多金属矿床锡矿石，富铜硫化物矿石和贫铜硫化物矿石中锡石的微量元素电子探针分析结果的综合研究表明，该矿床存在高温（＞300度），富W的早期锡矿化阶段，钞晚的贫W，富Cu，温度略低（245－295度）的Cu,Sn主矿化阶段，以旬晚的贫W，贫Cu温度更低（约200度）的Cu,Sn矿化阶段，结合Pb同位素研究可以推测矿床中Sn可能来源于矿体下部深处未出露的，与板块俯冲有关的富Sn古老地壳岩石，与其他类型锡矿床的微量元素对比表明，Neves Corvo矿床属于处于火山岩容矿（VHMS）型和沉积岩容矿（SHMS）型块状硫化物矿床之间的一种过渡类型－－伊比利亚型。     

Trace element chemistry of Apollo 14 lunar soil from Fra Mauro

Analytical data are presented for Apollo 14 fines ( < 1 mm) sample 14163,136 for 31 trace elements. The heavy REE are enriched monotonically by factors of 105 ± 10 over chondrites. Eu shows a large depletion (30 × chondrites) and the light REE show a smooth progressive enrichment with a slight fall at La. Ba, Cs, Th, U, Nb, Zr and Hf are strongly enriched, relative to chondritic abundances. Thus the outer portions of the moon sampled by the Imbrium event, and now represented by the Fra Mauro Formation, possessed high concentrations (100–200 × chondrites) for many elements, prior to the excavation of the mare basins. A correlation may exist between Gd/Eu and Zr/Hf ratios in lunar materials.     

Trace element chemistry of major rivers in Orissa State, India

 Geochemical analyses of surface waters from rivers flowing through Orissa State, India, indicated that trace element concentrations were extremely variable and consistently higher than world river average. The Brahmani River was the most solute-rich river studied, followed by the Baitarani and Mahanadi Rivers. Although all three rivers drain similar geology, the Brahmani River catchment is heavily industrialized, and water samples collected upstream and downstream from industries indicated that anthropogenic activity directly influenced its chemical composition. Samples collected from several towns, in all three river systems, did not invariably show similar patterns, with various elements having higher dissolved concentrations upstream. Because the concentration of total solids increased downstream, this implied that some components of the sewage had effectively sequestered available elements from solution and converted them to particulate material. Although the impact of pollution is clearly recognizable in water samples collected in proximity to the anthropogenic source, there are only slight elemental accumulations in the lower reaches of the Mahanadi River, with no accumulation in the Brahmani River. Apparently for these large rivers, discharged effluent becomes rapidly diluted, while complexation and sedimentation further removes trace elements from the water column. However, in the less voluminous Baitarani River, elementar enrichment near the river's mouth suggests that in this secondary river, where dilution effects are less, the concerns over regional water quality may be more prevalent. Received: 1 April 1995 · Accepted: 30 August 1995     

Application of pyrite trace element chemistry to exploration for SEDEX style Zn-Pb deposits: McArthur Basin,Northern Territory,Australia

Sedimentary pyrites in black shales contain abundant trace elements that provide information on the chemistry of the seawater at the time of sedimentation. This study focuses on the Barney Creek Formation (~ 1640 Ma) in the McArthur Basin in the Northern Territory of Australia, which is host to one of the world's largest SEDEX Zn-Pb-Ag deposits, and several smaller deposits. Fine-grained sedimentary pyrite has been sampled from three drill holes through the Barney Creek Formation at various distances from SEDEX mineralisation. Samples were selected through the stratigraphy of each hole and analysed by LA-ICPMS for a suite of 14 trace elements. The data show that sedimentary pyrite at the base of the Barney Creek Formation, closest (within 1 km) to SEDEX mineralisation, is strongly enriched in Zn and Tl by one to two orders of magnitude compared to the global average for sedimentary pyrite. In contrast sedimentary pyrite from the hole furthest from SEDEX mineralisation (~ 60 km) contains mean Zn and Tl values equal to, or less than, the global average. Based on the three drill hole pyrite data sets it is concluded that trace elements that are contributed to the basin during hydrothermal exhalation, and adsorbed into contemporaneous sedimentary pyrite, are principally Zn, Tl, Cu, Pb, Ag and As. In contrast, trace elements that are adsorbed into sedimentary pyrite from background seawater are principally Mo, Ni, Co, Se and As. These differences have enabled the development of a SEDEX fertility diagram for sedimentary basins, based on the composition of sedimentary pyrite, that distinguish high Zn, but barren shales, from high zinc SEDEX-related shales. In parallel with the increase in Zn and Tl in sedimentary pyrite approaching mineralisation there is a decrease in Ni, Co and Mo. This means that the ratios Zn/Ni and Tl/Co are particularly good pyrite vectors to SEDEX mineralisation in the McArthur Basin, varying over 4 to 6 orders of magnitude from barren shales to mineralised shales. It is speculated that the reason for the reverse relationship between Ni, Co and Zn, Tl may be caused by hydrothermal exhalations into the water column that effect the ion-exchange pyrite surface complexation processes that alter the uptake of these elements into sedimentary pyrite.Another important conclusion of this study is that hydrothermal exhalations into a sedimentary basin may affect the redox sensitive trace element chemistry of sedimentary pyrite and therefore the trace element chemistry of pyritic black shales. Nickel, Co and Mo all decrease in proximity to hydrothermal vents that form SEDEX deposits, whereas Zn, Tl and Pb increase. Selenium and bismuth are the only redox sensitive trace elements that appear to be unaffected by hydrothermal activity in the McArthur Basin. This has implications on how trace element concentrations of black shales and pyrite are used to reflect past global ocean chemistry.     

A secondary precious and base metal mineralization in chromitites linked to the development of a Paleozoic accretionary complex in Central Chile

Platinum-group element (PGE) and gold inclusions are usually present in peridotites and chromitite deposits associated with ophiolites. Here, we present the first detailed study of the mineralogy of precious metals in ultramafic rocks hosted in the Paleozoic Coastal Accretionary Complex of Central Chile. In these ultramafic rocks the mineralization of precious metals is associated with small meter-size pods and veins of massive chromitite hosted in serpentinite-filled shear zones. Crystallographic orientation maps of single chromite grains, obtained using the Electron-Backscattered Secondary Diffraction technique, allow us to identify two types of chromite in the precious-metal bearing chromitites: (1) Type A chromite, characterized by an average misorientation per grain of ≤ 2° and chemically homogeneous cores surrounded by a porous rim with abundant inclusions of chlorite, and (2) Type B chromite, which exhibits higher degrees of misorientation (2–8°) and porosity, and abundant silicate inclusions, but a relatively homogeneous chemical composition. In situ analyses using EMPA and LA-ICP-MS for major, minor and trace elements indicate that composition of the magmatic chromite is only preserved in the cores of Type A chromite grains. Core to rim chemical trends in these Type A chromites are characterized by a progressive increase of the Cr# with a decrease of the Mg#, loss of Al and addition of Fe^2 + in the porous rim. The observed changes in the microstructure and chemistry of chromite are associated with the infiltration of external fluids through shear zones filled with antigorite (± talc) developed in partly serpentinized peridotites (i.e., olivine–lizardite dunites). Thermodynamic calculations using the phase equilibria relations in the system Cr₂O₃–MgO–FeO–Al₂O₃–SiO₂–H₂O (CrMFASH) indicate that Fe^2 +-rich porous chromite + chlorite replaced the original assemblage chromite + olivine in the chromitite while prograde antigorite was formed. According to our results this transformation occurred at ~ 510–560 °C when external fluids penetrated the ultramafic/chromitite bodies through shear zones. These temperatures are slightly higher than estimated for the metamorphic peak in the host metapelitic rocks (i.e., ~ 420 °C at 9.3 kbar), suggesting that a hotter ultramafic body was captured by the metasediments of the accretionary prism during their exhumation through subduction channel. Chlorite geothermometry yielded a wide range of lower temperature from 430 to 188 °C, for chlorite present in the porous chromite rims. These results are in agreement with the retrograde overprint under greenchist-facies metamorphism conditions recorded by metapelitic host rocks and minor volcanogenic massive sulphide deposits in the area (300–400 °C, ~ 3–4 kbar). We suggest that although initially decoupled, the chromitite-bearing ultramafic rocks and their metasedimentary host undergone a common metamorphic PT pathway of exhumation during the formation and evolution of the subduction-related accretionary complex.The chromitites contain appreciable amounts of the platinum-group elements (up to 347 ppb total) and gold (up to 24 ppb), present as inclusions of platinum-group minerals (PGM) and alloys as well as native gold. The PGM identified include native osmium, laurite (RuS₂), irarsite (IrAsS), osarsite (OsAsS), omeiite (OsAs₂), Pt–Fe alloy (possibly isoferroplatinum) and a suite of inadequately identified phases such as PtSb (possibly stumpflite), PdHg (possibly potarite), RhS, Ir–Ni and Ir–Ni–Ru compounds. Only a few grains of osmium and laurite were identified in unaltered cores of chromite and therefore considered as magmatic in origin formed during the high-T event of chomite crystallisation in the upper mantle. The other PGM were located in the porous chromite associated with chlorite or base-metal minerals (BMM) that often fill the pores of this altered chromite or are intergrowth with antigorite in the host serpentinized ultramafic rock. The assemblage of BMM identified in the studied rocks include sulphides [millerite (NiS), polydymite (Ni₃S₄), violarite (FeNi₂S₄), galena (PbS), sphalerite (ZnS), chalcocite (CuS)], arsenides [(orcelite (Ni_5 − xAs₂) and maucherite (Ni₁₁As₈)], the sulpharsenide gersdorfitte (NiAsS), and native bismuth. The irregular shape of several PGM grains observed in porous chromite suggest disequilibrium, whereas others exhibit perfectly developed crystal faces with the associated secondary silicate or base-metal mineral suggesting neoformation of PGMs in situ from metamorphic fluids. We suggest that the origin of these PGM inclusions is magmatic, but some grains were reworked in situ when metalloid (i.e., As, Sb, Pb, Zn and Hg)-rich fluids released from metasediments penetrated the ultramafic rocks through active shear zones, once the ultramafic bodies became tectonically mixed with the host metasedimentary host rocks. During this event, gold sourced from the (meta)sediments was also precipitated within chromitites and serpentinites.     

H-chondrites: Trace element clues to their origin

We have analyzed 10 H-chondrites for 20 trace elements, using RNAA. The meteorites included 4 of petrologic type 4 and 2 each of types 3, 5 and 6.The data show that H-chondrites are not isochemical. H3's are depleted by some 10% not only in Fe (Dodd, 1976), but also in the siderophiles Os, Re, Ir, Ni, Pd, Au, and Ge. Moreover, the abundance pattern of siderophiles varies systematically with petrologic type. As similar fractionations of REE have been observed by Nakamura (1974), it appears that both the proportions and compositions of the main nebular condensates varied slightly during accretion of the H-chondrites. Thus the higher petrologic types are independent nebular products, not metamorphosed descendants of lower petrologic types.Abundances of highly volatile elements (Cs, Br, Bi, Tl, In, Cd, Ar³⁶) correlate with petrologic type, declining by ≤ 10^?3 from Type 3 to Type 6. The trends differ from those for artificially heated Type 3's (Ikramuddinet al., 1977b; Herzoget al., 1979), but agree passably with theoretical curves for nebular condensation. Apparently the low volatile contents of higher petrologic types are a primary feature, not the result of metamorphic loss.The mineralogy of chondrites suggests that they accreted between 405 K (absence of Fe₃O₄) and 560 K (presence of FeS), and the abundances of Tl, Bi, and In further restrict this interval to 420–500 K. Accretion at 1070 ± 100 K, as proposed by Hutchisonet al. (1979, 1980), leads to some extraordinary problems. Volatiles must be injected into the parent body after cooling, which requires permeation of the body by 10¹¹ times its volume of nebular gas. This process must also achieve a uniform distribution of the less volatile elements (Rb, Cu, Ag, Zn, Ga, Ge, Sn, Sb, Se, F), without freezeout in the colder outer layers.Factor analysis of our data shows 3 groupings: siderophiles (Os, Re, Ir, Ni, Pd, Au, and Ge), volatiles (Ag, Br, In, Cd, Bi, and Tl) and alkalis (Rb and Cs). The remaining 5 elements (U, Zn, Te, Se, and Sb) remain unassociated.     

Ureilites: Trace element clues to their origin

Carbonaceous vein separates from Kenna and Haverö, as well as bulk Kenna, were analyzed by RNAA for Ag, Au, Bi, Br, Cd, Cs, Ge, In, Ir, Ni, Pd, Os, Rb, Re, Sb, Se, Te, Tl. U, and Zn. The data are reviewed together with four earlier Chicago analyses of bulk ureilites. Linear regressions confirm the presence of two metal components, with the following Cl-normalized ratios: Ir/Ni = 14.6, ≤ 1; Ge/Ni = 5.4, 2.4; Au/Ni = 2.3, 0.9. The high-Ir component is enriched in vein separates and hence belongs to veins; the lowIr component belongs to the ultramafic rock. Vein material is enriched in all elements analyzed by us except Zn, and accounts for most of the C, noble gases, and presumably siderophiles in the meteorite. Most of the properties of ureilites apparently can be explained by the cumulate model of Berkley et al. (1980), with certain modifications. Comparison of ureilites with three other ultramafic rocks from different planets (Earth's mantle, lunar dunite, and Chassigny) suggests that the ureilite parent body had a primitive chondritic composition, similar to C3V chondrites but richer in metal and carbon. It melted, causing depletion of incompatibles to a mean abundance of ~0.02 × Cl and incomplete segregation of metal, FeS, and C. Fractional crystallization or melting of metal in the presence of S and C apparently can explain the fractionations of Ir, Re, Ni, Au, and perhaps Ge, obviating the need for extraneous sources of vein metal or unusual parent-body compositions. Noble gases from the parent material may have been retrapped in carbon during magmatism, provided the system was closed.     

Geochemical and isotopic composition of organic matter in the Kupferschiefer of the Polish Zechstein basin: relation to maturity and base metal mineralization

max vs the present depth of the Kupferschiefer, soluble organic matter (SOM) yields, and relative proportions of saturated and aromatic hydrocarbons of the SOM provide evidence for an oxidative alteration of organic matter in highly mineralized Kupferschiefer samples near the Rote F?ule zones. This is confirmed by differences in the composition of the saturated and aromatic hydrocarbon fractions of the soluble organic matter: Saturated hydrocarbons from Rote F?ule samples are dominated by short-chain n-alkanes and higher abundances of pristane and phytane relative to heptadecane (n-C17) and octadecane (n-C18), respectively, compared with samples more distant to the Rote F?ule zone. Compositional changes of the aromatic hydrocarbon fractions with decreasing distance to that zone are characterized by the occurrence of polycyclic aromatic hydrocarbons and elevated ratios of phenanthrene to methylphenanthrenes that are attributed to demethylation reactions and resulted in a decrease of the methylphenanthrene index (MPI 1). Kupferschiefer samples from the barren zone of the Polish Basin do not show these alteration patterns. The observed variations in organic matter composition with burial depth are consistent with changes due to increasing thermal maturation. Maturity assessment is achieved from MPI 1 and the methyldibenzothiophene ratio (MDR). From the relationship between the maturity of organic matter in terms of vitrinite reflectance values and depth of the Kupferschiefer strata, a continuous increase in reflectance of vitrinite is obtained within the Polish Basin. The alteration pattern of organic matter related to base metal mineralization of the Kupferschiefer corresponds to changes in the isotopic composition of organic carbon and calcite. Kerogen within, or close to, Rote F?ule zone is enriched in ¹³C caused by the preferential release of isotopically light organic compounds through progressive degradation of organic matter. The opposite tendency towards lower δ ¹³C and δ ¹⁸O values of calcite provides evidence for isotopic exchange between carbonate and the oxidizing, ore-bearing solutions and for organic matter remineralization. In contrast, organic matter and calcite from the Kupferschiefer do not show regular trends in δ ¹³C with increasing thermal maturation. Received: 25 June 1999 / Accepted: 1 December 1999     

Chemistry of Fe-Ti oxide minerals in the Hobenzan granitic complex,SW Japan: Subsolidus reduction in relation to base metal mineralization

Summary The mineralized stock of the Hobenzan granitic complex is composed of tonalite and a continuous differentiation series of biotite-hornblende granodiorite, hornblende biotite granite and biotite granite. Texture and mineral chemistry of the Fe-Ti oxide minerals in the Hobenzan granitic complex exhibit two different processes of magma evolution: one is an oxyexsolution process related to the magmatic and high temperature subsolidus stage, and the other is a reduction process of consecutive subsolidus stage. Rocks distributed in the northern part of the granitic complex preserve well the oxyexsolution process and show higher magnetic susceptibility, whereas those in the southern part of the complex, record the reduction process and show lower magnetic susceptibility.The magnetite-ilmenite geothermometer indicates temperatures of ca. 730°C for the oxide pairs of the early stage. Oxygen fugacity of one to three orders of magnitude higher than the annite-sanidine-magnetite (ASM) univariant curve, and an aqueous sulfur composition,fSO₂/fH₂S, of around 1.0 is indicated. This first stage corresponds to the crystallization of phenocrystic hornblende and plagioclase at depth. At about 700°C crystallization changed to biotite, K-feldspar and quartz, and continued to about 600°C. ThefO₂ during this second stage is buffered by the ASM assemblage. This second stage defines the oxyexsolution process. Below about 600°C, a reduction process, caused by assimilation of carbonaceous matter of country rocks, overprinted the southern part of the complex. Oxide pairs show that thefO₂ is about four orders of magnitude lower than the ASM univariant curve, andfSO₂/fH₂S is 10^–8.0 or less at 550°C for this reduced assemblage. The drastic change in composition of sulfur-bearing aqueous species may be one of the principal factors allowing base metal mineralization.

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Chemismus von Fe-Ti Oxiden des Hobenzan Granitkomplexes, SW Japan: Subsolidus Reduktion und ihre Beziehung zu metallischen Vererzungen

Zusammenfassung Der mineralisierte Hobenzan Granitkomplex setzt sich aus Tonaliten und einer kontinuierlichen Differentiationsserie, bestehend aus Biotit-Hornblende-Granodioriten, Hornblende-Biotit-Graniten und Biotit-Graniten, zusammen. Die Texturen und die Mineralchemie der Fe-Ti Oxide belegen zwei unterschiedliche Prozesse bei der Entwicklung des Hobenzan Granitkomplexes: einerseits einen Oxyexsolution-Prozeß, während des magmatischen und hochtemperierten Subsolidus-Stadiums, andererseits einen Reduktionsprozeß während des tiefertemperierten Subsolidus-Stadiums. Gesteine im nördlichen Hobenzan Komplex belegen vor allem den Oxyexsolution Prozeß und zeigen höhere magnetische Suszeptibilität, während jene im südlichen Teil den Reduktionsprozeß widerspiegeln und niedrigere magnetische Suszeptibilität zeigen.Das Magnetit-Ilmenit Geothermometer ergab Temperaturen von ca. 730°C für Oxidpaare des Frühstadiums. Die Sauerstoff Fugazität liegt um eine bis drei Größenordnungen über der univarianten Reaktionskurve Annit-Sanidin-Magnetit (ASM), und dasfSO₂/fH₂S Verhältnis der wässrigen Schwefelkomplexe bei ca. 1.0. Dieses Frühstadium korrespondiert mit der Kristallisation von Horblende und Plagioklas im Magma in größerer Tiefe. Ab ca. 700°C erfolgt die Kristallisation von Biotit, Alkalifeldspat und Quarz bis etwa 600°C, wobeifO₂ durch die ASM Mineralassoziation gepuffert wird. Dieses zweite Stadium wird als Oxyexsolution Prozeß beschrieben. Unter 600°C erfolgte eine Reduktion durch Assimilation von kohlenstoffreichem Material vor allem im südlichen Teil des Komplexes. Oxidpaare dieses Stadiums belegen, daßfO₂ um etwa vier Größenordnungen unterhalb des ASM Puffers liegt, undfSO₂/fH₂S ist 10^–8 bei 550°C. Die dramatische Änderung in der Zusammensetzung der Schwefelkomplexe in den Lösungen wird als der Hauptfaktor für die Bildung der Erzmineralisationen angesehen.

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With 5 Figures     

华南与花岗岩有关的一种新类型的锡成矿作用：矿物化学、元素和同位素地球化学证据

华南是我国最重要的锡成矿省,产有大量的与花岗岩有关的大型-超大型锡多金属矿床。近年来,在湘南新探明一个超大型锡矿床-芙蓉锡矿床,其中,最重要的锡矿化产在骑田岭花岗岩体西南部的破碎蚀变带内,与绿泥石化密切相关。骑田岭花岗岩富含角闪石,具有较高的氧逸度,显示出准铝的地球化学特征,在花岗岩形成过程中发生过壳-幔岩浆混舍作用。这些特点都表明骑田岭花岗岩并不同于一般的S型含锡花岗岩,而显示出A型花岗岩的地球化学特征。同位素定年分析表明,芙蓉锡矿床主成矿阶段的形成时代要晚于骑田岭花岗岩侵位年龄近20Ma。氢、氧同位素分析表明,发生过水-岩反应的大气降水在成矿流体中占有很重要的地位。硫同位素分析表明花岗岩和地层都提供了成矿所需的硫。因此,用花岗岩浆结晶分异过程中分离出富锡的岩浆流体来形成锡矿的传统模式并不适合于解释芙蓉锡矿的形成。我们认为芙蓉锡矿的形成主要与骑田岭花岗岩的绿泥石化蚀变有关,循环的大气降水与花岗岩发生水-岩反应,富锡的铁镁矿物在蚀变成绿泥石的同时释放出Sn和Ti等金属到流体中,当物理化学条件改变时,沉淀形成锡矿体。这是一种比较独特的锡矿化模式,丰富了华南与花岗岩有关的锡矿化类型。     

Reply to comments by Taylor and Neal on “Trace element crystal chemistry of mantle eclogites”

Conclusion In summary, there are no existing clinopyroxene-liquid REE distribution data obtained under appropriate conditions to permit numerical modeling of trace elements to constitute a critical test of the pyroxene fractionation process. There are, however, numerous clinopyroxeneliquid partitioning data in the literature that give qualitatively similar patterns to those observed in grospydites. Further, the high pressure fractionation model accounts for the major-element and exsolution phenomena in a manner directly consistent with experimental petrologic studies, and can qualitatively account for the trace element and isotopic characteristics of the rocks in a manner consistent with the crystal chemistry of the phases. We therefore continue to prefer the high-pressure clinopyroxene fractionation model over a low-pressure plagioclase fractionation model for the origin of the grospydites.     

Rudny Altai base-metal belt: Localization of massive sulfide mineralization

The geodynamic evolution, deep structure, and metallogenic regionalization of the Rudny Altai are considered in terms of plate tectonics. The base-metal massive sulfide deposits are genetically related to the group of basalt-andesite-rhyolite sequences formed in rift or island-arc geodynamic setting in the Devonian at the early stage of Hercynian tectogenesis. Taking into account economic reserves of ore and major metals (Cu, Pb, Zn, Au, Ag), as well as lateral and vertical regional metallogenic zoning of the Rudny Altai, the localization of massive sulfide mineralization in ore-bearing structural elements and particular deposits has been specified. The ore productivity of ore-bearing geochronological levels for base metals and the contribution of these levels to the total reserves of the region are characterized in detail. The Rudny Altai basemetal belt is regarded as a continuous ore-bearing structural unit situated in Russia and Kazakhstan.     

Modes of trace element occurrence in galena from the Partizansky base metal-skarn deposit, Primorye

The localization and chemical composition of the galena from the Partizansky base metal-skarn deposit have been studied in the Second Contact ore body and Bol’nichnaya ore lode. The Partizansky deposit was formed during two stages: base metal-skarn and silver-sulfosalt. Much of the galena was deposited with the productive galena-sphalerite assemblage at the first stage. The galena of the productive stage of the Second Contact body shows wide variations in trace element composition. The galena from the root zone of the ore-bodies (the level of ?135 m) is characterized by steady high contents of economically important isomorphic and mechanical admixtures of bismuth and silver. The galena from the middle levels is almost devoid of isomorphic admixtures and occasionally contains fine inclusions of Ag-tetrahedrite. The high silver (and stibium) contents in the galena from the uppermost horizon (the level of +285 m) are mainly related to mineral inclusions of diverse silver minerals of the late silver-bearing assemblage. The galena from the Bol’nichnaya lode over a large depth interval has elevated contents of isomorphic silver and bismuth, with abundant inclusions of native bismuth.