Lithogeochemical halos and geochemical vectors to stratiform sediment hosted Zn–Pb–Ag deposits, 1. Lady Loretta Deposit, Queensland

Stratiform sediment hosted Zn–Pb–Ag deposits, often referred to as SEDEX deposits, represent an economically important class of ore, that have received relatively little attention in terms of defining lithochemical halos and geochemical vectors useful to exploration. This study concentrates on the Lady Loretta deposit which is a typical example of the class of Proterozoic SEDEX deposits in northern Australia. We examined the major and trace element chemistry of carbonate-bearing sediments surrounding the deposit and defined a series of halos which extend for several hundred metres across strike and up to 1.5 km along strike. The stratiform ore lens is surrounded by an inner sideritic halo [Carr, G.R., 1984. Primary geochemical and mineralogical dispersion in the vicinity of the Lady Loretta Zn–Pb–Ag deposit, North Queensland. J. Geochem. Expl. 22, 217–238], followed by an outer ankerite/ferroan dolomite halo which merges with low iron dolomitic sediments representative of the regional background compositions. Carbonate within the inner siderite halo varies in composition from siderite to pistomesite (Fe_0.6Mg_0.4CO₃), whereas carbonate in the outer ankerite halo varies from ferroan dolomite to ankerite (Ca_0.5Mg_0.3Fe_0.2CO₃). Element dispersion around the stratiform ore lens is variable with Pb, Cu, Ba and Sr showing very little dispersion (<50 m across strike), Zn and Fe showing moderate dispersion (<100 m) and Mn and Tl showing broad dispersion (<200 m). Within the siderite halo Cu, Mg and Na show marked depletion compared to the surrounding sediments. The magnitude of element dispersion and change in carbonate chemistry around the Lady Loretta orebody has enabled the development of three geochemical vectors applicable to exploration. Whole rock analyses are used to calculate the three vector quantities as follows: (1) SEDEX metal index = Zn + 100Pb + 100Tl; (2) SEDEX alteration index = (FeO + 10MnO)100/(FeO + 10MnO + MgO); (3) manganese content of dolomite: MnO_d = (MnO × 30.41)/CaO. All three vectors increase to ore both across strike and along strike. The manganese content of dolomite (MnO_d) exhibits the most systematic pattern increasing from background values of about 0.2 wt% to a maximum of around 0.6 wt% at the boundary between the ankerite and siderite halos. Siderite within the inner halo contains considerably more Mn with MnO values of 0.4 to 4.0 wt%. It is suggested here that the basket of indices defined at Lady Loretta (Zn, Tl, metal index, alteration index, MnO_d and MnO_s) is applicable in the exploration for stratiform Zn–Pb–Ag deposits in dolomite-rich sedimentary basins generally. The indices defined can firstly assist in the identification of sedimentary units favourable for SEDEX mineralisation, and secondly provide vectors along these units to ore. The alteration index and MnO_d, however, should only be used for exploration dolomitic sequences; they are not recommended for exploration in clastic sequences devoid of carbonates.     

Geochemistry of subsurface Late Quaternary ironstones in Rajshahi and Bogra Districts,Bangladesh: implications for genetic and depositional conditions

The present study deals with the geochemistry of Late Quaternary ironstones in the subsurface in Rajshahi and Bogra districts, Bangladesh with the lithological study of the boreholes sediments. Major lithofacies of the studied boreholes are clay, silty clay, sandy clay, fine to coarse grained sand, gravels and sands with (fragmentary) ironstones. The ironstones contain major oxides, Fe₂O₃* (* total Fe) (avg. 66.6 wt%), SiO₂ (avg. 15.3 wt%), Al₂O₃ (avg. 4.0 wt%), MnO (avg. 7.7 wt%), and CaO (avg. 3.4 wt%). These geochemical data imply that the higher percentage of Fe₂O₃* along with Al₂O₃ and MnO indicate the ironstone as goethite and siderite, which is also validated by XRD data. A comparatively higher percentage of SiO₂ indicates the presence of relative amounts of clastic quartz and manganese-rich silicate or clay in these rocks. These ironstones also have significant amounts of MnO (avg. 7.7 wt%) suggesting their depositional environments under oxygenated condition. Chemical data of these ironstones suggest that the source rock suffered deep chemical weathering and iron was mostly carried in association with the clay fraction and organic matter. Iron concretion was mostly formed by bacterial build up in swamps and marshes, and was subsequently embedded in clayey mud. Within the coastal environments, the water table fluctuates and goethite and siderite with mud and quartz became dry and compacted to form ironstone.

     

Geology of the Early Devonian oolitic iron ore of the Gara Djebilet Field, Saharan Platform, Algeria

The oolitic iron ore of the Gara Djebilet field occurs within the Early Devonian sediments of the Tindouf Basin (Algerian Sahara), particularly in the Upper Djebilet Formation of Pragian age. Three large lenses form three individual deposits, extending E-W for about 60 km, namely Gara West, Gara Center and Gara East.The mineralization is interbedded with argillaceous to sandy sediments and it can be related to a barrier island palaeoenvironment, bordered by an inner lagoon or shallow embayment and an epicontinental sea. Trapped by Palaeozoic shoals, the oolitic sediments show a mineralogy marked mainly by magnetite, hematite, goethite, maghemite, chamosite (bavalite), siderite, apatite and quartz. Three paragenetic associations present a vertical distribution with a Lower non-magnetitic ore, a magnetitic ore and an Upper non-magnetitic ore.Three petrographical facies types have been defined: a cemented facies (FOC); a detrital facies (FOD); and a non-detrital facies (FOND).Chemical data for the whole field show a difference between the Lower non-magnetitic ore (Fe=54.6%), the Magnetitic ore (Fe=57.8%) and the Upper non-magnetitic ore (Fe=53%). The Magnetitic ore, which corresponds mainly to the workable ore (cutoff grade at 57%), has the following composition: SiO₂=4.9%, Al₂O₃=4.2%, Fe₂O₃=61.43%, FeO=19.2%, and P₂O₅=1.8%. The corresponding calculated economical ore reserves are 985×10⁶t, with 57.8% Fe.Regarding the genesis of the oolitic iron ore, a southern source is suggested for the iron, with deposition taking place in a quiet environment. There, the ooids developed by an intrasedimentary accretion mechanism around detrital grain within an iron-rich mud.The Gara Djebilet field is an important occurrence of the “North African Palaeozoic Ironstone Belt” extending from the Zemmour to Libya which also includes ironstones of Ordovician, Silurian and Devonian age.     

Structural changes and valence states in the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–FeCr<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution series

The influence on the structure of Fe²⁺ Mg substitution was studied in synthetic single crystals belonging to the MgCr₂O₄–FeCr₂O₄ series produced by flux growth at 900–1200 °C in controlled atmosphere. Samples were analyzed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption-, infrared- and Mössbauer spectroscopy. The Mössbauer data show that iron occurs almost exclusively as ^IVFe²⁺. Only minor Fe³⁺ (<0.005 apfu) was observed in samples with very low total Fe. Optical absorption spectra show that chromium with few exceptions is present as a trivalent cation at the octahedral site. Additional absorption bands attributable to Cr²⁺ and Cr³⁺ at the tetrahedral site are evident in spectra of end-member magnesiochromite and solid-solution crystals with low ferrous contents. Structural parameters a₀, u and T–O increase with chromite content, while the M–O bond distance remains nearly constant, with an average value equal to 1.995(1) Å corresponding to the Cr³⁺ octahedral bond distance. The ideal trend between cell parameter, T–O bond length and Fe²⁺ content (apfu) is described by the following linear relations: a₀=8.3325(5) + 0.0443(8)Fe²⁺ (Å) and T–O=1.9645(6) + 0.033(1)Fe²⁺ (Å) Consequently, Fe²⁺ and Mg tetrahedral bond lengths are equal to 1.998(1) Å and 1.965(1) Å, respectively.     

Partitioning of ferric and ferrous iron between plagioclase and silicate melt

Using the thermodynamic algorithm of Sugawara (Contributions to Mineralogy and Petrology 141, 2001, p. 659–686), FeO and Fe₂O₃ concentrations in plagioclase were computed for 420 published experiments on tholeiitic, FeTi-tholeiite, calc-alkaline, and alkaline magma compositions. Estimates of the partition coefficient between plagioclase and liquid range from 0.19 to 0.92 for Fe₂O₃ and from 0.008 to 0.050 for FeO, i.e. ca. twenty times greater for Fe₂O₃ than for FeO. Partitioning of Fe₂O₃ and FeO is independent of both oxygen fugacity and plagioclase composition, contradicting the common assumption that partitioning of Fe₂O₃ correlates positively with the amount of aluminium in plagioclase. In contrast, the SiO₂-content of the magma correlates positively with the partition coefficients for Fe₂O₃ and FeO. This is ascribed to increasing activity of iron in polymerised SiO₂-rich magma. Advances of micro-beam Fe-XANES techniques allow the determination of Fe³⁺/Fe in plagioclase. Using such plagioclase data and the partition coefficients for Fe₂O₃ and FeO, the Fe₂O₃/FeO and oxygen fugacity of equilibrium magma may be estimated. As petrological examples, we estimate that the oxygen fugacity of the Palisades sill ranged from the QFM buffer to 0.5 log unit below it (QFM to QFM –0.5), the Lake County basalt from QFM to QFM –2, and Upper Zone a of the Skaergaard intrusion from QFM –1 to QFM –1.5.Editorial responsibility: I. Parsons     

Mineralogy and geochemistry of Late Ordovician phosphate-bearing oolitic ironstones from NW Sardinia, Italy

Summary. ?In the Nurra region, NW Sardinia, oolitic ironstones are interlayered within coarsening upward metasedimentary sequences of siltstone, sandstone, breccia, and conglomerate. A Caradoc-Early Ashgill age is suggested by the analogies with metasediments of Central-Southern Sardinia following the Sardinian tectonic phase. The sequences including oolitic ironstones are overlain by black metapelite of inferred Hirnantian to early Silurian age. The ooids consist of chamosite, siderite or magnetite or, rarely, stilpnomelane. Chamosite ooids consist of up to 30 lamellae and sporadically show clustering of magnetite grains in core and rim, and widespread late replacement by siderite. The alternation of chamosite and Fe-oxide observed in a few samples points to an ooid transport over the crests and hollows of megaripples in a continental shelf at 0–60 m depth, and/or a random displacement of the littoral environments in a rapidly evolving continent-sea transition zone producing an alternation of oxidizing and reducing conditions. Black phosphate clasts, including older Fe-ooids, frequently occur. The oolitic ironstones of Nurra are variable mixtures of an Al-Si-Ti rich- detrital component and a Fe-rich chemical component. The abundance of chamosite and siderite explains the high values of LOI and the high Fe_tot, Fe²⁺ and Al contents and the low Si amounts in comparison with other Phanerozoic oolitic ironstones. The detrital elements are Al, Si, Ti, Mg, Zr, Th. Chemical precipitation processes supplied Fe, Ca, P, Sr, HREE. The chondrite-normalized pattern shows a slight LREE enrichment, a clear negative Eu anomaly, and a flat HREE trend typical of many Ordovician oolitic ironstones. The NASC-normalized pattern has a convex shape, with peaks for Sm, Gd, like in all the pre-Devonian phosphate deposits. The numerous phosphate clasts, pyrite pockets, diffuse organic matter, and lack of glauconite suggest an upward extension of the oxygen minimum layer in a stratified basin, up to a depth of 60 m, and allow the estimation of log fO₂ = − 72 to − 80 and pH = 9.0–9.5. for the underlying pyrite zone (depth > 60 m). Here the pore waters leached Eu²⁺ from the bottom sediments giving the observed negative anomaly of the chondrite-normalized REE pattern.

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Résumé ?Dans la région de la Nurra, Sardaigne nord-ouest, des niveaux ferrugineux oolithiques sont intercalés dans des séquences métasédimentaires composées de silts, grès, brèches et conglomerats. Un age Caradoc-Ashgill inférieur est suggéré par les analogies avec les métasédiments de la Sardaigne centrale-méridionale postérieurs à la phase tectonique Sarde. Les séquences qui contiennent les niveaux ferrugineux oolithiques sont surmontées par des métapélites noires pour lesquelles on suppose un age Hirnantien à Siliurien inférier. Les oolithes sont constituées de chamosite, siderite ou magnétite ou rarement, stilpnomelane. Les oolithes de chamosite peuvent avoir jusq’à 30 enveloppes dans le cortex et sporadiquement elles montrent une concentration de grains de magnétite au centre et sur le bord et un vaste replacement tardif par de la sidérite. L’alternation de enveloppes à chamosite et à oxydes de fer observée dans quelques échantillons indique un transport des oolithes sur la crête et dans la dépression de rides géantes sur une plateforme continentale à 0–60 m de profondeur et/ou bien un déplacement casuel des milieux c?tiers dans une zone de transition entre mer et continent en rapide évolution, ce qui produisait une alternation de conditions oxydantes et réduisantes. On trouve fréquemment des intraclastes noirs de phosphate qui contiennent des oolithes ferrugineuses plus anciennes. Les niveaux oolithiques ferrugineux de la Nurra sont le résultat d’un mélange en proportions variables entre une composante détritique riche en Al, Si,Ti et une composante chimique riche en fer. L’abondance de chamosite et sidérite explique les hautes valeurs de perte au feu et la haute teneur en Fe_tot, Fe²⁺ et Al et la basse teneur en Si en comparaison avec d’autres formations oolithiques ferrugineuses Phanérozo?ques. Les éléments détritiques sont Al, Si, Ti, Mg, Zr, Th. Les processus de précipitation chimique ont fourni Fe, Ca., P, Sr, HREE. Les teneurs de terres rares normalisées aux chondrites montrent un léger enrichissement en LREE, une évidente anomalie négative de Eu, et une disposition en plateau des HREE, qui est tipique de beaucoup de formations oolithiques ferrugineuses Ordoviciennes. Les teneurs normalisées aux NASC forment une courbe convexe avec deux maxima pour Sm et Gd, comme dans tout les dép?ts phosphatés pré-Dévoniens. Les nombreux intraclastes de phosphate, les cavités pleines de pyrite, l’abondance de matière organique et l’absence de glacounie suggèrent une extension vers plus faible profondeurs ( jusq’à 60 m) de la couche d’eau marine ayant la moindre teneur en oxygène dans un bassin stratifié. Pour la zone à pyrite qui est en dessous de la zone oolithique (profondeur > 60 m) on estime les conditions suivantes: log fO₂ = − 72 à− 80 et pH = 9.0–9.5. Les eaux intergranulaires solubilisent et emportent le Eu²⁺ des sediments du fond et donnent l’anomalie négative de Eu pour les teneurs de terres rares normalisées aux chondrites.

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Received February 10, 1999;/revised version accepted June 30, 1999     

Geology and characterisation of the Pecket coal deposit, Magellan Region, Chile

The geology, petrography and chemical variation of the Pecket coal sequence, Magellan Region (52°57′S, 71°10′W), the only Chilean coal used for electricity generation on a large scale, has been studied in order to predict their combustion behaviour, especially in coal blends. The depositional environment of formation of the coal seams was a swamp rarely exposed to subaerial conditions and was associated with the development of the folded foreland of the Magellan basin during the Tertiary (Oligo–Miocene). The general tectonic regime of the collision of the Antarctic and South American plates is reflected by a system of joints with 40°N–50°W strike. The maceral composition of all six seams studied indicates high contents of vitrinite (>90%), minor content of liptinite (4.7%) and inertinite (<2%). Occurrence of tonstein horizons altered to kaolinite indicates a distal volcanism during peat accumulation. Coal rank varies between lignite and subbituminous (Ro=0.28–0.42%) with an average dry basis calorific value of 5450 kcal/kg, 17 wt.% moisture, 41 wt.% volatile matter, and sulphur content below 0.5 wt.%. The mineral matter (LTA) associated with the coal shows a dominance of kaolinite with quartz, smectite, and minor basanite. SiO₂/Al₂O₃ and Fe₂O₃/CaO ratios of the ashes diminish towards the lower seams. With respect to the utilisation of Pecket coals in combustion, base/acid ratios (B/A) and silica ratios (SR) indicate potential fouling for seams 1, 2, 5, and 6i, with high fouling indexes (Rf) for seams 2 and 5. Pecket coal is excellent for blend combustion due to its low sulphur content.     

Experimental identification of CO2–water–rock interactions caused by sequestration of CO2 in Westphalian and Buntsandstein sandstones of the Campine Basin (NE-Belgium)

Geological sequestration of CO₂ is one of the options studied to reduce greenhouse gas emissions. Although the feasibility of this concept is proven, apart from literature data on modelling still little is known about the CO₂–water–rock interactions induced by CO₂-injection.To evaluate the effect of CO₂–water–rock interactions on three sandstone aquifers in NE-Belgium an experimental setup was built. Eighteen experiments were performed in which sandstones were exposed to supercritical CO₂. CO₂–water–rock interactions were deduced from the evolution of aqueous concentrations of 25 species and a thorough characterisation of the sandstones before and after treatment. The results show that dissolution of ankerite/dolomite and Al-silicates could enhance porosity/permeability. The observed precipitation of end-member carbonates could increase storage capacity if it exceeds carbonate dissolution. Precipitation of the latter and of K-rich clays as observed, however, can hamper the injection.     

Ferromanganese carbonate metasediments of the Sob area,Polar Urals: Bedding conditions,composition, and genesis

The paper presents the results of study of ferromanganese carbonate rocks in the Sob area (Polar Urals), which is located between the Rai-Iz massif and the Seida–Labytnangi Railway branch. These rocks represent low-metamorphosed sedimentary rocks confined to the Devonian carbonaceous siliceous and clayey–siliceous shales. In terms of ratio of the major minerals, ferromanganese rocks can be divided into three varieties composed of the following minerals: (1) siderite, rhodochrosite, chamosite, quartz, ± kutnahorite, ± calcite, ± magnetite, ± pyrite, ± clinochlore, ± stilpnomelane; (2) spessartite, rhodochrosite, and quartz, ± hematite, ± chamosite; (3) rhodochrosite, spessartite, pyroxmanite, quartz ± tephroite, ± fridelite, ± clinochlore, ± pyrophanite, ± pyrite. In all varieties, the major concentrators of Mn and Fe are carbonates (rhodochrosite, siderite, kutnahorite, Mn-calcite) and chlorite group minerals (clinochlore, chamosite). The chemical composition of rocks is dominated by Si, Fe, Mn, carbon dioxide, and water (L.O.I.): total SiO₂ + Fe₂O ₃ ^tot + MnO + L.O.I. = 85.6?98.4 wt %. The content of Fe and Mn varies from 9.3 to 55.6 wt % (Fe₂O ₃ ^tot + MnO). The Mn/Fe ratio varies from 0.2 to 55.3. In terms of the aluminum module Al_M = Al/(Al + Mn + Fe), the major portion of studied samples corresponds to metalliferous sediments. The δ¹³C_carb range (–30.4 to–11.9‰ PDB) corresponds to authigenic carbonates formed with carbon dioxide released during the microbial oxidation of organic matter in sediments at the dia- and/or catagenetic stage. Ferromanganese sediments were likely deposited in relatively closed seafloor zones (basin-traps) characterized by periodic stagnation. Fe and Mn could be delivered from various sources: input by diverse hydrothermal solutions, silt waters in the course of diagenesis, river discharges, and others. The diagenetic delivery of metals seems to be most plausible. Mn was concentrated during the stagnation of bottom water in basin-traps. Interruption of stagnation promoted the precipitation of Mn. The presence of organic matter fostered a reductive pattern of postsedimentary transformations of metalliferous sediments. Fe and Mn were accumulated initially in the oxide form. During the diagenesis, manganese and iron oxides reacted with organic matter to make up carbonates. Relative to manganese carbonates, iron carbonates were formed under more reductive settings and higher concentrations of carbon dioxide in the interstitial solution. Crystallization of manganese and iron silicates began already at early stages of lithogenesis and ended during the regional metamorphism of metalliferous sediments.     

Paleoenvironmental significance of aluminum phosphate-sulfate minerals in the upper Cretaceous ooidal ironstones,E-NE Aswan area,southern Egypt

Aluminum phosphate-sulfate (APS) minerals are present as small, disseminated crystals in the upper Cretaceous shallow marine ooidal ironstones, E-NE Aswan area, southern Egypt. Their association with the ironstones is considered as a proxy of subaerial weathering and post-diagenetic meteoric water alteration. The mineralogical composition of the ooidal ironstones was investigated by optical and scanning electron microscopes, X-ray diffraction, Fourier transform infrared and Raman spectroscopy. The ooidal ironstones are composed mainly of ooids and groundmass, both of which consist of a mixture of detrital (quartz) and diagenetic (fluorapatite, chamosite and pyrite) mineral assemblages. These mineral assemblages are destabilized under acidic and oxidizing, continental conditions. These conditions resulted from the oxidation of pyrite and probably organic matter under warm and humid, tropical climate followed the Santonian Sea regression and subaerial exposure. These pedogenic conditions promoted corrosion of quartz, dissolution of chamosite and apatite and hydrolysis of feldspars of the nearby exposed granitoids. The released Si, Al and Sr from quartz, chamosite and feldspars; Fe and S from pyrite and P, Ca and light rare earth elements (LREE) from apatite are reprecipitated as hematite, kaolinite, apatite and APS minerals from the pore fluids or along fractures. The paragenetic sequence and textural relationships of this post-diagenetic mineral assemblage indicate that hematite was formed by replacement of chamosite followed by formation of a secondary generation of pore filling chlorapatite and APS minerals and finally the precipitation of kaolinite in the remaining pore spaces. The formation of APS minerals and chlorapatite is simultaneous, but APS minerals are stable at shallow depths under acidic to neutral pH conditions, whereas chlorapatite is stable under alkaline pH conditions. Alkaline conditions were maintained at greater depths when the infiltrated acidic fluids reacted with chamosite. The APS minerals display a homogeneous chemical composition in all ironstone locations in Aswan area, corresponding to a solid solution between crandallite (CaAl₃(PO₄)₂(OH)₅·H₂O), goyazite (SrAl₃(PO₄)₂(OH)₅·H₂O), svanbergite (SrAl₃(PO₄)(SO₄)(OH)₆) and woodhouseite (CaAl₃(PO₄)(SO₄)(OH)₆) end-members. The variations in the APS mineral chemistry (AB₃(XO₄)₂(OH)₆) are essentially due to variable substitutions of Sr and LREE for Ca at the A site and limited S for P at the X site. The spatial distribution of APS minerals and their composition in the ooidal ironstones of Aswan area permitted to consider them as good tracers of physicochemical and paleoenvironmental changes, in particular those associated with subaerial exposure and pedogenesis. The post-diagenetic phosphatization and kaolinization of the Aswan ironstones decrease their economic potentiality; thus, understanding paragenetic sequence and textural relationships is essential for the iron ore beneficiation.     

Geochemistry and mineralogy of laterites in the Sula Mountains greenstone belt, Lake Sonfon gold district, Sierra Leone

Geochemical and mineralogical investigations have been carried out on laterite profiles developed in the Lake Sonfon Au district of northern Sierra Leone. The area is underlain by Archean metavolcanics and constitutes part of the Sula Mountains greenstone belt, which is mineralized in Au. Extensive lateritization has affected the rocks of this region, resulting in a profile which from bottom to top consists typically of a decomposed bedrock zone, a pisolitic laterite layer and a duricrust layer. Both the pisolitic and duricrust layers of the laterite are sometimes punctuated by lenses of ironstones containing high amounts of Cu, Zn, Ni, Co and Ce. Gold occurs as small grains within the heavy mineral fraction recovered from the decomposed rock zones and pisolitic layers of the profiles and also in gravels of streams draining the area. The mineralogy of the duricrust and pisolitic layers is dominated by goethite, gibbsite and quartz, with minor amounts (<5% by volume) of ilmenite, magnetite, haematite, rutile and kaolinite. The kaolinite content increases towards the decomposed rock zone, where talc, vermiculite and other layer lattice silicates become abundant. The heavy-mineral fraction of stream sediments is composed essentially of ilmenite, magnetite, haematite, and traces of rutile, zircon, tourmaline and Au. The Au grains are often characterized by a 10–200-μm-wide rim having a much lower content of Ag (0.3 wt.% or lower) than the grain interior (about 5 wt.% on average). Dissolution effects are also observed on the grain surfaces. It is considered that Au derived from the amphibolite parent rock is dissolved, transported, and redeposited during laterization.The duricrust cover of the laterite profiles is characterized by high contents of Fe₂O₃ (ca. 60 wt.%) and Al₂O₃ (ca. 32wt.%) and low content of SiO₂ (ca. 9 wt.%). In comparison, the pisolitic layer is higher in SiO₂ (ca. 18 wt.%) as well as a slightly higher in Al₂O₃ (ca. 34 wt.%). Lateritic weathering has resulted in the removal of CaO, Na₂O, MgO and SiO₂, with relative enrichment of Fe₂O₃ and Al₂O₃. The geochemical distribution of the trace elements in the laterite profiles can be related to the occurrence of the auriferous mineralization. The significance of these observations is discussed in relation to the origin of the lateritic Au and the role of the associated trace elements as indicators of the mineralization.     

Nickel und Kobalt in Gesteinen des Nördlinger Ries

Zusammenfassung Von Glasbomben aus dem Suevit und kristallinen Gesteinen verschiedener Auswurfbreccien des Rieskraters wurden die Nickel- und Kobaltgehalte bestimmt. Die Gläser enthalten 10,0–51,5 ppm Ni (Mittel von 70 Analysen: 30,1 ppmNi) und 4,8–15,8 ppm Co (Mittel von 50 Analysen: 12,1 ppm Co). Die höchsten Nickel- und Kobaltgehalte finden sich in den nicht rekristallisierten und chemisch unveränderten Bomben des Typ I. Die kristallinen Gesteine des Grundgebirges enthalten 2,5–140 ppm Ni (22 Analysen) und 2,2–29,8 ppm Co (22 Analysen).Die Kobaltgehalte der nicht rekristallisierten Gläser sind ziemlich einheitlich (10,7–15,8 ppm) und ebenso hoch wie diejenigen der kristallinen Gesteine ähnlicher Gehalte an MgO, MgO+FeO+Fe₂O₃ und SiO₂. Die Nickelgehalte der nicht rekristallisierten Gläser dagegen streuen inhomogen über einen größeren Bereich (30,0–51,5 ppm). Sie sind im Mittel höher als die der kristallinen Gesteine mit ähnlichen Gehalten an MgO, MgO+FeO+Fe₂O₃ und SiO₂. Der maximale Unterschied beträgt 25 ppm Ni.

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Ni and Co in rocks from the Nördlinger Ries

Ni and Co have been determined in glass bombs from the suevite and crystalline rocks from different breccia outcrops in the Ries crater. The glasses contain 10.0–51.5 ppm Ni (average of 70 analyses: 30.1 ppm Ni) and 4.8–15.8 ppm Co (average of 50 analyses: 12.1 ppm Co). Highest contents of Ni and Co are to be found in non-recrystallized and chemically unchanged bombs of type I. Crystalline rocks from the basement contain 2.5–140 ppm Ni (22 analyses) and 2.2–29.8 ppm Co (22 analyses).The Co-contents of non-recrystallized glasses are rather uniform (10.7–15.8 ppm) and as high as those of crystalline rocks of similar content of MgO, MgO+FeO+Fe₂O₃ and SiO₂. The Ni-contents of non-recrystallized glasses are inhomogeneously scattered over a larger range (30.0–51.5 ppm). On the average, they are higher than those of crystalline rocks with similar contents of MgO, MgO+FeO+Fe₂O₃ and SiO₂. The maximum difference is 25 ppm Ni.

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Herr Prof. W. von Engelhardt veranlaßte die Bearbeitung dieses interessanten Themas und nahm am Fortgang der Untersuchungen regen Anteil. Herr Dr. D. Stöffler stellte freundlicherweise Probenmaterial zur Verfügung und Herr Dr. H. Puchelt war mir bei analytischen Fragen behilflich. Ihnen allen danke ich für die Förderung dieser Arbeit.     

Mineralogical and compositional characteristics of Late Permian coals from an area of high lung cancer rate in Xuan Wei, Yunnan, China: Occurrence and origin of quartz and chamosite

Some townships in Xuan Wei County, Yunnan Province, have one of the highest lung cancer mortality rates in China and the epidemic disease in the area has generally been attributed to the polycyclic aromatic hydrocarbons (PAHs) released from domestic coal burning. However, the cancer-causing culprit is not settled as Tian [Tian, L., 2005. Coal Combustion Emissions and Lung Cancer in Xuan Wei, China. Ph.D. thesis, University of California, Berkeley.] found nanometer quartz in these coals, soot emissions, and lung cancer tissues. We have conducted mineralogical and geochemical studies of the coals from Xuan Wei for the purpose of shedding light on the minerals which may be related to the epidemic lung cancer. In this paper, abundances, modes of occurrence, and origins of minerals and elements in the coals from two mines in Xuan Wei have been studied using optical microscope, low-temperature ashing, X-ray diffraction analysis, scanning electron microscope equipped with energy-dispersive X-ray spectrometer, and inductively-coupled plasma mass spectrometry. The minerals in the coals are mainly composed of quartz, chamosite, kaolinite, and calcite. The particle size of quartz is rather small, mostly less than 20 μm and it is of authigenic origin. Chamosite occurs mainly as cell-fillings. The occurrence of quartz and chamosite indicates that they were derived from the hydrothermal fluids. Epigenetic calcite is derived from calcic fluids. Kaolinite is derived mainly from sediment source region of Kangdian Oldland to the west of coal basin. The composition of Xuan Wei coal is high in SiO₂, Fe₂O₃, TiO₂, CaO, MnO, V, Co, Ni, Cu, and Zn. The high SiO₂ content is attributed to quartz, and the Fe₂O₃ content to chamosite. The high Mn and low Mg contents in the coal indicate the inputs of hydrothermal fluids. CaO occurs mainly in epigenetic calcite. Elements Ti, Co, Ni, Cu, Zn, and rare earth elements were derived from the basaltic rocks at sediment source region.     

The MgCr2O4–MgFe2O4 solid solution series: effects of octahedrally coordinated Fe3+ on T–O bond lengths

The influence on the spinel structure of Fe³⁺ → Cr substitution was studied in flux-grown synthetic single crystals of the magnesiochromite–magnesioferrite (MgCr₂O₄–MgFe₂O₄) solid solution series. Samples were analysed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption and Mössbauer spectroscopy. With the exception of iron-poor samples (3–12 mol-% MgFe₂O₄), optical absorption and Mössbauer spectra show that iron occurs almost exclusively as trivalent Fe in the present samples. A very intense and broad absorption band at ca 7,800 cm^?1 dominates the optical absorption spectra of samples with higher Fe-contents. The appearance of this band is related to a distinct structural disorder of Fe³⁺ and a development of magnetic ordering as demonstrated by Mössbauer spectra. Profound composition-related changes are observed in the Mössbauer spectra, which are magnetically unsplit in the range 2–41 mol-% magnesioferrite, but become magnetically split in the range 59–100 mol-% magnesioferrite. Structural parameters a ₀ and M–O increase with magnesioferrite content and inversion degree, while u and T–O decrease. Our study confirms the previously reported (Lavina et al. 2002) influence of Fe³⁺ at the M site on T–O bond lengths in the spinel structure.     

Breakdown of hydrous ringwoodite to pyroxene and spinelloid at high P and T and oxidizing conditions

To get deeper insight into the phase relations in the end-member system Fe₂SiO₄ and in the system (Fe, Mg)₂SiO₄ experiments were performed in a multi-anvil apparatus at 7 and 13 GPa and 1,000–1,200°C as a function of oxygen fugacity. The oxygen fugacity was varied using the solid oxygen buffer systems Fe/FeO, quartz–fayalite–magnetite, MtW and Ni/NiO. The run products were characterized by electron microprobe, Raman- and FTIR-spectroscopy, X-ray powder diffraction and transmission electron microscopy. At fO₂ corresponding to Ni/NiO Fe-ringwoodite transforms to ferrosilite and spinelloid according to the reaction: 9 Fe₂SiO₄ + O₂ = 6 FeSiO₃ + 5 Fe_2.40Si_0.60O₄. Refinement of site occupancies in combination with stoichiometric Fe³⁺ calculations show that 32% of the total Fe is incorporated as Fe³⁺ according to From the Rietveld refinement we identified spl as spinelloid III (isostructural with wadsleyite) and/or spinelloid V. As we used water in excess in the experiments the run products were also analyzed for structural water incorporation. Adding Mg to the system increases the stability field of ringwoodite to higher oxygen fugacity and the spinel structure seems to accept higher Fe³⁺ but also water concentrations that may be linked. At oxygen fugacity corresponding to MtW conditions similar phase relations in respect to the breakdown reaction in the Fe-end-member system were observed but with a strong fractionation of Fe into spl and Mg into coexisting cpx. Thus, through this strong fractionation it is possible to stabilize very Fe-rich wadsleyite with considerable Fe³⁺ concentrations even at an intermediate Fe–Mg bulk composition: assuming constant K _D independent on composition and a bulk composition of x _Fe = 0.44 this fractionation would stabilize spl with x _Fe = 0.72. Thus, spl could be a potential Fe³⁺ bearing phase at P–T conditions of the transition zone but because of the oxidizing conditions and the Fe-rich bulk composition needed one would expect it more in subduction zone environments than in the transition zone in senso stricto.

Stability of sapphirine + quartz in the oxidized rocks of the Wilson Lake terrane,Labrador: calculated equilibria in NCKFMASHTO

The equilibrium coexistence of sapphirine + quartz is inferred to record temperatures in excess of 980 °C, based on the stability of this assemblage in the simplified chemical system FeO–MgO–Al₂O₃–SiO₂ (FMAS) system. However, the potential for sapphirine to contain significant Fe³⁺ suggests that the stability of sapphirine + quartz could extend to lower temperatures than those constrained in this ideal system. The Wilson Lake terrane in the Grenville Province of central Labrador preserves sapphirine + quartz‐bearing assemblages in highly oxidized bulk compositions, and provides an opportunity to explore the stability of sapphirine + quartz in such rock compositions within the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (NCKFMASHTO) chemical system. Starting with the phase equilibria in FeO–MgO–Al₂O₃–SiO₂–TiO₂–O (FMASTO), expansion into K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (KFMASHTO) allows the effect of the stability of the additional phases, biotite, K‐feldspar and melt, on the stability of sapphirine + quartz to be assessed. These phase relations are evaluated generally using P–T projections, and the ultimate extension into NCKFMASHTO is done with pseudosections. Conditions of peak metamorphism in the Wilson Lake terrane are constrained using P–T pseudosections, and the appropriate H₂O and O contents to use in the modelled compositions are investigated using T–M_H2O and T–M_O pseudosections. The peak P–T estimates from a sapphirine + quartz‐bearing sample are ～960 to 935 °C at ～10 to 8.6 kbar, similar to estimates from orthopyroxene + sillimanite + quartz ± garnet‐bearing samples. Whereas the sapphirine + quartz‐bearing sample is more Fe‐rich than the orthopyroxene + sillimanite‐bearing sample on an all‐Fe‐as‐FeO basis, once the oxidation state is taken into account, the former is effectively more magnesian than the latter, accounting for the sapphirine occurrence.     

How Cr<Superscript>3+</Superscript> and Fe<Superscript>3+</Superscript> affect Mg–Al order–disorder transformation at high temperature in natural spinels

Three natural Mg(Al_2-yCr_y)O₄ spinels (y 0.07–0.16), highly ordered in terms of Mg–Al, and one Mg(Al_2–yFe³⁺_y)O₄ spinel (y0.08), highly ordered also in terms of Fe³⁺, were studied by means of X-ray single-crystal diffraction. All samples were heated in situ from 25 to 1000 °C in order to follow both thermal expansion and evolution of the structural state of spinel with temperature. Thermal expansion was monitored by means of the variation of cell edge a with temperature, and found to be well represented throughout the temperature range by a regression line a = a₀ (1+T), slightly different at lower and higher temperatures. Thermal expansion coefficient ₁, referring to the lower temperature range (i.e. during pure thermal expansion), was slightly lower than ₂, calculated only over the highest temperatures. The trend showed different slopes for individual crystals. Structural evolution with temperature was studied by means of the variation of oxygen positional parameter u, which is strongly influenced by intersite cation exchange and thus closely correlated with inversion parameter x. In particular, in the three Cr samples, in which Cr resides only in the octahedral site, u parameter variations and hence the order–disorder process, started at about 700 °C. Instead, in the Fe³⁺ sample, this process was triggered at lower temperatures, starting at 550 °C with Fe³⁺–Mg exchange followed at higher temperatures by that of Mg–Al. Cr contents in the Cr samples affected the occupancy of Al in the tetrahedral site at the highest temperatures. In both Mg–Al–Cr and Mg–Al–Fe³⁺ compositions, if CrFe³⁺, parameter u reached the same value only when the Mg–Al exchange was dominant, i.e. at the highest temperatures, but not before. Cation distribution at each temperature was obtained by the bond-length model, applying thermal expansion to pure bond lengths. This method is applied here to complex compositions for the first time.     

Primary cracking of kerogens. Experimenting and modelling C1, C2–C5, C6–C15 and C15+ classes of hydrocarbons formed

Mathematical models of hydrocarbon formation can be used to simulate the natural evolution of different types of organic matter and to make an overall calculation of the amounts of oil and/or gas produced during this evolution. However, such models do not provide any information on the composition of the hydrocarbons formed or on how they evolve during catagenesis.From the kinetic standpoint, the composition of the hydrocarbons formed can be considered to result from the effect of “primary cracking” reactions having a direct effect on kerogen during its evolution as well as from the effect of “secondary cracking” acting on the hydrocarbons formed.This report gives experimental results concerning the “primary cracking” of Types II and III kerogens and their modelling. For this, the hydrocarbons produced have been grouped into four classes (C₁, C₂–C₅, C₆–C₁₅ and C₁₅₊). Experimental data corresponding to these different classes were obtained by the pyrolysis of kerogens with temperature programming of 4°C/min with continuous analysis, during heating, of the amount of hydrocarbons corresponding to each of these classes.The kinetic parameters of the model were optimized on the basis of the results obtained. This model represents the first step in the creation of a more sophisticated mathematical model to be capable of simulating the formation of different hydrocarbon classes during the thermal history of sediments. The second step being the adjustment of the kinetic parameters of “secondary cracking”.     

The garnets of the eastern area of the Sierra de Guadarrama,Sistema Central,Spain

Electron-probe microanalysis of a series of garnets in metapelitic rocks of the chloritoid staurolite, kyanite and sillimanite metamorphic zones, eastern area of the Sierra de Guadarrama, Sistema Central, Spain, manifest the well-known cryptozonation commonly observed in these minerals, with MgO and FeO increasing and MnO and CaO decreasing from the center to the outer rim of the crystals.The differences in composition of the garnets, from one metamorphic zone to another, is mainly a result of small differences in composition of the host-rock, since: (1) the amounts of MnO in the garnet are controlled by the amounts of SiO₂, Al₂O₃ and FeO present in the host-rock; and (2) the percentages of MnO and MgO of the parent-rock influence in some way the concentration of CaO in the garnet, and those of MnO, Al₂O₃ and CaO influence the concentration of FeO. Nevertheless, the amount of FeO in the garnet is finally controlled, due to the diadochy, by the concentration of MnO + CaO in this mineral.     

Tin mineralization in the Dajing tin–polymetallic deposit, Inner Mongolia, China

Dajing is a large-scale tin–polymetallic deposit that hosts the largest tin mine in North China. It is a hydrothermal vein-type deposit containing Sn, Cu, Pb, Zn, Ag, and minor components Co and In. The deposit consists of more than 690 veins hosted within Upper Permian sedimentary rocks.Three mineralization stages and six ore types are recognized with cassiterite constituting the dominant tin mineral. The SnO₂ content of cassiterite increases in the sequence of mineralization stages shear-deformation→cassiterite–quartz→cassiterite–sulfide (or chalcopyrite–pyrite) stage, while the content of FeO, TiO₂, Nb₂O₅, Ta₂O₅, and In₂O₅ tends to decrease with increases in NiO and Ga₂O₅. It is considered that the negative correlation between SnO₂ and FeO, Nb₂O₅, Ta₂O₅, and In₂O₅ results from elemental substitutions. The early stage cassiterite is much richer in Ta and the later stage cassiterite is much poorer in Ti and Fe than is usual in hydrothermal vein type tin deposits. This is interpreted to indicate that the component of early stage cassiterite reflects a granitic magma source while the composition of later stage cassiterite has a more obvious strata source. The compositional variation of cassiterite corresponds to decreasing crystallization temperatures within each stage and between sequential stages with time. The characteristics of REE in cassiterite from two stages are in accord with that of subvolcanic rocks and the Linxi formation. It suggests that tin transported during the cassiterite–quartz stage may have originated from subvolcanic dikes (e.g., dacite porphyry), while in the cassiterite–sulfide stage, tin may have been derived from wallrock (e.g. siltstone) of the Upper Permian-age Linxi Formation.