Significance of the chemistry and morphology of diagenetic siderite in clastic rocks of the Mesozoic Scotian Basin

Siderite (FeCO₃) is a widespread minor diagenetic mineral in clastic sedimentary basins. Although eodiagenetic authigenesis of siderite is well-known, siderite formed during burial diagenesis shows habits and chemical compositions that are poorly understood. This study tests the hypothesis that diagenetic siderite cements in sandstones in the Scotian Basin, offshore eastern Canada, show systematic variability in chemistry and habit that is a response to recrystallization and changing composition of basinal fluids. Mineral textures were determined from backscattered electron images, and chemistry mostly from electron microprobe analyses. Five chemical types of siderite are identified using k-means cluster analysis, based on the amount of substitution of Ca, Mg and Mn for Fe. Eodiagenetic microcrystalline coated grains, concretions and intraclasts in sandstones are principally Fe-rich siderite and locally have recrystallised to blocky equant crystals. Mesodiagenetic Mg-rich siderite partly replaced these equant crystals and also framework mica and K-feldspar grains, showing textural evidence for coupled dissolution–reprecipitation. Slender Mg-rich siderite rhombs (lozenges, bladed or wheat-seed siderite) have precipitated before and after the formation of quartz overgrowths in geochemical microenvironments. Magnesium substitution reflects Mg-rich formation waters resulting from smectite to illite conversion. Equivalent Ca-rich siderite occurs where sandstones overlie a Jurassic carbonate bank. Late Mn-rich siderite has complex textures resembling those of Mississippi-Valley type ores, with spheroidal rims, a honeycomb-like mesh and concentric infill around secondary pores. It also occurs in veins or replacing intraclasts, post-dating late ferroan-calcite cements in sandstones that show strong dissolution by hot basinal brines. The Ca, Mg and Mn content of diagenetic siderite, coupled with textural evidence for recrystallization, can thus be used to track changes in ambient formation fluids. Siderite habits and chemistry described from the Scotian Basin are found in many clastic basins, suggesting that the observed recrystallization textures and variation in chemical type are of broad application.     

Inorganic synthesis of Fe–Ca–Mg carbonates at low temperature

A set of free-drift experiments was undertaken to synthesize carbonates of mixed cation content (Fe, Ca, Mg) from solution at 25 and 70 °C to better understand the relationship between the mineralogy and composition of these phases and the solutions from which they precipitate. Metastable solid solutions formed at 25 °C which are not predicted from the extrapolation of higher temperature equilibrium assemblages; instead, solids formed that were intermediary in chemical composition to known magnesite–siderite and dolomite solid solutions. A calcite–siderite solid solution precipitated at 25 °C, with the percentage of CaCO₃ in the solid being proportional to the aqueous Ca/Fe ratio of the solution, while Mg was excluded from the crystal structure except at relatively high aqueous Mg/Ca and Mg/Fe ratios and a low Ca content. Alternatively, at 70 °C Mg was the predominant cation of the solid solutions. These results are compatible with the hypothesis that the relative dehydration energies of Fe, Ca and Mg play an important role in the formation of mixed cation carbonates in nature.     

Siderite mineralization of the Gemericum superunit (Western Carpathians, Slovakia): review and a revised genetic model

The Gemericum is a segment of the Variscan orogen subsequently deformed by the Alpine–Carpathian orogeny. The unit contains abundant siderite–sulphide and quartz–antimony veins together with stratabound siderite replacement deposits in limestones and stratiform sulphide mineralization in volcano-sedimentary sequences. The siderite–sulphide veins and siderite replacement deposits of the Gemericum represent one of the largest accumulations of siderite in the world, with about 160 million tonnes of mineable FeCO₃. More than 1200 steeply dipping hydrothermal veins are arranged in a regional tectonic and compositional pattern, reflecting the distribution of regional metamorphic zones. Siderite–sulphide veins are typically contained in low-grade (chlorite zone) sedimentary, volcano-sedimentary or volcanic Lower and Upper Paleozoic rocks. Quartz–antimony veins are hosted by higher-grade units (biotite zone). Siderite–sulphide veins are dominated by early siderite followed by a complex set of stages, including quartz–sulphide (chalcopyrite, tetrahedrite), barite, tourmaline–quartz, and sulphide-remobilization stages. The temporal evolution of these stages is difficult to study because of the widespread and repeated tectonic processes, within-vein replacement and recrystallization. Siderite–sulphide veins show considerable vertical (up to 1200 m) and lateral (up to 15 km) extent, and a thickness typically reaching several metres. Carbonate-replacement siderite deposits of the Gemericum are hosted by a Silurian limestone belt and are similar to stratabound siderite deposits of the Eastern Alps (e.g., Erzberg, Austria).Based on a review of geological, petrological and geochronological data for the Gemericum, and extensive stable and radiogenic isotope data and fluid inclusion data on hydrothermal minerals, the siderite–sulphide veins and siderite replacement deposits are classified as metamorphogenic in a broad sense. The deposits were formed during several stages of regional crustal-scale fluid flow. Isotope (S, C, Sr, Pb) fingerprinting identifies the metamorphosed rock complexes of the Gemericum as a source of most components of hydrothermal fluids. Fluid inclusion and stable isotope data evidence the participation of several contrasting fluid types, and the existence of contrasting P–T conditions during vein evolution. A high-δ¹⁸O, medium- to high-salinity, H₂O-type fluid is the most important component during siderite deposition, whereas H₂O–CO₂-type fluid inclusion containing dense liquid CO₂ and corresponding to minimal pressures between 1 and 3 kbar were found in a younger tourmaline–quartz stage. Younger quartz–ankerite(±siderite)–sulphide stages are characterized by high-salinity (17 to 35 wt.% NaCl equivalent) and low-temperature (T_h=90 to 180 °C) H₂O-type fluids.The vein deposits are interpreted as a result of multistage hydrothermal circulation, with Variscan and Alpine mineralization phases. Based on available indirect data, the most important mineralization phase was related to regional fluid flow during the uplift of a Variscan metamorphic core complex, producing siderite–sulphide (±barite) mineralization, while tourmaline–quartz stage and sulphide remobilization stages are related to Alpine processes. Two phases of vein evolution are evident from two groups of ⁸⁷Sr/⁸⁶Sr isotope ratios of Sr-rich, Rb-poor hydrothermal minerals: 0.71042–0.71541 in older barite and 0.7190–0.7220 in late-stage celestine and strontianite.     

The crystallographic fabric and texture of siderite in concretions: implications for siderite nucleation and growth processes

The crystallographic fabric of siderite in siderite concretions has been determined for upper Carboniferous (Westphalian‐A) non‐marine concretions and lower Jurassic (Pliensbachian) marine concretions. Compositional zoning indicates that individual siderite crystals grew over a period of changing pore water chemistry, consistent with the concretions being initially a diffuse patch of cement, which grew progressively. The siderite crystallographic fabric was analysed using the anisotropy of magnetic susceptibility, which is carried by paramagnetic siderite. The siderite concretions from marine and non‐marine formations exhibit differences in fabric style, although both display increases in the degree of preferred siderite c‐axis orientation towards the concretion margins. The Westphalian non‐marine siderites show a preferred orientation of siderite c‐axes in the bedding plane, whereas the Pliensbachian marine siderites have a preferred orientation of c‐axes perpendicular to the bedding. In addition, a single marine concretion shows evidence of earlier formed, inclined girdle‐type fabrics, which are intergrown with later formed vertical c‐axis siderite fabrics. The marine and non‐marine fabrics are both apparently controlled by substrate processes at the site of nucleation, which was probably clay mineral surfaces. Siderite nucleation processes on the substrate were most probably controlled by the (bio?) chemistry of the pore waters, which altered the morphology and crystallographic orientation of the forming carbonate. The preferred crystallographic orientation of siderite results from the orientation of the nucleation substrate. Fabric changes across the concretions partially mimic the progressive compaction‐induced alignment of the clay substrates, while the concretion grew during burial.     

Magnetic fabric variations in Mesozoic black shales, Northern Siberia, Russia: Possible paleomagnetic implications

A 28-m-long section situated on the coast of the Arctic Ocean, Russia (74°N, 113°E) was extensively sampled primarily for the purpose of magnetostratigraphic investigations across the Jurassic/Cretaceous boundary. The section consists predominantly of marine black shales with abundant siderite concretions and several distinct siderite cemented layers. Low-field magnetic susceptibility (k) ranges from 8 × 10^− 5 to 2 × 10^− 3 SI and is predominantly controlled by the paramagnetic minerals, i.e. iron-bearing chlorites, micas, and siderite. The siderite-bearing samples possess the highest magnetic susceptibility, usually one order of magnitude higher than the neighboring rock. The intensity of the natural remanent magnetization (M₀) varies between 1 × 10^− 5 and 6 × 10^− 3 A/m. Several samples possessing extremely high values of M₀ were found. There is no apparent correlation between the high k and high M₀ values; on the contrary, the samples with relatively high M₀ values possess average magnetic susceptibility and vice versa. According to the low-field anisotropy of magnetic susceptibility (AMS), three different groups of samples can be distinguished. In the siderite-bearing samples (i), an inverse magnetic fabric is observed, i.e., the maximum and minimum principal susceptibility directions are interchanged and the magnetic fabric has a distinctly prolate shape. Triaxial-fabric samples (ii), showing an intermediate magnetic fabric, are always characterized by high M₀ values. It seems probable that the magnetic fabric is controlled by the preferred orientation of paramagnetic phyllosilicates, e.g., chlorite and mica, and by some ferromagnetic mineral with anomalous orientation in relation to the bedding plane. Oblate-fabric samples (iii) are characterized by a bedding-controlled magnetic fabric, and by moderate magnetic susceptibility and M₀ values. The magnetic fabric is controlled by the preferred orientation of phyllosilicate minerals and, to a minor extent, by a ferrimagnetic fraction, most probably detrital magnetite. Considering the magnetic fabric together with paleomagnetic component analyses, the siderite-bearing, and the high-NRM samples (about 15% of samples) were excluded from further magnetostratigraphic research.     

Distinct sedimentary processes reflected in the isotopic signatures of dolomitic concretions in the Miocene Pohang Basin (southwestern East Sea)

Dolomitic concretions in diatomaceous hemipelagic sediments of the Miocene Pohang Basin in the southwestern East Sea (Sea of Japan) preserve distinct signals of two independent sedimentary processes, which controlled the extents of isotopic compositions. Variable δ¹⁸O (−9.1‰ to +0.7‰) and high δ¹³C (+3.1‰ to +17.9‰) values suggest that the concretions formed in the methanogenic zone with alteration of the residual mid-Miocene seawater by volcanogenic sediments. Remarkable δ¹⁸O and δ¹³C values show a strong linear relationship, indicating that distinctly independent depositional processes operated during the formation of the concretions. The degree of methanogenesis was enhanced during rapid hemipelagic sedimentation of organic-rich particles, resulting in higher δ¹³C values, and the effect of volcaniclastics was diluted, maintaining the original properties of ambient mid-Miocene seawater. In contrast, lower δ¹⁸O and ⁸⁷Sr/⁸⁶Sr values characterize the effect of volcaniclastic sediments that were transported by intermittent gravity flows and interacted with mid-Miocene seawater. The input of volcaniclastic sediment probably degraded the role of methanogenesis by lowering the contents of organic matter and thereby decreased the δ¹³C values within the concretions. Isotopic signals recorded within the concretions highlight understanding of the depositional environment and evolution of the pore-water chemistry.     

Formation of siderite-Mg-calcite-iron sulphide concretions in intertidal marsh and sandflat sediments, north Norfolk, England

Concretions cemented mainly by siderite, Mg-calcite and iron monosulphide are common in late Holocene marsh and sandflat sediments on parts of the north Norfolk coast. Field experiments have shown that the concretions are actively forming in reduced sediments in which sulphate-reducing bacteria are active. δ¹³C values ranging from ?3 to ?11·8% (mean ?5·9%0) suggest that the carbonate in the concretions is derived partly from marine sources and partly from microbial degradation of organic matter. δ¹⁸O values ranged from ?6·4% to + 0·8% (mean ?1·0%) suggesting that carbonate precipitated in porewaters ranging from pure sea water to-sea water diluted with meteoric water. Chemical analysis of porewaters showed no evidence of significant sulphate depletion at the depth of concretion formation. Some concretions have formed around fragments of wood or metal, but others contain no apparent nucleus. In field experiments siderite, FeS and Mg-calcite were precipitated around several different nuclei within a period of six months. We suggest that siderite may form wherever the rate of iron reduction exceeds the rate of sulphate reduction, such that insufficient dissolved sulphide is available to precipitate all the available dissolved ferrous iron.     

Fluid geochemistry in the Ivigtut cryolite deposit, South Greenland

The 1.27 Ga old Ivigtut (Ivittuut) intrusion in South Greenland is world-famous for its hydrothermal cryolite deposit [Na₃AlF₆] situated within a strongly metasomatised A-type granite stock. This detailed fluid inclusion study characterises the fluid present during the formation of the cryolite deposit and thermodynamic modelling allows to constrain its formation conditions.Microthermometry revealed three different types of inclusions: (1) pure CO₂, (2) aqueous-carbonic and (3) saline-aqueous inclusions. Melting temperatures range between − 23 and − 15 °C for type 2 and from − 15 to − 10 °C for type 3 inclusions. Most inclusions homogenise between 110 and 150 °C into the liquid.Stable isotope compositions of CO₂ and H₂O were measured from crushed inclusions in quartz, cryolite, fluorite and siderite. The δ¹³C values of about − 5‰ PDB are typical of mantle-derived magmas. The differences between δ¹⁸O of CO₂ (+ 21 to + 42‰ VSMOW) and δ¹⁸O of H₂O (− 1 to − 21.7‰ VSMOW) suggest low-temperature isotope exchange. δD (H₂O) ranges from − 19 to − 144‰ VSMOW. The isotopic composition of inclusion water closely follows the meteoric water line and is comparable to Canadian Shield brines. Ion chromatography revealed the fluid's predominance in Na, Cl and F. Cl/Br ratios range between 56 and 110 and may imply intensive fluid–rock interaction with the host granite.Isochores deduced from microthermometry in conjunction with estimates for the solidification of the Ivigtut granite suggest a formation pressure of approximately 1–1.5 kbar for the fluid inclusions. Formation temperatures of different types of fluid inclusions vary between 100 and 400 °C. Thermodynamic modelling of phase assemblages and the extraordinary high concentration in F (and Na) may indicate that the cryolite body and its associated fluid inclusions could have formed during the continuous transition from a volatile-rich melt to a solute-rich fluid.     

Rinded iron‐oxide concretions: hallmarks of altered siderite masses of both early and late diagenetic origin

Iron‐bearing concretions are valuable records of oxidation states of subsurface waters, but the first concretions to form can be altered drastically during later diagenetic events. Distinctive concretions composed of heavy rinds of iron oxide that surround iron‐poor, mud‐rich cores are common along bases of fluvial cross‐bed sets of the Cretaceous Dakota Formation, Nebraska, USA. Concretion rinds thicken inward and cores contain 46 to 89% void space. Millimetre‐scale spherosiderites are abundant in palaeosols that developed in floodplain facies. Evolution of rinded concretions began when intraformational clasts were eroded from sideritic soils, transported, abraded and deposited in river channels. Alteration of siderite and formation of rinds occurred much later, perhaps in the Quaternary when sandstone pore waters became oxic. Dakota concretions are analogous to ‘rattlestones’ in Pleistocene fluvial channels of The Netherlands, and their rinded structure is analogous to that of iron‐rich concretions in the aeolian Navajo Sandstone of Utah. In all three deposits, rinded concretions formed when pre‐existing, siderite‐cemented concretions were oxidized within a sand matrix. Unlike fluvial examples, siderite in the Navajo Sandstone was autochthonous and of late diagenetic origin, having precipitated from carbon dioxide and methane‐enriched waters moving through folded and jointed strata. Iron‐rich rinds formed in all these strata because concretion interiors remained anaerobic, even as oxygen accumulated in the pore waters of their surrounding, permeable matrix. Iron oxide first precipitated at redox boundaries at concretion perimeters and formed an inward‐thickening rind. Acid generated by the oxidation reaction drove siderite dissolution to completion, creating the iron‐poor core. Iron‐oxide rinds are indicators of the former presence of siderite, a mineral that forms only under reducing conditions, during either early or late diagenesis. Siderite is vulnerable to complete oxidation upon exposure, so the distinctive rinded concretions are valuable clues that aid in deciphering diagenetic histories and for recognizing methanic floodplain palaeoenvironments and wet palaeoclimate.     

Carbon and Oxygen Isotope Geochemistry of the Amba Dongar Carbonatite Complex, Gujarat, India

A carbon and oxygen isotope survey based on 42 samples from the Amba Dongar carbonatite complex of Gujarat, India, indicates that the magmatic differentiation series sövite → alvikite → ankeritic carbonatite is beset with a distinct isotope trend characterized by a moderate rise in ¹³C coupled with a sizeable increase in ¹⁸O. From an average of −4.6 ± 0.4 ‰ [PDB] for the least differentiated (coarse) sövite member, δ¹³C values slowly increase in the alvikite (−3.7 ± 0.6 ‰) and ankeritic fractions (−3.0 ± 1.1 ‰), whereas δ¹⁸O rises from 10.3 ± 1.7 ‰ [SMOW] to 17.5 ± 5.8 ‰ over the same sequence, reaching extremes between 20 and 28 ‰ in the latest generation of ankeritic carbonatite. While an apparent correlation between δ¹³C and δ¹⁸O over the δ¹⁸O range of 7–13 ‰ conforms with similar findings from other carbonatite complexes and probably reflects a Rayleigh fractionation process, the observed upsurge of ¹⁸O notably in the ankeritic member is demonstrably related to a late phase of low-temperature hydrothermal activity involving large-scale participation of ¹⁸O-depleted groundwaters. As a whole, the Amba Dongar carbonatite province displays the characteristic ¹³C/¹²C label of deep-seated (primordial) carbon, reflecting the carbon isotope composition of the subcontinental upper mantle below the Narmada Rift Zone of the Indian subcontinent.     

Geochemistry and stable isotopic composition of tufa waters and precipitates from the Interlake Region, Manitoba, Canada: Constraints on groundwater origin, calcitization, and tufa formation

New major, trace and isotopic geochemical results from a regional study of springs discharging from the major carbonate rock aquifer in the Interlake Region of Manitoba, Canada, are used to understand water–rock reactions, timing of recharge/discharge, tufa formation processes, and as baseline data. Spring waters are fresh with total dissolved solids (TDS) concentrations ranging from 150 to 880 mg/L. Waters discharging in the northern part of the study area have lower TDS, are dominantly Ca–Mg–HCO₃ waters with low SO₄ concentrations (<< 50 mg/L), and appear to have interacted primarily with Silurian carbonate lithologies. In contrast, waters in the southeastern part of the study area have higher TDS and have elevated SO₄ concentrations (up to 210 mg/L). Spring waters have elevated Mg/Ca_molar (1.23 ± 0.23), typically greater than congruent dissolution of dolomite. Ca and Mg concentrations and Mg/Ca_molar indicate that groundwater residence times were sufficient to allow equilibration with bedrock dolomite lithologies; elevated tritium in northern waters indicates a significant recharge component in the 1960's and 1970's. Tufa precipitates that have formed from many of the spring waters are low-Mg calcite (MgO = 1.70 to 5.80 wt.%). Sr concentrations are variable (57 to 657 ppm) and tufa Sr/Ca_molar ratios appear to be entirely controlled by spring water Sr/Ca_molar. Empirically determined Sr distribution coefficients (D_Sr = 0.389 ± 0.083) indicate rapid crystallization following CO₂ degassing, consistent with heavier δ¹³C_VPDB compared to spring waters. Sulfate concentrations are generally too low for calcitization (dedolomitization) reactions driven by anhydrite dissolution to be the dominant control on the elevated groundwater Mg/Ca_molar, implying either extensive sulfate reduction along the flow paths (however, δ¹³C_DIC suggests the elevated SO₄ is more consistent with Fe-sulfide oxidation), or that other processes are involved. Major ion ratios suggest that the waters in the southern part of the study area are more consistent with interaction with siliciclastic rocks than with anhydrite dissolution. We suggest that calcitization (dedolomitization) reactions driven by anhydrite dissolution may not dominate all carbonate aquifers and that mixing of waters in karst conduits combined with ion exchange reactions are important controls on water chemistry in these systems.     

Palaeomagnetism of the Loch Doon Granite Complex, Southern Uplands of Scotland: The Late Caledonian palaeomagnetic record and an Early Devonian episode of True Polar Wander

The Southern Uplands terrane is an Ordovician–Silurian back-arc/foreland basin emplaced at the northern margin of the Iapetus Ocean and intruded by granite complexes including Loch Doon (408.3 ± 1.5 Ma) during Early Devonian times. Protracted cooling of this 130 km³ intrusion recorded magnetic remanence comprising a predominant (‘A’) magnetisation linked to initial cooling with dual polarity and mean direction D / I = 237 / 64° (α₉₅ = 4°, palaeopole at 316°E, 21°N). Subsidiary magnetisations include Mesozoic remanence correlating with extensional tectonism in the adjoining Irish Sea Basin (‘B’, D / I = 234/− 59°) and minority populations (‘C’, D / I = 106/− 2° and ‘D’, D / I = 199/1°) recording emplacement of younger ( 395 Ma) granites in adjoining terranes and the Variscan orogenic event. The ‘A’ directions have an arcuate distribution identifying anticlockwise rotation during cooling. A comparable rotation is identified in the Orthotectonic Caledonides to the north and the Paratectonic Caledonides to the south following closure of Iapetus. Continental motion from midsoutherly latitudes ( 40°S) at 408 Ma to equatorial palaeolatitudes by  395 Ma is identified and implies minimum rates of continental movement between 430 and 390 Ma of 30–70 cm/year, more than double maximum rates induced by plate forces and interpreted as a signature of true polar wander. Silurian–Devonian palaeomagnetic data from the British–Scandinavian Caledonides define a 430–385 Ma closed loop comparable to the distributed contemporaneous palaeomagnetic poles from Gondwana. They reconcile pre-430 Ma and post-380 Ma APW from this supercontinent and show that Laurentia–Baltica–Avalonia lay to the west of South America with a relict Rheic Ocean opening to the north which closed to produce Variscan orogeny by a combination of pivotal closure and right lateral transpression.     

Precipitation kinetics and carbon isotope partitioning of inorganic siderite at 25°C and 1 atm

Siderite was precipitated from NaHCO₃ and Fe(ClO₄)₂ solutions under anaerobic conditions at 25°C and 1 atm total pressure using a modified version of the chemo-stat technique and the free-drift technique. Samples of solution and solid were withdrawn at different time intervals during time course experiments to determine the bulk and isotope composition of the solution and solid, and the morphology and mineralogy of the solid. A series of metastable precursors precipitated and dissolved sequentially, culminating in well-crystallized siderite rhombohedra having an average edge of ∼ 2 μm and a limited size distribution. Siderite precipitation rate ranged from 10^0.23 to 10^2.44 μmol•m⁻²•h⁻¹ for saturation states (with respect to siderite) ranging from near equilibrium to 10^3.53. Calculated carbon isotope fractionation factors (10³lnα) averaged 8.5 ± 0.2 (1σ n = 4) for the siderite-CO_2(g) system and 0.5 ± 0.2 (1σ n = 4) for the siderite-HCO₃⁻_(aq) system.     

Geology and geochemistry of the adjacent Changkeng gold and Fuwang silver deposits, Guangdong Province, South China

The Changkeng Au and Fuwang Ag deposits represent an economically significant and distinct member of the Au–Ag deposit association in China. The two deposits are immediately adjacent, but the Au and Ag orebodies separated from each other. Ores in the Au deposit, located at the upper stratigraphic section and in the southern parts of the orefield, contain low Ag contents (< 11 ppm); the Ag orebodies, in the lower stratigraphic section, are Au-poor (< 0.2 ppm). Changkeng is hosted in brecciated cherts and jasperoidal quartz and is characterized by disseminated ore minerals. Fuwang, hosted in the Lower Carboniferous Zimenqiao group bioclastic limestone, has vein and veinlet mineralization associated with alteration comprised of quartz, carbonate, sericite, and sulfides. Homogenization temperatures of fluid inclusions from quartz veinlets in the Changkeng and Fuwang deposits are in the range of 210 ± 80 °C and 230 ± 50 °C, respectively. Salinities of fluid inclusions from the two deposits range from 1.6 to 7.3 wt.% and 1.6 to 2.6 wt.% equiv. NaCl, respectively. The δD_H2O, δ¹⁸O_H2O, δ¹³C_CO2 and ³He/⁴He values of the fluid inclusions from the Changkeng deposit range from − 80‰ to − 30‰, − 7.8‰ to − 3.0‰, − 16.6‰ to − 17.0‰ and 0.0100 to 0.0054 Ra, respectively. The δD_H2O, δ¹⁸O_H2O, δ¹³C_CO2 and ³He/⁴He values of fluid inclusions from the Fuwang deposit range from − 59‰ to − 45‰, − 0.9‰ to 4.1‰, − 6.7‰ to − 0.6‰ and 0.5930 to 0.8357 Ra, respectively. The δD_H2O, δ¹⁸O_H2O, δ¹³C_CO2 and ³He/⁴He values of the fluid inclusions suggest the ore fluids of the Changkeng Au-ore come from the meteoric water and the ore fluids of the Fuwang Ag-ore are derived from mixing of magmatic water and meteoric water. The two deposits also show different Pb-isotopic signatures. The Changkeng deposit has Pb isotope ratios (²⁰⁶Pb/²⁰⁴Pb: 18.580 to 19.251, ²⁰⁷Pb/²⁰⁴Pb: 15.672 to 15.801, ²⁰⁸Pb/²⁰⁴Pb: 38.700 to 39.104) similar to those (²⁰⁶Pb/²⁰⁴Pb: 18.578 to 19.433, ²⁰⁷Pb/²⁰⁴Pb: 15.640 to 15.775, ²⁰⁸Pb/²⁰⁴Pb: 38.925 to 39.920) of its host rocks and different from those (²⁰⁶Pb/²⁰⁴Pb: 18.820 to 18.891, ²⁰⁷Pb/²⁰⁴Pb: 15.848 to 15.914, ²⁰⁸Pb/²⁰⁴Pb: 39.579 to 39.786) of the Fuwang deposit. The different signatures indicate different sources of ore-forming material. Rb–Sr isochron age (68 ± 6 Ma) and ⁴⁰Ar–³⁹Ar age (64.3 ± 0.1 Ma) of the ore-related quartz veins from the Ag deposit indicate that the Fuwang deposit formed during the Cenozoic Himalayan tectonomagmatic event. Crosscutting relationships suggests that Au-ore predates Ag-ore. The adjacent Changkeng and Fuwang deposits could, however, represent a single evolved hydrothermal system. The ore fluids initially deposited Au in the brecciated siliceous rocks, and then mixing with the magmatic water resulted in Ag deposition within fracture zones in the limestone. The deposits are alternatively the product of the superposition of two different geological events. Age evidence for the Fuwang deposit, together with the Xiqiaoshan Tertiary volcanic-hosted Ag deposit in the same area, indicates that the Pacific Coastal Volcanic Belt in the South China Fold Belt has greater potential for Himalayan precious metal mineralization than previous realized.     

Paleomagnetism and geochronology of an Early Proterozoic quartz diorite in the southern Rind River Range, Wyoming, USA

We present geochronologic and paleomagnetic data from a north-trending quartz diorite intrusion that cuts Archean metasedimentary and metaigneous rocks of the South Pass Greenstone Belt of the Wyoming craton. The quartz diorite was previously thought to be either Archean or Early Proterozoic (?) in age and is cut by north and northeast-trending Proterozoic diabase dikes of uncertain age, for which we also report paleomagnetic data. New U–Pb analyses of baddeleyite and zircon from the quartz diorite yield a concordia upper intercept age of 2170±8 Ma (95% confidence). An ⁴⁰Ar/³⁹Ar amphibole date from the same sample yields a similar apparent age of about 2124±30 Ma (2σ), thus confirming that the intrusion is Early Proterozoic in age and that it has probably not been thermally disturbed since emplacement. A magmatic event at ca. 2.17 Ga has not previously been documented in the Wyoming craton. The quartz diorite and one of the crosscutting diabase dikes yield essentially identical, well-defined characteristic remanent magnetizations. Results from eight sites in the quartz diorite yield an in situ mean direction of north declination and moderate to steep positive inclination (Dec.=355°, Inc.=65°, k=145, α₉₅=5°) with a paleomagnetic pole at 84°N, 215°E (δm=6°, δp=7°). Data from other diabase dike sites are inconsistent with the quartz diorite results, but the importance of these results is uncertain because the age of the dikes is not well known. Interpretation of the quartz diorite remanent magnetization is problematic. The in situ direction is similar to expected directions for magnetizations of Late Cretaceous/early Tertiary age. However, there is no compelling evidence to suggest that these rocks were remagnetized during the late Mesozoic or Cenozoic. Assuming this magnetization to be primary, then the in situ paleomagnetic pole is strongly discordant with poles of 2167, 2214, and 2217 Ma from the Canadian Shield, and is consistent with proposed separation of the Wyoming Craton and Laurentia prior to about 1.8 Ga. Correcting the quartz diorite pole for the possible effects of Laramide-age tilting of the Wind River Range, based on the attitude of nearby overlying Cambrian Flathead Sandstone (dip=20°, N20°E), gives a tilt corrected pole of 75°N, 58°E (δm=4°, δp=6°), which is also discordant with respect to time-equivalent poles from the Superior Province. Reconstruction of the Superior and Wyoming Province using a rotation similar to that proposed by Roscoe and Card [Can. J. Earth Sci. 46(1993)2475] is problematic, but reconstruction of the Superior and Wyoming Provinces based on restoring them to their correct paleolatitude and orientation using a closest approach fit indicates that the two cratons could have been adjacent at about 2.17 Ga prior to rifting at about 2.15 Ga. The paleomagnetic data presented are consistent with the hypothesis that the Huronian and Snowy Pass Supergroups could have evolved as part of a single epicratonic sedimentary basin during the Early Proterozoic.     

Fluid inclusion and stable isotope study of the Cobre–Babilonia polymetallic epithermal vein system, Taxco district, Guerrero, Mexico

The Cobre–Babilonia vein system formed during a single major hydrothermal stage and is part of the Taxco district in Guerrero, southern Mexico. Homogenization and ice melting temperatures range from 160 to 290 °C and from − 11.6 to − 0.5 °C, respectively. We determined an approximate thermal gradient of 17 to 20 °C per 100 m using fluid inclusions. A thermal peak marked by the 290 °C isotherm is interpreted as a major feeder channel to the veins. The highest content of Zn + Pb in ore coincides with the 220 and 240 °C isotherms. Salinities of mineralizing fluids range from 0.8 to 15.6 wt.% NaCl equiv, and are distributed in two populations that can be related with barren or ore-bearing vein sections, with 0.8 to 6 wt.% NaCl equiv and 7 to 15.6 wt.% NaCl equiv, respectively. δ¹³C and δ¹⁸O water values from calcite from the Cobre–Babilonia vein system and the Esperanza Vieja and Guadalupe mantos range − 5.4‰ to − 10.4‰ and 9.9‰ to 13.4‰, respectively. δ³⁴S values range from 0‰ to 3.2‰ and − 0.7‰ to − 4.3‰ in sphalerite, − 4‰ to 0.9‰ in pyrite, and − 1.4‰ to − 5.5‰ in galena. Both fluid inclusion and stable isotope data are compatible with magmatic and meteoric sources for mineralizing fluids. Also, sulfur isotope compositions suggest both magmatic and sedimentary sources for sulfur.     

Silicon isotope fractionation between plant parts in banana: In situ vs. in vitro

We recently showed that silicon isotopic fractionation in banana (Musa acuminata Colla, cv Grande Naine) was related to phytolith production, and therefore to silica content in plant. The present study focuses on isotopic fractionation between the different plant parts. Silicon isotopic compositions were measured using a Nu plasma multicollector plasma source mass spectrometer (MC–ICP–MS) operating in dry plasma mode. The results are expressed as δ²⁹Si relatively to the NBS28 standard, with an average precision and accuracy of ± 0.08‰ (± 2σ). On mature banana (Musa acuminata Colla, cv Grande Naine) from Cameroon, δ²⁹Si ranged from + 0.13‰ in the petiole to + 0.49‰ in the lamina, yielding to a 0.36‰ change towards heavier isotopic composition in the upper parts of the plant. This strongly accords with results obtained on in vitro banana plantlets cultivated in hydroponics, where the δ²⁹Si increase from pseudostems to lamina is 0.26‰. These preliminary results on in situ banana show a trend of intra-plant fractionation comparable with that of in vitro hydroponics banana plantlets and with previous data obtained on bamboo.     

Magnesium isotopic composition of igneous rock standards measured by MC-ICP-MS

To provide inter-lab comparison for high-precision Mg isotope analysis, Mg isotope compositions (expressed as δ²⁶Mg relative to DSM-3) for commercially accessible peridotite, basalt, andesite, and granite geo-standards have been measured by multi-collector inductively coupled mass-spectrometry (Nu-Plasma) using sample-standard bracketing method. There is a large tolerance of matrix cations during the measurement of Mg isotopes, as intensity ratios of ²³Na/²⁴Mg and ²⁷Al/²⁴Mg of about 20% only change the δ²⁶Mg by less than 0.1‰, and low ⁵⁵Mn/²⁴Mg (<0.1) and ⁵⁸Ni/²⁴Mg (<0.01) do not cause significant mass bias either. Concentration match between samples and standards within 90% is adequate to obtain accurate isotope analysis, which also mitigates the isobaric interference of ¹²C¹⁴N⁺ on ²⁶Mg. Organic matrix from chemical purification can cause significant analytical errors when the mass of Mg processed is small. The long-term reproducibility of δ²⁶Mg_DSM-3 for samples with relatively higher MgO content is about 0.11‰ (2SD), and granites with lower MgO content is about 0.2‰ (2SD). Although the standards in this study have wide ranges of major element compositions with SiO₂ from 40 to 70 wt.% and MgO from 0.75 to 49.6 wt.%, they exhibit a variation of Mg isotopic compositions with δ²⁶Mg from −0.07 to −0.40‰. δ²⁶Mg do not correlate with SiO₂ or MgO contents, suggesting homogenous Mg isotope compositions in igneous rocks at the level of current precision, relative to low temperature samples including sediments and riverine and sea waters. Our data do not support a non-chondritic Mg isotope composition of the Earth.     

台湾国姓地区中新世海相菱铁矿的成因

菱铁矿很好地记录了过去地质流体的信息,能够用于示踪生物地球化学反应相关的成岩作用带。台湾国姓地区中新世海相泥页岩中发育自生的菱铁矿结核,其成因尚未厘清。野外观察发现菱铁矿以不连续透镜体平行散布于泥页岩中,主要由自生碳酸盐菱铁矿（78.63%）等矿物组成。菱铁矿的稀土元素配分模式为轻稀土亏损、中稀土富集,无Ce异常,指示菱铁矿形成于弱氧化的沉积环境,弱氧化的环境促进了菱铁矿在次氧化带的沉淀。菱铁矿的δ13C_VPDB和δ18O_VPDB值分别为-3.69‰~+0.08‰和-1.09‰~+0.25‰,指示菱铁矿形成于次氧化带,碳源很可能是海水和有机质降解混合产生。研究表明自生菱铁矿能够被用于识别沉积物中的生物地球化学过程和指示成岩作用带。     

Iron isotopes in acid mine waters and iron-rich solids from the Tinto–Odiel Basin (Iberian Pyrite Belt, Southwest Spain)

The isotopic composition of Fe was determined in water, Fe-oxides and sulfides from the Tinto and Odiel Basins (South West Spain). As a consequence of sulfide oxidation in mine tailings both rivers are acidic (1.45 < pH < 3.85) and display high concentrations of dissolved Fe (up to 420 mmol l^− 1) and sulphates (up to 1190 mmol l^− 1).The δ⁵⁶Fe of pyrite-rich samples from the Rio Tinto and from the Tharsis mine ranged from − 0.56 ± 0.08‰ to + 0.25 ± 0.1‰. δ⁵⁶Fe values for Fe-oxides precipitates that currently form in the riverbed varied from − 1.98 ± 0.10‰ to 1.57 ± 0.08‰. Comparatively narrower ranges of values (− 0.18 ± 0.08‰ and + 0.21 ± 0.14‰) were observed in their fossil analogues from the Pliocene–Pleistocene and in samples from the Gossan (the oxidized layer that formed through exposure to oxygen of the massive sulfide deposits) (− 0.36 ± 0.12‰ to 0.82 ± 0.07‰). In water, δ⁵⁶Fe values ranged from − 1.76 ± 0.10‰ to + 0.43 ± 0.05‰.At the source of the Tinto River, fractionation between aqueous Fe(III) and pyrite from the tailings was less than would be expected from a simple pyrite oxidation process. Similarly, the isotopic composition of Gossan oxides and that of pyrite was different from what would be expected from pyrite oxidation. In rivers, the precipitation of Fe-oxides (mainly jarosite and schwertmannite and lesser amounts of goethite) from water containing mainly (more than 99%) Fe(III) with concentrations up to 372 mmol l^− 1 causes variable fractionation between the solid and the aqueous phase (− 0.98‰ < Δ⁵⁶Fe_{solid–water} < 2.25‰). The significant magnitude of the positive fractionation factor observed in several Fe(III) dominated water may be related to the precipitation of Fe(III) sulphates containing phases.