Nodular chert from the Arbuckle Group, Slick Hills, SW Oklahoma: a combined field, petrographic and isotopic study

Nodular chert from the middle and upper Arbuckle Group (Early Ordovician) in the Slick Hills, SW Oklahoma, was formed by selective replacement of grainstones, burrow fillings, algal structures, and evaporite nodules. Chert nodules are dominantly microquartz with minor fibrous quartz (both quartzine and chalcedony), megaquartz, and microflamboyant quartz. Lepisphere textures of an opal-CT precursor are preserved in many (especially in finely-crystalline) chert nodules. The δ¹⁸O values of microquartz chert range from +23.4 to + 28.8^0/00 (SMOW), significantly lower than those of Cenozoic and Mesozoic microquartz chert formed both in the deep sea and from near-surface sea water. The δ¹⁸O values of chert decrease with increasing quartz crystal size. Silicification in the Arbuckle Group occurred during early diagenesis, with the timing constrained by the relative temporal relationships among silicification, burial compaction, and early dolomite stabilization. Silica for initial chert nucleation may have been derived from both dissolution of sponge spicules and silica-enriched sea water. Chert nucleation appears to have been controlled by the porosity, permeability, and organic matter content of precursor sediments. This conclusion is based on the fact that chert selectively replaced both porous grainstones and burrows and algal structures enriched in organic matter. Growth of chert probably occurred by a maturation process from opal-A(?), to opal-CT, to quartz, as indicated by the presence of opal-CT precursor textures in many chert nodules. Although field and petrographic evidence argues for an early marine origin for chert in the Arbuckle Group, the light δ¹⁸O values are inconsistent with this origin. Meteoric resetting of the δ¹⁸O values of the chert during exposure of the carbonate platform best explains the light δ¹⁸O values because: (i) the δ¹⁸O values of chert nodules decrease with decreasing δ¹⁸O values of host limestones, and (ii) chert nodules from early dolomite, which underwent more extensive meteoric modification than associated limestones, have lighter δ¹⁸O values than chert nodules from limestones. Increasing recrystallization of chert nodules by meteoric water resulted in progressive ¹⁸O depletion and (quartz) crystal enlargement.     

Diagenesis of spiculites and carbonates in a Permian temperate ramp succession – Tempelfjorden Group,Spitsbergen, Arctic Norway

This paper explores little investigated diagenesis of spicule‐dominated sediments, based on Permian spiculites and cool‐water carbonates of the Tempelfjorden Group in central Spitsbergen. Field observations, petrography, stable isotope geochemistry, and mineralogical and chemical analyses reveal that the strata have been subjected to multistage diagenesis as the result of silica phase transitions at medium burial depths and deep‐burial overprinting. The growth of silica concretions occurred during the opal‐A/opal‐CT conversion and was controlled by the content and distribution of clay and spicules in the sediment, resulting in a variety of megascopic silica fabrics. Opal‐CT was subsequently dissolved, and all silica is now in a stable quartz stage. Petrographically, the rocks are characterized by a variety of chalcedony and quartz cements which perfectly preserve precursor textures. Most cements precipitated from silica‐oversaturated fluids, and their shapes reflect the silica saturation state and geometry of the pore space. Some microquartz and cryptoquartz also formed by a solid–solid inversion (recrystallization) of chalcedony. The cements have δ ¹⁸O values between +30‰ and +20‰ Standard Mean Ocean Water and display a systematic depletion in ¹⁸O from the first to the last crystallized, interpreted to reflect a gradual increase in temperature during burial. The precipitation of quartz cements started in the Middle Triassic when the strata passed the 19°C isotherm at burial depths of ca 600 m, and was completed in the mid‐Cretaceous, 2·3 km beneath the sea floor at temperatures of 75°C. Late diagenetic overprinting of the chert includes fracturing, brecciation and cementation with carbonate cements having δ ¹⁸O values between +2‰ and −30‰ Pee Dee Belemnite and δ ¹³C values between +4‰ and −14‰ Pee Dee Belemnite; they are linked to hot solutions introduced during Cretaceous volcanism or Palaeogene tectonism. This study illustrates the diagenetic pathway during burial of spicule‐rich sediments in a closed system and thereby provides a baseline for studies of more complexly altered chert deposits.     

Ordovician low- to intermediate-Mg calcite marine cements from Sweden: marine alteration and implications for oxygen isotopes in Ordovician seawater

Petrography demonstrates the presence of three types of fibrous calcite cement in buildup deposits of the Kullsberg Limestone (middle Caradoc), central Sweden. Translucent fibrous calcite has intrinsic blue luminescence (CL) indicative of pure calcite. This cement has 2–5 mol% MgCO₃, low Mn and Fe (≤ 100 p.p.m.), and is considered to be slightly altered to unaltered, primary low- to intermediate-Mg calcite. Grey turbid fibrous calcite has variable but generally low MgCO₃ content (most analyses <2 mol%) and variable CL response, with Mn and Fe concentrations up to 1200 and 500 p.p.m., respectively. The heterogeneous characteristics of this variety of fibrous calcite are caused by diagenetic alteration of a translucent fibrous calcite precursor. Light-brown turbid fibrous calcite has low MgCO₃ (near 1 mol%) and variable Mn (up to 800 p.p.m.) and Fe (up to 500 p.p.m.) concentrations, with an abundance of bright luminescent patches, which formed during alteration caused by reducing diagenetic fluids. The δ¹³C and δ¹⁸O values of all fibrous calcite form a tight field (δ¹³C=1·7 to 3·1‰ PDB, δ¹⁸O= ? 2·6 to ? 4·1‰ PDB) compared with fibrous calcite isotope values from other units. Fibrous calcite δ¹⁸O values are larger than adjacent meteoric or burial cements, which have δ¹⁸O δ ? 8‰ PDB. Consequently, most diagenetic alteration of Kullsberg fibrous calcite is interpreted to have occurred in the marine diagenetic realm. First-generation equant and bladed calcite cements, which pre-date fibrous calcite, are interpreted as unaltered, low-Mg calcite marine cements based on δ¹³C and δ¹⁸O data (δ¹³C = 2·3 to 2·7‰ PDB, δ¹⁸O= ? 2·8 to ? 3·5‰ PDB). Unlike fibrous cement, which reflects global sea water chemistry, first-generation equant and bladed calcite are indicators of localized modification of seawater chemistry in restricted settings. Kullsberg abiotic marine cements have larger δ¹⁸O values than most Caradoc marine precipitates from equatorial Laurentia. Positive Kullsberg δ¹⁸O values are attributed to lower seawater temperatures and/or slightly elevated salinity on the Baltic platform relative to seawater from which other marine precipitates formed.     

Isotopic constraints on growth conditions of multiphase calcite–pyrite–barite concretions in Carboniferous mudstones

Carbonate concretions in the Lower Carboniferous Caton Shale Formation contain diagenetic pyrite, calcite and barite in the concretion matrix or in different generations of septarian fissures. Pyrite was formed by sulphate reduction throughout the sediment before concretionary growth, then continued to form mainly in the concretion centres. The septarian calcites show a continuous isotopic trend from δ¹³C=?28·7‰ PDB and δ¹⁸O=?1·6‰ PDB through to δ¹³C=?6·9‰ PDB and δ¹⁸O=?14·6‰ PDB. This trend arises from (1) a carbonate source initially from sulphate reduction, to which was added increasing contributions of methanogenic carbonate; and (2) burial/temperature effects or the addition of isotopically light oxygen from meteoric water. The concretionary matrix carbonates must have at least partially predated the earliest septarian cements, and thus used the same carbonate sources. Consequently, their isotopic composition (δ¹³C=?12·0 to ?10·1‰ PDB and δ¹⁸O=?5·7 to ?5·6‰ PDB) can only result from mixing a carbonate cement derived from sulphate reduction with cements containing increasing proportions of carbonate from methanogenesis and, directly or indirectly, also from skeletal carbonate. Concretionary growth was therefore pervasive, with cements being added progressively throughout the concretion body during growth. The concretions contain barite in the concretion matrix and in septarian fissures. Barite in the earlier matrix phase has an isotopic composition (δ³⁴S=+24·8‰ CDT and δ¹⁸O=+16·4‰ SMOW), indicating formation from near‐surface, sulphate‐depleted porewaters. Barites in the later septarian phase have unusual isotopic compositions (δ³⁴S=+6 to +11‰ CDT and δ¹⁸O=+8 to +11‰ SMOW), which require the late addition of isotopically light sulphate to the porewaters, either from anoxic sulphide oxidation (using ferric iron) or from sulphate dissolved in meteoric water. Carbon isotope and biomarker data indicate that oil trapped within septarian fissures was derived from the maturation of kerogen in the enclosing sediments.     

Microscale oxygen isotope variations in 1.9 Ga Gunflint cherts: Assessments of diagenesis effects and implications for oceanic paleotemperature reconstructions

Variations in the oxygen isotope composition (δ¹⁸O) of five cherts from the 1.9 Ga Gunflint iron formation (Canada) were studied at the micrometer scale by ion microprobe to try to better understand the processes that control δ¹⁸O values in cherts and to improve seawater paleotemperature reconstructions. Gunflint cherts show clearly different δ¹⁸O values for different types of silica with for instance a difference of ≈15‰ between detrital quartz and microquartz. Microquartz in the five samples is characterized by large intra sample variations in δ¹⁸O values, (δ¹⁸O of quartz varies from 4.6‰ to 6.6‰ at the 20 μm scale and from ≈12‰ to 14‰ at 2 μm scale). Isotopic profiles in microquartz adjacent to hydrothermal quartz veins demonstrate that microquartz more than ≈200 μm away from the veins has preserved its original δ¹⁸O value.At the micrometer spatial resolution of the ion probe, data reveal that microquartz has preserved a considerable δ¹⁸O heterogeneity that must be regarded as a signature inherited from its diagenetic history. Modelling of the δ¹⁸O variations produced during the diagenetic transformation of sedimentary amorphous silica precursors into microquartz allows us to calculate seawater temperature (T_sw at which the amorphous silica precipitated) and diagenesis temperature (T_diagenesis at which microquartz formed) that reproduce the δ¹⁸O distributions (mean, range and shape) measured at micrometer scale in microquartz. The two critical parameters in this modelling are the δ¹⁸O value and the mass fraction of the diagenetic fluid. Under these assumptions, the most likely ranges for T_sw and T_diagenesis are from 37 to 52 °C and from 130 to 170 °C, respectively.     

Conditions of meteoric calcite formation along a Variscan fault and their possible relation to climatic evolution during the Jurassic–Cretaceous

Two calcite cements, filling karst cavities and replacing Lower Carboniferous limestones at the Variscan Front Thrust, were precipitated after mid-Jurassic Cimmerian uplift and subsequent erosion but before late Cretaceous strike-slip movement. The first calcite (stage A) is nonferroan and crystals are coated by hematite and/or goethite. These minerals also occur as inclusions along growth zones. The calcite lattice contains < 0·07 mol.% Fe, but Mn concentrations can be as high as 0·72 mol.% in bright yellow luminescent zones. Primary, originally one-phase, all-liquid, aqueous inclusions have a final melting temperature between ?0·2° and +0·2 °C, indicating a meteoric origin of the ambient water. The δ¹³C and δ¹⁸O values of the calcites are between ?7·3‰ and ?6·3‰, ?7·8‰ and ?5·5‰ on the Vienna PeeDee Belemnite (VPDB) scale, respectively. The second calcite (stage B) consists of ferroan (0·13–0·84 mol.% Fe) blocky crystals with Mn concentrations between 0·34 and 0·87 mol.%. Primary, single-phase aqueous fluid inclusions indicate precipitation from a meteoric fluid below 50 °C . The δ¹³C values of stage B calcites vary between ?7·3‰ and ?2·1‰ VPDB and the δ¹⁸O values between ?7·9‰ and ?7·2‰ VPDB. A precipitation temperature below 50 °C for the stage A calcites and the presence of iron oxide/hydroxide inclusions in the crystals indicate near-surface precipitation conditions. Within this setting, the geochemistry of the nonferroan stage A calcites reflects precipitation under oxic to suboxic conditions. The ferroan stage B calcites precipitated in a reducing environment. The evolution from the stage A to stage B calcites and the associated geochemical changes are interpreted to be related to the change from semiarid to humid conditions in western Europe during late Jurassic–Cretaceous times. A change in humidity can explain the evolution of groundwater from oxic/suboxic to reducing conditions during calcite precipitation. The typically higher δ¹³C values of the stage B compared to the stage A calcites can be explained by a smaller contribution of carbon derived from soil-zone processes than from carbonate dissolution in the groundwater under humid conditions. The small shift to lower δ¹⁸O between stage A and B calcites may be caused by a higher precipitation temperature or a decrease in the δ¹⁸O value of the meteoric water. This decrease could have been caused by a change in the source of the air masses or by an increase in the amount of rainfall during the early mid-Cretaceous. Although the latter interpretation is preferred, it cannot be proven.     

Fibrous calcite from the Ordovician of Tennessee: preservation of marine oxygen isotopic composition and its implications

Three categories of fibrous calcite from early to middle Caradoc platform-marginal buildups in east Tennessee can be delineated using cathodoluminescent microscopy, minor element chemistry and stable C-O isotopic composition. Bright luminescent fibrous cement has elevated Mn (>1000 p.p.m.), negative δ¹³C and intermediate δ¹⁸O values relative to other types of fibrous calcite. This cement reflects fibrous calcite that interacted with reducing Mn-rich fluids. Dully luminescent fibrous cement has elevated Fe (>400 p.p.m.), positive δ¹³C and negative δ¹⁸O values relative to other fibrous cements. This cement was stabilized by burial fluids. Nonluminescent fibrous cement has low Mn and Fe (generally below 400 p.p.m.) and positive δ¹³C and δ¹⁸O values relative to other types of fibrous calcite. The latter cement is interpreted to be the best material for determining the isotopic composition of calcite precipitated in equilibrium with early to middle Caradoc seawater, which is δ¹³C=1% PDB and δ¹⁸O=?4 to ?5‰ PDB. Results from this study and Ashgillian brachiopods indicate that the average δ¹⁸O composition of the Ordovician ocean, during nonglacial periods, was probably never more negative than ?3‰ SMOW. Assuming an Ordovician seawater δ¹⁸O value of ?1‰ SMOW, Holston Formation fibrous cements would have precipitated at temperatures between 27 and 36 °C, which is near the upper temperature limit for metazoans. A seawater δ¹⁸O value of ?2‰ SMOW yields temperatures ranging from 23 to 31 °C, while a ?3‰ SMOW value yields temperatures of 18–26 °C.     

Petrogenesis of low-δ<Superscript>18</Superscript>O quartz porphyry dykes,Koegel Fontein complex,South Africa

This paper investigates the origin of low-δ¹⁸O quartz porphyry dykes associated with the 144–133 Ma Koegel Fontein Igneous Complex, which was intruded during the initial phase of breakup of Africa and South America. The 25-km diameter Rietpoort Granite is the largest and youngest phase of activity, and is roofed by a 10-km diameter pendant of gneiss. Quartz porphyry (QP) dykes, up to 15 m in width, strike NW–SE across the complex. The QP dykes that intruded outside the granite have similar quartz phenocryst δ¹⁸O values (average 8.0‰, ± 0.7, n?=?33) to the granite (average 8.3?±?1.0, n?=?7). The QP dykes that intruded the roof pendant have quartz phenocrysts with more variable δ¹⁸O values (average 1.6‰, ± 2.1, n?=?55). In some cases quartz phenocrysts have δ¹⁸O values as low as ? 2.5‰. The variation in δ¹⁸O value within the quartz crystal population of individual dykes is small relative to the overall range, and core and rim material from individual quartz phenocrysts in three samples are identical within error. There is no evidence that quartz phenocryst δ¹⁸O values have been affected by fluid–rock interaction. Based on a ?_quartz?magma value of 0.6‰, magma δ¹⁸O values must have been as low as ? 3.1‰. Samples collected along the length of the two main QP dykes that traverse the roof pendant have quartz phenocryst δ¹⁸O values that range from +?1.1 to +?4.6‰, and ? 2.3 to +?5.6‰, respectively. These δ¹⁸O values correlate negatively (r = ? 0.96) with initial ⁸⁷Sr/⁸⁶Sr, which can be explained by the event that lowered δ¹⁸O values of the source being older than the dykes. We suggest that the QP dykes were fed by magma produced by partial melting of gneiss, which had been variably altered at high temperature by ¹⁸O-depleted meteoric water during global glaciation at ~?550 Ma. The early melts had variable δ¹⁸O value but as melt pockets interconnected during melting, the δ¹⁸O values approached that of average gneiss. Variable quartz phenocryst δ¹⁸O values in the same dyke can be explained by vertical emplacement, at variable rates of ascent along the dyke. The lateral variation in quartz, and hence magma δ¹⁸O value at a particular point along a single dyke would depend on the rate of ascent of magma at that point along the dyke, and the ‘age’ of the particular magma batch.     

Fracturing and fluid migration during Palaeogene compression and Neogene extension in the Catalan Coastal Ranges, Spain

The Catalan Coastal Ranges (NE part of the Eastern Iberian Margin) correspond to a system of grabens formed at the north-western margin of the Valencia Trough. Extensional activity in the Catalan Coastal Ranges occurred at least from early to late Miocene and reactivated earlier transpressive faults related to the Palaeogene compression. In the central part of the Catalan Coastal Ranges, tectonic micro and macrostructures (faults, joints, stylolites) are well developed in the Mesozoic (mainly Cretaceous) limestones as well as in the Miocene graben fill deposits. In these rocks, seven generations of fractures, which formed during different tectonic phases, have been distinguished. Type 1–4 fractures affect only the Cretaceous limestones, type 5 and 6 fractures the Cretaceous and Miocene deposits, and type 7 fractures only the Miocene sediments. The fractures are filled with calcites, and locally with an internal sediment or a dolomite cement. The Cretaceous host-rock has an average δ¹⁸O value of –4·3‰ PDB (Peedee Belemnite), an average δ¹³C value of +0·6‰ PDB, a ⁸⁷Sr/⁸⁶Sr ratio of 0·70741, up to 5630 p.p.m. of Mg²⁺, up to 2615 p.p.m. of Sr²⁺, and up to 1560 p.p.m. of Fe²⁺. Type 2 fractures are related to Palaeogene compression. The calcite cement filling this type of fracture has an average δ¹⁸O value of –8·2‰ PDB, an average δ¹³C value of –0·6‰ PDB, a ⁸⁷Sr/⁸⁶Sr ratio of 0·70714, up to 4560 p.p.m. of Mg²⁺, up to 3275 p.p.m. of Sr²⁺, and up to 3540 p.p.m. of Fe²⁺. These results indicate a fluid characterized by a high rock–fluid interaction approaching a closed system equilibrium. Type 5 fractures are related to the syn-rift stage. The calcite cement filling this type of fracture has an average δ¹⁸O value of –6·9‰ PDB, an average δ¹³C value of –4·3‰ PDB, a ⁸⁷Sr/⁸⁶Sr ratio of 0·70787, up to 5375 p.p.m. of Mg²⁺, up to 1750 p.p.m. of Sr²⁺ and up to 2855 p.p.m. of Fe²⁺. These results indicate a fluid characterized by a low rock–fluid interaction and an open hydrogeological system. The cements filling the compressional fractures are characterized by undulose extinction, subgrain formation and deformed mechanical twin planes indicating formation under stressed conditions. In contrast, cements filling extensional fractures are characterized by translucent crystals with uniform extinction, indicating free growth not subjected to stress.     

Combining in situ isotopic, trace element and textural analyses of quartz from four magmatic-hydrothermal ore deposits

This study couples in situ ¹⁶O, ¹⁷O and ¹⁸O isotope and in situ trace element analyses to investigate and characterize the geochemical and textural complexity of magmatic-hydrothermal quartz crystals. Euhedral quartz crystals contemporaneous with mineralization were obtained from four magmatic-hydrothermal ore deposits: El Indio Au–Ag–Cu deposit; Summitville Au–Ag–Cu deposit; North Parkes Cu–Au deposit and Kingsgate quartz-Mo–Bi–W deposit. The internal features of the crystals were imaged using cathodoluminescence and qualitative electron microprobe maps. Quantitative isotopic data were collected in situ using 157 nm laser ablation inductively coupled plasma mass spectrometry (for 40 trace elements in quartz) and sensitive high-resolution ion microprobe (for 3 isotopes in quartz). Imaging revealed fine oscillatory zoning, sector zoning, complex “macromosaic” textures and hidden xenocrystic cores. In situ oxygen isotope analyses revealed a δ¹⁸O range of up to 12.4 ± 0.3 ‰ in a single crystal—the largest isotopic range ever ascribed to oscillatory zonation in quartz. Some of these crystals contain a heavier δ¹⁸O signature than expected by existing models. While sector-zoned crystals exhibited strong trace element variations between faces, no evidence for anisotropic isotope fractionation was found. We found: (1) isotopic heterogeneity in hydrothermal quartz crystals is common and precludes provenance analysis (e.g., δD–δ¹⁸O) using bulk analytical techniques, (2) the trace element signature of quartz is not an effective pathfinder toward noble metal mineralization and (3) in three of the four samples, both textural and isotopic data indicate non-equilibrium deposition of quartz.     

Columnar calcites as testimony of diagenetic overprinting at the boundary between Upper Tournaisian dolomites and limestones (Belgium): multiple origins for apparently similar features

In topographic flat areas, sedimentary settings may vary from one outcrop to another. In these settings, calcite precipitates may yield macroscopically similar columnar features, although they are products of different sedimentary or diagenetic processes. Three columnar calcite crystal fabrics, i.e. rosettes, palisade crusts and macro-columnar crystal fans, have been differentiated near and at the contact between Upper Tournaisian dolomites and limestones along the southern margin of the Brabant-Wales Palaeohigh. Their petrographic characteristics, and geochemical and fluid inclusion data provide information on the (dia)genetic processes involved. Rosettes composed of non-luminescent columnar calcite crystal fans (1–5 cm in diameter) developed on top of one another, forming discrete horizons in repetitive sedimentary cycles. The cycles consist of three horizons: (I) a basal horizon with fragments from the underlying horizon, (II) a micrite/microspar horizon with incipient glaebules, (III) an upper horizon consisting of calcite rosettes, with desiccation features. The petrographical features and δ¹⁸O signatures of −10·0 to −5·5‰ and δ¹³C values of −5·5 to −3·2‰ support either evaporative growth, an evaporative pedogenic origin, or overprinting of marine precipitates. Palisade crusts, composed of a few to 10 mm long non-luminescent calcite crystals, coat palaeokarst cavities. Successive palisade growth-stages occur which are separated by thin laminae of micrite or detrital quartz, displaying a geopetal arrangement. Palisade crusts are interpreted as intra-Mississippian speleothems. This interpretation is supported by their petrographic characteristics and isotopic signature (δ¹⁸O = −8·7 to −6·5‰ and δ¹³C = −4·8 to −2·5‰). Macro-columnar crystals, 1–50 cm long, developed mainly perpendicular to cavity walls and dolomite clasts. Crystal growth stages in the macro-columnar crystals are missing. δ¹⁸O values vary between −16·4 and −6·8‰ and δ¹³C values between −5·2 and −0·9‰. These features possibly support a late diagenetic high temperature precipitation in relation to hydrothermal karstification.     

Changes in carbon and oxygen isotope composition during limestone diagenesis

The calcite fossils of the Derbyhaven Beds, Isle of Man, have δ¹³C values (+ 1·8 PDB) similar to modern, shallow-water marine skeletons, but the δ¹⁸O values (?6·1 PDB) are much lighter than modern skeletons. The light oxygen values indicate either re-equilibration with isotopically light water before cementation started, or Carboniferous sea water with δ¹⁸O of ?6‰. Aragonite dissolution was followed by precipitation of zoned calcite cement. In this cement, up to six intracrystalline zones, recognized in stained thin sections, show isotopic variation. Carbon varies from + 3-8 to + 1-2‰. and oxygen from ? 2-6 to ? 12-4‰. with decreasing age of the cement. This trend is attributed to increasing temperature and to isotopic evolution of the pore waters during burial. The zoned calcite is sequentially followed by dolomite and kaolinite cements which continue the trend towards light isotopic values. This trend is continued with younger, fault-controlled dolomite, and is terminated by vein-filling calcite and dolomite. The younger calcite, interpreted as a near-surface precipitate from meteoric waters, is unrelated to the older sequence of carbonates and has distinctly different carbon isotope ratios: δ¹³C ? 6-8‰.     

Petrographic and geochemical evidence for the formation of primary, bacterially induced lacustrine dolomite: La Roda 'white earth' (Pliocene, central Spain)

Upper Pliocene dolomites (‘white earth’) from La Roda, Spain, offer a good opportunity to evaluate the process of dolomite formation in lakes. The relatively young nature of the deposits could allow a link between dolomites precipitated in modern lake systems and those present in older lacustrine formations. The La Roda Mg‐carbonates (dolomite unit) occur as a 3·5‐ to 4‐m‐thick package of poorly indurated, white, massive dolomite beds with interbedded thin deposits of porous carbonate displaying root and desiccation traces as well as local lenticular gypsum moulds. The massive dolomite beds consist mainly of loosely packed 1‐ to 2‐μm‐sized aggregates of dolomite crystals exhibiting poorly developed faces, which usually results in a subrounded morphology of the crystals. Minute rhombs of dolomite are sparse within the aggregates. Both knobbly textures and clumps of spherical bodies covering the crystal surfaces indicate that bacteria were involved in the formation of the dolomites. In addition, aggregates of euhedral dolomite crystals are usually present in some more clayey (sepiolite) interbeds. The thin porous carbonate (mostly dolomite) beds exhibit both euhedral and subrounded, bacterially induced dolomite crystals. The carbonate is mainly Ca‐dolomite (51–54 mol% CaCO₃), showing a low degree of ordering (degree of ordering ranges from 0·27 to 0·48). Calcite is present as a subordinate mineral in some samples. Sr, Mn and Fe contents show very low correlation coefficients with Mg/Ca ratios, whereas SiO₂ and K contents are highly correlated. δ¹⁸O‐ and δ¹³C‐values in dolomites range from ?3·07‰ to 5·40‰ PDB (mean=0·06, σ=1·75) and from ?6·34‰ to ?0·39‰ PDB (mean=?3·55, σ=1·33) respectively. Samples containing significant amounts of both dolomite and calcite do not in general show significant enrichment or depletion in ¹⁸O and ¹³C between the two minerals. The correlation coefficient between δ¹⁸O and δ¹³C for dolomite is extremely low and negative (r=?0·05), whereas it is higher and positive (r=0·47) for calcite. The lacustrine dolomite deposit from La Roda is interpreted mainly as a result of primary precipitation of dolomite in a shallow, hydrologically closed perennial lake. The lake was supplied by highly saturated HCO₃^?/CO₃^2? groundwater that leached dolomitic Mesozoic formations. Precipitation of dolomite from alkaline lake waters took place under a semi‐arid to arid climate. However, according to our isotopic data, strong evaporative conditions were not required for the formation of the La Roda dolomite. A significant contribution by bacteria to the formation of the dolomites is assumed in view of both petrographic and geochemical evidence.     

The δ18O of UST Quartz in Two Porphyry Deposits,China

The unidirectional solidification textures (UST) quartz is generally thought to form from fluids exsolved from shallow intrusions and/or magma chambers, but such an idea is still poorly constrained from the evidence of stable isotopes. In this study, we report for the first time the δ¹⁸O of quartz that shows UST from the Qulong Cu–Mo and the Yechangping Mo porphyry deposits in China. The analysis results show that the UST quartz samples from the Qulong deposit have δ¹⁸O values ranging from +6.2 ‰ to +7.6 ‰, which are similar to that of quartz phenocrysts (+6.7 ‰ to +7.8 ‰). In contrast, the UST quartz samples from the Yechangping porphyry Mo deposit yield a high δ¹⁸O value (+10.0 ‰). The δ¹⁸O_water value of Yechangping UST quartz (+8.5 ‰) is also higher than that of Qulong (+4.6 ‰ to +5.8 ‰). Hydrothermal biotite from potassic alteration and sericite from early phyllic alteration at Qulong have similar δ¹⁸O values to UST quartz, suggesting the involvement of magmatic fluids during this stage of deposit evolution.     

Dolomitization of the Waulsortian Limestone (Lower Carboniferous) in the Irish Midlands

The Waulsortian Limestone (Lower Carboniferous) of the southern Irish Midlands is dolomitized pervasively over a much larger region than previous studies have documented. This study indicates a complex, multistage, multiple fluid history for regional dolomitization. Partially and completely dolomitized sections of Waulsortian Limestones are characterized by finely crystalline (0·01–0·3 mm) planar dolomite. Planar replacive dolomite is commonly followed by coarse (≥0·5 mm) nonplanar replacive dolomite, and pervasive void‐filling saddle dolomite cement is frequently associated with Zn–Pb mineralization. Planar dolomite has average δ¹⁸O and δ¹³C values (‰ PDB) of –4·8 and 3·9 respectively. These are lower oxygen and slightly higher carbon isotope values than averages for marine limestones in the Waulsortian (δ¹⁸O=–2·2, δ¹³C=3·7). Mean C and O isotope values of planar replacive dolomite are also distinct from those of nonplanar and saddle dolomite cement (–7·0 and 3·3; –7·4 and 2·4 respectively). Fluid inclusions indicate a complex history involving at least three chemically and thermally distinct fluids during dolomite cementation. The petrography and geochemistry of planar dolomites are consistent with an early diagenetic origin, possibly in equilibrium with modified Carboniferous sea water. Where the Waulsortian was exposed to hydrothermal fluids (70–280 °C), planar dolomite underwent a neomorphic recrystallization to a coarser crystalline, planar and nonplanar dolomite characterized by lower δ¹⁸O values. Void‐filling dolomite cement is isotopically similar to nonplanar, replacive dolomite and reflects a similar origin from hydrothermal fluids. This history of multiple stages of dolomitization is significantly more complex than earlier models proposed for the Irish Midlands and provides a framework upon which to test competing models of regional vs. localized fluid flow.     

Hydrogen and Oxygen Isotope Study on the Water-Rock Interaction of the Yinshan (Cu-) Pb-Zn-Ag Ore Deposit, Jiangxi Province

The δ18O values of vein quartz of different stages from the Yinshan ore deposit are constant around 16‰ and the calculated δ18OH2O values attain 8‰± ; the δDH2O values of fluid inclu-sions in vein quartz are constant at about-60‰. From the surface down to 1200 m below the δ18O values of altered rocks gradually decrease from 15‰± to 11‰± . Various water-rock inversion calculations indicate that the ore fluids were formed by the interaction between meteoric water and phyllite at 350℃ and the effective W/ R value of around 0.1. When the water-rock exchange in the upper mineralization system took place, the effective W / R value increased to 5.0 or more. As a result, an evolution and mineralization model of a buffered open system with two-stage water-rock interactions is proposed in this study.     

Channelized fluids in subducted continental crust: constraints from δD–δ18O of quartz and fluid inclusions in quartz veins from the Chinese Continental Scientific Drilling Project

Fluid inclusions hosted by quartz veins in high-pressure to ultrahigh-pressure (HP-UHP) metamorphic rocks from the Chinese Continental Scientific Drilling (CCSD) Project main drillhole have low, varied hydrogen isotopic compositions (δD?=??97‰ to??69‰). Quartz δ¹⁸O values range from??2.5‰ to 9.6‰; fluid inclusions hosted in quartz have correspondingly low δ¹⁸O values of??11.66‰ to 0.93‰ (T _h?=?171.2～318.8°C). The low δD and δ¹⁸O isotopic data indicate that protoliths of some CCSD HP-UHP metamorphic rocks reacted with meteoric water at high latitude near the surface before being subducted to great depth. In addition, the δ¹⁸O of the quartz veins and fluid inclusions vary greatly with the drillhole depth. Lower δ¹⁸O values occur at depths of ～900–1000 m and ～2700 m, whereas higher values characterize rocks at depths of about 1770 m and 4000 m, correlating roughly with those of wall-rock minerals. Given that the peak metamorphic temperature of the Dabie-Sulu UHP metamorphic rocks was about 800°C or higher, much higher than the closure temperature of oxygen isotopes in quartz under wet conditions, such synchronous variations can be explained by re-equilibration. In contrast, δD values of fluid inclusions show a different relationship with depth. This is probably because oxygen is a major element of both fluids and silicates and is much more abundant in the quartz veins and silicate minerals than is hydrogen. The oxygen isotope composition of fluid inclusions is evidently more susceptible to late-stage re-equilibration with silicate minerals than is the hydrogen isotope composition. Therefore, different δD and δ¹⁸O patterns imply that dramatic fluid migration occurred, whereas the co-variation of oxygen isotopes in fluid inclusions, quartz veins, and wall-rock minerals can be better interpreted by re-equilibration during exhumation.

Quartz veins in the Dabie-Sulu UHP metamorphic terrane are the product of high-Si fluids. Given that channelized fluid migration is much faster than pervasive flow, and that the veins formed through precipitation of quartz from high-Si fluids, the abundant veins indicate significant fluid mobilization and migration within this subducted continental slab. Many mineral reactions can produce high-Si fluids. For UHP metamorphic rocks, major dehydration during subduction occurred when pressure–temperature conditions exceeded the stability of lawsonite. In contrast, for low-temperature eclogites and other HP metamorphic rocks with peak metamorphic P–T conditions within the stability field of lawsonite, dehydration and associated high-Si fluid release may have occurred as hydrous minerals were destabilized at lower pressure during exhumation. Because subduction is a continuous process whereas only a minor fraction of the subducted slabs returns to the surface, dehydration during underflow is more prevalent than exhumation even in subducted continental crust, which is considerably drier than altered oceanic crust.     

Recrystallization of dolomite: evidence from the Monterey Formation (Miocene), California

Dolomites from the upper calcareous-siliceous member of the Miocene Monterey Formation exposed west of Santa Barbara, California, were analysed for geochemical, isotopic and crystallographic variation. The data clearly document the progressive recrystallization of dolomite during burial diagenesis in marine pore fluids. Recrystallization is recognized by the following compositional and crystallographic variations. Dolomites have decreasing δ¹⁸O and δ¹³C compositions, decreasing Sr contents and increasing Mg contents with increasing burial depths and temperatures from east to west in the study area. δ¹⁸O values vary from 5·3‰ in the east to − 5·5‰ PDB in the west and are interpreted to reflect the greater extent and higher temperature of dolomite recrystallization in the west. δ¹³C values correlate with δ¹⁸O and decrease from 13·6‰ in the east to − 8·7‰ PDB in the west. Sr concentrations correlate positively with δ¹⁸O values and decrease from a mean of 750 ppm in the east to a mean of 250 ppm in the west. Mol% MgCO₃ values inversely correlate with δ¹⁸O values and increase from a minimum of 41·0 in the east to a maximum of 51·4 in the west. Rietveld refinements of powder X-ray diffraction data indicate that the more recrystallized dolomites have more contracted unit cells and increased cation ordering. The fraction of the Ca sites in the dolomites that are occupied by Ca atoms increases slightly with the approach to stoichiometry. The fraction of the Mg sites occupied by Mg atoms strongly correlates with mol% MgCO₃. Even in early diagenetic, non-stoichiometric dolomites, there is little substitution of Mg in Ca sites. During recrystallization, the amount of Mg substituting for Ca in Ca sites decreases even further. Most of the disorder in the least recrystallized, non-stoichiometric dolomites is related to substitution of excess Ca on Mg sites.     

Origin of quartz geodes from Laño and Tubilla del Agua sections (middle–upper Campanian,Basque‐Cantabrian Basin,northern Spain): isotopic differences during diagenetic processes

Quartz geodes and nodular chert have been found within middle–upper Campanian carbonate sediments from the Laño and Tubilla del Agua sections of the Basque‐Cantabrian Basin, northern Spain. The morphology of geodes together with the presence of anhydrite laths included in megaquartz crystals and spherulitic fibrous quartz (quartzine‐lutecite), suggest an origin from previous anhydrite nodules. The anhydrite nodules at Laño were produced by the percolation of marine brines, during a period corresponding to a sedimentary gap, with δ³⁴S and δ¹⁸O mean values of 18.8‰ and 13.6‰ respectively, consistent with Upper Cretaceous seawater sulphate values. Higher δ³⁴S and δ¹⁸O mean values of 21.2‰ and 21.8‰ recorded in the Tubilla del Agua section are interpreted as being due to a partial bacterial sulphate reduction process in a more restricted marine environment. The idea that sulphates may have originated from the leaching of previously deposited Keuper sulphate evaporites with subsequent precipitation as anhydrite, is rejected because the δ³⁴S, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr values of anhydrite laths observed at both the Tubilla del Agua and Laño sections suggest an origin from younger marine brines. Later calcite replacement and precipitation of geode‐filling calcite is recorded in both sections, with δ¹³C and δ¹⁸O values indicating the participation of meteoric waters. Synsedimentary activity of the Peñacerrada diapir, which lies close to the Laño section, played a significant role in the local shallowing of the basin and the formation of quartz geodes. In contrast, eustatic shallowing of the inner marine series of the Tubilla del Agua section led to the generation of morphologically similar quartz geodes. Copyright © 2002 John Wiley & Sons, Ltd.     

Dedolomitization and calcite cementation in the Middle Devonian Winnipegosis Formation in Central Saskatchewan,Canada

Limestone consisting of finely to medium crystalline calcite mosaics is present in the upper part of the Winnipegosis Formation on the east‐central margin of the Elk Point Basin where the overlying Prairie Evaporite deposits have been removed. This type of crystalline limestone is interpreted as dedolomite, based on petrographic observations. The δ¹⁸O and δ¹³C values of the Winnipegosis dedolomite vary from ?12·8‰ to ?11·9‰ VPDB (Vienna Pee Dee Belemnite) and from ?0·5‰ to +1·7‰ VPDB, respectively; both values are significantly lower than those for the corresponding dolomite. The ⁸⁷Sr/⁸⁶Sr ratios of the dedolomite are significantly higher, between 0·7082 and 0·7087. The spatial distribution and geochemical data of the Winnipegosis dedolomite suggest that dedolomitization was related to an influx of fresh groundwater and dissolution of the Prairie Evaporite anhydrite during the latest Mississippian to the Early Cretaceous when the basin was subjected to uplift and erosion. The Winnipegosis dedolomite displays a series of replacement fabrics showing progressive calcitization of dolomite, including the occurrence of dedolomite restricted along fractures and adjacent areas, dolomite patches ‘floating’ in the dedolomite masses and massive dedolomite with sparsely scattered dolomite relicts. However, the characteristic fabrics resulting from dedolomitization documented in the literature have not been observed in the Winnipegosis dedolomite. Coarsely to very coarsely crystalline, subhedral to euhedral calcite cement is restricted in the dedolomite. The petrographic features, isotopic compositions and homogenization temperatures, coupled with the burial history of the Winnipegosis Formation, constrain the precipitation of the calcite cement from a mixing of basinal brines and fresh groundwater during Late Cretaceous to Neogene time. The more negative C‐isotopic signatures of the calcite cement (?5·3‰ to ?2·3‰ VPDB) probably reflect a hydrocarbon‐derived carbon.