Low-Mg calcite marine cement in Cretaceous turbidites: origin, spatial distribution and relationship to seawater chemistry

Lower Cretaceous (Hauterivian) bioclastic sandstone turbidites in the Scapa Member (North Sea Basin) were extensively cemented by low-Mg calcite spars, initially as rim cements and subsequently as concretions. Five petrographically distinct cement stages form a consistent paragenetic sequence across the Scapa Field. The dominant and pervasive second cement stage accounts for the majority of concretions, and is the focus of this study. Stable-isotope characterization of the cement is hampered by the presence of calcitic bioclasts and of later cements in sponge spicule moulds throughout the concretions. Nevertheless, trends from whole-rock data, augmented by cement separates from synlithification fractures, indicate an early calcite δ¹⁸O value of+0·5 to -1·5‰ PDB. As such, the calcite probably precipitated from marine pore fluids shortly after turbidite deposition. Carbon isotopes (δ¹³C=0 to -2‰ PDB) and petrographic data indicate that calcite formed as a consequence of bioclastic aragonite dissolution. Textural integrity of calcitic nannoplankton in the sandstones demonstrates that pore fluids remained at or above calcite saturation, as expected for a mineral-controlled transformation. Electron probe microanalyses demonstrate that early calcite cement contains <2 mol% MgCO₃, despite its marine parentage. Production of this cement is ascribed to a combination of an elevated aragonite saturation depth and a lowered marine Mg²⁺/Ca²⁺ ratio in early Cretaceous ‘calcite seas’, relative to modern oceans. Scapa cement compositions concur with published models in suggesting that Hauterivian ocean water had a Mg²⁺/Ca²⁺ ratio of ≤1. This is also supported by consideration of the spatial distribution of early calcite cement in terms of concretion growth kinetics. In contrast to the dominant early cement, late-stage ferroan, ¹⁸O-depleted calcites were sourced outwith the Scapa Member and precipitated after 1–2 km of burial. Our results emphasize that bioclast dissolution and low-Mg calcite cementation in sandstone reservoirs should not automatically be regarded as evidence for uplift and meteoric diagenesis.     

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.     

Zoned calcites in Jurassic ammonite chambers: trace elements, isotopes and neomorphic origin

Zoned calcites were found in the phragmacone chambers of three Sonniniid ammonites from marine Middle Jurassic sandstones (Isle of Skye, U.K.). Each ammonite has a unique sequence of up to nine zones of calcite which fill or partially fill the chambers. Zones are defined by changes in the density of minute opaque inclusions and variation in trace-element composition. Proximal (early) calcites have undulose extinction and some exhibit the specific fabrics of fascicular-optic and radiaxial fibrous calcites. Microdolomite inclusions are found in one specimen. Early calcites, interpreted as replacements after a single isopachous fringe of acicular carbonate (probably high magnesium calcite), are succeeded by blocky ferroan calcite cement. In one specimen there are two distinct generations of calcite, in the others there is a continuous mosaic incorporating both early calcites and late cement. Isotopic composition of the early calcite zones demonstrates the initial importance of organic derived carbon (δ¹³C =— 26‰, δ¹⁸O ‰ O). Further cementation and mineralogical stabilization took place at increased temperatures and probably after modification of the pore water isotopic composition (calcites with δ¹³C =— O‰, δ¹⁸O～— 10‰). The distinctive fabrics and zonal patterns probably developed during the replacement of the precursor cement and are not primary growth features. Reversals in isotopic and trace element trends are believed to be related to the rate of neomorphic crystal growth and hence to the degree of exchange with external pore waters. Further increase in temperature, probably during Tertiary igneous activity, gave rise to the extremely light δ¹⁸O values of the late cements in the ammonite which had previously had least contact with external waters (cements with δ¹³C ～ O, δ¹⁸O ～— 20‰).     

Jurassic septarian concretions from NW Scotland record interdependent bacterial, physical and chemical processes of marine mudrock diagenesis

Septarian concretions in the Staffin Shales Formation (Kimmeridgian, Isle of Skye) allow controls on concretion rheology and septarian cracking to be investigated. Stratabound concretions consist of anhedral ferroan calcite microspar enclosing clay and minor pyrite. Intergranular volumes range from 77% to 88%, and calcite δ¹³C and δ¹⁸O values in most concretion bodies range from ?10·0‰ to ?17·3‰ and +0·3‰ to ?0·6‰ respectively, consistent with rapid and pervasive cementation in marine pore fluids. Septarian rupture occurred during incipient cementation, with a sediment volume reduction of up to 43%. Crack‐lining brown fibrous calcite records pore fluid re‐oxygenation during a depositional hiatus, followed by increasing Fe content and δ¹³C related to bacterial methanogenesis. Brown colouration results from an included gel‐like polar organic fraction that probably represents bacterially degraded biomass. A new hypothesis for concretion growth and septarian cracking argues that quasi‐rigid ‘proto‐concretions’ formed via binding of flocculated clays by bacterial extracellular polysaccharide substances (EPS). This provided rheological and chemical conditions for tensional failure, subcritical crack growth, volume contraction, calcite nucleation, and incorporation of degraded products into crack‐lining cements. Bacterial decay of EPS and syneresis of host muds provided internal stresses to initiate rupture at shallow burial. Development of septarian (shrinkage) cracks in muds is envisaged to require pervasive in situ bacterial colonization, and to depend on rates of carbonate precipitation versus EPS degradation and syneresis. Subsequent modification of septarian concretions included envelopment by siderite and calcite microspar, hydraulic fracturing associated with Cretaceous shallow burial or Palaeogene uplift; and cementation by strongly ferroan, yellow sparry calcite that records meteoric water invasion of the host mudrocks. An abundance of fatty acids in these spars indicates aqueous transport of organic breakdown products, and δ¹³C data suggest a predominantly methanogenic bicarbonate source. However, the wide δ¹⁸O range for petrographically identical cement (?1·3‰ to ?15·6‰) is difficult to explain.     

REE and C-O Isotopic Geochemistry of Calcites from the World-class Huize Pb-Zn Deposits, Yunnan, China: Implications for the Ore Genesis

<正>The world-class Huize Pb-Zn deposits of Yunnan province,in southwestern China,located in the center of the Sichuan-Yunnan-Guizhou Pb-Zn polymetallic metallogenic province,has Pb+Zn reserves of more than 5 million tons at Pb+Zn grade of higher than 25%and contains abundant associated metals,such as Ag,Ge,Cd,and Ga.The deposits are hosted in the Lower Carboniferous carbonate strata and the Permian Emeishan basalts which distributed in the northern and southwestern parts of the orefield.Calcite is the only gangue mineral in the primary ores of the deposits and can be classified into three types,namely lumpy,patch and vein calcites in accordance with their occurrence.There is not intercalated contact between calcite and ore minerals and among the three types of calcite,indicating that they are the same ore-forming age with different stages and its forming sequence is from lumpy to patch to vein calcites. This paper presents the rare earth element(REE) and C-O isotopic compositions of calcites in the Huize Pb-Zn deposits.From lumpy to patch to vein calcites,REE contents decrease as LREE/ HREE ratios increase.The chondrite-normalized REE patterns of the three types of calcites are characterized by LREE-rich shaped,in which the lumpy calcite shows(La)_N(Ce)_N(Pr)_N≈(Nd)_N with Eu/Eu~*1,the patch calcite has(La)_N(Ce)_N(Pr)_N≈(Nd)_N with Eu/Eu~*1,and the vein calcite displays(La)_N(Ce)_N(Pr)_N(Nd)_N with Eu/Eu~*1.The REE geochemistry of the three types of calcite is different from those of the strata of various age and Permian Emeishan basalt exposed in the orefield.Theδ~(13) C_(PDb) andδ~(18)O_(Smow) values of the three types of calcites vary from-3.5‰to-2.1‰and 16.7‰to 18.6‰,respectively,falling within a small field between primary mantle and marine carbonate in theδ~(13)C_(PDb) vsδ~(18)O_(Smow) diagram. Various lines of evidence demonstrate that the three types of calcites in the deposits are produced from the same source with different stages.The ore-forming fluids of the deposits resulted from crustal -mantle mixing processes,in which the mantle-derived fluid components might be formed from degassing of mantle or/and magmatism of the Permian Emeishan basalts,and the crustal fluid was mainly provided by carbonate strata in the orefield.The ore-forming fluids in the deposits were homogenized before mineralization,and the ore-forming environment varied from relatively reducing to oxidizing.     

Physical and chemical growth conditions of Ordovician organogenic deep-water dolomite concretions: implications for the δ18O of Early Palaeozoic sea water

The estimated depth of formation of authigenic dolomite concretions in the Middle Ordovician Cloridorme Formation, Quebec, ranges from < 1 m to 150–200 m below sea floor (mbsf) (mostly between < 1 and 25 mbsf), based on centre‐to‐margin variations in minus‐cement porosity (80–90% to 45–75%). Formation depths are > 350 mbsf (25–17% porosity) in the Lower Ordovician Levis Formation. Outward‐decreasing δ¹³C_VPDB values (10·2–0·8‰) suggest precipitation in the methane generation zone with an increasing contribution of light carbonate derived by advection from thermocatalytic reactions at depth. Anomalously low δ¹⁸O_VPDB values (centre‐to‐margin variations of ?0·4 to ?7·5‰) give reasonable temperatures for the concretion centres only if the δ¹⁸O of Ordovician sea water was negative (?6‰) and the bottom water was warm (> 15 °C). The 3–5‰ lower values for the concretion margins compared with the centres can be explained if, in addition, volcanic‐ash alteration, organic‐matter decomposition and/or advection of ¹⁸O‐depleted water lowered the δ¹⁸O of the pore water further by 2·0–4·0‰ during the first 25–200 m of burial. Reasonable growth temperatures for the margins of 17–20 °C are compatible with a lowering of the isotopic ratios by 1 to < 1·3‰ as a temperature effect. The systematic concentric isotope zonation of the concretions suggests that the well‐ordered near‐stoichiometric dolomite is a primary feature and not the result of recrystallization. Diagenetic dolomite beds of the Cloridorme Formation appear to have formed by coalescence of concretions, as shown by randomly sampled traverses that indicate formation at different subsurface depths. Growth of the Cloridorme dolomites was probably limited by calcium availability, at least 50% of which was derived from connate water, and the remainder by diffusion from sea water. Dolomite precipitation was favoured over calcite by very high sedimentation rates, the abundance of marine organic matter in the host sediment and a correspondingly thin sulphate reduction zone. Deep‐seated concretion growth in the Levis Formation required either internal sources for the participating ions (carbonate dissolution event) or porewater advection along faults.     

'Pseudobreccias' revealed as calcrete mottling and bioturbation in the Late Dinantian of the southern Lake District, UK

Two types of ‘pseudobreccia’, one with grey and the other with brown mottle fabrics, occur in shoaling‐upward cycles of the Urswick Limestone Formation of Asbian (Late Dinantian, Carboniferous) age in the southern Lake District, UK. The grey mottle pseudobreccia occurs in cycle‐base packstones and developed after backfilling and abandonment of Thalassinoides burrow systems. Burrow infills consist of a fine to coarse crystalline microspar that has dull brown to moderate orange colours under cathodoluminescence. Mottling formed when an early diagenetic ‘aerobic decay clock’ operating on buried organic material was stopped, and sediment entered the sulphate reduction zone. This probably occurred during progradation of grainstone shoal facies, after which there was initial exposure to meteoric water. Microspar calcites then formed rapidly as a result of aragonite stabilization. The precipitation of the main meteoric cements and aragonite bioclast dissolution post‐date this stabilisation event. The brown mottle pseudobreccia fabrics are intimately associated with rhizocretions and calcrete, which developed beneath palaeokarstic surfaces capping cycle‐top grainstones and post‐date all depositional fabrics, although they may also follow primary depositional heterogeneities such as burrows. They consist of coarse, inclusion‐rich, microspar calcites that are always very dull to non‐luminescent under cathodoluminescence, sometimes with some thin bright zones. These are interpreted as capillary rise and pedogenic calcrete precipitates. The δ¹⁸O values (?5‰ to ?8‰, PDB) and the δ¹³C values (+2‰ to ?3‰, PDB) of the ‘pseudobreccias’ are lower than the estimated δ¹⁸O values (?3‰ to ?1‰ PDB) and δ¹³C values of (+2‰ to +4‰ PDB) of normal marine calcite precipitated from Late Dinantian sea water, reflecting the influence of meteoric waters and the input of organic carbon.     

Carbon and Oxygen Isotope Compositions of Some Upper Cretaceous–Paleocene Sequences in Argentina and Chile

The Cretaceous-Paleocene (K-T) transition has been recorded in sedimentary carbonate rocks in northwestern Argentina and southern Chile. In the Yacoraite Basin, Argentina, this transition has been preserved in a 2 m thick marly layer, at the base of the Tunal Formation, which overlies lacustrine/marine carbonates of the Yacoraite Formation (Cabra Corral dam). The K-T transition is also preserved at Maimara, where Tertiary sandstones overlie a 50 m thick limestone bed of the Yacoraite Formation. In the Magellan Basin, Chile, glauconitic sandstones with calcitic cement and limestone concretions of the Maastrichtian Punta Rocallosa Formation are overlain by sandstones, claystones, and limestones of the Chorillo Chico Formation. The K-T transition is preserved in the lower portion of the Chorillo Chico Formation.

Carbonates of the Yacoraite Formation display bulk-rock δ¹³C values from +1 to +2‰ PDB, with a negative incursion (?4‰ PDB) at the K-T transition. δ¹³C values in the Tunal Formation marls vary from ?3 to ?1‰ PDB. At Rocallosa Point, δ¹³C values in limestone strata, calcite cement, and limestone concretions vary from ?4 to ?33 ‰ PDB, and the lowest value in the Chorillo Chico Formation apparently marks the K-T transition. The δ¹⁸O fluctuations in the Yacoraite and Magellan carbonate rocks suggest a temperature drop at the K-T transition, followed by a temperature rise.

High ⁸⁷Sr/⁸⁶Sr ratios (0.7140-0.7156) characterize the studied profiles of the Yacoraite Formation, documenting an important ⁸⁷Sr-enriched source of Sr to the water from which these carbonates precipitated. At the Magellan basin, ⁸⁷Sr/⁸⁶Sr ratios are closer to the expected values for the global Late Cretaceous-Paleocene ocean.     

Formation mechanisms of calcite cements in tight sandstones of the Jurassic Lianggaoshan Formation,northeastern Central Sichuan Basin

The characteristics and formation mechanism of calcite cements in the tight sandstone of the Jurassic Lianggaoshan Formation in the northeastern Central Sichuan Basin were analysed using petrographic and isotopic techniques. In the tight sandstone of the Lianggaoshan Formation, cements are mostly calcite and occur as poikilitic, pore-filling, fracture-filling and replacement of clastic particles. Contents of Al, Si, Fe and Mn in the poikilitic calcites are significantly less than that in the dissolution pore-filling and metasomatic calcites. Three stages (early, middle and late) of authigenic calcites correspond to temperature ranges of <60, 60–100 and ≥100?°C, respectively, with most calcite cements formed under lower temperature (<100?°C) conditions. The δ¹⁸O values of the early–middle authigenic calcites are in equilibrium with connate water, and the δ¹⁸O values of late calcites are depleted in ¹⁸O indicating equilibrium at higher temperatures. The early authigenic calcites precipitated in a relatively open system associated with CO₂ from bacterial fermentation at an immature to low-mature stage, and a Ca²⁺- and alkaline-rich environment owing to hydration–hydrolysis and dissolution of silicate minerals during phase A of eodiagenesis. The middle–late authigenic calcites precipitated in a relatively closed system with CO₂ from decarboxylation of organic acids and Ca²⁺ from dissolution of silicate minerals and transformation of clay minerals during phase B of eodiagenesis to mesodiagenesis. Calcite cements mainly occur in the medium and fine sandstones of sand flats and beach bars. Authigenic calcite dissolution is extremely weak, and calcite cementation is pore-space destructive.     

Carbon and Oxygen Isotope Compositions of Calcite and Rhodochrosite from Geothermal Exploratory Drills TH‐4 and TH‐6 near the Toyoha Deposit,Hokkaido, Japan

We studied calcite and rhodochrosite from exploratory drill cores (TH‐4 and TH‐6) near the Toyoha deposit, southwestern Hokkaido, Japan, from the aspect of stable isotope geochemistry, together with measuring the homogenization temperatures of fluid inclusions. The alteration observed in the drill cores is classified into four zones: ore mineralized zone, mixed‐layer minerals zone, kaolin minerals zone, and propylitic zone. Calcite is widespread in all the zones except for the kaolin minerals zone. The occurrence of rhodochrosite is restricted in the ore mineralized zone associated with Fe, Mn‐rich chlorite and sulfides, the mineral assemblage of which is basically equivalent to that in the Toyoha veins. The measured δ¹⁸O_SMOW and δ¹³C_PDB values of calcite scatter in the relatively narrow ranges from ?2 to 5‰ and from ?9 to ?5‰, respectively; those of rhodochrosite from 3 to 9‰ and from ?9 to ?5‰, excluding some data with large deviations. The variation of the isotopic compositions with temperature and depth could be explained by a mixing process between a heated surface meteoric water (100°C δ¹⁸O =?12‰, δ¹³C =?10‰) and a deep high temperature water (300°C, δ¹⁸O =?5‰, δ¹³C =?4‰). Boiling was less effective in isotopic fractionation than that of mixing. The plots of δ¹⁸O and δ¹³C indicate that the carbonates precipitated from H₂CO₃‐dominated fluids under the conditions of pH = 6–7 and T = 200–300°C. The sequential precipitation from calcite to rhodochrosite in a vein brought about the disequilibrium isotopic fractionation between the two minerals. The hydrothermal fluids circulated during the precipitation of carbonates in TH‐4 and TH‐6 are similar in origin to the ore‐forming fluids pertaining to the formation of veins in the Toyoha deposit.     

Deep‐burial alteration of early‐diagenetic carbonate concretions formed in Palaeozoic deep‐marine greywackes and mudstones (Bardo Unit,Sudetes Mountains,Poland)

Carbonate concretions formed in bathyal and deeper settings have been studied less frequently than those formed in shallow‐marine deposits. Similarly, concretions affected by catagenetic conditions have rarely been reported. Calcite concretions in deep‐marine mudstones and greywackes of the Bardo Unit (Sudetes Mountains, Poland) formed during early diagenesis and were buried to significant depths. Petrographic and geochemical (elemental and stable C and O isotopic) analyses document their formation close to the sediment–water interface, prior to mechanical compaction within the sulphate reduction zone and their later burial below the oil window. Although the concretions were fully formed during early diagenesis, the effects of increased temperature and interaction with late‐diagenetic interstitial fluids can be discerned. During maximum burial, the concretions underwent thorough recrystallization that caused alteration of fabric and elemental and O isotope composition. The initial finely crystalline cement was replaced by more coarsely crystalline, sheaf‐like, poikilotopic calcite in the concretions. These large calcite crystals engulf and partially replace unstable detrital constituents. The extremely low δ¹⁸O values (down to ?21·2‰ Vienna Pee Dee Belemnite) in the concretions are the result of the increased temperature in combination with alteration of volcanic glass, both causing a significant ¹⁸O‐depletion of bicarbonate dissolved in the interstitial fluids. Recrystallization led to uniform O isotope ratios in the concretions, but did not affect the C isotope signature. The δ¹³C values of the late‐diagenetic cements precipitated in the greywacke and in cracks cutting through concretions imply crystallization in the catagenetic zone and decarboxylation as a source of the bicarbonate. These late‐diagenetic processes took place in a supposedly overpressured setting, as suggested by clastic dykes and hydrofractures that cut through both concretions and host rock. All of these features show how the effects of early and late diagenesis can be distinguished in such rocks.     

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.     

Carbon,oxygen and sulphur isotope variations in concretions from the Upper Lias of N.E. England

Carbon, oxygen and sulphur isotope data for transects across two pyrite-bearmg carbonate concretions, and their host sediments, from the Upper Lias of N.E. England show symmetrical zonation. δ¹³C_PDB values of the calcite cement (?12.9 to ?15.4%.) indicate that most of it originated from organic matter by bacterial reduction of sulphate, augmented with marine and, to a lesser extent, fermentation derived carbonate. Organic carbon (δ¹³C_PDB = ?26.1 to ?37.0%.). reflects the admixture of allochtho-nous terrestrial organic matter with marine material and the selective preservation of isotopically light organic material through microbiological degradation.Two phases of pyrite are present in each concretion. The earlier framboidal pyrite formed throughout the sediment prior to concretionary growth and has δ³⁴S_CD values of ?22 to ?26%. indicating formation by open system sulphate reduction. The later euhedral phase is more abundant and reaches values of ? 2.5 to ? 5.5%. at concretion margins. This phase of sulphate reduction provided the carbonate source for concretionary growth and occurred in a partially closed system. The δ¹³C and δ³⁴S data are consistent with mineralogical and chemical evidence which suggest that both concretions formed close to the sediment surface. The δ₁₈O values of the calcite in one concretion (δ¹⁸O_PDB = 2.3 to ?4.8%.) indicate precipitation in pore waters whose temperature and isotopic composition was close to that of overlying seawater. The other concretion is isotopically much lighter (δ¹⁸O_PDB?8.9 to ?9.9%.) and large δ¹⁸O differences between concretions in closely-spaced horizons imply that local factors control the isotopic composition of pore waters.     

黔西南灰家堡金矿田热液方解石稀土元素与C-O-Sr同位素地球化学特征

为探讨灰家堡金矿田矿化剂和成矿物质来源,系统开展了热液方解石的稀土元素和C-O-Sr同位素研究。结果表明,热液方解石的稀土元素具有"上凸型"配分模式,低的(La/Sm)N值(0.003~0.580),较高的(Gd/Yb)_N值(1.21~15.73),Eu正异常,显示成矿流体的壳源特征;产于龙潭组(P3l)的矿体中的方解石δ13CPDB为-9.3‰~1.7‰(均值为-3.93‰);产于构造蚀变体(SBT)的矿体中的方解石δ¹³CPDB为-7.8‰~3.3‰(均值为1.04‰),C-O同位素组成介于地幔碳酸岩与海相碳酸盐岩之间,在δ¹³CPDB-δ¹⁸OSMOW图解上呈近水平分布,与矿体全岩及围岩碳同位素组成相似,表明成矿流体的C可能具有多来源特征。成矿流体与围岩之间的水-岩反应并未改变矿石的碳、氧同位素组成,流体-岩石相互作用不是导致热液方解石沉淀的主要机制,而更可能与CO₂的脱气作用有关;方解石的⁸⁷Sr/⁸⁶Sr值接近碳酸盐岩围岩、明显高于幔源物质的平均值,表明成矿热液中的Sr可能主要来自碳酸盐岩围岩。     

The concretions of the Bearreraig Sandstone Formation: geometry and geochemistry

The sandbodies of the Bearreraig Sandstone Formation (Inner Hebrides, UK) are cemented by two generations of calcite. The first generation, an inhomogeneous ferroan calcite (0.05?3.28 mol% FeCo₃) formed during sulphate reduction (δ¹³C =?24 to ?32%o PDB) in marine porewaters (δ¹⁸O of cement from ?1 to ?4%o PDB) at very shallow burial depths (a few centimetres). These cements are rare but form millimetre-scale clusters of crystals which acted as nuclei to the later, concretionary cements. The second generation of cements are more homogeneous ferroan calcites (mean 1?58% mol% FeCo₃) which evolve to progressively higher Fe/Mg ratios. They are sourced by shell dissolution (δ¹³C of cement from +1 to ?3%o PDB) into meteoric (δ¹⁸O of cement from ?6 to ?10%o PDB) or mixed marine meteoric waters (δ¹⁸O of cement from ?4 to ?6%o SMOW). These were introduced into the formation either during Bathonian times as a freshwater lens, or, subsequent to partial inversion, by confined aquifer flow. Corroded feldspars within the concretions suggest that an interval of at least 8 Ma separated the deposition of the sediments from the onset of concretion growth. Abundant concretions are preferentially developed at certain horizons within the sandbodies, where the early generation of ferroan calcite cements provided nuclei. The latter formed close to the sediment-water interface, the concentration of cement within the sediment being related to sedimentation rate. The relatively high concentrations of the first generation of cement, upon which the concretionary horizons are nucleated, formed during periods of minimal sedimentation.     

Spherical and columnar, septarian, 18O-depleted, calcite concretions from Middle–Upper Permian lacustrine siltstones in northern Mozambique: evidence for very early diagenesis and multiple fluids

Calcite septarian concretions from the Permian Beaufort Group in the Maniamba Graben (NW Mozambique) allow controls on the composition and nature of diagenetic fluids to be investigated. The concretions formed in lacustrine siltstones, where they occur in spherical (1 to 70 cm in diameter) and columnar (up to 50 cm long) forms within three closely spaced, discrete beds totalling 2·5 m in thickness. Cementation began at an early stage of diagenesis and entrapped non‐compacted burrows and calcified plant roots. The cylindrical concretions overgrew calcified vertical plant roots, which experienced shrinkage cracking after entrapment. Two generations of concretionary body cement and two generations of septarian crack infill are distinguished. The early generation in both cases is a low‐Mn, Mg‐rich calcite, whereas the later generation is a low‐Mg, Mn‐rich calcite. The change in chemistry is broadly consistent with a time (burial)‐related transition from oxic to sub‐oxic/anoxic conditions close to the sediment–water interface. Geochemical features of all types of cement were controlled by the sulphate‐poor environment and by the absence of bacterial sulphate reduction. All types of cement present have δ¹³C ranging between 0‰ and −15‰(Vienna Peedee Belemnite, V‐PDB), and highly variable and highly depleted δ¹⁸O (down to 14‰ Vienna Standard Mean Ocean Water, V‐SMOW). The late generation of cement is most depleted in both ¹³C and ¹⁸O. The geochemical and isotopic patterns are best explained by interaction between surface oxic waters, pore waters and underground, ¹⁸O‐depleted, reducing, ice‐meltwaters accumulated in the underlying coal‐bearing sediments during the Permian deglaciation. The invariant δ¹³C distribution across core‐to‐rim transects for each individual concretion is consistent with rapid lithification and involvement of a limited range of carbon sources derived via oxidation of buried plant material and from dissolved clastic carbonates. Syneresis of the cement during an advanced stage of lithification at early diagenesis is considered to be the cause of development of the septarian cracks. After cracking, the concretions retained a small volume of porosity, allowing infiltration of anoxic, Ba‐bearing fluids, resulting in the formation of barite. The results obtained contribute to a better understanding of diagenetic processes at the shallow burial depths occurring in rift‐bound, lacustrine depositional systems.     

Pedogenic-phreatic carbonates on a Middle Devonian (Givetian) terrigenous alluvial-deltaic plain, Gilwood Member (Watt Mountain Formation), northcentral Alberta, Canada

In the Muskeg Trough of northcentral Alberta the Gilwood Member contains widespread carbonate deposits that formed within terrigenous mudstone and sandstone hosts. Stratigraphic, depositional and petrographic relationships indicate that these carbonates represent calcretes and dolocretes. Calcretes, observed best with cathodoluminescence, display microcrystalline alpha fabrics, circumgranular cracks, root networks, displacive growth fabrics, elongate channel voids and rare coloform growths with flower spar. Similarly, dolocretes have microcrystalline alpha fabrics, brecciation, gradational contacts with host mudstones, extensive layered nodular horizons and are associated with anhydrite and pyrite. δ¹³C values range between ?7‰ to +1‰ and –6‰ to +3‰ for calcretes and dolocretes, respectively. Oxygen isotopes are more variable and differ with host lithologies. δ¹⁸O of calcretes ranges between ?11‰ to ?8‰ for sandstones and ?8‰ to ?3‰ for mudstones, whereas δ¹⁸O of dolocretes ranges between ?3‰ to 1‰ for marine mudstones and ?6‰ to ?2‰ for pedogenic mudstones. Regional mapping indicates that calcretes thicken towards the deepest parts of the Muskeg Trough. Widespread dolocretes extend beyond the eastern and western limits of Muskeg Trough and are useful marker intervals for regional correlations. Dolocretes of restricted lateral extent are found within gleyed palaeosol mudstones next to calcretized channel sandstones. Calcrete isotopic values are interpreted as indicative of carbonate precipitation from waters with meteoric water input. However, the higher δ¹⁸O values in dolocretes are indicative of a contribution from an isotopically heavier source such as seawater. Stratigraphically, calcretes are most common along the western and northern edges of Muskeg Trough; thus, calcrete accumulation was further controlled by meteoric water in-flow from the highland to the west and sluggish groundwater flow in Muskeg Trough. In contrast, regionally widespread dolocrete horizons appear to have formed from mixing of fresh waters derived from the highland to the west and seawaters introduced from the east. Regionally restricted dolocretes which are found next to channel sandstones formed from groundwater out-flow from the permeable channel sandstones which resulted in calcretization in channel proximal mudstones and dolomitization in channel distal mudstones.     

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.     

Microscopic calcite dendrites in cold-water tufa: implications for nucleation of micrite and cement

Dendritic calcite forms in an active cold-water tufa system in association with extracellular polymeric substances (EPS) that discontinuously coat bryophytes and cyanobacteria. Dendrites consist of 100–200 nm thick calcite fibres that form 3D lattice-like domains. In each dendrite domain, fibres have three structurally equal orientations, which correspond in disposition to radii from the centre of a calcite unit cell to the convex triple face junctions on its surface. Fibres do not form in the orientation of the c-axis. The external form of each dendrite has the shape of half of a shortened octahedron, with an upper triangular surface parallel to the substrate. Dendrite nucleation takes place on or in microbial EPS, whether microbial cells are present or not, and is probably effected by attraction of Ca²⁺ cations to negatively charged EPS, together with CO₂-degassing and concomitant pH increase of supersaturated spring water in stream splash zones. Ensuing dendrite growth is abiogenic and controlled by diffusion. Dendrite c-axes are perpendicular to the substrate, probably because the negative charge of EPS forces the orientation of Ca²⁺ and CO planes within the developing dendrite crystal to be parallel to the EPS film surface. Dendrites are eventually filled and overgrown by solid, syntaxial calcite, which gradually and completely obliterates the dendrites as more familiar calcite crystal forms develop. No trace of the dendritic nucleus remains in the rock record. Calcite crystal nucleation may take place by this mechanism in many marine and meteoric settings, given that microbial EPS is now assumed to be virtually ubiquitous in these environments. This phenomenon could contribute to the development of familiar fabrics such as marine micrite cement and fibrous calcite cement, radial ooids, peloids, ‘abiogenic’ stromatolites, sea floor precipitates, microbialites, tufa, travertine, speleothems, and some meteoric cements. It may also contribute to the substrate-normal orientation of c-axes of common cement fabrics.     

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.