Determining fluid source and possible pathways during burial dolomitization of Maryville Limestone (Cambrian), Southern Appalachians, USA

Detailed petrographic analyses along a depositional transect from a carbonate platform to shale basin reveals that dolomite is the principal burial diagenctic mineral in the Maryville Limestone. This study examines the role of burial dolomitization of subtidal carbonates. Dolomite occurs as a replacement of precursor carbonate and as inter- and intraparticle cements. Four different types of dolomite are identified based on detailed petrographic and gcochemical analyses. Type I dolomite occurs as small, irregular disseminations typically within mud-rich facies.Type II dolomite typically occurs as inclusions of planar euhedral rhombs (ferroan), 5–300 μm in size, in blocky clear ferroan calcite (meteoric) spar. Type II dolomite is non-luminescent. Type I and II dolomite formed during shallow to intermediate burial diagenesis. Type III dolomite consists of subhedral to anhedral crystals 10–150 μm in size occurring as thin seams along stylolites and as thick bands a few millimetres in width. This dolomite consists of dominantly non-luminescent rhombs and, less commonly, orange luminescent and zoned rhombs. Type IV dolomite consists of baroque or saddle-shaped, 100–1500 μm crystals, and is non-luminescent. Type IV dolomite formed during the period of maximum burial. Types III and IV dolomite increase in abundance downslope. Type III dolomite contains 1.2–2.6 wt% Fe and a maximum of 1000 ppm Mn. The distribution of these elements displays no distinct vertical or lateral trends. In contrast, Fe and Mn distributions in Type IV dolomite exhibit distinct spatial trends, decreasing from 3.5–4.5 wl% Fe and 0.1–0.3 wt% Mn in the west (slope/basin) to 1.5–2.5 wt% Fe and less than 600 ppm Mn in the east (shelf margin), a distance of approximately 60 km. Spatial trends in Fe and Mn distributions in Type IV saddle dolomite, suggest a west-east fluid flow during late burial diagenesis. Types III and IV dolomite have a mean δ¹⁸O value of - 7.8%₀₀ and a mean δ¹³C value of + 1.1%₀₀ (relative to the PDB standard). Based on a range of assumed basinal water composition of 2.8%₀₀ SMOW, temperatures calculated from δ¹⁸O values of Types III and IV dolomite range between 75 and 160°C. ⁸⁷Sr/⁸⁶Sr data for Types III and IV dolomite range from 0.7111 to 0.7139. These values are radiogenic when compared to Cambrian marine values and are consistent with the presence of a diagenetic fluid that interacted with siliciclastic sediments. The distribution of Palaeozoic facies in the southern Appalachians indicates a Cambrian shale source for the fluids, whilst burial curves suggest a Middle Ordovician age for burial fluid movement.     

Meteoric diagenesis and dedolomite fabrics in precursor primary dolomicrite in a mixed carbonate–evaporite system

Dedolomitization is a common diagenetic process in shallow burial environments and is often associated with sulphates in mixed carbonate‐evaporite successions. In these settings, elevated Ca²⁺/Mg²⁺ ratios necessary for dedolomitization result from the dissolution of sulphate phases by the incursion of undersaturated groundwater. Reported dedolomite textures from other studies are varied, but the most prevalent is a rhombic texture interpreted to result from the partial to complete pseudomorphic replacement of secondary dolomite rhombs formed in the burial diagenetic realm. In this study of primary cryptocrystalline to finely crystalline dolomicrites in the Prairie Evaporite Formation of north‐eastern Alberta, dedolomitization has resulted in sutured to loosely packed mosaics of dedolomite that range from subhedral to distinctly euhedral (rhombic) crystal fabrics; however, no prior aggrading neomorphism producing dolomite rhombs is evident in the precursor dolomicrites. Non‐pseudomorphic dedolomitization of the dolomicrites results in textures that include rhombic dedolomite crystals with cloudy cores comprising remnant dolomicrite and clear rims. These textures are similar to those observed in the pseudomorphic dedolomitization of secondary dolomite rhombs. The Prairie Evaporite Formation of north‐eastern Alberta has experienced extensive karstification near the erosional margin of the sedimentary succession. Dedolomitization of dolomicrites occurs in marker beds within the Prairie Evaporite succession associated with evaporite karstification. Along with stratigraphic and petrographic considerations, stable isotope results support the interpretation of a shallow dedolomitization event influenced by meteoric waters derived from the basin margin. Negative δ ¹⁸O and low δ ¹³C values (averages of −13·6‰_VPDB and 0·5‰_VPDB, respectively) of the dedolomite, compared with those of the primary dolomicrite (averages of −6·0‰_VPDB and 1·2‰_VPDB, respectively), point to isotopically light diagenetic fluids. These results show that rhombic dedolomite textures can form through shallow, non‐pseudomorphic dedolomitization of dolomicrites by meteoric fluids in the presence of sulphates, with resulting textures that are similar to the pseudomorphic dedolomitization of secondary dolomite rhombs.     

Conceptual model for early diagenetic chert and dolomite, Amuri Limestone Group, north-eastern South Island, New Zealand

The Late Cretaceous to Early Eocene, dominantly micritic, Amuri Limestone Group (ALG) was deposited in an approximately NW trending trough, in eastern Marlborough, New Zealand. The ALG comprises: the Mead Hill Formation; the Teredo, Lower and Middle Limestone formations; and the Upper and Lower Marl formations. Chert and dolomite are concentrated in the Mead Hill Formation, which contains five of six recognized diagenetic zones: Zone I at the base of the ALG consists almost entirely of chert; Zone II consists solely of chert and dolomite; Zone III comprises chert and limestone; Zone IV is composed of chert plus dolomite; Zone V is a chertified mudstone; and the minor amounts of chert found in the Middle Limestone Formation comprise Zone VI. With the exception of Zones IV and V, chert decreases stratigraphically upwards and away from the basin centre. All the dolomites are composed of <1 mm diameter rhombohedra in discontinuous beds and lenses. Generally Ca-rich, and non- to slightly ferroan, the dolomite contains approximately 500–900 ppm Mn and 200–400 ppm Sr. δ¹³C values average 1–2%_PDB with δ¹⁸O ratios of about -4%_PDB. Mass balance calculations indicate that the Mg²⁺ for dolomitization was derived from sea water. Sr, Fe and Mn concentrations are interpreted as indicating dolomite formation in the marine environment, with no influence from meteoric waters. The intimate association with pyrite implies dolomite formation in association with sulphate reduction, in the upper sediment column. δ¹⁸O data show that the bulk of the dolomite formed at temperatures below 50°C. All chert samples contain in excess of 90 wt% SiO₂, about 1 wt% Al₂O₃ and 1 wt% from losses on ignition. Generally all other major elements total less than 2 wt% oxide. δ¹⁸O values range from 26·8 to 29·0%_SMOW. Chert chemistry is consistent with the replacement of host carbonate and expulsion of carbonate-bound components from the site of chertification, and the effective dilution by SiO₂ of non-carbonate-bound insoluble residues. δ¹⁸O data indicate that chert formed in fluids of similar composition and temperature as the dolomite. The abundance of disseminated pyrite in cherts implies an association with sulphate reduction. Silica for chertification is thought to have initially come from dissolution of siliceous organisms. However, there is insufficient biogenic silica available to form the volumes of chert observed. It is suggested that the bulk of the silica came from SiO₂-rich pore waters generated by clay mineral reactions in the thick underlying mudstones. The ALG compacted down through these pore waters. Chert and dolomite nucleation are considered to have been penecontemporaneous. Dolomitization was initially probably the faster process, continuing as long as sulphate reduction prevailed and there was an adequate supply of Mg²⁺. The nucleation of chert, although initially slower (probably due to a relatively lower initial SiO₂ supply), continued after cessation of dolomitization to the extent of completely chertifying the dolomite intercrystalline matrix. The amount of chertification decreased progressively as SiO₂ supplies diminished, both stratigraphically upwards and away from the basin centre.     

新疆乌鲁木齐地区中二叠统芦草沟组湖相微生物成因白云石特征*

新疆乌鲁木齐地区红雁池南剖面中二叠统芦草沟组主要发育浅湖至半深湖背景下的中、薄层深灰色白云岩、灰岩、粉砂岩与中、厚层灰黑色页岩、泥岩互层。白云岩主要由泥晶白云石、铁白云石及少量方解石、高镁方解石组成,富含有机质。白云石粒径约3～10 μm,阴极发光呈现均匀昏暗的砖红色。白云石主要有微球状（直径约5～8 μm）、微簇状（长度约2 μm）及他形（1～10 μm）等3种微形貌。微球状白云石具有显微纹层结构,似为生长纹层,放大至6万倍发现显微纹层是由无数纳米级颗粒构成。他形白云石放大至4万倍发现主要由大量直径约0.25 μm的球状微粒聚集粘结而成,具有微生物矿化的特征。将研究区白云石与现代典型微生物成因白云石相比,其显微形态特征非常相似。研究区白云岩δ¹³C_PDB为1.8‰～13.8‰,δ¹⁸O_PDB为-12.1‰～-4.1‰,偏高的δ¹³C可能是产甲烷菌活动引起有机质碳同位素分馏的结果。以上特征表明,芦草沟组具有特殊形貌白云石的沉淀很可能与厌氧微生物密切相关。     

Salinity reflux and dolomitization of southern Australian slope sediments: the importance of low carbonate saturation levels

Anomalously saline waters in Ocean Drilling Program Holes 1127, 1129, 1130, 1131 and 1132, which penetrate southern Australian slope sediments, and isotopic analyses of large benthic foraminifera from southern Australian continental shelf sediments, indicate that Pleistocene–Holocene meso‐haline salinity reflux is occurring along the southern Australian margin. Ongoing dolomite formation is observed in slope sediments associated with marine waters commonly exceeding 50‰ salinity. A well‐flushed zone at the top of all holes contains pore waters with normal marine trace element contents, alkalinities and pH values. Dolomite precipitation occurs directly below the well‐flushed zone in two phases. Phase 1 is a nucleation stage associated with waters of relatively low pH (ca 7) caused by oxidation of H₂S diffusing upward from below. This dolomite precipitates in sediments < 80 m below the sea floor and has δ¹³C values consistent with having formed from normal sea water (? 1‰ to + 1‰ Vienna Pee Dee Belemnite). The Sr content of Phase 1 dolomite indicates that precipitation can occur prior to substantial metastable carbonate dissolution (< 300 ppm in Holes 1129 and 1127). Dolomite nucleation is interpreted to occur because the system is undersaturated with respect to the less stable minerals aragonite and Mg‐calcite, which form more readily in normal ocean water. Phase 2 is a growth stage associated with the dissolution of metastable carbonate in the acidified sea water. Analysis of large dolomite rhombs demonstrates that at depths > 80 m below the sea floor, Phase 2 dolomite grows on dolomite cores precipitated during Phase 1. Phase 2 dolomite has δ¹³C values similar to those of the surrounding bulk carbonate and high Sr values relative to Phase 1 dolomite, consistent with having formed in waters affected by aragonite and calcite dissolution. The nucleation stage in this model (Phase 1) challenges the more commonly accepted paradigm that inhibition of dolomitization by sea water is overcome by effectively increasing the saturation state of dolomite in sea water.     

Petrography and geochemistry of early-stage, fine- and medium-crystalline dolomites in the Middle Devonian Presqu'ile Barrier at Pine Point, Canada

The petrography and geochemistry of fine- and medium-crystalline dolomites of the Middle Devonian Presqu’ile barrier at Pine Point (Western Canada Sedimentary Basin) are different from those of previously published coarse-crystalline and saddle dolomites that are associated with late-stage hydrothermal fluids. Fine-crystalline dolomite consists of subhedral to euhedral crystals, ranging from 5 to 25 μm (mean 8 μm). The dolomite interbedded with evaporitic anhydrites that occur in the back-barrier facies in the Elk Point Basin. Fine-crystalline dolomite has δ¹⁸Ο values between ?1·6 to –3·8‰ PDB and ⁸⁷Sr/⁸⁶Sr ratios from 0·7079–0·7081, consistent with derivation from Middle Devonian seawater. Its Sr concentrations (55–225 p.p.m., mean 105 p.p.m.) follow a similar trend to modern Little Bahama seawater dolomites. Its rare earth element (REE) patterns are similar to those of the limestone precursors. These data suggest that this fine-crystalline dolomite formed from Middle Devonian seawater at or just below the sea floor. Medium-crystalline dolomite in the Presqu’ile barrier is composed of anhedral to subhedral crystals (150–250 μm, mean 200 μm), some of which have clear rims toward the pore centres. This dolomite occurs mostly in the southern lower part of the barrier. Medium-crystalline dolomite has δ¹⁸O values between ?3·7 to ?9·4‰ PDB (mean ?5·9‰ PDB) and ⁸⁷Sr/⁸⁶Sr ratios from 0·7081–0·7087 (mean 0·7084); Sr concentrations from 30 to 79 p.p.m. (mean 50 p.p.m.) and Mn content from 50 to 253 p.p.m. (mean 161 p.p.m.); and negative Ce anomalies compared with those of marine limestones. The medium-crystalline dolomite may have formed either (1) during shallow burial at slightly elevated temperatures (35–40 °C) from fluids derived from burial compaction, or, more likely (2) soon after deposition of the precursor sediments by Middle Devonian seawater derived from the Elk Point Basin. These results indicate that dolomitization in the Middle Devonian Presqu’ile barrier occurred in at least two stages during evolution of the Western Canada Sedimentary Basin. The geochemistry of earlier formed dolomites may have been modified if the earlier formed dolomites were porous and permeable and water/rock ratios were large during neomorphism.     

Dolomitization,gypsum calcitization and silicification in carbonate–evaporite shallow lacustrine deposits

This paper describes and interprets the mineral and facies assemblages that occur in carbonate–evaporite shallow lacustrine deposits, considering the importance of the processes pathway (i.e. dolomitization, gypsum calcitization and silicification). The Palaeogene deposits of the Deza Formation (Almazán Basin, central‐northern Spain) are selected as a case study to determine the variety of physicochemical processes taking place in carbonate–evaporite shallow lakes and their resulting diagenetic features. Dolostones are the predominant lithology and are composed mainly of dolomite with variable amounts of secondary calcite (5 to 50%), which mainly mimic lenticular gypsum (pseudomorphs). Five morphological types of dolomite crystal were identified as follows: dolomite tubes, dolomite cylinders, rhombohedral dolomite, spheroidal and quasi‐rhombohedral dolomite, and cocoon‐shaped dolomite. The dolomite cylinders and tubes are interpreted as the dolomitized cells of a widespread microbial community. The sequence of diagenetic processes started with growth of microlenticular interstitial gypsum in a calcareous mud deposited on the playa margin mudflats, and that sometimes included microbial sediments. Immediately following growth of gypsum, dolomite replaced the original calcite (or possibly aragonite) muds, the microbial community and the gypsum. Partial or total replacement of gypsum by dolomite was related mainly to the biomineralization of endolithic microbial communities on gypsum crystals. Later calcitization took place under vadose, subaerial exposure conditions. The development of calcrete in distal alluvial settings favoured the release of silica and subsequent silicification on the playa margin mudflats. Stable isotope compositions of calcite range from ?9·02 to ?5·83‰ δ¹³C_PDB and ?7·10 to 1·22‰ δ¹⁸O_PDB; for the dolomite, these values vary from ?8·93 to ?3·96‰ δ¹³C_PDB and ?5·53 to 2·4‰ δ¹⁸O_PDB. Quartz from the cherts has δ¹⁸O_SMOW values ranging from 27·1 to 31·1‰. Wide variation and relatively high δ¹⁸O_SMOW values for dolomite indicate evaporitic and closed hydrological conditions; increased influx of meteoric waters reigned during the formation of secondary calcite spar.     

Origin and diagenesis of lacustrine algal bioherms at the margin of the Ries crater, Upper Miocene, southern Germany

The marginal carbonate facies of the Miocene Ries meteorite crater lake in southern Germany contain bioherms up to 7 m high and 15 m across built by the green alga Cladophorites. The algae were externally encrusted during life by micrite, probably precipitated in response to photosynthetic uptake of CO₂, which produced tufts of fine (100 μm diameter), calcareous tubes. Coalescence of tufts, together with incorporation of peloidal and skeletal sand, created nodules and cones of algal tufa which in turn formed larger masses some of which are in the form of compound cones up to 2 m high. The bioherms are constructed by beds and groups of these cones and masses, and are surrounded by poorly cemented peloid, ostracod and gastropod sands. Five depositional and diagenetic stages of development can be distinguished: (1) growth and calcification (probably calcitic) of Cladophorites in shallow fresh- or slightly brackish water; (2) emergence due to a temporary fall in lake level and veneering of the algal tufa and adjacent sediments by laminated sinter; (3) resubmergence and deposition of peloidal and skeletal sands; (4) burial and partial phreatic dolomitization, together with dissolution of aragonite and penecontemporaneous deposition of thin isopachous rims of dolomite rhombs; (5) local vadose cementation by rhombs, spar and spikes of low-magnesian calcite. Stages 1–3 probably occurred several times. Most of the biohermal and surrounding sediments were produced by biological processes in the lake; subaerial sinter deposition and meteoric cementation have contributed relatively minor amounts of material and the majority of the sediments retain porosities of 10–30%.     

Origin of zircon in jadeitite from the Nishisonogi metamorphic rocks,Kyushu, Japan

On the basis of internal structures, laser ablation U–Pb ages and trace element compositions, the origin of zircon in jadeitite in the Nishisonogi metamorphic rocks was examined. The zircon comprises euhedral zoned cores overgrown by euhedral rims. The cores contain inclusions of muscovite, quartz, albite and possibly K‐feldspar, yield ²³⁸U–²⁰⁶Pb ages of 126 ± 6 Ma (±2 SD, n = 45, MSWD = 1.0), and have Th/U ratios of 0.48–1.64. The rims contain inclusions of jadeite, yield ²³⁸U–²⁰⁶Pb ages of 84 ± 6 Ma (±2 SD, n = 14, MSWD = 1.1), and have Th/U ratios of <0.06. The cores are richer in Y, Th, Ti and rare earth elements (REEs), but the rims are richer in Hf and U. Chondrite‐normalized REE patterns of the cores indicate higher Sm_N/La_N ratios, lower Yb_N/Gd_N ratios and larger positive Ce anomalies compared with those of the rims. Thus, the cores and rims have different ²³⁸U–²⁰⁶Pb ages and trace element compositions, suggesting two stages of zircon growth. Although the ²³⁸U–²⁰⁶Pb ages of the rims are consistent with the reported ⁴⁰Ar/³⁹Ar spot‐fusion ages of matrix muscovite in the jadeitite, the ²³⁸U–²⁰⁶Pb ages of the cores are older. The mineral inclusions and high Th/U ratios in the cores are best explained by crystallization from felsic magma. Therefore, the cores are considered relicts from igneous precursor rocks. The rims surrounding the inherited cores possibly precipitated from aqueous fluids during jadeitite formation. The elevated U concentrations in the rims suggest that infiltration of external fluids was responsible for the precipitation. This study provides an example of jadeitite formation by metasomatic replacement of a protolith.     

Petrographic and geochemical characteristics of dolomite types and the origin of ferroan dolomite in the Trenton Formation, Ordovician, Michigan Basin, U.S.A.

Three major types of dolomite occur in the Trenton Formation (Mid-Ordovician) of the Michigan Basin. These are: (1) ‘regional dolomite’ which is confined to the extreme western edge of the basin; (2) ‘cap dolomite’ which occurs in the upper portion of the Trenton and is confined to the basin's southern margin; and (3) ‘fracture-related’ dolomite which occurs in association with both large- and small-scale faults and fractures. These three dolomite types can be distinguished from one another by their major element chemistry, oxygen isotope ratios and rock texture. The regional dolomite is fine-grained, has <0.34 mol% FeCO₃, and mean δ¹⁸O of ?6·8‰_OPBD. The cap dolomite is texturally similar to regional dolomite but contains 3–13·0 mol% FeCO₃ and has a mean δ¹⁸O of ?7·7‰. Fracture-related dolomites are coarse-grained, low in iron, and have the most depleted δ¹⁸O ratios (x?=–9·0%_PDB). Petrographic relationships imply that the regional dolomite, formed prior to the cap dolomite probably during early diagenesis. The cap dolomite formed at relatively shallow depths as a result of the interaction of the overlying Utica Shale and the Trenton Limestone. Fracture-related dolomites post-date the cap dolomite and formed during deeper burial. A temperature of precipitation of approximately 80°C was calculated for fracture-related dolomites using oxygen isotope data. The distribution of the cap dolomite was controlled by the availability of Fe^2? which was in turn controlled by the availability of S^2?. In the centre of the basin Trenton-Utica deposition was continuous. The upper Trenton contained relatively high concentrations of organic matter which was used by sulphate reducing bacteria to produce H_2S from seawater sulphate. The precipitation of iron sulphides (pyrite + iron monosulphide) followed and used up most of the available Fe^2?. As a result only small amounts of ferroan dolomite formed. On the periphery of the basin, subaerial exposure resulted in the oxidation of most of the available organic matter. Sulphate reducing bacteria were therefore limited and produced limited amounts of H₂S. As a result only a minor amount of iron sulphide (iron monosulphide) formed. The remaining Fe^2- was then available for the formation of the ferroan cap dolomite. This model is supported by the following: (1) In the southern margin of the basin, the contact between Trenton cap dolomite and the overlying Utica Shale is sharp and probably unconformable. In the centre of the basin the contact is gradational. (2) In the centre of the basin, the total organic carbon content in the upper Trenton is an order of magnitude higher than in the cap dolomite. (3) The whole-rock concentration of iron is high in both the cap dolomite and in slightly dolomitized equivalent beds in the basin centre. (4) Iron sulphides are abundant in the centre of the basin and mostly in the form of pyrite. In the cap dolomite, iron sulphide is minor and primarily in the form of iron monosulphide.     

Reaction kinetics of dolomite rim growth

Reaction rims of dolomite (CaMg[CO₃]₂) were produced by solid-state reactions at the contacts of oriented calcite (CaCO₃) and magnesite (MgCO₃) single crystals at 400 MPa pressure, 750–850 °C temperature, and 3–146 h annealing time to determine the reaction kinetics. The dolomite reaction rims show two different microstructural domains. Elongated palisades of dolomite grew perpendicular into the MgCO₃ interface with length ranging from about 6 to 41 µm. At the same time, a 5–71 µm wide rim of equiaxed granular dolomite grew at the contact with CaCO₃. Platinum markers showed that the original interface is located at the boundary between the granular and palisade-forming dolomite. In addition to dolomite, a 12–80 µm thick magnesio-calcite layer formed between the dolomite reaction rims and the calcite single crystals. All reaction products show at least an axiotactic crystallographic relationship with respect to calcite reactant, while full topotaxy to calcite prevails within the granular dolomite and magnesio-calcite. Dolomite grains frequently exhibit growth twins characterized by a rotation of 180° around one of the $[11\bar{2}0]$ equivalent axis. From mass balance considerations, it is inferred that the reaction rim of dolomite grew by counter diffusion of MgO and CaO. Assuming an Arrhenius-type temperature dependence, activation energies for diffusion of CaO and MgO are E _a (CaO) = 192 ± 54 kJ/mol and E _a (MgO) = 198 ± 44 kJ/mol, respectively.     

Mixed-water and hydrothermal dolomitization of the Pliocene Shirahama Limestone, Izu Peninsula, central Japan

The early Pliocene Shirahama Limestone is a grainstone-packstone principally composed of fragments of algae, bryozoa, and echinoderm and subordinate volcanic rocks. The limestone was variously dolomitized and the regional distribution of dolomite is patchy. Dolomite occurs as isolated crystals filling pores, moulds, and solution vugs, and mosaic aggregates replacing bioclasts. Calcite occurs as rim and pore-filling sparry cements, and as calcareous skeletons. Isotopically, the dolomites are classified into a heavy oxygen group (?2 to ? 3.5%₀ PDB) and a light oxygen group (?5.5 to ? 7.5%₀ PDB). Calcite associated with heavy oxygen dolomite has δ¹⁸O of ? 6.5 to ?8.5%₀ PDB, whereas those associated with light oxygen dolomite have a wide range from ?7.5 to ?14%₀ PDB. Calcite in dolomite-free limestone has an oxygen isotopic composition of ?2 to ?8.5%₀ PDB. Textures, chemistry, and isotopic evidence indicate that heavy oxygen calcite formed in freshwater, and heavy oxygen dolomite in a meteoric-marine mixture of 10–30% seawater. Light oxygen calcite and dolomite precipitated from modified hydrothermal fluids at approximately 30–65°C. Petrographic features, and both isotopic and chemical evidence suggest that the Shirahama Limestone was exposed to freshwater soon after deposition. Subsequently blocky calcite precipitated (Stage I). The limestone was locally submerged in the meteoric-marine mixture due to gradual subsidence or eustatic movement. This led to the precipitation of heavy oxygen, zoned dolomite and dolospar (Stage II). Hydrothermal alterations occurred in the area a few Myr ago, and related hydrothermal fluids and mixed meteoric-hydrothermal waters caused dedolomitization of some zoned dolomite, partial dissolution of vuggy dolomite, precipitation of limpid dolomite and recrystallization of some earlier dolomites (Stage III). Zeolites were also precipitated from these fluids. Finally, the Shirahama Limestone was exposed again to freshwater and sparry calcite precipitated to plug some of the remaining pores (Stage IV).     

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.     

Trace element composition and Lu-Hf isotope systematics of zircon from plagiogneisses of the Kola superdeep well: Contribution of a Paleoarchean crust in Mesoarchean metavolcanic rocks

Zircons have been studied in three samples of Archean plagiogneisses from the Kola superdeep well (SG-3). The crystals consist of cores, magmatic shells, and metamorphic rims. The cores and shells are characterized by similar lowered concentrations of most trace elements, which is typical of zircons from plagiogranitoids, rocks of elevated basicity, and basites. At a wide range of Hf isotope characteristics, the cores and shells have similar average ¹⁷⁶Hf/¹⁷⁷Hf_i, which determines the close composition of their sources. The metamorphic rims have close ¹⁷⁶Hf/¹⁷⁷Hf_i ratio. The minimum age of the crustal contaminant of parental melts is estimated at 3.4 and 3.3 Ga for cores and 3.3–3.2 Ga for shells at almost equal proportions of mantle and crustal components in them. The contribution of Paleoarchean crust established in zircons from plagiogneisses of SG-3 using Lu-Hf isotope systematics is confirmed by the presence of 3.3and 3.4-Ga old zircons in surrounding TTG.     

Shallow-burial dolomite cement: a major component of many ancient sucrosic dolomites

Dolomite cement is a significant and widespread component of Phanerozoic sucrosic dolomites. Cements in dolomites that were never deeply buried are limpid, have planar faces (non‐saddle forms), often distinct zonation in cathodoluminescence and form syntaxial overgrowths on crystals facing pores. Five samples of sucrosic dolomites, interpreted as having had mostly lime‐mudstone or wackestone precursors in four carbonate aquifers, provide insights into the abundance of planar cements in sucrosic dolomites. Such cement comprises 11% to 45% (32% mean) of peritidal to sub‐tidal dolomites on an outcrop in the Edwards aquifer (Early Cretaceous) of central Texas; 19% to 33% (25% mean) of ramp dolomites in the Hawthorn Group (Oligo‐Miocene) and 50% to 70% in shelf dolomites of the Avon Park Formation (Eocene) in the Upper Floridan aquifer of sub‐surface peninsular Florida; 18% to 45% (32+% mean) of sub‐tidal shelf dolomites in quarry sections of the Burlington‐Keokuk Formation (Early Mississippian) in south‐eastern Iowa; and 18% to 76% (50% mean) in shallow cores and outcrops of outer‐shelf dolomites from the Gambier Limestone (Oligo‐Miocene) of South Australia. Backstripping the cement phases revealed by cathodoluminescence colour photomicrographs documents the effects of cements on textural coarsening, pore‐space reduction, induration and general ‘maturation’ of these dolomites. Most pre‐Holocene dolomites are multiphase crystalline rocks composed of: (i) seed crystals or ‘cores’; (ii) crystal cortices that concentrically enlarged the cores; and (iii) free‐space, syntaxial precipitates of limpid cement around the crystals. Remaining CaCO₃ grains and micrite can be replaced by dolomite, but typically they are dissolved between stages (ii) and (iii), creating systems of intercrystal and mouldic pores typical of sucrosic dolomites. Networks of cement overgrowths, aided by water‐filled pore systems under hydrostatic to lithostatic pressure, are judged to slow or prevent compaction in sucrosic dolomites. It can be argued that cortex growth involves both replacement of CaCO₃ particles and microcementation of their interparticle pores. This interpretation, and the abundance of cements in so many dolomites, would obviate the controversy over the volumetrics of ‘replacement dolomitization’. Limpid, planar and syntaxial dolomite cements of early diagenetic origin are interpreted to have precipitated from clear pore waters, at low temperatures (<30 to 35 °C) and shallow burial depths (<100 m), in water‐saturated networks of dolomite ‘silt’ and ‘sand’. Cements in many dolomites in island and continental–aquifer systems appear to result from event‐driven processes related to sea‐level highstands. Cementation events can follow ‘replacement dolomitization’ events by time intervals ranging from geologically ‘instantaneous’ to tens of million years.     

Stable isotope evidence for the origin of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel

The oxygen isotope compositions of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel, have been used to identify porewater types during diagenesis. Changes in porewater composition can be related to major geological events within southern Israel. In particular, saline brines played an important role in late (Pliocene-Pleistocene) dolomitization of these rocks. Diagenetic carbonates included early siderite (δ¹⁸O_SMOW=+24.4 to +26.5‰δ¹³C_PDB=?1.1 to +0.8‰), late dolomite, ferroan dolomite and ankerite (δ¹⁸O_SMOW=+18.4 to +25.8‰; δ¹³C_PDB=?2.1 to +0.2‰), and calcite (δ¹⁸O_SMOW=+21.3 to +32.6‰; δ¹³C_PDB=?4.2 to + 3.2‰). The petrographic and isotopic results suggest that siderite formed early in the diagenetic history at shallow depths. The dolomitic phases formed at greater depths late in diagenesis. Crystallization of secondary calcite spans early to late diagenesis, consistent with its large range in isotopic values. A strong negative correlation exists between burial depth (temperature) and the oxygen isotopic compositions of the dolomitic cements. In addition, the δ¹⁸O values of the dolomitic phases in the northern Negev and Judea Mountains are in isotopic equilibrium with present formation waters. This behaviour suggests that formation of secondary dolomite post-dates the tectonic activity responsible for the present relief of southern Israel (Upper Miocene to Pliocene) and that the dolomite crystallized from present formation waters. Such is not the case in the Central Negev. In that locality, present formation waters have much lower salinities and δ¹⁸O values, indicating invasion of freshwater, and are out of isotopic equilibrium with secondary dolomite. Recharge of the Inmar Formation by meteoric water in the Central Negev occurred in the Pleistocene, and halted formation of dolomite.     

Origin of Dinantian zebra dolomites south of the Brabant-Wales Massif, Belgium

Zebra dolomites, characterized by a repetition of dark grey (a) and light (b) coloured dolomite sheets building up abbabba-sequences, occur in Dinantian strata from deep boreholes (> 2000 m) south of the Brabant-Wales Massif in Belgium. These zebra dolomite sequences are several tens of metres thick. The dark grey dolomite sheets (a) consist of non-planar crystals, 80–150 μm in diameter. These crystals display a mottled red–orange luminescence and are interpreted to be replacive in origin. The white dolomite sheets (b) consist of coarse crystalline nonplanar b₁ dolomite, which evolves outwards into transparent saddle shaped b₂ dolomite. The b₁ dolomites possess a mottled red–orange luminescence similar to the a dolomites, while the saddle shaped b₂ rims display red to dark brown luminescent-zones. The b₁ dolomites are possibly partly replacive and partly cavity filling. Their b₂ rims display criteria typical for a cement origin. Locally, cavities exist between two succeeding white dolomite sheets. These cavities make up ≈5% of the zebra rocks and are locally filled by saddle shaped ankerite and/or xenomorphic ferroan calcite. Geochemical and fluid inclusion data (T_h ≈ 120 °C) indicate a burial diagenetic origin for these zebra dolomites. The a and b₁ dolomites are characterized by similar geochemical compositions and fluid inclusion data pointing toward a related origin. To explain the development of the zebra textures, suprahydrostatic pressures in conjunction with late Variscan tectonic compression are invoked. A model involving dolomitizing fluids expelled during the Variscan orogeny is proposed. An overpressured system is also invoked to explain the important porosity development, the creation of centimetre-scale subvertical displacements of the zebra pattern and the microfractures affecting the b₁–b₂ dolomite crystals.     

Monitoring groundwater flow and chemical and isotopic composition at a demonstration site for carbon dioxide storage in a depleted natural gas reservoir

Between March 2008 and August 2009, 65,445 tonnes of ∼75 mol% CO₂ gas were injected in a depleted natural gas reservoir approximately 2000 m below surface at the Otway project site in Victoria, Australia. Groundwater flow and composition were monitored biannually in two overlying aquifers between June 2006 and March 2011, spanning the pre-, syn- and post-injection periods. The shallower (∼0–100 m), unconfined, porous and karstic aquifer of the Port Campbell Limestone and the deeper (∼600–900 m), confined and porous aquifer of the Dilwyn Formation contain valuable fresh to brackish water resources. Groundwater levels in either aquifer have not been affected by the drilling, pumping and injection activities that were taking place, or by the rainfall increase during the project. In terms of groundwater composition, the Port Campbell Limestone groundwater is brackish (electrical conductivity = 801–3900 μS cm⁻¹), cool (temperature = 12.9–22.5 °C), and near-neutral (pH = 6.62–7.45), whilst the Dilwyn Aquifer groundwater is fresher (electrical conductivity = 505–1473 μS cm⁻¹), warmer (temperature = 42.5–48.5 °C), and more alkaline (pH = 7.43–9.35). Carbonate dissolution, evapotranspiration and cation exchange control the composition of the groundwaters. Comparing the chemical and isotopic composition of the groundwaters collected before, during and after injection shows no statistically significant changes; even if they were statistically significant, they are mostly not consistent with those expected if CO₂ addition had taken place. The monitoring program reveals no impact on the groundwater resources attributable to the C storage demonstration project.     

Massive dolomitization of a late Miocene carbonate platform: a case of mixed evaporative brines with meteoric water,Nijar, Spain

Late Miocene platform carbonates from Nijar, Spain, have been extensively dolomitized. Limestones are present in the most landward parts of the platform, in stratigraphically lower units and topographically highest outcrops, suggesting that dolomitizing fluids were derived from the adjacent Nijar Basin. The dolomite crystals range from <10 to ≈100 μm existing as both replacements and cements. Na, Cl and SO₄ concentrations in the dolomites range from 200 to 1700 p.p.m., 250–650 p.p.m., and 600–7000 p.p.m., respectively, comparable with other Tertiary and modern brine dolomite values, and also overlapping values from mixing-zone dolomites. Sr concentrations range between 50 and 300 p.p.m., and the molar Sr/Ca ratios of dolomitizing fluids are estimated to range between 7× seawater brine to freshwater ratios. The δ¹⁸O and δ¹³C of the dolomites range from ?1·0 to +4·2‰ PDB, and ?4·0 to +2·0‰ PDB, respectively. ⁸⁷Sr/⁸⁶Sr values (0·70899–0·70928) of the dolomites range from late Miocene seawater to values greater than modern seawater. Mixtures of freshwater with seawater and evaporative brines probably precipitated the Nijar dolomites. Modelled covariations of molar Sr/Ca vs. δ¹⁸O and Na/Ca vs. δ¹⁸O from these mixtures are consistent with those of the proposed Nijar dolomitizing fluids. Complete or partial dolomite recrystallization is ruled out by well preserved CL zoning, nonstoichiometry and quantitative water–rock interaction modelling of covariations of Na vs. Sr and δ¹⁸O vs. δ¹³C. The possibility of multiple dolomitization events induced by evaporative brines, seawater and freshwater, respectively, is consistent with mineral-mineral mixing modelling. The basin-derived dolomitizing brines probably mixed with freshwater in the Nijar Basin or mixed with fresh groundwater in the platform, and were genetically related either to deposition of the Yesares gypsum or the Feos gypsum. Dolomitization occurred during either the middle Messinian or the early upper Messinian. Nijar dolomitization models may be applicable to dolomitization of other late Miocene platform carbonates of the western Mediterranean. Moreover, the Nijar models may offer an analogue for more ancient evaporite-absent platform carbonates fringing evaporite basins.     

Geochemistry and petrology of the Main Limestone Series (Lower Carboniferous), South Wales,U.K.

Dolomitized Main Limestone rocks of the Lower Carboniferous crop out in a narrow band of about three fourths of a mile along the south, east and northeast rims of the South Wales Coalfield Basin which encompasses the general regions of Miskin, Taffs Well and the Clydach, respectively. The thickness of these rocks varies from a maximum of 2,750 feet to nothing.The Ca/Mg ratio in the Main Limestone in general ranged from 1.7 : 1 to over 100 : 1 with less than 2 : 1 to 3.5 : 1 being the commonest. Magnesium content ranged from less than 5% to over 60% (mole percent MgCO₃), with 40–50 mole percent p.f. MgCO₃ being the commoner.Petrographic study of the Main Limestone led to recognition of six major microfacies. They are: (1) biosparite; (2) dolobiomicrite; (3) quartz-dolomicrite; (4) dolomicrite; (5) oosparite; and (6) dolorudite. In terms of their geographic distribution, dolobiomicrite predominates in the Taffs Well region, while quartz-dolobiomicrite is common in the Clydach region. In terms of their distribution in time, biosparite is common in the basal part (Lower ZC₁ zone), dolobiomicrites (including the quartz-bearing variety) in the middle part (ZC₁ and C₂S₁ zone) of the Taffs Well region and its corresponding Calcite-Mudstone Group in the Clydach region.The bulk of dolomitization in these rocks occurred in the Caninia-Seminula zone or the Calcite-Mudstone Group. In this study, it marks geochemical stage B: the sea-connected lagoonal phase similar to one observed today in South Australia. It is suggested that such a sea-connected Lagoon in the Main Limestone Sea formed largely in response to a reef barrier (or a ridge) - a remnant of which is found today between Miskin and the Taffs Well region where the transition from lime to dolomite facies occurs. The Miskin area represented the deeper-water reef flank towards the open sea whereas the Taffs Well region marked the shallow-water reef flank landward.It is concluded that the Main Limestone Series contains predominantly diagenetic dolostones whilst the syngenetic and epigenetic dolostones are restricted in time and space. The diagenetic dolostone dominates in the Taffs Well and Clydach regions.