Formation of modern dolomite in hypersaline pans of the Western Cape,South Africa

Authigenic calcite and dolomite and biogenic aragonite occur in Holocene pan sediments in a Mediterranean‐type climate on the western coastal plain of South Africa. Sediment was analysed from a Late Pleistocene coastal pan at Yzerfontein and four Holocene inland pans ranging from brackish to hypersaline. The pans are between 0·08 and 0·14 km² in size. The δ¹⁸O_PDB values of carbonate minerals in the pan sediments range from ?2·41 to 5·56‰ and indicate precipitation from evaporative waters. Covariance of total organic content and percentage carbonate minerals, and the δ¹³C_PDB values of pan carbonate minerals (?8·85 to ?1·54‰) suggest that organic matter degradation is a significant source of carbonate ions. The precipitation of the carbonate minerals, especially dolomite, appears to be mediated by sulphate‐reducing bacteria in the black sulphidic mud zone found in the brine‐type hypersaline pans. The knobbly, sub‐spherical texture of the carbonate minerals suggests that the precipitation of the carbonate minerals, particularly dolomite, is related to microbial processes. The ⁸⁷Sr/⁸⁶Sr ratios of pan carbonate minerals (0·7108 to 0·7116) are slightly higher than modern sea water and indicate a predominantly sea water (marine aerosol) source for calcium (Ca²⁺) ions with relatively minor amounts of Ca²⁺ derived from the chemical weathering of bedrock.     

Pleistocene speleothems of Mallorca: implications for palaeoclimate and carbonate diagenesis in mixing zones

The Pleistocene speleothems of Sa Bassa Blanca cave, Mallorca, are excellent indicators of palaeoclimate variations, and are samples that allow evaluation of the products and processes of mixing‐zone diagenesis in an open‐water cave system. Integrated stratigraphic, petrographic and geochemical data from a horizontal core of speleothem identified two main origins for speleothem precipitates: meteoric‐marine mixing zone and meteoric‐vadose zone. Mixing‐zone precipitates formed at and just below the water–air interface of cave pools during interglacial times, when the cave was flooded as a result of highstand sea‐level. Mixing‐zone precipitates include bladed and dendritic high‐Mg calcite, microporous‐bladed calcite with variable Mg content, and acicular aragonite; their presence suggests that calcium‐carbonate cementation is significant in the studied mixing‐zone system. Fluid inclusion salinities, δ¹³C and δ¹⁸O compositions of the mixing‐zone precipitates suggest that mixing ratio was not the primary control on whether precipitation or dissolution occurred, rather, the proximity to the water table and degassing of CO₂ at the interface, were the major controls on precipitation. Thus, simple two‐end‐member mixing models may apply only in mixing zones well below the water table. Meteoric‐vadose speleothems include calcite and high‐Mg calcite with columnar and bladed morphologies. Vadose speleothems precipitated during glacial stages when sea level was lower than present. Progressive increase in δ¹³C and δ¹⁸O of the vadose speleothems resulted from cooling temperatures and more positive seawater δ¹⁸O associated with glacial buildup. Such covariation could be considered as a valid alternative to models predicting invariant δ¹⁸O and highly variable δ¹³C in meteoric calcite. Glacio‐eustatic oscillations of sea‐level are recorded as alternating vadose and mixing‐zone speleothems. Short‐term climatic variations are recorded as alternating aragonite and calcite speleothems precipitated in the mixing zone. Fluid‐inclusion and stable‐isotope data suggest that aragonite, as opposed to calcite, precipitated during times of reduced meteoric recharge.     

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.     

Geochemistry of meteoric calcite cements in some Pleistocene limestones

In this study, the stable isotope and trace element geochemistries of meteoric cements in Pleistocene limestones from Enewetak Atoll (western Pacific Ocean), Cat Island (Bahamas), and Yucatan were characterized to help interpret similar cements in ancient rocks. Meteoric calcite cements have a narrow range of δ¹⁸O values and a broad range of δ¹³C values in each geographical province. These Pleistocene cements were precipitated from water with stable oxygen isotopic compositions similar to modern rainwater in each location. Enewetak calcite cements have a mean δ¹⁸O composition of ?6.5%₀ (PDB) and δ¹³C values ranging from ?9.6 to +0.4%0 (PDB). Sparry calcite cements from Cat Island have a mean δ¹⁸O composition of ?4.1%₀ and δ¹³C values ranging from ?6.3 to + 1.1%₀. Sparry cements from Yucatan have a mean δ¹⁸O composition of ?5.7%₀ and δ¹³C values of ?8.0 to ?2.7%₀. The mean δ¹⁸O values of these Pleistocene meteoric calcite cements vary by 2.4%₀ due to climatic variations not related directly to latitude. The δ¹³C compositions of meteoric cements are distinctly lower than those of the depositional sediments. Variations in δ¹³C are not simply a function of distance below an exposure surface. Meteoric phreatic cements often have δ¹³C compositions of less than —4.0%₀, which suggests that soil-derived CO₂ and organic material were washed into the water table penecontemporaneous with precipitation of phreatic cements. Concentrations of strontium and magnesium are quite variable within and between the three geographical provinces. Mean strontium concentrations for sparry calcite cements are, for Enewetak Atoll, 620 ppm (σ= 510 ppm); for Cat Island, 1200 ppm (σ= 980 ppm); and for Yucatan, 700 ppm (σ= 390 ppm). Equant cements, intraskeletal cements, and Bahamian cements have higher mean strontium concentrations than other cements. Equant and intraskeletal cements probably precipitated in more closed or stagnant aqueous environments. Bahamian depositional sediments had higher strontium concentrations which probably caused high strontium concentrations in their cements. Magnesium concentrations in Pleistocene meteoric cements are similar in samples from Enewetak Atoll (mean =1.00 mol% MgCO₃; σ= 0.60 mol% MgCO₃) and Cat Island (mean = 0.84 mol% MgCO₃; σ= 0.52mol% MgCO₃) but Yucatan samples have higher magnesium concentrations (mean = 2.20 mol% MgCO₃: σ= 0.84mol% MgCO₃). Higher magnesium concentrations in some Yucatan cements probably reflect precipitation in environments where sea water mixed with fresh water.     

Dolomitization of Quaternary reef limestone, Aitutaki, Cook Islands

Six holes were drilled to depths of 30–69 m in the shallow lagoon of Aitutaki in the southern Cook Islands. One hole encountered pervasively dolomitized reef limestones at 36 m subbottom depth, which extended to the base of the drilled section at 69·3 m. This hole was drilled near the inner edge of the present barrier reef flat on the flank of a seismically defined subsurface ridge. Both the morphology and biofacies indicate that this ridge may represent an outer reef crest. Mineralogy, porosity and cementation change in concert downhole through three zones. Zone 1, 0–9 m, is composed of primary skeletal aragonite and calcite with minor void-filling aragonite and magnesian calcite cement of marine phreatic origin. Zone 2, 9–36 m, is composed of replacement calcite and calcite cement infilling intergranular, intragranular, mouldic and vuggy porosity. Stable isotopes (mean δ¹⁸O=—5·4‰ PDB for carbonate; δD =—50‰ SMOW for fluid inclusions) support the petrographic evidence indicating that sparry calcite cements formed in predominantly freshwater. Carbon isotope values of —4·0 to —11·0‰ for calcite indicate that organic matter and seawater were the sources of carbon. Zone 3, 36–69·3 m, is composed of replacement dolostone, consisting of protodolomite with, on average, 7 mol% excess CaCO₃ and broad and weak ordering X-ray reflections at 2·41 and 2·54 A. The fine-scale replacement of skeletal grains and freshwater void-filling cements by dolomite did not significantly reduce porosity. Stable isotopes (mean δ¹⁸O=+2·6‰₀ PDB for dolomite; maximum δD =—27‰ SMOW for fluid inclusions) and chemical composition indicate that the dolomite probably formed from seawater, although formation in the lower part of a mixed freshwater-seawater zone, with up to 40% freshwater contribution, cannot be completely ruled out. The carbon (δ¹³C=2·7‰) and magnesium were derived from seawater. Low-temperature hydrothermal iron hydroxides and associated transition metals occur in void space in several narrow stratigraphic intervals in the limestone section that was replaced by dolomite. The entire section of dolomite is also enriched in these transition metals. The metals dispersed throughout the dolostone section were introduced at the time of dolomitization by a different and later episode of hydrothermal circulation than the one(s) that produced the localized deposits near the base of the section. The primary reef framework is considered to have been deposited during several highstands of sea level. Following partial to local recrystallization of the limestone, a single episode of dolomitization occurred. Both tidal and thermal pumping drove large quantities of seawater through the porous rocks and perhaps maintained a wide mixing zone. However, the isotopic, geochemical and petrographic data do not clearly indicate the extent of seawater mixing.     

Late Pleistocene mixing zone dolomitization, southeastern Barbados, West Indies

ABSTRACT Field, geochemical, and petrographic data for late Pleistocene dolomites from southeastern Barbados suggest that the dolomite precipitated in the zone of mixing between a coastal meteoric phreatic lens and normal marine waters. The dolomite is localized in packstones and wackestones from the algalAmphistegina fore-reef calcarenite facies. Stable isotopic evidence suggests that meteoric water dominated the diagenetic fluids responsible for dolomitization. Carbon isotopes in pure dolomite phases average about -15%₀ PDB. This light carbon is attributed to the influence of soil gas CO₂, and precludes substantial mixing with seawater. A narrow range of oxygen isotopic compositions coupled with a wide range of carbon compositions attest to the meteoric diagenetic overprint. Dolomitization likely occurred with as little as a five per cent admixture of seawater. Strontium compositions of the dolomites indicate probable replacement dolomitization of original unstable mineralogy. The dolomite is characterized by low sodium values. Low concentrations of divalent manganese and iron suggest oxidizing conditions at the time of dolomitization. A sequence of petrographic features suggests a progression of diagenetic fluids from more marine to more meteoric. Early marine diagenesis was followed by replacement dolomitization of skeletal grains and matrix. Limpid, euhedral dolomite cements precipitated in primary intra- and interparticle porosity subsequent to replacement dolomitization. As waters became progressively less saline, dolomite cements alternated with thin bands of syntaxial calcite cement. The final diagenetic phase precipitated was a blocky calcite spar cement, representing diagenesis in a fresh-water lens. This sequence of diagenetic features arose as the result of a single fall in eustatic sea-level following deposition. A stratigraphic-eustatic-diagenetic model constrains both the timing and rate of dolomitization in southeastern Barbados. Dolomitization initiated as sea-level began to fall immediately following the oxygen isotope stage 7–3 high stand, some 216 000 yr bp . Due to the rapidity of late Pleistocene glacio-eustasy, dolomitization (locally complete) is constrained to have occurred within about 5000 yr.     

Multistage hydrothermal dolomites in the Middle Devonian (Givetian) carbonates from the Guilin area, South China

Pervasive dolomites occur preferentially in the stromatoporoid biostromal (or reefal) facies in the basal Devonian (Givetian) carbonate rocks in the Guilin area, South China. The amount of dolomites, however, decreases sharply in the overlying Frasnian carbonate rocks. Dolostones are dominated by replacement dolomites with minor dolomite cements. Replacement dolomites include: (1) fine to medium, planar‐e floating dolomite rhombs (Rd1); (2) medium to coarse, planar‐s patchy/mosaic dolomites (Rd2); and (3) medium to very coarse non‐planar anhedral mosaic dolomites (Rd3). They post‐date early submarine cements and overlap with stylolites. Two types of dolomite cements were identified: planar coarse euhedral dolomite cements (Cd1) and non‐planar (saddle) dolomite cements (Cd2); they post‐date replacement dolomites and predate late‐stage calcite cements that line mouldic vugs and fractures. The replacement dolomites have δ¹⁸O values from ?13·7 to ?9·7‰ VPDB, δ¹³C values from ?2·7 to + 1·5‰ VPDB and ⁸⁷Sr/⁸⁶Sr ratios from 0·7082 to 0·7114. Fluid inclusion data of Rd3 dolomites yield homogenization temperatures (T_h) of 136–149 °C and salinities of 7·2–11·2 wt% NaCl equivalent. These data suggest that the replacive dolomitization could have occurred from slightly modified sea water and/or saline basinal fluids at relatively high temperatures, probably related to hydrothermal activities during the latest Givetian–middle Fammenian and Early Carboniferous times. Compared with replacement dolomites, Cd2 cements yield lower δ¹⁸O values (?14·2 to ?9·3‰ VPDB), lower δ¹³C values (?3·0 to ?0·7‰ VPDB), higher ⁸⁷Sr/⁸⁶Sr ratios (≈ 0·7100) and higher T_h values (171–209 °C), which correspond to trapping temperatures (T_r) between 260 and 300 °C after pressure corrections. These data suggest that the dolomite cements precipitated from higher temperature hydrothermal fluids, derived from underlying siliciclastic deposits, and were associated with more intense hydrothermal events during Permian–Early Triassic time, when the host dolostones were deeply buried. The petrographic similarities between some replacement dolomites and Cd2 dolomite cements and the partial overlap in ⁸⁷Sr/⁸⁶Sr and δ¹⁸O values suggest neomorphism of early formed replacement dolomites that were exposed to later dolomitizing fluids. However, the dolomitization was finally stopped through invasion of meteoric water as a result of basin uplift induced by the Indosinian Orogeny from the early Middle Triassic, as indicated by the decrease in salinities in the dolomite cements in veins (5·1–0·4 wt% NaCl equivalent). Calcite cements generally yield the lowest δ¹⁸O values (?18·5 to ?14·3‰ VPDB), variable δ¹³C values (?11·3 to ?1·2‰ VPDB) and high T_h values (145–170 °C) and low salinities (0–0·2 wt% NaCl equivalent), indicating an origin of high‐temperature, dilute fluids recharged by meteoric water in the course of basin uplift during the Indosinian Orogeny. Faults were probably important conduits that channelled dolomitizing fluids from the deeply buried siliciclastic sediments into the basal carbonates, leading to intense dolomitization (i.e. Rd3, Cd1 and Cd2).     

Late Pliocene to Holocene platform evolution in northern Belize, and comparison with coeval deposits in southern Belize and the Bahamas

Lithostratigraphy, depositional facies architecture, and diagenesis of upper Pliocene to Holocene carbonates in northern Belize are evaluated based on a ca 290 m, continuous section of samples from a well drilled on Ambergris Caye that can be linked directly to outcrops of Pleistocene limestone, and of overlying Holocene sediments. Upper Pliocene outer‐ramp deposits are overlain unconformably by Pleistocene and Holocene reef‐rimmed platforms devoid of lowstand siliciclastics. Tectonism controlled the location of the oldest Pleistocene platform margin and coralgal barrier reef, and periodically affected deposition in the Holocene. A shallow, flat‐topped, mostly aggradational platform was maintained in the Holocene by alternating periods of highstand barrier‐reef growth and lowstand karstification, differential subsidence, and the low magnitude of accommodation space increases during highstands. Facies in Pleistocene rocks to the lee of the barrier reef include: (i) outer‐shelf coralgal sands with scattered coral patch reefs; (ii) a shoal–water transition zone comprising nearshore skeletal and oolitic sands amidst scattered islands and tidal flats; and (iii) micritic inner‐shelf deposits. Four glacio‐eustatically forced sequences are recognized in the Pleistocene section, and component subtidal cycles probably include forced cycles and autocycles. Excluding oolites, Holocene facies are similar to those in the Pleistocene and include mud‐mounds, foraminiferal sand shoals in the inner shelf, and within the interiors of Ambergris and surrounding cayes, mangrove swamps, shallow lagoons, and tidal and sea‐marginal flats. Meteoric diagenesis of Pliocene and Pleistocene rocks is indicated by variable degrees of mineralogic stabilization, generally depleted whole‐rock δ¹⁸O and δ¹³C values, and meniscus and whisker‐crystal cements. Differences in the mineralogy and geochemistry of the Pliocene and Pleistocene rocks are attributed to variable extent of meteoric alteration. Dolomitization in the Pliocene carbonates may have begun syndepositionally and continued into the marine shallow‐burial environment. Positive dolomite δ¹⁸O and δ¹³C values suggest precipitation from circulating, near‐normal marine fluids that probably were modified somewhat by methanogenesis. Sedimentologic and diagenetic attributes of the Pliocene–Pleistocene rocks in the study area are similar to those in the Bahamas with which they share a common history of sea‐level fluctuations and climate change.     

Diagenetically altered sabkha-type Pleistocene dolomite from the Arabian Gulf

Diagenetically altered Pleistocene dolomite occurs in the shallow subsurface of the Arabian Gulf, offshore of Al Jubayl, Saudi Arabia. This dolomite accumulated in relatively shallow marine to sabkha depositional environments. In contrast with the thin extent of most other Quaternary sabkha and sabkha-related dolomite deposits, these deposits comprise a thick (>56 m) accumulation. Additionally, this Pleistocene dolomite displays a high degree of ordering and has a more nearly ideal stoichiometric composition than the dolomite from the depositionally and diagenetically analogous Abu Dhabi sabkha complex. The Pleistocene dolomite also has lower δ¹³ and δ¹⁸O values than the modern Abu Dhabi sabkha dolomite, and higher values than those commonly reported for analogous dolomite from the ancient rock record. The low δ¹⁸O values, in conjunction with the geological setting, indicate that the diagenetic waters were meteoric or mixed meteoric and marine in composition. Thus, the degree of ordering, stoichiometric and stable isotopic values indicate that this dolomite has undergone diagenetic alteration relative to its presumed Holocene precursor.     

Aragonite–calcite veins of the ‘Erzberg’ iron ore deposit (Austria): Environmental implications from young fractures

The well‐known Erzberg site represents the largest siderite (FeCO₃) deposit in the world. It consists of various carbonates accounting for the formation of prominent CaCO₃ (dominantly aragonite) precipitates filling vertical fractures of different width (centimetres to decimetres) and length (tens of metres). These commonly laminated precipitates are known as ‘erzbergite’. This study focuses on the growth dynamics and environmental dependencies of these vein fillings. Samples recovered on‐site and from mineral collections were analyzed, and these analyses were further complemented by modern water analyses from different Erzberg sections. Isotopic signatures support meteoric water infiltration and sulphide oxidation as the principal hydrogeochemical mechanism of (Ca, Mg and Fe) carbonate host rock dissolution, mobilization and vein mineralization. Clumped isotope measurements revealed cool formation temperatures of ca 0 to 10°C for the aragonite, i.e. reflecting the elevated altitude Alpine setting, but unexpectedly low for aragonite nucleation. The ²³⁸U–²³⁴U–²³⁰Th dating yielded ages from 285·1 ± 3·9 to 1·03 ± 0·04 kyr bp and all samples collected on‐site formed after the Last Glacial Maximum. The observed CaCO₃ polymorphism is primarily controlled by the high aqueous Mg/Ca ratios resulting from dissolution of Mg‐rich host rocks, with Mg/Ca further evolving during prior CaCO₃ precipitation and CO₂ outgassing in the fissured aquifer. Aragonite represents the ‘normal’ mode of erzbergite formation and most of the calcite is of diagenetic (replacing aragonite) origin. The characteristic lamination (millimetre‐scale) is an original growth feature and mostly associated with the deposition of stained (Fe‐rich) detrital particle layers. Broader zonations (centimetre‐scale) are commonly of diagenetic origin. Petrographic observations and radiometric dating support an irregular nature for most of the layering. Open fractures resulting from fault tectonics or gravitational mass movements provide water flow routes and fresh chemical reaction surfaces of the host rock carbonates and accessory sulphides. If these prerequisites are considered, including the hydrogeochemical mechanism, modern water compositions, young U‐Th ages and calculated precipitation rates, it seems unlikely that the fractures had stayed open over extended time intervals. Therefore, it is most likely that they are geologically young.     

Geochemical,and stable and radiogenic isotope records in Devonian and Early Carboniferous carbonates from Valle de Tena,central Pyrenees (Spain): evidence for their diagenetic environments

Mineralogical, textural and geochemical investigations were made to determine the post-depositional evolution of Devonian and Early Carboniferous carbonates from Valle de Tena. The carbonate association is made up of low-Mg calcite, which occurs as micrite, spar cements, neomorphic patches and spar filling veinlets. Non-stoichiometric dolomite and ankerite occur as cements (dolomite also as replacements) in the Middle Devonian, post-dating calcite types. All these phases pre-date tectonic stylolites, indicating compaction after stabilization of the carbonate minerals. Strontium concentrations indicate that Early Devonian and Early Carboniferous micrites initially precipitated as aragonite; Middle and Late Devonian micrites precipitated as high-Mg calcites. Both precursors were diagenetically stabilized to low-Mg calcites through interaction with meteoric waters in phreatic environments. Trace elements in dolomite and ankerite indicate precipitation from Sr-enriched meteoric water. All studied carbonates, except Middle Devonian limestones, precipitated in reducing environments, which favoured incorporation of Fe and Mn. Late calcite generations precipitated from more saline waters than micrites. Light ¹⁸O values in micrites suggest alteration mainly in meteoric-phreatic environments. The dolomites and ankerites precipitated from more ¹⁸O-depleted fluids than the calcites, suggesting a greater contribution from meteoric waters. Variations in ¹³C of micrites represent primary secular trends, according to published ¹³C variations. The ¹³C oscillations within each succession probably relate to sea-level oscillations. Strontium isotopes also point to a meteoric origin of diagenetic fluids. Model calculations suggest that O and Sr isotopes equilibrated between calcites and fluid at relatively low water/rock ratios, whereas C isotopic signatures are inherited from limestones.     

Diagenetic development of a Precambrian limestone as interpreted from a modern analogue

A strong correlation in the geometry and mineralogy of two cement generations of a Quaternary with a Precambrian calcarenite enables us to reconstruct the diagenetic history of the Precambrian limestone. Both calcarenites contain two cement generations (A and B) of which A consists of dolomite, B of calcite. The following diagenetic stages can be recognized: after deposition of the allochems in a shallow marine environment, cementation in the intertidal zone with magnesian calcite (cement A) led to the formation of beachrock (Stage 1). By lowering of the sea level, the beach rock was shifted into the supratidal zone, but still remained under the predominant influence of the sea water (breakers, spray). During longer periods of aridity, the magnesian calcite of cement A and of the allochems was transformed into dolomite by brines derived from sea water with very high Mg/Ca ratio (> 15), whereas aragonite and calcite remained unaffected. After further lowering of the sea, an increasing influence of meteoric water caused the wet transformation of aragonitic allochems to sparry calcite and to the precipitation of sparry calcitic cement B.     

Multistage dolomitization and distribution of dolomitized bodies in Early Jurassic carbonate platforms (Southern Alps,Italy)

The Early Jurassic dolomitized carbonates are a hydrocarbon exploration target in Northern Italy. Of these carbonates, the Liassic Albenza Formation platform and the overlying Sedrina Formation shelf were studied to define a pervasive dolomitization model and to shed light on dolomite distribution in the sub‐surface. Field work, as well as analyses of well cores, stable isotopes, trace elements and fluid inclusions, was carried out on the outcropping thrust belt and sub‐surface deformed foreland of the Southern Alps. Petrographic analyses showed a first, pervasive, replacement dolomitization phase (D1) followed by volumetrically less important dolomite cement precipitation phases (D2, D3 and D4). The δ¹⁸O values fall between ?8·2‰ and 0·1‰ Vienna‐Pee Dee Belemnite with the more depleted samples belonging to dolomite cement‐rich dolostones; the δ¹³C ranges from 2·6‰ to 3·7‰ Vienna‐Pee Dee Belemnite. Analysis of trace elements showed different Fe and Mn contents in the sub‐surface and outcropping dolostones, and a higher Fe in the younger dolomite cements. An increase in the precipitation temperature (up to 130 °C from fluid inclusion data) and a decrease in diagenetic fluid salinity (from sea water to brackish) are observed from the first pervasive replacement dolomite to the dolomite cement phases. Field observations indicate that, in the Albenza Formation, dolomitization was limited to palaeohighs or faulted platform margins in the Early Jurassic carbonates. The pervasive replacement phase is interpreted based on a ‘compaction model’; the formation fluids expelled from compacting basinal carbonates could have funnelled along faults into permeable palaeohighs. The high homogenization temperature of the dolomite cements and decreased salinities indicate precipitation at great depth with an influx of meteoric water. These data, along with the thermal history, suggest that the dolomite cements precipitated according to the ‘tectonic squeegee’ dolomitization model. The dolomite precipitation temperature was set against the thermal history of the carbonate platform to interpret the timing of dolomite precipitation. The dolomite precipitation temperatures (90 to 100 °C) were reached in the studied formations first in the thrust fold belt (Early Tertiary, 60 Ma), and then in the foreland succession during the Late Tertiary (10 Ma). This observation suggests that the dolomite precipitation fronts moved southwards over time, recording a ‘diagenetic wave’ linked to the migration of the orogenic system. Observations suggest that the porosity increased during the first phase of replacement dolomitization while the dolomite cementation phases partially occluded the pores. The distribution of porous dolomitized bodies is therefore linked to the ‘compaction dolomitization’ model.     

Effect of orthophosphate on the dissolution kinetics of biogenic magnesian calcites

The dissolution behavior of two biogenic Mg-calcites, the echinoid, Tripneustes (12 mol% MgCO₃), and the red alga, Neogoniolithon (18 mol% MgCO₃ plus brucite), was studied using free-drift methods in distilled water and phosphate-spiked solutions at 25°C and P_CO2 = 1 atm. Small concentrations of phosphate strongly inhibit dissolution rates. Inhibition increases with increased phosphate levels and with approach toward saturation. Near saturation, dissolution rates are reduced by 10³ by the presence of 0.6 μmol adsorbed-P/m². The magnitude of phosphate inhibition is similar to that observed for low-Mg calcite, and like calcite, the mechanism of inhibition is probably by adsorption of P at surface kink sites. Phosphate appears to inhibit removal of Mg and Ca equally during Mg-calcite dissolution. Rates of brucite dissolution are unaffected by phosphate.Mg-calcites containing >8.5 mol% MgCO₃ should be thermodynamically unstable relative to aragonite in most natural waters. Recent work, however, shows that in contrast to its effect on the behavior of Mg-calcites. phosphate does not inhibit aragonite dissolution. The presence of phosphate might thus reverse the relative stability of these two minerals during diagenesis of shallow marine carbonate sediments.     

Botryoidal aragonite and its diagenesis

Botryoidal aragonite is a spectacular growth-form occurring as mamelons, up to 100 mm in diameter. Three examples of this particular carbonate cement have been discovered in two distinct areas: in New Caledonia, small-scale mamelons have been recognized within Pleistocene reefal terraces at Ouvea, an Island of the Loyalty archipelago, and in the Red Sea, large-scale mamelons of botryoidal aragonite exist within Pleistocene reefal terraces along the Um Gheig region of the Egyptian Coast. In addition, a similar botryoidal cement, partly dolomitized but exhibiting aragonite relics, occurs within a Miocene reef in the same region. Mamelons of botryoidal aragonite are isolated and/or coalescent but grow only on fixed substrates. They occur within cavities of varied origin. Their fabrics are characterized by fans of elongate euhedral crystals of aragonite fibres. Botryoidal aragonite can be preceded or followed by other types of cements or internal sediment. Despite similar mineralogy, petrography and ultrastructure, there are differences between the fabrics of the Pleistocene botryoids from the Red Sea and Ouvea and the Miocene botryoids from the Red Sea. The former are of submarine origin as confirmed by the strontium content (8500–10,500 ppm) and isotopic composition (δ¹⁸O between -0.10 and +0.19% PDB). The latter, related to a Miocene karst, are rich in strontium (average 13,600 ppm), and have an isotopic composition (average δ¹⁸O -10.50% PDB) indicative of non-marine precipitation. Diagenesis of these botryoidal aragonites consists of slight dissolution for Pleistocene botryoids and mineralogical transformation for the Miocene botryoids. The latter exhibit the diagenetic sequence aragonite → calcite → dolomite. The aragonite to calcite transformation is a dissolution-reprecipitation process, the void distribution and size influencing the distribution and the size of the replacement calcite crystals.     

Hydrogeochemical and isotopic study of groundwater in the Habor Lake Basin of the Ordos Plateau,NW China

Hydrogeochemistry and isotopes were used to understand the origin and geochemical evolution in the Habor Lake Basin, northwestern China. Groundwater samples were taken, and the isotopic compositions δD, δ¹⁸O and major ions were analyzed. The groundwater can be divided into three types: the Quaternary groundwater, the shallow Cretaceous groundwater and the deep Cretaceous groundwater. The groundwater chemistry is mainly controlled by the feldspar weathering and dolomite weathering, the dissolution of Glauber’s salt, and cation exchange. Chemistry of lake water is mainly controlled by evaporation and precipitation. The stable isotopes of oxygen and hydrogen in groundwater cluster along the local meteoric water line, indicating that groundwater is of meteoric origin. Comparing with shallow groundwater, deep groundwater is depleted in heavy isotopes indicating that deep groundwater was recharged during late Pleistocene and Holocene, during which the climate was more wetter and colder than today.     

Testing the preservation potential of early diagenetic dolomites as geochemical archives

Early marine diagenetic dolomite is a rather thermodynamically-stable carbonate phase and has potential to act as an archive of marine porewater properties. However, the variety of early to late diagenetic dolomite phases that can coexist within a single sample can result in extensive complexity. Here, the archive potential of early marine dolomites exposed to extreme post-depositional processes is tested using various types of analyses, including: petrography, fluid inclusion data, stable δ¹³C and δ¹⁸O isotopes, ⁸⁷Sr/⁸⁶Sr ratios, and U-Pb age dating of various dolomite phases. In this example, a Triassic carbonate platform was dissected and overprinted (diagenetic temperatures of 50 to 430°C) in a strike-slip zone in Southern Spain. Eight episodes of dolomitization, a dolostone cataclasite and late stage meteoric/vadose cementation were recognized. The following processes were found to be diagenetically relevant: (i) protolith deposition and fabric-preservation, and marine dolomitization of precursor aragonite and calcite during the Middle–Late Triassic; (ii) intermediate burial and formation of zebra saddle dolomite and precipitation of various dolomite cements in a Proto-Atlantic opening stress regime (T ca 250°C) during the Early–Middle Jurassic; (iii) dolomite cement precipitation during early Alpine tectonism, rapid burial to ca 15 km, and high-grade anchizone overprint during Alpine tectonic evolution in the Early Eocene to Early Miocene; (iv) brecciation of dolostones to cataclasite during the onset of the Carboneras Fault Zone activity during the Middle Miocene; and (v) late-stage regression and subsequent meteoric overprint. Data shown here document that, under favourable conditions, early diagenetic marine dolomites and their archive data may resist petrographic and geochemical resetting over time intervals of 10⁸ or more years. Evidence for this preservation includes preserved Late Triassic seawater δ¹³C_DIC values and primary fluid inclusion data. Data also indicate that oversimplified statements based on bulk data from other petrographically-complex dolomite archives must be considered with caution.     

Palaeoproterozoic magnesite: lithological and isotopic evidence for playa/sabkha environments

Magnesite forms a series of 1‐ to 15‐m‐thick beds within the ≈2·0 Ga (Palaeoproterozoic) Tulomozerskaya Formation, NW Fennoscandian Shield, Russia. Drillcore material together with natural exposures reveal that the 680‐m‐thick formation is composed of a stromatolite–dolomite–‘red bed’ sequence formed in a complex combination of shallow‐marine and non‐marine, evaporitic environments. Dolomite‐collapse breccia, stromatolitic and micritic dolostones and sparry allochemical dolostones are the principal rocks hosting the magnesite beds. All dolomite lithologies are marked by δ¹³C values from +7·1‰ to +11·6‰ (V‐PDB) and δ¹⁸O ranging from 17·4‰ to 26·3‰ (V‐SMOW). Magnesite occurs in different forms: finely laminated micritic; stromatolitic magnesite; and structureless micritic, crystalline and coarsely crystalline magnesite. All varieties exhibit anomalously high δ¹³C values ranging from +9·0‰ to +11·6‰ and δ¹⁸O values of 20·0–25·7‰. Laminated and structureless micritic magnesite forms as a secondary phase replacing dolomite during early diagenesis, and replaced dolomite before the major phase of burial. Crystalline and coarsely crystalline magnesite replacing micritic magnesite formed late in the diagenetic/metamorphic history. Magnesite apparently precipitated from sea water‐derived brine, diluted by meteoric fluids. Magnesitization was accomplished under evaporitic conditions (sabkha to playa lake environment) proposed to be similar to the Coorong or Lake Walyungup coastal playa magnesite. Magnesite and host dolostones formed in evaporative and partly restricted environments; consequently, extremely high δ¹³C values reflect a combined contribution from both global and local carbon reservoirs. A ¹³C‐rich global carbon reservoir (δ¹³C at around +5‰) is related to the perturbation of the carbon cycle at 2·0 Ga, whereas the local enhancement in ¹³C (up to +12‰) is associated with evaporative and restricted environments with high bioproductivity.     

Aragonite stromatolitic buildups from Santorini (Aegean Sea,Greece): Geochemical and palaeontological constraints of the caldera palaeoenvironment prior to the Minoan eruption (ca 3600 yr bp)

The pyroclastic deposits of the Minoan eruption (ca 3600 yr bp ) in Santorini contain abundant xenoliths. Most of these deposits are calcareous blocks of laminated‐botryoidal, stromatolite‐like buildups that formed in the shallow waters of the flooded pre‐Minoan caldera; they consist of (i) light laminae, of fibrous aragonite arranged perpendicular to layering, and (ii) dark laminae, with calcified filaments of probable biological origin. These microstructures are absent in the light laminae, suggesting a predominant inorganic precipitation of aragonite on substrates probably colonized by microbes. Internal cavities contain loose skeletal grains (molluscs, ostracods, foraminifera and diatoms) that comprise taxa typical of shallow marine and/or lagoon environments. Most of these forms are typical of warm water environments, although no typical taxa from hydrothermal vents have been observed. Past gasohydrothermal venting is recorded by the occurrence of barite, pyrolusite and pyrite traces. The most striking features of the stable isotopic data set are: (i) an overall wide range in δ¹³C_PDB (0·16 to 12·97‰) with a narrower variation for δ¹⁸O_PDB (?0·23 to 4·33‰); and (ii) a relatively uniform isotopic composition for the fibrous aragonite (δ¹³C = 12·40 ± 0·43‰ and δ¹⁸O = 2·42 ± 0·77‰, n = 21). The δ¹³C and δ¹⁸O values from molluscs and ostracods display a covariant trend, which reflects a mixing between sea water and a fluid influenced by volcano‐hydrothermal activity. Accordingly, ⁸⁷Sr/⁸⁶Sr from the studied carbonates (0·708758 to 0·709011 in fibrous aragonite and 0·708920 to 0·708991 in molluscs) suggests that the aragonite buildups developed in sea water under the influence of a hydrothermal/volcanic source. Significant differences in trace elements have been detected between the fibrous aragonite and modern marine aragonite cements. The caldera water from which the fibrous aragonite crusts formed received an input from a volcano‐hydrothermal system, probably producing diffuse venting of volcanogenic CO₂ gas and of a fluid enriched in Ca, Mn and Ba, and depleted in Mg and probably in Sr.     

川东三叠系飞仙关组白云岩锶含量、锶同位素组成与白云石化流体

川东飞仙关组白云岩包括微晶白云岩、具原始结构的粒屑白云岩和结晶白云岩等3种主要的结构类型,其中结晶白云岩是重要的天然气储集岩。根据白云岩的锶舍量和锶同位素组成,结合相关岩石学和地球化学资料,本文研究了白云石化过程中锶的迁移和相应的同位素变化。三种类型白云岩具有类似的锶含量,但其(87)~Sr/(86)~Sr 比值均不同程度地高于同期海水值,锶在白云石和方解石(或文石)中分配系数的差别是影响白云石化过程中白云石锶含量最为重要的因素。不同流体中锶的混合方程计算表明:如果白云石化流体是大气淡水和海水的混合流体,则结晶白云岩的白云石化流体相当于94%的大气淡水和6%的海水混合,具原始结构的粒屑白云岩的白云石化流体相当于81%的大气淡水和19%的海水混合,微晶白云岩的白云石化流体相当于92%的大气淡水和8%的海水混合。但极低的锰含量、相对较高的锶含量和包裹体均一化温度等资料均不支持有94%的大气淡水参与了结晶白云岩的白云石化作用,其白云石化流体应是埋藏成岩过程中囚禁的近同期、但是非同期的海源流体,其来源可能与埋藏成岩过程中该时间段蒸发盐的溶解有关。锰含量、锶含量、(87)~Sr/(86)~Sr 比值都表明具原始结构的粒屑白云岩和微晶白云岩的白云石化过程都存在大气淡水的介入,微晶白云岩的白云石化可能与潮坪环境的蒸发泵机理有关;具原始结构的粒屑白云岩的白云石化可能与混合水白云石化作用有关,这类白云岩分布于向上浅滩化旋回滩体的顶部,这是埋藏前或浅埋藏阶段大气淡水与海水混合白云石化作用最容易发生地带。