Speleothem preservation and diagenesis in South African hominin sites implications for paleoenvironments and geochronology

Plio‐Pleistocene speleothems from australopithecine‐bearing caves of South Africa have the potential to yield paleoenvironmental and geochronological information using isotope geochemistry. Prior to such studies it is important to assess the preservation of geochemical signals within the calcitic and aragonitic speleothems, given the tendency of aragonitic speleothems to recrystallize to calcite. This study documents the geochemical suitability of speleothems from the principal hominin‐bearing deposits of South Africa. We use petrography, together with stable isotope and trace element analysis, to identify the occurrence of primary aragonite, primary calcite, and secondary calcite. This study highlights the presence of diagenetic alteration at many of the sites, often observed as interbedded primary and secondary fabrics. Trace element and stable isotopic values distinguish primary calcite from secondary calcite and offer insights into geochemical aspects of the past cave environment. δ¹³C values of the primary and secondary calcites range from +6 to −9‰ and δ¹⁸O values range from −4 to −6‰. The data are thus typical of meteoric calcites with highly variable δ¹³C and relatively invariant δ¹⁸O. High carbon isotope values in these deposits are associated with the effects of recrystallization and rapid outgassing of CO₂ during precipitation. Mg/Ca and Sr/Ca ratios differ between primary and secondary calcite speleothems, aiding their identification. Carbon and oxygen isotope values in primary calcite reflect the proportion of C₃ and C₄ vegetation in the local environment and the oxygen isotope composition of rainfall. Primary calcite speleothems preserve the pristine geochemical signals vital for ongoing paleoenvironmental and geochronological research. © 2009 Wiley Periodicals, Inc.     

Assessing the past thermal and chemical history of fluids in crystalline rock by combining fluid inclusion and isotopic investigations of fracture calcite

Fluid inclusion studies combined with the isotope geochemistry of several generations of fracture calcite from the Olkiluoto research site, Finland, has been used to better understand the past thermal and fluid history in the crystalline rock environment. Typically, fracture mineral investigations use O and C isotopes from calcite and an estimate of the isotopic composition of the water that precipitated the calcite to perform δ¹⁸O geothermometry calculations to estimate past temperature conditions. By combining fluid inclusion information with calcite isotopes, one can directly measure the temperature at which the calcite formed and can better determine past fluid compositions. Isotopic, petrologic and fluid inclusion studies at the Olkiluoto research site in Finland were undertaken as part of an investigation within the Finnish nuclear waste disposal program. The study revealed that four fluids were recorded by fracture calcites. From petrologic evidence, the first fluid precipitated crystalline calcite at 151–225°C with a δ¹³C signature of −21 to −13.9‰ PDB and a δ¹⁸O signature of 12.3–13.0‰ SMOW. These closed fracture fillings were found at depths greater than 500 m and were formed from a high temperature, low salinity, Na–Cl fluid of possible meteoric water altered by exchange with wallrock or dilute basinal origin. The next fluid precipitated crystalline calcite with clay at 92–210°C with a δ¹³C signature of −2.6 to +3.8‰ PDB and a δ¹⁸O signature of 19.4–20.7‰ SMOW. These closed fracture fillings were found at depths less than 500 m and were formed from a moderate to high temperature, low to moderate salinity, Na–Cl fluid, likely of magmatic origin. The last group of calcites to form, record the presence of two distinct fluid types. The platy (a) calcite formed at 95–238°C with a δ¹³C signature of −12.2 to −3.8‰ PDB and a δ¹⁸O signature of 14.9–19.6‰ SMOW, from a high temperature, low salinity, Na–Cl fluid of possible magmatic origin. The platy (b) calcite formed at 67–98°C with a δ¹³C signature of −13.0 to −6.2‰ PDB and a δ¹⁸O signature of 15.1–20.1‰ SMOW, from a low temperature, high salinity, Ca–Na–Cl fluid of possible basinal brine origin. The two calcites are related through a mixing between the two end members. The source of the fluids for the platy grey (a) calcites could be the olivine diabase dykes and sills that cut through the site. The source of fluids for the platy (b) calcites could be the Jotnian arkosic sandstone formations in the northern part of the site. At the Olkiluoto site, δ¹⁸O geothermometry does not agree with fluid inclusion data. The original source of the water that forms the calcite has the largest effect on the isotopic signature of the calcites formed. Large isotopic shifts are seen in any water by mineral precipitation during cooling under rock–water equilibrium fractionation conditions. Different calcite isotopic signatures are produced depending on whether cooling occurred in an open or closed system. Water–rock interaction, at varying W/R ratios, between a water and a host rock can explain the isotopic shifts in many of the calcites observed. In some cases it is possible to shift the δ¹⁸O of the water by +11.5‰ (SMOW) using a realistic water–rock ratio. This process still does not explain some of the very positive δ¹⁸O values calculated using fluid inclusion data. Several other processes, such as low temperature recrystallization, boiling, kinetic effects and dissolution of calcite from fluid inclusion walls can affect isotopic signatures to varying degrees. The discrepancy between fluid inclusion data and δ¹⁸O geothermometry at the Olkiluoto site was most likely due to poor constraint on the original source of the water.     

Formation of complex fibrous calcite veins in Upper Triassic strata of Wrangellia Terrain, British Columbia, Canada

Fibrous calcite veins are ubiquitous throughout the thinly bedded, organic-rich Upper Triassic marine mdrocks of the Queen Charlotte Islands and their lateral equivalents on Vancouver Island. These veins show variable and complex morphologies and can be grouped into several types: (a) simple; (b) anastomosing or composite; (c) boxwork; and (4) polygonal network oriented normal to bedding. Field, petrographic, and geochemical evidence suggest that vein opening, resulting from hydraulic fracturing due to elevated pore-fluid pressures, was an early phenomenon and occurred prior to significant compaction of the host sediments.Calcite fibers in the veins are up to 30 mm long and commonly oriented perpendicular to the wall but locally display conical structures. Fibrous calcites, with the exception of those in boxwork veins, are generally non-ferroan and dull to very weakly orange luminescent. The boxwork calcites are ferroan, zoned and show dull luminescence with some bright rims.δ¹⁸O values range from −8.2 to −21.6‰ (PDB) and δ¹³C values range from 2.0 to −4.4‰ (PDB). Although some variations are present among the different morphological types of calcite veins, oxygen and carbon isotopic values display important variations when compared geographically. The most depleted oxygen and carbon isotopic values are those of boxwork calcite and they are associated with areas where the effects of early Mesozoic plutonism were most severe. Precipitation of boxwork fibrous calcites is interpreted to have been related to hydrothermal discharge into unconsolidated host sediment, rather than to later burial. Although the hydrothermal influence on the formation of vein calcite is related to geological events specific to the Wrangellia Terrain, this study provides an alternative mechanism for the generation of fibrous calcite veins and demonstrates the local importance of hydrothermal input in the evolution of pore-water chemistry.     

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.     

Pleistocene paleoclimate of the arid region of Israel as recorded in calcite deposits along regional transverse faults and in veins

The δ¹⁸O and δ¹³C values of the calcites associated with E-W and NE-SW transverse faults in the Negev, Israel, indicate that calcite was deposited from meteoric water. A regional change in the δ¹⁸O and δ¹³C values was observed. The ¹⁸O content in the calcite increases, from the southwestern (δ¹⁸O = −17.8‰) to the northeastern (δ¹⁸O = −2.9‰) part of the region. The δ¹³C values show the opposite trend of the ¹³C content decrease: from +2‰ in the south to −10‰ in the northeast. These trends had to reflect changes in regional paleoclimate, suggesting a change in the isotopic composition of the solution from which the calcite was deposited in different periods. The variations in the δ¹⁸O values reflect shifts in the δ¹⁸O values of precipitation and are associated with a change in the source of moist air masses which came from the equatorial Atlantic in the early Pleistocene and from the Mediterranean during a later period. Variations in δ¹³C values reflect changes from humid to arid conditions. Two modes of calcite deposition are suggested: (1) precipitation of calcite minerals in the unsaturated zone following the dissolution in the soil or (2) calcite deposition that occurred as CO₂ was lost during emergence of paleogroundwater from Lower Cretaceous and Jurassic aquifers.     

Diagenetic model of carbonate rocks of Guri Member of Mishan Formation (Lower to Middle Miocene) SE Zagros basin,Iran

In order to understand the post-depositional history of carbonate rocks of Guri Member (Lower to Middle Miocene), three stratigraphic sections were selected in north Bandar-Abbas in southeast of Iran. Sampling was carried out, analyzed for selective parameters such as oxygen and carbon isotopic compositions (δ¹⁸O and δ¹³C) and interpreted in the present study. We recognized several diagenetic processes including micritization, cementation, neomorphism, compaction, dissolution, silicification, dolomitization, fracturing and vein filling. Some of the diagenetic processes occurred at different conditions, so in order to achieve precise interpretation, samples from different carbonate components such as, micrite, fracture cement, solution pore cement, intergranular cement, and some biotic allochems were analyzed. In this study micrite samples were subdivided into two groups including micro-spary and micrite. They were recognized under Cathodoluminescence microscope. In addition, micrite samples were classified into five groups based on their depositional environments: supratidal, lagoon, coral bar, open sea, and open basin. There were minor changes in stable isotope ratios based on the sedimentary environments, stratigraphy successions, and micro-spary or micrite properties. In this study, similar calcite cements in petrography studies were differentiated by stable isotope data. Those calcite cements have formed in different diagenetic environments such as meteoric and burial cements. Paragenetic sequence of carbonate rocks were interpreted by integration of petrographic and isotopic studies. We have reconstructed diagenetic models of Guri Member into four stages including marine, meteoric, burial, and uplifting.     

Matrix micrite δC and δO reveals synsedimentary marine lithification in Upper Jurassic Ammonitico Rosso limestones (Betic Cordillera, SE Spain)

Matrix micrites are a commonly used carbonate archive for the reconstruction of past environmental parameters, but one that is submitted to known limitations. Main reasons for the often ambiguous value of many micrite-based isotope data sets are the unknown origin of the micrite components and their poorly resolved diagenetic history. Here we present carbon and oxygen-isotope data retrieved from Oxfordian to Tithonian Ammonitico Rosso nodular micrites sampled from three sections in the Betic Cordillera (Southern Spain). All three sections were correlated and sampled using a rigorous biostratigraphic framework. A noteworthy feature is that analyzed matrix micrites are more conservative in terms of their isotopic composition than other carbonate materials commonly considered to resist diagenetic alteration under favourable circumstances. Remarkably, this refers not only to δ¹³C ratios, which reflect the typical Late Jurassic global trend, but also to δ¹⁸O ratios that range around 0.3‰. The ¹⁸O-enriched oxygen-isotope ratios are considered to represent diagenetic stabilization of carbonate ooze under the influence of marine porewaters within the sediment–water interphase (i.e., the immature sedimentary section, usually submitted to biogenic activity). This interpretation agrees with the very early lithification of micrite nodules with cements precipitated from marine porewaters, enriched by the dissolution of aragonite skeletals (i.e., ammonite shells). According to the model proposed, low sedimentation rates as well as rapid early marine differential cementation, under the influence of currents and seawater pumping, affected the sediment–water interphase of epioceanic swells where deposition resulted in early lithified Ammonitico Rosso facies. The data obtained show that special care must be taken to prevent oversimplified interpretations of carbonate archives, particularly in the context of epioceanic settings.     

Stable carbon and oxygen isotope investigation in historical lime mortar and plaster – Results from field and experimental study

Lime mortar and plaster were sampled from Roman, medieval and early modern buildings in Styria. The historical lime mortar and plaster consist of calcite formed in the matrix during setting and various aggregates. The stable C and O isotopic composition of the calcite matrix was analyzed to get knowledge about the environmental conditions during calcite formation. The δ¹³C_matrix and δ¹⁸O_matrix values range from −31 to 0‰ and −26 to −3‰(VPDB), respectively. Obviously, such a range of isotope values does not represent the local natural limestone assumed to be used for producing the mortar and plaster. In an ideal case, the calcite matrix in lime mortar and plaster is isotopically lighter in the exterior vs. the interior mortar layer according to the relationship δ¹⁸O_matrix = 0.61 · δ¹³C_matrix − 3.3 (VPDB). Calcite precipitation by uptake of gaseous CO₂ into alkaline Ca(OH)₂ solutions shows a similar relationship, δ¹⁸O_calcite = 0.67 · δ¹³C_calcite − 6.4 (VPDB). Both relationships indicate that the ¹³C/¹²C and ¹⁸O/¹⁶O values of the calcite reflect the setting behaviour of the lime mortar and plaster. Initially, CO₂ from the atmosphere is fixed as calcite, which is accompanied by kinetic isotope fractionation mostly due to the hydroxylation of CO₂ (δ¹³C_matrix ≈  −25‰ and δ¹⁸O_matrix ≈ −20‰). As calcite formation continued the remaining gaseous CO₂ is subsequently enriched in ¹³C and ¹⁸O causing later formed calcite to be isotopically heavier along the setting path in the matrix. Deviations from such an ideal isotopic behaviour may be due to the evolution of H₂O, e.g. evaporation, the source of CO₂, e.g. from biogenic origin, relicts of the natural limestone, and secondary effects, such as recrystallization of calcite. The results of the field and experimental study suggest that isotope values can be used as overall proxies to decipher the origin of carbonate and the formation conditions of calcite in the matrix of ancient and recent lime mortar and plaster. Moreover, these proxies can be used to select calcite matrix from historical lime mortar and plaster for ¹⁴C dating.     

Micritization of crinoids by diagenetic dissolution

Bands within the Chalk of Kansas made up of masses of Uintacrinus socialis show an unusual preservation of crinoid ossicles: in contrast to their normal preservation in full relief as single large calcite crystals the ossicles are compressed and transformed to micrite. The micrite originated by a process different from the well-known micritization by algal and fungal borings and subsequent cementation of the borings: it is the outcome of partial dissolution. Dissolution proceeded inside the sediment and preferentially attacked the echinoderms as the most soluble calcareous component of the chalk sediment. Later, the remains of the Uintacrinus crystals preferentially attracted syntaxial cement so that the layer changed to a hard band of limestone within the soft chalk. In addition to a second process of micritization the preservation of Uintacrinus demonstrates (1) that the magnesium content of magnesian calcites survives the earliest stages of diagenesis within chalk, and (2) that a diagenetic comminution of large crystals (in an optical sense) to smaller ones is possible. Provided the ossicles of echinoderms are true single crystals (the knowledge in this field is summarized), this is an example of the often discussed ‘crystal diminution’.     

Α high-resolution late Holocene speleothem record from Kaite Cave, northern Spain: δO variability and possible causes

A high-resolution calcite oxygen stable isotopic (δ¹⁸O) record, covering the past 4000 years, was obtained from Kaite Cave, northern Spain. The record has a mean δ¹⁸O value of -6.25‰ VPDB and a range of 2‰. Spectral analysis of the δ¹⁸O data shows significant periodicities of 2400–1900, 600, 150, 27, and 22 years. The amplitudes during these periods range from 0.2‰ to 2‰. Factors controlling the isotopic ratio in the speleothem were evaluated. The calcite is most likely precipitated under equilibrium conditions, with the cave calcite δ¹⁸O interpreted as a proxy of oxygen isotopic composition in local rainwater. Other factors such as temperature or fractionation in the karst system prior to calcite precipitation are considered of negligible or of minor importance. Mechanisms affecting rainfall isotopic composition were also investigated on different time scales. Precipitation amount is the primary factor controlling the high-frequency δ¹⁸O oscillations. Other climate parameters, such as changes of storm tracks may have significant contributions on centennial and millennial time scales.     

Oxygen and carbon isotopic systematics of aragonite speleothems and water in Furong Cave, Chongqing, China

To understand oxygen and carbon stable isotopic characteristics of aragonite stalagmites and evaluate their applicability to paleoclimate, the isotopic compositions of active and fossil aragonite speleothems and water samples from an in situ multi-year (October 2005-July 2010) monitoring program in Furong Cave located in Chongqing of China have been examined. The observations during October 2005-June 2007 show that the meteoric water is well mixed in the overlying 300-500-m bedrock aquifer, reflected by relatively constant δ¹⁸O, ±0.11-0.14‰ (1σ), of drip waters in the cave, which represents the annual status of rainfall water. Active cave aragonite speleothems are at oxygen isotopic equilibrium with drip water and their δ¹⁸O values capture the surface-water oxygen isotopic signal. Aragonite-to-calcite transformation since the last glaciation is not noticeable in Furong stalagmites. Our multi-year field experiment approves that aragonite stalagmite δ¹⁸O records in this cave are suitable for paleoclimate reconstruction. With high U, 0.5-7.2 ppm, and low Th, 20-1270 ppt, the Furong aragonite stalagmites provide very precise chronology (as good as ±20s yrs (2σ)) of the climatic variations since the last deglaciation. The synchroneity of Chinese stalagmite δ¹⁸O records at the transition into the Bølling-Allerød (t-BA) and the Younger Dryas from Furong, Hulu and Dongge Caves supports the fidelity of the reconstructed East Asian monsoon evolution. However, the Furong record shows that the cold Older Dryas (OD) occurred at 14.0 thousand years ago, agreeing with Greenland ice core δ¹⁸O records but ∼200 yrs younger than that in the Hulu record. The OD age discrepancy between Chinese caves can be attributable to different regionally climatic/environmental conditions or chronological uncertainty of stalagmite proxy records, which is limited by changes in growth rate and subsampling intervals in absolute dating. Seasonal dissolved inorganic carbon δ¹³C variations of 2-3‰ in the drip water and 5-7‰ in the pool and spring waters are likely attributed to variable degrees of CO₂ degassing in winter and summer. The variable δ¹³C values of active deposits from −11‰ to 0‰ could be caused by kinetically mediated CO₂ degassing processes. The complicated nature of pre-deposition kinetic isotopic fractionation processes for carbon isotopes in speleothems at Furong Cave require further study before they can be interpreted in a paleoclimatic or paleoenvironmental context.     

Stable isotope and geochemical evidence of formation pore fluid evolution during diagenesis of Tertiary sandstones and mudrocks of the Niger Delta

Petrological data provide evidence that framboidal pyrite, Fe-carbonates and kaolinite are the major diagenetic minerals developed during burial diagenesis in the Tertiary Niger Delta sandstones and associated mudrocks. The pyrite sulphur, carbonate carbon and oxygen and kaolinite oxygen and hydrogen isotope compositions have been determined. These data (pyrite, δ³⁴S = −24.8 to 21.0‰; “siderite”, δ¹³C(PDB) = −14.7 to +5.0‰, δ¹⁸O(PDB) = −19.1 to −0.6‰; Fe-calcite, δ¹³C(PDB) = +17.5 to 17.9‰, δ¹⁸O(PDB) = −8.3 to −8.0‰; kaolinite, δ¹⁸O(SMOW) = +14.7 to 17.5‰, δD (SMOW) = −86 to −43‰) have been used to interpret the isotopic compositions of the precipitating pore fluids and/or the temperatures of mineral formation. The interpretation of these results indicate that in the deltaic depositional setting the syndepositional pore waters had a significant but variable marine influence that favoured the early formation of pyrite. Subsequently the subsurface influence of meteoric waters, showing varying degrees of modification involving organic and/or water-rock reactions, played an increasingly significant role in the development of later diagenetic cements in the sediments when abundant authigenic carbonates and kaolinites were formed.     

Stable isotope variations in modern tropical speleothems: Evaluating equilibrium vs. kinetic isotope effects

Applications of speleothem calcite geochemistry in climate change studies require the evaluation of the accuracy and sensitivity of speleothem proxies to correctly infer paleoclimatic information. The present study of Harrison’s Cave, Barbados, uses the analysis of the modern climatology and groundwater system to evaluate controls on the C and O isotopic composition of modern speleothems. This new approach directly compares the δ¹⁸O and δ¹³C values of modern speleothems with the values for their corresponding drip waters in order to assess the degree to which isotopic equilibrium is achieved during calcite precipitation. If modern speleothems can be demonstrated to precipitate in isotopic equilibrium, then ancient speleothems, suitable for paleoclimatic studies, from the same cave environment may also have been precipitated in isotopic equilibrium. If modern speleothems are precipitated out of isotopic equilibrium, then the magnitude and direction of the C and O isotopic offsets may allow specific kinetic and/or equilibrium isotopic fractionation mechanisms to be identified.Carbon isotope values for the majority of modern speleothem samples from Harrison’s Cave fall within the range of equilibrium values predicted from the combined use of (1) calcite-water fractionation factors from the literature, (2) measured temperatures, and (3) measured δ¹³C values of the dissolved inorganic carbon of drip waters. Calcite samples range from ∼0.8‰ higher to ∼1.1‰ lower than predicted values. The ¹³C depletions are likely caused by kinetically driven departures in the fractionation between HCO₃⁻ (aq) and CaCO₃ from equilibrium conditions, caused by rapid calcite growth. ¹³C enrichments can be accounted for by Rayleigh distillation of the HCO₃⁻ (aq) reservoir during degassing of ¹³C-depleted CO₂.Modern speleothems from Harrison’s Cave are not in O isotopic equilibrium with their corresponding drip waters and are 0.2‰ to 2.3‰ enriched in ¹⁸O relative to equilibrium values. δ¹⁸O variations in modern calcite are likely controlled by kinetically driven changes in the fractionation between HCO₃⁻ (aq) and CaCO₃ from equilibrium conditions to nonequilibrium conditions, consistent with rapid calcite growth. In contrast to δ¹³C, δ¹⁸O values of modern calcite may not be affected by Rayleigh distillation during degassing because CO₂ hydration and hydroxylation reactions will buffer the O isotopic composition of the HCO₃⁻ (aq) reservoir. If the effects of Rayleigh distillation manifest themselves in the O isotopic system, they will result in ¹⁸O enrichment in the HCO₃⁻ (aq) reservoir and ultimately in the precipitated CaCO₃.     

Carbon isotopes of Middle–Lower Jurassic coal-derived alkane gases from the major basins of northwestern China

Coal-derived hydrocarbons from Middle–Lower Jurassic coal-bearing strata in northwestern China are distributed in the Tarim, Junggar, Qaidam, and Turpan-Harmi basins. The former three basins are dominated by coal-derived gas fields, distributed in Cretaceous and Tertiary strata. Turpan-Harmi basin is characterized by coal-derived oil fields which occur in the coal measures. Based on analysis of gas components and carbon isotopic compositions from these basins, three conclusions are drawn in this contribution: 1) Alkane gases with reservoirs of coal measures have no carbon isotopic reversal, whereas alkane gases with reservoirs not of coal measures the extent of carbon isotopic reversal increases with increasing maturity; 2) Coal-derived alkane gases with high δ¹³C values are found in the Tarim and Qaidam basins (δ¹³C₁: − 19.0 to − 29.9‰; δ¹³C₂: − 18.8 to − 27.1‰), and those with lowest δ¹³C values occur in the Turpan-Harmi and Junggar basins (δ¹³C₁: − 40.1 to − 44.0‰; δ¹³C₂: − 24.7 to − 27.9‰); and 3) Individual specific carbon isotopic compositions of light hydrocarbons (C_5–8) in the coal-derived gases are lower than those in the oil-associated gases. The discovered carbon isotopic reversal of coal-derived gases is caused by isotopic fractionation during migration and secondary alteration. The high and low carbon isotopic values of coal-derived gases in China may have some significance on global natural gas research, especially the low carbon isotope value of methane may provide some information for early thermogenic gases. Coal-derived methane typically has much heavier δ¹³C than that of oil-associated methane, and this can be used for gas–source rock correlation. The heavy carbon isotope of coal-derived ethane is a common phenomenon in China and it shed lights on the discrimination of gas origin. Since most giant gas fields are of coal-derived origin, comparative studies on coal-derived and oil-associated gases have great significance on future natural gas exploration in the world.     

Cryogenic carbonates in cave environments: A review

Cryogenic cave carbonate (CCC) represents a specific type of speleothem. Its precipitation proceeds at the freezing point and is triggered by freezing-induced concentration of solutes. Compared to classical speleothems (stalagmites, flowstones), CCC occurs as accumulations of loose uncemented aggregates. The grain sizes range from less than 1 μm to over 1 cm in diameter. Karst groundwater chemistry and its freezing rate upon entering the cave are responsible for highly variable grain morphology. Rapid freezing of water results in the formation of CCC powders with grain size typically below 50 μm. Slow freezing of water in caves (usually in systems where the CO₂ escape is partly restricted; e.g., ice covered water pools) results in the formation of large mineral grains, with sizes from less than 1 mm to about 20 mm. The range of carbon and oxygen stable isotope compositions of CCC is larger than for a typical carbonate speleothem. Rapid freezing of water accompanied by a quick kinetic CO₂ degassing results in large ranges of δ¹³C of the CCC powders (between –10‰ and +18‰ PDB). Slow freezing of water, with a restricted CO₂ escape results in gradual increase of δ¹³C values (from −9‰ to +6‰ PDB; data ranges in individual caves are usually much more restricted), accompanied by a δ¹⁸O decrease of the precipitated carbonate (overall range from −10‰ to −24‰ PDB). These unusual trends of the carbonate δ¹⁸O evolution reflect incorporation of the heavier ¹⁸O isotope into the formed ice. New isotope data on CCC from three Romanian ice caves allow better understanding of the carbon and oxygen isotope fingerprint in carbonates precipitated from freezing of bulk water. CCCs are proposed as a new genetic group of speleothems.     

Diagenesis of Pennsylvanian phylloid algal mounds from the southern Cantabrian Zone (Spain)

The Pennsylvanian phylloid algal mounds exposed in the Cervatina Limestone of the Cantabrian Zone (NW Spain) developed during the highstands of high-frequency shallowing-upward cycles and lack evidence of subaerial exposure at their tops. Mound core facies are composed of massive bafflestones with variable amounts of calcite cements and anchicodiacean phylloid algae with cyathiform thalli preserved in growth position. Through standard petrographic, isotopic (δ¹⁸O and δ¹³C), major and trace element (Ca, Mg, Fe, Mn, Sr) and cathodoluminescence analyses, five calcite cement phases (cement 1 (C1)–cement 5 (C5)) have been identified filling primary and secondary pores. Early marine diagenesis is represented by micritization and non-luminescent to mottled-dull luminescent high-Mg calcite fibrous marine cement (C1). A dissolution phase then occurred and created vuggy and moldic pores. Based on the absence of field or petrographical or geochemical evidence of exposure, it is inferred that dissolution occurred in near-surface undersaturated marine waters with respect to aragonite related to progressive organic matter oxidation. Secondary porosity was subsequently filled by dull-bright-dull bladed high-Mg calcite (C2), which precipitated in the early shallow burial from marine-derived pore waters. Remaining porosity was occluded by shallow-burial precipitates consisting of non-luminescent scalenohedral low-Mg calcite (C3) followed by non-ferroan dull luminescent calcite spar (C4). Latter phases of calcite spar exhibiting non- and dull luminescence (C5) are associated with burial calcite veins. Low δ¹⁸O values (around ?8‰), moderately depleted δ¹³C values (around 0.5‰) and the homogeneity of trace element contents of carbonate matrix, cements and vein-filling calcites suggest burial isotopic re-equilibration and recrystallization, probably in Early Permian times during post-thrusting orocline formation.     

Calcite cementation during bacterial manganese, iron and sulphate reduction in Jurassic shallow marine carbonates

Faunally restricted argillaceous wackestones from the Middle Jurassic of eastern England contain evidence of early diagenetic skeletal aragonite dissolution and stabilization of the carbonate matrix, closely followed by precipitation of zoned calcite cements, and precipitation of pyrite. Distinctive cathodoluminescence and trace element trends through the authigenic calcites, their negative δ¹³C compositions and the location of pyrite in the paragenetic sequence indicate that calcite precipitation took place during sequential bacterial Mn, Fe and sulphate reduction. Calcite δ¹⁸O values are compatible with cementation from essentially marine pore fluids, although compositions vary owing to minor contamination with ¹⁸O-depleted ‘late’cements. Mg and Sr concentrations in the calcites are lower than those in recent marine calcite cements. This may be a result of kinetic factors associated with the shallow burial cementation microenvironments. Bicarbonate for sustained precipitation of the authigenic calcites was derived largely from aragonite remobilization, augmented by that produced through anaerobic organic matter oxidation in the metal and sulphate reduction environments. Aragonite dissolution is thought to have been induced by acidity generated during aerobic bacterial oxidation of organic matter. Distinction of post-oxic metal reduction and anoxic sulphate reduction diagenetic environments in modern carbonate sediments is uncommon outside pelagic settings, and early bacterially mediated diagenesis in modern platform carbonates is associated with extensive carbonate dissolution. High detrital Fe contents of the Jurassic sediments, and their restricted depositional environment, were probably the critical factors promoting early cementation. These precipitates constitute a unique example of calcite authigenesis in shallow water limestones during bacterial Mn and Fe reduction.     

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.     

Oxygen isotopic fractionation during inorganic calcite precipitation ― Effects of temperature, precipitation rate and pH

Stable oxygen isotopic fractionation during inorganic calcite precipitation was experimentally studied by spontaneous precipitation at various pH (8.3 < pH < 10.5), precipitation rates (1.8 < log R < 4.4 μmol m^− 2 h^− 1) and temperatures (5, 25, and 40 °C) using the CO₂ diffusion technique.The results show that the apparent stable oxygen isotopic fractionation factor between calcite and water (α_{calcite–water}) is affected by temperature, the pH of the solution, and the precipitation rate of calcite. Isotopic equilibrium is not maintained during spontaneous precipitation from the solution. Under isotopic non-equilibrium conditions, at a constant temperature and precipitation rate, apparent 1000lnα_{calcite–water} decreases with increasing pH of the solution. If the temperature and pH are held constant, apparent 1000lnα_{calcite–water} values decrease with elevated precipitation rates of calcite. At pH = 8.3, oxygen isotopic fractionation between inorganically precipitated calcite and water as a function of the precipitation rate (R) can be described by the expressions

at 5, 25, and 40 °C, respectively.The impact of precipitation rate on 1000lnα_{calcite–water} value in our experiments clearly indicates a kinetic effect on oxygen isotopic fractionation during calcite precipitation from aqueous solution, even if calcite precipitated slowly from aqueous solution at the given temperature range. Our results support Coplen's work [Coplen T. B. (2007) Calibration of the calcite–water oxygen isotope geothermometer at Devils Hole, Nevada, a natural laboratory. Geochim. Cosmochim. Acta 71, 3948–3957], which indicates that the equilibrium oxygen isotopic fractionation factor might be greater than the commonly accepted value.     

Stable isotope evidence for multiple fluid regimes during carbonate cementation of the Upper Tertiary Hazeva Formation, Dead Sea Graben, southern Israel

Stable carbon- and oxygen-isotope compositions of calcite and dolomite cements have been used to understand porewater evolution in the Upper Tertiary Hazeva Formation within the Dead Sea Graben, southern Israel. Sandstone samples were obtained from four boreholes in three tectonic blocks of the graben over depths of 253–6448 m, a variation that largely reflects differential subsidence of individual fault-bounded blocks. Early carbonate cements dominate diagenesis. Calcite occurs at <1600 m, but was replaced by dolomite at greater depths. Dolomite at 1600–2700 m is Fe-poor (<0.8 mol% FeCO₃), and at 4700–6200 m, Fe-rich (0.5–7.2 mol% FeCO₃). Magnesite, anhydrite and halite are the final diagenetic phases. Calcite has positively correlated δ¹⁸O (+21‰ to +25‰) and δ¹³C (−6‰ to −2‰) values that generally decrease with depth. Dolomite has a wider variation in δ¹⁸O (+18‰ to +30‰) and δ¹³C (−8‰ to −1‰) values, which also generally are lower with increasing depth. However, the δ¹³C and δ¹⁸O values of dolomite from the uppermost 400 m of the Hazeva Formation in the Sedom Deep-1 borehole are anomalous in spanning the entire range of stable carbon and oxygen isotopic compositions over this relatively small interval.The decreasing dolomite δ¹³C values likely indicate an increased contribution of carbon from organic sources with increasing depth. Except for the uppermost 400 m, Hazeva Formation dolomite in the Sedom Deep-1 borehole has stable carbon-isotope compositions that imply initial dolomitization at much shallower levels, prior to the preferential subsidence of this tectonic block. The oxygen isotopic compositions of the calcite cement are best explained by equilibration at present burial temperatures (≤55 °C) with porewater of meteoric origin. Its δ¹⁸O values increased from −5‰ at the shallowest depths to 0‰ at 1600 m. The dolomite oxygen isotopic compositions also reflect equilibration at present burial temperatures with porewaters ranging from 0‰ at 1600 m to +7‰ at 3600 m (100 °C). In the deepest fault block (Sedom Deep-1 borehole), however, increasingly Fe-rich dolomite has (re)equilibrated with porewater whose δ¹⁸O values decreased from +9‰ at 4750 m (120 °C) to +1‰ to +2‰ by 6200 m (150 °C).Much of the dolomite likely formed at relatively shallow depths from saline brines derived from precursors to the Dead Sea. These infiltrated the Hazeva Formation, mixing with and largely displacing meteoric water, and dolomitizing calcite. Rock–water ratios tended to be high during these processes. However, the upper 400 m of the Hazeva Formation in the deepest fault block were likely deposited during its rapid tectonic subsidence, and largely escaped the initial style of dolomitization pervasive elsewhere in the study area. These sediments were also capped by evaporites. This relatively thin interval likely became a preferential conduit for brines that escaped underlying and overlying strata, including the Fe-rich, lower ¹⁸O fluids (evolved seawater?) present in the deepest part of the graben. These rocks present the most promising target for the passage and accumulation of hydrocarbons in the study area.