δ18OVPDB Values Research Articles

Multi-stage hydrothermal activity affecting the early Jurassic K7 coal seam from the Gaosheng coal Mine, Sichuan Basin, southwest China: Evidence from whole-rock geochemistry and C-O-Sr isotopes in authigenic carbonates

Hydrothermal fluid is one of the major sources of elevated concentrations of elements in coals from southwestern China. However, the sources, timing, migration pathways of hydrothermal fluids remain unclear. This study investigated the petrology, mineralogy, elemental geochemistry of whole rocks, and isotope geochemistry (δ13C, δ18O, and 87Sr/86Sr) of carbonate minerals, to reveal the sources and migration of fluids associated with hydrothermal mineralization within the K7 coal seam from northeastern Sichuan Basin, China. This seam was deposited in an intermontane basin under fresh-water conditions. It contains a complex epigenetic mineral assemblage including carbonates, quartz, pyrophyllite, clay, and minor sulfides and sulfates (gypsum, barite). Syngenetic siderite from the roof and floor mudstones with relatively high 87Sr/86Sr values (0.710993 and 0.710994) was deposited from fresh water. The δ18OVPDB and δ13CVPDB values (from −16.4 ‰ to −13.8 ‰ and from −11.7 ‰ to −8.1 ‰, respectively) of epigenetic calcite and ankerite in the coal indicate their formation from hydrothermal fluids originating from igneous, organic-sedimentary, and, less significantly, marine-carbonate sources. The low 87Sr/86Sr values (0.708556 to 0.708870) and positive Eu anomaly in coal further indicate the influence of hydrothermal fluids. Elevated Sr/Ba ratios (0.9–1.5) and enriched Ca, Fe, and Mg in the lowermost seam section are attributed to the exfiltration of fluids along coal seam boundaries. The fluids probably penetrated the Mesozoic strata of the northeastern Sichuan Basin through fractures connected with the deep-seated detachment faults. This faulting was associated with Palaeo Pacific-Plate subduction and the Yanshanian post-collisional strike-slip movements in the East China region.

New diagenetic constraints for the interpretation of Neoarchaean stromatolitic dolostone geochemical composition and their palaeoenvironmental significance

Abstract The stromatolitic dolostones of the Ramonnedi Formation in the Lower Transvaal Supergroup of Botswana formed along a shallow carbonate platform during the transition between the Archaean and Proterozoic eons. These dolostones are bound to reveal more details of the mechanisms and timing of Earth oxygenation and particularly the role of microbial communities in the formation of carbonate platforms in the Archaean; but only if we are able to discriminate what signature is pristine and what is due to diagenetic overprinting. Here, the focus is on the isotopic composition of stromatolitic dolostone, pyrite grains and chert laminations found within the Ramonnedi Formation. Oxygen and carbon isotopes were investigated from the Ramonnedi Formation stromatolitic dolostones in order to constrain chemo-physical conditions at the time of deposition and, eventually, evaluate to what extent the system was re-set during diagenetic processes. In situ δ34S and δ18O compositions were determined by secondary ionisation mass spectrometry (SIMS) from pyrite and chert, respectively. These novel results complement previous analyses and reveal that: (i) the pyrite grains are not common in the dolostones and when present have sulphur isotope compositions that point toward abiotic formation; (ii) dolostone δ13CVPDB values between -1.2 and -0.7‰ are close to marine values and might reflect pristine Archaean signature; (iii) the dolostone δ18OVPDB values, between -9 and -11‰, on the other hand, might reflect diagenetic resetting or very warm Archaean seawater, in line with the δ18O values from the chert laminae in the upper Ramonnedi Formation. (iv) The correct interpretation of these results has important implications in the interpretation of the geochemical proxies coming from the lower Transvaal Supergroup carbonate platform and for the interpretation of the onset of the Great Oxidation Event (GOE). Aim of this work is to complement the existing data on the Lower Transvaal Supergroup of Botswana and assess to what extent the geochemistry of these dolostone was overprinted during diagenesis/metasomatism. These results indicate that a multi-analytical approach is required to ensure the correct interpretation of geochemical proxy data related to the onset of the GOE.

Home on the range: A multi-isotope investigation of ungulate resource partitioning at Ashfall Fossil Beds, Nebraska, USA

During the Miocene (ca. 23.0–5.3 Ma), North America's Great Plains were a broad mosaic of savanna-woodlands inhabited by a diverse ungulate fauna. We investigated resource partitioning among ungulates at Ashfall Fossil Beds State Historical Park (henceforth “Ashfall”) in north-central Nebraska to establish how taxa shared the landscape. This mid-Miocene (11.86 ± 0.13 Ma) site preserves a watering-hole filled with volcanic ash that entombed hundreds of skeletons of medium- and large-bodied ungulates. We analyzed carbon (δ13C), oxygen (δ18O), and strontium (87Sr/86Sr) isotopes in enamel from seven species: the rhinoceros Teleoceras major (n = 13); three horses (Cormohipparion occidentale, Pliohippus pernix, and Pseudhipparion gratum; n = 3 each); two camels (Procamelus grandis and Protolabis heterodontus; n = 1 each); and one small ruminant artiodactyl (Longirostromeryx wellsi; n = 3). Carbon isotope data indicate that all seven ungulates foraged in open habitats dominated by C3 plants (enamel δ13CVPDB range from −9.6‰ to −6.9‰) with little to no evidence of C4 plant consumption. The overall range in δ18OVPDB values is ca. 6‰ (−7.6‰ to −1.3‰), while the range for 87Sr/86Sr is narrow (0.70864–0.70898). Horses have significantly higher δ18O and 87Sr/86Sr than T. major, which we suggest indicates horses foraged in relatively dry habitats, while T. major inhabited wet habitats with different strontium sources. Both camels isotopically resemble horses, and Longirostromeryx wellsi has intermediate 87Sr/86Sr and wide-ranging δ18O values. Plotting Teleoceras and co-occurring ungulates in a model that tests for semi-aquatic behavior using δ18O suggests that T. major from Ashfall was semi-aquatic; ecology and behavior may have varied among Teleoceras species living in different places at different times. This study exemplifies how 87Sr/86Sr data complement δ13C and δ18O analyses when reconstructing ancient environments; they can provide nuanced ecological information even in landscapes with homogeneous bedrock.

Alteration effects of karstification and hydrothermalism on middle Permian Qixia formation at the Wulong section, South China

Middle Permian Qixia Formation in the southwestern region of Sichuan (SW China) has experienced multiphase fluidisation, resulting in an unclear understanding of the reservoir reconstruction effect. In this study, a systematic analysis of the Qi2 member in Wulong Town was carried out by combining field outcrop petrology and geochemistry. The results demonstrated that multiple sets of crystalline dolomite-bioclastic limestone cycles were stacked vertically in the Qi2 member, accompanied by the development of fractures and karst channels. The dolomite was mainly composed of silty-fine dolomite (D1) and recrystallised dolomite (D2). Furthermore, obvious multiphase dolomitic cements (Cd1-Cd2) were present in the fractures and pores. Early karst is known to have lithologic mutation surface development and karst channel development at the top of several secondary cycles. The vadose silt dolomites (Cd1) having karst channels developed dull luminescence under cathode luminescence (CL). Both the geochemical indicators of elements and rare earth element (REE) content indicated dysoxic-oxic environmental conditions. The hydrothermal solution displayed tectonic carniole characteristics in the strata burial stage. Fractures and pores were filled with hydrothermal minerals such as coarse dolomites-saddle dolomites (Cd2, with some caused by recrystallisation of the Cd1 hydrothermal solution) and fluorites. Coarse dolomites-saddle dolomites developed dull-red luminescence with a bright-red rim under CL and their δ18OVPDB values were more negative than those of middle Permian limestone samples. Both the geochemical indicators of elements and REE content indicated the suboxic-anoxic environmental conditions. Karstification had minor constructive impact on the reservoir of the Qi2 member in Baoxing in southwestern Sichuan. Most products of karstification were distributed as fillings in channels. Aside from creating certain networked fractures, the hydrothermal solution was mainly filled with hydrothermal minerals along the fractures, pores and early karst channels. Karst and the hydrothermal solution mainly damaged the middle and upper parts of the middle Permian Qixia Formation in Southwest Sichuan. The impact of episodic fluid on the restoration of the carbonate reservoir was mainly restricted by channels for fluid migration and thickness differences among the reservoir. However, certain thick-layered and massive crystalline dolomite may hold promise for exploration.

Genesis and Geological Significance of Siderite in the First Member of the Nantun Formation of Dongming Sag, Hailar Basin

Multiple siderite beds developed in the first member of the Lower Cretaceous Nantun Formation (K1n1) in the basin. The results show that the siderites in K1n1 of the study area are mostly stratiform or massive, with three micromorphological features (dense micronized crystals, bands, and paragenesis with quartz and calcite). The siderite beds are mainly composed of siderite, clay, quartz, calcite, and feldspar. Under the microscope, charcoal, algal fossils, granular pyrite crystals, vein-like siliceous bands, etc., were observed. The oxides in the siderite beds include Fe2O3, SiO2, Al2O3, etc. The trace elements are typically characterized by high Mn and Be contents; low Sr/Ba, Th/U, and Al/Ti ratios; and high V/Cr ratios. These indicate weakly reducing, freshwater depositional paleoenvironments. The δ13Cv-PDB and δ18Ov-PDB values of siderite are −0.20–1.11‰ (mean: 0.62‰) and −18.22‰ to −10.14‰ (mean: −14.23‰), respectively, which shows that the carbon in siderite came mainly from carbonate dissolution. The Fe-bearing rocks in the source area migrated to the basin after undergoing physical and chemical weathering, and when the resultant Fe2+ concentration reached saturation, Fe2+ combined with CO32− in the water bodies to form authigenic siderite.

A craton-wide geochemical study of Neoarchaean carbonate rocks of Zimbabwe

Neoarchaean greenstone belts of the Zimbabwe craton host microbialite-bearing limestone successions that range in age from ~2.82 to 2.68 Ga. The best-preserved successions, according to Raman geothermometry, are situated in the Bulawayo and Belingwe greenstone belts where they have been subjected to lower greenschist facies metamorphism with a peak temperature of ~350 °C. Elsewhere, such as in the Masvingo belt, peak temperatures reached ~540 °C, giving rise to marbles. The carbonate rocks consist mainly of calcite and, to a lesser extent, dolomite and contain variably admixtures of siliciclastic detritus. Samples with the least amount of siliciclastic detritus have shale-normalized rare earth element and Y distribution patterns that indicate open marine conditions, with positive La, Eu, and Gd anomalies, superchondritic Y/Ho ratios, and depleted light rare earth elements relative to the heavy rare earth elements. The δ13СVPDB values are −2.0 to 2.1 ‰, and δ18OVPDB values cluster in the range of −20 to −10 ‰. Strontium isotope ratios vary in concert with siliciclastic detritus. The lowest initial 87Sr/86Sr ratio of 0.70155 is close to the depleted mantle value at the time of deposition, suggesting minimal contribution from evolved felsic crust to the Neoarchean ocean. Only samples from the Masvingo belt show radiogenic Sr isotope ratios (0.70202–0.70340) indicative of an epicratonic setting with exposed felsic basement. For the rest, open marine conditions prevailed in a proto-cratonic setting characterized by mantle-derived greenstone volcanism. Carbonate sedimentation on the Zimbabwe craton thus predate the fundamental rise in the marine 87Sr/86Sr Sr isotope signal in the late Neoarchaean.

Meteoric Water Incursion, Crude Oil Degradation and Calcite Cementation of an Upper Cretaceous Reservoir in the Zagros Foreland Basin (Kurdistan Region of Iraq)

Field observations, together with the results of gas chromatography–mass spectrometry (GC-MS) and stable carbon isotope analysis of bitumen, coupled with fluid inclusion microthermometry and stable isotope analyses of closely associated vug- and fracture-filling columnar calcite in the Upper Cretaceous Bekhme Formation, Kurdistan Region of Iraq, suggest that the degradation of crude oil was caused by the regional incursion of meteoric waters. This incursion, which is interpreted to have occurred during tectonic uplift during the Zagros Orogeny, is evidenced by: (i) the depletion of n-alkanes and acyclic isoprenoid alkanes (pristane and phytane) in the bitumen; (ii) low δ13CVPDB values (−8.5‰ to −3.9‰) and δ18OVPDB values (−22.9‰ to −15.0‰), with more radiogenic Sr isotopic ratios (0.70771–0.70772) compared to Cretaceous seawater; and (iii) low salinity and low temperatures (20 to 40 °C) in fluid inclusions of the columnar calcite. This study demonstrates that regional meteoric water incursion into sedimentary basins can be linked to crude oil degradation accompanied by calcite cementation events in carbonate reservoirs.

Impact of meteoric water flushing on diagenesis of deep-marine turbidite sandstones: A case study from the Tertiary sandstones of Frigg and Grane fields, northern North sea

Meteoric water flushing into deep-marine environments is a topic of debate since the actual transport mechanism remains elusive. In order to evaluate the potential impact of meteoric water on early diagenesis of deep-marine sandstones, two submarine fan sandstone reservoirs, the Eocene Frigg (Frigg oilfield) and the Palaeocene Heimdal (Grane field) that have the same source area, were compared and contrasted. Petrographic studies reveal that both sandstone reservoirs are at the eodiagenesis stage (<70 °C) at the present day. However, the Eocene Frigg sandstones are characterized by geological features suggestive of potential meteoric water diagenesis, such as dissolution and kaolinization of the silicate grains, whereas the Palaeocene Heimdal sandstones show negligible alteration. The δ13CV-PDB and δ18OV-PDB values of siderites in the Eocene Frigg sandstones range from +5.2‰ to +16.7‰, and from −8.2‰ to −6.6‰, respectively, indicating siderite formation during methanogenesis in meteoric pore water. Results from generic hydrogeochemical modelling scenarios lend further support to the hypothesis of meteoric water flushing. Thus, we suggest that massive meteoric water might have been brought into the Frigg turbidite sands by basinward migration of the meteoric water. This occurred because the East Shetland Platform experienced two stages of relative sea-level fall (during and at the end of the Eocene, Priabonian), and flushing might have taken place via connected incised canyons. The location of the Frigg sands deposited immediately below the Shetland escarpment and the narrow palaeo-shelf area may have facilitated such meteoric water incursions. Our study suggests meteoric water intrusions as a possible diagenetic control of deep-marine sandstones, and, therefore, meteoric water diagenesis should be considered in the prediction of properties of deep-marine sandstone reservoirs.

The origin of Ediacaran phosphogenesis event: New insights from Doushantuo Formation in the Danzhai phosphorite deposit, South China

The Ediacaran-early Cambrian period is not only the key period of global climate and life evolution, but also recorded the occurrence of the second large-scale phosphogenesis event in history of the Earth. South China records a large number of phosphorus-forming events of that period, which the late Ediacaran Doushantuo Formation (Doushantuo Fm.) is the most important example. Although the Ediacaran Doushantuo Fm. of China contains only 5 % of global reserves, it accounts for 45 % of the world’s phosphorous (P) production. Therefore, the study on the formation of phosphorite in the Ediacaran Doushantuo Fm., South China will help in our better understanding of the role of the phosphorus-forming event in that period. Here, we present a detailed study of geology, petrology, and geochemistry and CO isotopes of the Doushantuo Fm. phosphorite, shale and dolomite samples at Danzhai, southwest Guizhou. The rare earth element + Y (REY) signature of phosphorites display a “hat-shaped” post-Archean Australian Shale (PAAS)-normalized REY distributions, with systematically lower Ce/Ce* ranging from −0.56 to −0.60 (average −0.58, n = 4). The δ13CVPDB δ18OVPDB and δ18OV-SMOW values range from −12.88 to 4.39 ‰, −10.3–7.18 ‰, and 20.29 – 23.51 ‰, respectively. Our field, petrologic, geochemical and isotopic data suggest that: (1) The ore-forming materials of the Danzhai phosphorite deposit may have an input of marine hydrothermal and the organic-rich water brought by up-welling; (2) The Ce/Ce* and pyrite speciation data suggest that the Danzhai phosphorite deposit was formed in a suboxic-oxic conditon; (3) The phosphogenesis of the late Doushantuo phosphate deposit is mainly the result of growth and mineralization of microorganisms, accompanied by the mechanical dynamic action of seawater.

Comparison of diagenesis and reservoir quality of microporous lime mudstones (Aptian) between anticline crest and flanks: Abu Dhabi, United Arab Emirates

The impact of in-situ and migrated oil on diagenesis and reservoir quality of microporous (porosity ≤ nil to 26%; permeability ≤ nil to 3 mD) intra-shelf basinal lime mudstones (Aptian) is constrained by comparing samples from anticline crest (i.e. oil zone) versus flanks (i.e. water zone), Abu Dhabi, United Arab Emirates. Higher porosity and permeability and larger pore-throat radii in the crest than in the flank mudstones is attributed to retardation of calcite cementation in the crest due to oil emplacement. Calcite cement has precipitated as syntaxial micro-overgrowths around micrite particles and as equant microspar in moldic pores and small vugs. Deviation of a large number of samples from this crest versus flanks porosity and permeability trend reflects the impact of other parameters, including: (i) subtle grain-size variations (ii) proportion of intact (i.e. with intragranular pores), versus broken coccolith tests, and (ii) degree of calcite cementation. Calcite cement was sourced by stylolitization of the limestones, which is more frequent and extensive in the flanks than in the crest. Similar bulk δ18OVPDB values of calcite in the crest (−7.3‰ to −4.6‰) and flanks (−6.9‰ to −5.5‰) is attributed to closed diagenetic system in the microporous mudstones, which masks the role of burial temperature in fractionation of oxygen isotopes during continued cementation of the water-saturated flank mudstones. The presence of miscellaneous saddle dolomite in the crest and flanks is attributed to the field-wide flow of hot basinal fluids along fractures and stylolites. A conceptual model unravelling the diagenetic and related reservoir-quality evolution pathways of mudstones across an oilfield anticline has been developed. This model has important implications for exploration of tight hydrocarbon reservoirs and improves our understanding of oil migration and emplacement in source rocks.

Carbonate clumped isotope analysis using isotope dilution

The large sample size requirement is a major obstacle while conducting the measurement of isotopic abundances in carbonates for clumped isotope thermometry using MAT 253 isotope ratio mass spectrometer employing McCrea type setup or improved break-seal method at a reaction temperature of 25 °C. A long integration time at high (∼10000 mV) major ion beam intensity permits the highest analytical precision but requires a large sample size for CO2. However, in several instances, carbonate availability is restricted in the natural environment like foraminifera, otoliths, ostracods, etc., in sediment cores, prohibiting the application of the thermometry. Here we introduce a new isotope dilution method for stable and clumped isotope analysis for small size carbonates at a precision of ±0.005‰. In this method, two reference carbonate materials (MAR J1 and OMC) are quantitatively mixed with known proportions or weight fractions. The high-temperature reference carbonate (MAR J1) is treated as a spike end member, whereas the low-temperature carbonate reference is considered as unknown. The spike is identified based on similarity in mineralogy with the sample and well-defined isotopic composition as constrained by its formation temperature. These two carbonates used here are internal laboratory standards and are homogeneous, independently ascertained based on long-term reproducibility of δ13CVPDB and δ18OVPDB values lying within 0.002‰ and 0.003‰ respectively. These two reference carbonate powders have δ13CVPDB and δ18OVPDB values, which differ from each other by ∼6.3‰. The Δ47 values of these carbonates are 0.395‰ and 0.587‰, respectively. In our experiment, we observe a linear relationship governing δ13CVPDB and δ18OVPDB values of a mixture with a known weight fraction; however, Δ47 values follow a non-linear mixing trend upon exceeding the weight fraction ≥0.4 of the low-temperature carbonate (OMC). The linear trend allows the prediction of the Δ47 value of the unknown carbonate powders using a binary mixing model within an acceptable precision of 0.01–0.02‰ necessary for clumped isotope measurement. This new approach provides an alternative method of analyzing small size (∼3 mg) carbonate powder extending the application of the break-seal method for analysis at major ion beam intensity of 10000 mV. Here we demonstrate the application of this method for accurate determination of both stable and clumped isotopic composition of various low-temperature carbonates, including a deep-sea coral, an otolith, and ETH-3 reference carbonate.

Study on the origin and hydrocarbon generation potential of lacustrine organic-rich dolomite affected by volcanism: A case study of Lucaogou Formation in the Malang Sag, Santanghu Basin, Western China

Lacustrine organic-rich laminated dolomites are widespread in the Permian Lucaogou Formation (P2l) of the Santanghu Basin. However, the origin of the dolomites remains controversial due to the influence of volcanism and complex sedimentary environment. Therefore, a composite analysis of mineralogical and geochemical is utilized to study the origin and hydrocarbon generation potential of the P2l dolomite. The results showed that the P2l dolomite was the product of penecontemporaneous dolomitization, burial dolomitization, and local hydrothermal dolomitization. The evidence was as follows: (1) Under microscopy, a large number of dolomites had obvious trigonal rhomboid and zonal structure, indicating the existence of metasomatism. Besides, the P2l was characterized by an arid climate, suboxic-anoxic condition, and high salinity of the lake, with some evaporite minerals and low-order degree of the dolomite (0.4–0.6), which suggested that the dolomite was formed by penecontemporaneous rapid crystallization; (2) Part of the dolomites were characterized by a high content of Fe2+ and Mn2+, a moderately positive excursion of δ13CV-PDB values (2–12‰, avg. 7.4‰), a negative excursion of δ18OV-PDB values (−20 to −2.3‰, avg. −10.6‰), a high-order degree (0.7–0.8), a positive anomaly of Eu, and a certain enrichment of light rare earth elements (LREEs), indicating that it was caused by burial dolomitization; (3) Most of the dolomites were ankerite, and the speckled dolomite and veins were mostly developed near the fault zone, with a lower value of δ18OV-PDB (<−8‰), an obvious positive anomaly of Eu (1.01–1.68, avg. 1.28), and an obvious enrichment of LREEs, indicating a higher formation temperature. A large number of algal blooms caused by volcanic ash led to a high abundance of organic matter (OM) in the P2l dolomites, with total organic carbon (TOC) values ranging from 0.8 to 7.3% (avg. 2.7%). The lower limits of the TOC of the P2l dolomite as an effective source rock were determined to be 2.1%. Moreover, the hydrocarbon potential of the P2l dolomite, with abundant oil-prone OM (Type I and II1 kerogen with hydrogen index (HI) values ranging from 142 to 975 mg/g) in the stage of early mature to mature (Peak temperature of pyrolytic hydrocarbon peak (Tmax) and vitrinite reflectance (Ro) values ranging from 430 to 451 °C and 0.3–0.96%, respectively), is considerable. The values of the oil saturation index (OSIS1/TOC × 100) are 6.1–479 mg/g (avg. 59 mg/g), indicating that the P2l dolomite contains producible oil. High contents of brittle minerals and TOC, and traces of clay minerals show that the P2l holds a significant hydrocarbon generation potential.

Diagenetic evolution and its impact on reservoir porosity in Lower Triassic Jialingjiang Formation in eastern Sichuan Basin, SW China: Evidence from petrography, trace elements, and Isotopic Studies

The Lower Triassic Jialingjiang Formation, characterised by a carbonate–evaporite succession, is one of the important pay layers in the eastern Sichuan Basin. Several diagenetic events were identified in this study, including meteoric dissolution, dolomitisation, anhydrite/gypsum replacement/cementation, TSR, BSR, and multiple calcite cementation (C1–C3). Dolomitisation and anhydrite/gypsum replacement/cementation are the major diagenetic events affecting reservoir porosity. The dolostone is composed of D1, D2, and D3 dolomite. D1 dolomite is very finely crystalline, dominating in the low-energy, restricted depositional facies. D2 dolomite is finely crystalline, constituting a major portion of the dolostones. D3 dolomite is depositional fabric retentive dolomite, including dolo-wacke-/packstone, dolo-grainstone, and dolo-boundstone. Four types of anhydrites (A1–A4) were identified in the core and thin sections. A1 is stratabound anhydrite. A2 is the anhydrite in dolostones, filling in the interparticle spaces in dolo-grainstone and the intraparticle spaces in dolo-wackestone. A3 is the anhydrite in limestones, which occurs non-fabric-selectively. A4 is the anhydrite filling in the fractures. The diagenetic anhydrites (A2–A4) are interpreted to postdate to major dolomitisation. D1 and D2 dolomites are characterised by δ13CVPDB values of −3.4–+7.3 ‰ and δ18OVPDB values of −4.7−-2.4 ‰. The REE patterns of D1–D3 dolomites are characterised by light rare earth element (LREE) depletion relative to heavy rare earth elements (HREE) ((Pr/Tm)N of 0.54–1.16, 0.81 ± 0.20), middle rare earth elements (MREE) enrichment (BSI values of 1.06–1.38, 1.26 ± 0.10), and negative Ce anomalies (Ce/Ce* ratios of 0.74–0.94, 0.83 ± 0.07). The diagenetic anhydrites (A2–A4) show δ34SV-CDT values of +25.9–+45.7 ‰, similar to those of the stratabound anhydrite (+29.6–+43.0 ‰). The large variations in the δ13CVPDB values of D1 and D2 dolomites are attributed to methanogenesis and BSR. The δ18OVPDB values and REE characteristics of D1–D3 dolomites suggest that the carbonates are dolomitised by the mesohaline fluid. The δ34SV-CDT values of A1–A4 indicate that the diagenetic anhydrites are formed by redistribution in a closed system. The petrographical and geochemical data suggest that the Jialingjiang carbonate evolved in a closed system during burial diagenesis. Primary pores dominate in the Jialingjiang carbonate reservoirs, and the boundstone and grainstone show the best porosities based on the porosityversus lithofacies data. Therefore, we propose that the lithofacies, instead of the diagenetic events, are the key factors of the Jialingjiang carbonate. The resisting compaction of dolomitisation helps preserve the reservoir porosity, and anhydrite is the major diagenetic event destroying the reservoir porosity.

Petrography and Geochemistry of Dolomites of Samanasuk Formation, Dara Adam Khel Section, Kohat Ranges, Pakistan

Replacement dolomite occurs in Jurassic Samanasuk Formation in Dara Adam khel area of Kohat ranges, North-Western Himalayas, Pakistan. This study, for the first time, document the process of dolomitization and evolution of strata bound dolomitic bodies. Field investigation, petrography and geochemistry helped in unraveling the formation of several dolomitic bodies. Petrographically dolomites comprises of: (1) medium grain crystalline planer subhedral dolomite (Dol-I); (2) fine grained crystalline anhedral non-planer dolomite rhombs (Dol-II); (3) medium to coarse grained crystalline subhedral-anhedral non-planer dolomite (Dol-III) and coarse to very coarse grained crystalline saddle dolomite cements (SD). The saddle dolomites (SD) postdate the replacement dolomites and precede telogenetic calcite (TC) cements. Stable O and C isotope analysis shows that these dolomites have δ18Ovpdb ranging from -4.09% to -10.4 whereas the δ13Cvpdb ranges from +0.8 to +2.51. Major and trace elements data show that Sr concentrations of 145.5 to 173 ppm; Fe contents of 2198 to 8215 ppm; and Mn contents of 93.5 to 411 ppm. Petrographically replacive dolomites, saddle dolomite, and δ18Ovpdb values depicts neomorphism of replacement dolomites that were formed earlier were exposed to late dolomitizing fluids. As a result of basin uplift during the Himalayan orogeny in Eocene time, dolomitization event was stopped through occurrence of meteoric water. The Main Boundary Thrust (MBT) and its splays were most likely essential conduits that channelized dolomitizing fluids from siliciclastic rocks that were buried deeply into the Jurassic carbonates rocks, leading to more extreme dolomitization.

Tracking the Origin and Evolution of Diagenetic Fluids of Upper Jurassic Carbonate Rocks in the Zagros Thrust Fold Belt, NE-Iraq

Utilizing sophisticated tools in carbonate rocks is crucial to interpretating the origin and evolution of diagenetic fluids from the Upper Jurassic carbonate rocks along the Zagros thrust-fold Belt. The origin and evolution of the paleofluids utilizing in-situ strontium isotope ratios by high resolution laser ablation ICP-MS, integrated with stable isotopes, petrography and fieldwork are constrained. Due to the lack of information on the origin of the chemistry of the fluids, the cements that filled the Jurassic carbonate rocks were analysed from the fractures and pores. This allowed us to trace the origin of fluids along a diagenetic sequence, which is defined at the beginning from the sediment deposition (pristine facies). Based on petrography and geochemistry (oxygen-, carbon- and strontium-isotope compositions) two major diagenetic stages involving the fluids were identified. The initial stage, characterized by negative δ13CVPDB values (reaching −10.67‰), involved evaporated seawater deposited with the sediments, mixed with the input of freshwater. The second stage involved a mixture of meteoric water and hot fluids that precipitated as late diagenetic cements. The late diagenetic cements have higher depleted O–C isotope compositions compared to seawater. The diagenetic cements display a positive covariance and were associated with extra- δ13CVPDB and δ18OVPDB values (−12.87‰ to −0.82‰ for δ18OVPDB and −11.66‰ to −1.40‰ for δ13CVPDB respectively). The distinction between seawater and the secondary fluids is also evident in the 87Sr/86Sr of the host limestone versus cements. The limestones have 87Sr/86Sr up to 0.72859, indicative of riverine input, while the cements have 87Sr/86Sr of (0.70772), indicative of hot fluid circulation interacting with meteoric water during late diagenesis.

Early-stage marine dolomite altered by hydrothermal fluids in the Middle Permian Maokou Formation in the eastern Sichuan Basin, Southern China

Deciphering the dolomitization process is the key to understanding the formation of massive dolostones on shallow-marine platforms, it also improves our understanding of dolostone reservoirs. Hydrothermal fluids are suggested to be a potential mechanism for dolomitization; however, determining whether hydrothermal fluids are responsible for dolomitization or the recrystallization of an early dolostones is poorly understood. The dolomite of Maokou Formation (Guadalupain) in the eastern part of the Sichuan Basin is a good case study on the hydrothermal dolomitization and recrystallization. Based on petrographic observation, the massive dolostone (MD) consists of fine-crystalline dolomite (D1), fine to medium crystalline dolomite (D2) and coarse-crystalline dolomite (D3), and the patchy dolostone (PD) which is composed of medium to coarse dolomite with an euhedral to subhedral texture. Since the fine-crystalline dolomite is cross-cut by low amplitude stylolites, and is composed of euhedral dolomite with a dull red luminescence, dolomitization is interpreted to have occurred in near surface condition. While the Fe, Mn, and ∑REE concentrations, δ13CVPDB values, 87Sr/86Sr ratios, and REE Pattern of D1 are comparable to those of the coexisting limestone, and the δ18OVPDB values are slightly higher than that of the coeval limestone, indicating that the dolomitization fluid of D1 was derived from Middle Permian seawater. In contrast, zebra fabrics and saddle dolomites are common in D2 and D3, and their geochemical characteristics and cathluminescence are quite different from those of D1 but they are similar to those of the saddle dolomites. Besides, the fluid inclusions in D2 and D3 have high homogenization temperatures and salinities, which are also similar to those of the saddle dolomite. Moreover, the D2 shows an inequigranular texture, and there are no obvious boundaries between D1, D2 and D3. Therefore, the D2 and D3 were recrystallized upon D1 by hydrothermal fluids related to the Emeishan magmatism. The patchy dolostone exhibits a non-stoichiometric composition and low degree of cation ordering, suggests rapid and incomplete dolomitization. The dolomitization of PD is interpreted to be the replacement caused by hydrothermal fluids as the PD exhibits negative δ18OVPDB values, high homogenization temperatures and salinity, positive Eu anomalies and REE Patterns similar to those of the saddle dolomites. The porosity and stoichiometry of the D1 are higher and lower, respectively, than those of D2 and D3, and the vugs are almost entirely filled. Thus, the hydrothermal fluids were destructive for the formation of the dolostone reservoir of Maokou Formation in the study area.

Floating boat method for carbonate stable isotopic ratio determination in a GasBench II peripheral.

Efficient high-precision stable isotope ratio determination using the GasBench II peripheral for carbonates involves loading of a reaction vial with carbonate powder and injection of phosphoric acid of high density for carbonate digestion. Herein, we present an alternative method, which bypasses the need for acid dosing with an automated pump. The advantages of the new method include minimization of clogging within capillaries caused by the acid, acid spillage, and diffusive fractionation due to repeated piercing of the septa. The alternative method involves the use of low-cost boats preloaded with carbonate powder introduced into an Exetainer vial preinjected with phosphoric acid and placed within the compartment of a heated block maintained at a constant temperature in the GasBench II. The new method yielded an improvement in precision for δ13 CVPDB and δ18 OVPDB values during replicate analyses of NBS 19, with an overall precision of ±0.04‰ and ±0.06‰, respectively. The accuracy and precision of analysis using the conventional method and the floating boat method were statistically re-evaluated using a bootstrap error analysis and Monte Carlo simulation methods. The proposed floating boat method of acid digestion showed significant improvement in analytical procedure and overall precision. This method is easily adoptable in other laboratories and is free from frequent issues of needle clogging and irregular fractionation due to diffusion facilitated by repeated puncturing of septa, and can serve as an alternative method for high-precision carbonate stable isotope analysis.

Holocene Lake Evolution and Glacial Fluctuations Indicated by Carbonate Minerals and Their Isotopic Compositions in the Sediments of a Glacial Melt Recharge Lake on the Northwestern Tibetan Plateau

Lakes and glaciers are widely distributed on the Tibetan Plateau and are linked via hydrological processes. They are experiencing rapid changes due to global warming, but their relationships during the Holocene are less well known due to limited coupled geological records. Here, we analyzed the δ13C-VPDB and δ18O-VPDB values and ion content of calcite and aragonite in a 407-cm-long sediment core from Guozha Co, a closed basin on the northwestern Tibetan Plateau supplied by glacial meltwater, in order to understand how the lake responded to glacier changes during the Holocene. Our results indicate that the glacial meltwater lowered the lake’s temperature and the δ18Olake water and δ18Oendogenic + authigenic carbonate values and diluted the ion concentrations in the lake water. Three stages of evolution, 8.7–4.0, 4.0–1.5, and 1.5 kyr BP to present, are distinguished based on the decrease in glacial meltwater recharge. Guozha Co has been a closed basin since at least 8.7 kyr BP, and it has changed from a fresh water lake during 8.7–1.5 kyr BP to a brackish lake from 1.5 kyr BP to present due to several climate events. The famous 4.2 kyr BP cold event was identified in the core at 4.0 kyr BP, while warm events occurred at 6.2, 3.9, 2.2, 0.9, and 0.4 kyr BP. Both glaciers and lakes in this area are controlled by climate, but they exhibit opposite changes, that is, glaciers retreat and lakes expand, and vice versa. Our results provide an accurate interpretation of the cold events based on carbonate minerals and carbon–oxygen isotopes in glacial meltwater–recharged lake sediments.

Stable isotope geochemistry of the modern Shinfa River, northwestern Ethiopian lowlands: a potential model for interpreting ancient environments of the Middle Stone Age

Abstract Several years of weekly sampling of waters from the Shinfa River watershed in the lowlands of northwestern Ethiopia yielded 275 samples with δ D vsmow and δ 18 O vsmow values ranging from c. −10 to +100‰ and from c. −2 to +20‰, respectively. Wet season (summertime) Shinfa River water stable hydrogen and oxygen isotope values are among the lowest reported in this study, whereas the dry season (winter/spring) usually records a progressive trend towards +100 and +20‰, respectively. Overlapping with this interval of Shinfa River water sampling, air temperatures ( n = 155) also were recorded at the same time; temperatures range from c. 18 to 47°C. The coolest temperatures occur during the summer wet season, associated with the arrival of the Kiremt rains in the region, whereas the warmest temperatures occur towards the end of the dry season. In order to evaluate the extent to which this rather extreme isotope hydrology is recorded in the sediments and biota of the Shinfa River system, both hardwater calcareous deposits precipitated on basalt cobbles by evaporation in the Shinfa River channel during the dry season and aragonite from three different modern bivalve mollusc species were collected and analysed for their stable oxygen and carbon isotope compositions. Hardwater calcareous deposit δ 18 O vpdb and δ 13 C vpdb values range from c. −2 to +5‰ and c. −9 to +7‰, respectively, and preserve a trend towards progressively more positive δ 18 O vpdb and δ 13 C vpdb values through the course of the dry season. Shinfa River mollusc aragonite powders ( n = 51) were serially sampled from cf. Coelutura aegyptica , cf. Chambardia rubens and Etheria elliptica species. All species record oxygen and carbon isotopes between c. −2 and +7‰ and between c. −18 and −8‰, and each species records coherent trends between those extremes as well as a positive parametric correlation between measured oxygen and carbon isotope values. However, there does appear to be some variability of measured isotope values by species, suggesting that species-specific metabolic differences may impact the resulting range of aragonite stable carbon and oxygen values. Based upon the measured Shinfa River water δ 18 O vsmow and corresponding water temperatures at the time of sampling, a possible range of Shinfa River calcite and aragonite δ 18 O vpdb values were calculated in conjunction with well-established calcite–water and aragonite–water oxygen isotope fractionation equations. These ‘fictive’ calcite and aragonite δ 18 O vpdb values range from c. −5 to +15‰, which is a much larger range than previously documented from analyses of the hardwater calcareous deposits and mollusc aragonite samples. The narrower range of values in the natural calcite and aragonite samples may be attributed to several mechanisms, including time averaging and environmental stress. Nevertheless, the stable oxygen isotopic compositions of these natural samples offer a minimum assessment of the environmental extremes which occur in this region today, and provide a model for reconstructing the environments of the past.

Fossil, ichnofossil, or concretion: The enigma of “Dinocochlea ingens”

The misidentification of biomimetic or biomorphic structures (especially helical forms) as biogenic can lead to serious errors in the interpretation of depositional environments and stratigraphic relationships, and in the detection of primitive life. “Dinocochlea ingens” was originally described as a giant gastropod and recently has been interpreted as a diagenetically-modified ichnofossil, based on dextral- and sinistral-twist bodies reported from the Lower Cretaceous Wadhurst Clay Formation, near Hastings, Sussex, United Kingdom. Morphologically similar decimeter- to meter-scale helical concretions occur with spheroidal and macrobotryoidal concretions in the shale of the Ikalukrok unit in the upper part of the Mississippian Kuna Formation that hosts the Red Dog Mine in northwestern Alaska. The mineral assemblages of both the helical and spheroidal concretions at Ikalukrok Creek are identical. The calcite of these concretions consists of cm-scale radiating aggregates of elongate poikilotopic crystals; this texture is megaspherulitic. The calcite has a relatively narrow range of δ13CVDPB values between 1.9‰ to 3.0‰ and δ18OVPDB values from −5.9‰ to −8.0‰. Growth of the concretions is considered to be pre-compaction because there is no evidence of internal layering, or inclusions of the host shale, despite their preservation of numerous microfossils. There is no indication of a causative small-scale burrow or of large-scale burrows. Analogy with laboratory syntheses of biomimetic carbonates suggests that the megaspherulitic texture of the helical and spheroidal concretions probably resulted from crystallization under strong driving forces such as high supersaturation.