Calcite δ13C Research Articles

Petrological, mineralogical, carbonate C-O and sulfide S isotope study of the Bayinqinggeli sandstone-hosted uranium deposit in the northern Ordos Basin

Many sandstone-hosted uranium deposits have been discovered in the northern Ordos Basin, including the Bayinqinggeli deposit, exhibiting tremendous potential for uranium exploration and prospecting. This region is characterized by complex fluid activities, yet unknowns or controversies still exist regarding the source and properties of the fluids and their influence on uranium mineralization. In this study, we employed optical and scanning electron microscopy (SEM), X-ray diffraction (XRD), micro X-ray fluorescence (μ-XRF), C-O isotope of calcite, and in situ S isotope of pyrite, to investigate the genesis and evolution of the Bayinqinggeli deposit. Pyrite and calcite are closely associated with uranium minerals, and all exhibit distinct characteristics in rocks of varying grades. In high-grade mineralized rocks, ore-related pyrite, characterized by euhedral and colloidal forms, mainly predated uranium mineralization, evidenced by the extensive coffinite replacement. The mostly negative δ34S values with a broad range (−24.6 ‰ to 23.9 ‰; mean = −4.2 ‰) point to microbial sulfate reduction under restricted conditions. In low-grade and barren rocks, pyrite unrelated to mineralization, mainly as large granular or colloidal cement, shows generally positive δ34S values with a wide range (−49.5 ‰ to 67.4 ‰; mean = 15.3 ‰). This suggests the involvement of both biological and abiological processes during different stages, with the latter possibly associated with deep-sourced fluids. Considering the heterogeneous isotope compositions of sulfur in pyrite and carbon in calcite (δ13C ranging from −21.4 ‰ to −4.9 ‰), it can be deduced that the deposit was strongly affected by two types of fluids: (1) surface oxidizing fluids and (2) deep reducing fluids. The mineralizing fluids were derived from oxidizing surface water, which dissolved uranium ions, carbonates, and sulfates from weathered source rocks and during infiltration through the sandstone, resulting in the formation of abundant uranium minerals and associated pyrite and calcite. The presence of low δ13C calcite further corroborates the influence of deep hydrocarbon-bearing fluids, which played a protective role in post-ore stage preservation, corresponding to the widespread green alteration in the Lower Zhiluo formation. Overall, the development of sandstone-hosted uranium deposits is a continuous and progressive process, with early-formed mineralization being transformed by late-stage fluid events. Calcite has a significant impact on the formation, development, and extraction of uranium ores in the deposit, protecting the paleo-orebodies against remobilization and remigration. A significant portion of uranium ore is preserved by calcite cementation. Therefore, the careful management of carbonates during in situ leaching is essential for the effective extraction of uranium from the host sandstones.

Links between anhydrite precipitation and dolomitization during cycles of sea level change: Insights from the Late Jurassic Arab Formation, Abu Dhabi, United Arab Emirates

Despite extensive research in the field of evaporative dolomitization, the close link between anhydrite precipitation and dolomitization is still poorly explored within the context of sequence stratigraphy. This comprehensive diagenetic and sequence stratigraphic study of the Late Jurassic Arab Formation, Abu Dhabi, United Arab Emirates, provides important insights into the relationship between anhydrite precipitation and dolomitization within the 2nd, 3rd, and 4th orders of relative sea-level cycles. Initial good connectivity between the inner ramp and open sea during 2nd order late transgressive-early regression cycles accounts for the limestone-dominated lithology with limited anhydrite formation. Conversely, the following progressive 2nd order fall in the relative periodic restriction of the inner platform during 2nd order early regressive cycles (early highstand systems tracts, HST) caused seepage reflux dolomitization and the precipitation of scattered to pervasive anhydrite cement in the dolostones. Variations in the extent of dolomitization were controlled by the permeability and reactivity of the precursor limestones, resulting in the formation of what is known as dolomite fingers. The most laterally extensive dolomitization during late 2nd order regression resulted in the formation of microcrystalline dolostones with nodular and chickenwire anhydrite by a combination of evaporative sabkha pumping and the seepage reflux of lagoon brines. The δ1³C and δ1⁸O of calcite and dolomite reveal the influence of degree of restriction of the inner ramp, and related extent of seawater evaporation. The lower limestone-dominated interval (3rd order HST) is characterized by lower δ1³C values (+2.0‰ to +2.5‰) owing to periodic restriction of seawater circulation, which resulted in oxidation of organic matter during aging of the seawater. This study approach provides important insights into the genetic links between interbedded platform limestones, dolostones, and anhydrites, and hence a better understanding and prediction of reservoir quality distribution and compartmentalization.

Dual pathways of aragonite-to-calcite transformation in stalagmites: Implications for paleoclimate reconstructions

Multiple geochemical proxies (e.g., trace elements, δ18O and δ13C) and precise 230Th ages in speleothems are crucial for conducting robust paleoclimatic reconstructions, but the impact of diagenesis on these proxies and 230Th ages is not well-established. In this study, we investigate the petrography and geochemical composition of six aragonite-calcite stalagmites from Shennong Cave in southeastern China to analyze the transformation from aragonite to calcite (primary versus secondary) and its effects on geochemical proxies and 230Th ages. No aragonite relics are observed in columnar calcite in four aragonite-calcite stalagmites (SN55, SN49, SN104 and SNB1), although traces of aragonite exist between the calcite crystals or grow parallel at the aragonite-calcite borders. This is different from the obvious aragonite relics preserved in secondary mosaic calcite in the other two aragonite-calcite stalagmites (SN3 and SN15). Both mosaic and columnar calcite show various changes in geochemical proxies and 230Th ages compared with primary aragonite. The trend in the geochemical proxies analyzed (trace elements, δ18O and δ13C) of columnar calcite remains consistent with those of aragonite, despite significant differences in their absolute values within the overlapping periods. These differences are due to the different fractionation coefficients of isotopes and trace elements in aragonite and calcite formed under the same solution conditions rather than late diagenesis. The 230Th ages of columnar calcite are similar to those of primary aragonite, and the values of subsamples from the same calcite layer are consistent. In contrast, the trace elements and δ13C values of mosaic calcite are similar to those of primary aragonite, while its 230Th age significantly differs from that of primary aragonite, exhibiting no consistent patterns. Therefore, these geochemical characteristics of columnar calcite are significantly different from secondary mosaic calcite, indicating that the columnar calcite in these four aragonite-calcite stalagmites is primary. A comparison of trace elements and δ13C records between aragonite-calcite and pure aragonite stalagmites during the overlapping period further confirms that these columnar calcites are primary. Their geochemical proxies can be used for paleoclimate reconstruction after careful evaluation, and the transformation from aragonite to columnar calcite is caused by increased precipitation. However, due to age and geochemical proxies change, secondary mosaic calcite is unsuitable for paleoclimate reconstruction, unlike columnar calcite. This study provides competent evidence to identify whether calcite in aragonite-calcite stalagmites is primary versus secondary and whether it can be used for paleoclimatic reconstruction.

Authigenic carbonate and native sulfur formation in Messinian (upper Miocene) marine sediments: Sedimentological, petrographical and geochemical constraints

Carbonate concretions accompanied by elemental sulfur were found in an early Messinian (Late Miocene) marine succession of NW Italy. The rocks were studied with an integrated approach including sedimentological, petrographical, stable isotope (carbon, oxygen, and multiple sulfur isotopes), and lipid biomarker analyses. Unlike other examples from Messinian strata of the Mediterranean area, the studied carbonate and sulfur concretions did not derive from the diagenetic replacement of sulfate minerals. Three lithofacies were distinguished: a) laminated lithofacies representing aphotic carbonate stromatolites enclosing fossils of filamentous sulfide-oxidizing bacteria; b) brecciated lithofacies deriving from the brecciation of carbonate stromatolites by mud injections; c) sulfur-bearing lithofacies deriving from the precipitation of thin laminae of elemental sulfur at or close to the sediment-water interface. The carbon and oxygen stable isotope composition of authigenic carbonate minerals and lipid biomarkers indicate that the initial formation of the laminated lithofacies was favored by organoclastic sulfate reduction in the shallow subsurface close to the sediment-water interface, producing sulfide that sustained dense microbial mats of sulfide-oxidizing bacteria at the seafloor. Calcification of the mats and consequent formation of stromatolites were possibly favored by nitrate-driven sulfide oxidation at the seafloor. The subsequent brecciation of the stromatolites was apparently the consequence of sulfate-driven anaerobic oxidation of methane (SD-AOM) in an underlying sulfate-methane transition zone (SMTZ). Focused fluid flow from below, possibly resulting from destabilization of gas hydrates, was not only responsible for the brecciation of the stromatolites, but also for the delivery of bicarbonate ions and the consequent precipitation of additional, 13C-depleted calcite (δ13C values as low as −52‰). Along with bicarbonate, also hydrogen sulfide was produced by SD-AOM at the SMTZ and was transported upwards. The oxidation of hydrogen sulfide at or close to the seafloor promoted the formation of elemental sulfur characterized by δ34S values and Δ33S values close to coeval seawater sulfate.

The effect of cave ventilation on carbon and oxygen isotopic fractionation between calcite and drip water

Rapid CO2 degassing and calcite precipitation driven by cave ventilation influence the speleothem δ18O and δ13C. However, the drivers of cave ventilation are not completely understood due to the lack of monitoring of multiple environmental factors. Furthermore, the understanding of isotope fractionation caused by the dissolution of speleothem in undersaturated drip water is limited during the cave air stagnation. In this study, we displayed four years of cave microenvironment monitoring in Shawan Cave, Southwestern China, and analyzed the δ13CDIC and δ18O of drip water, and calcite precipitation δ18O and δ13C. The results show that the ventilation process is attributed to buoyancy airflow between external atmosphere, fissure air, and cave air. This causes that the higher (lower) cave air pCO2 in the summer (winter) is associated with upward airflow mode (downward airflow mode). Furthermore, cave ventilation could control the isotopic fractionation. Specifically, when cave air pCO2 is lower, the carbon isotopic disequilibrium between calcite and dissolved inorganic carbon (DIC) is controlled by the degassing of CO2 associated with calcite precipitation. The disequilibrium fractionation in carbon isotopes is less pronounced at slower drip-rate sites. The oxygen isotope fractionation between calcite and the drip water is found to be close to equilibrium. However, the high cave air pCO2 (exceeding 10,000 ppm) may result in drip water undersaturation to drive the dissolution of speleothem calcite. The δ18O values of drip water are pulled away from their original values to disequilibrate to the calcite because the exchange time of oxygen in the dissolved carbonates with the oxygen in the water is sufficiently long. Hence, the dissolution of speleothems may be a new mechanism to explain the oxygen isotopic disequilibrium between the calcite and drip water during the cave air stagnation. The carbon isotope fractionation between calcite and drip water is close to equilibrium.

Sulfur and Carbon–Oxygen Isotopic Geochemistry and Fluid Inclusion Characteristics of the Yolindi Cu-Fe Skarn Mineralization, Biga Peninsula, NW Turkey: Implications for the Source and Evolution of Hydrothermal Fluids

The current study sought to investigate the physiochemical conditions and fluid evolution within the Yolindi Cu-Fe skarn mineralization located in the Biga Peninsula, NW Turkey. This was accomplished through a comprehensive investigation of geological and mineralogical data, along with isotopic analyses of sulfur (δ34S), carbon (δ13C), and oxygen (δ18O) of sulfide and calcite minerals, respectively, as well as fluid inclusion data pertaining to various minerals (e.g., andradite, quartz, and calcite). The Yolindi area features a complex geological framework, including the Paleozoic Kalabak Group (which includes the Torasan, Yolindi, and Sazak formations) and the Triassic Karakaya Complex. These formations were subsequently intruded via Early Miocene Şaroluk granitoids and Hallaçlar volcanics. Skarn formation is zoned into endoskarn and exoskarn types (being categorized into proximal, intermediate, and distal zones), with distinct mineral assemblages indicating concentric and contact metamorphic alteration patterns around the western part of Şaroluk granitoid intrusion in contact with the Torasan formation. The ore mineralogy and paragenesis suggest three distinct stages of evolution: an initial phase of prograde metasomatism characterized by the formation of magnetite and pyrite alongside anhydrous calc-silicate minerals; a subsequent phase of retrograde alteration marked by the formation of epidote, actinolite, and scapolite, accompanied by the occurrence of chalcopyrite and specular hematite; and finally, a post-metasomatic stage involving oxidation processes that led to the development of secondary mineral assemblages containing cerussite, covellite, and malachite. Sulfur isotopes (δ34S) of sulfides from endoskarn (from +0.27 to +0.57‰VCDT) to intermediate exoskarn (from −9.44 to −5.46‰VCDT) zones indicate a diverse sulfur source, including magmatic, sedimentary, and possibly organic matter. δ34S values in hydrothermal fluids suggest a magmatic–hydrothermal origin, with endoskarn and proximal zone fluids showing a slight negative signature and intermediate zone fluids indicating a strong influence from organic-rich or metamorphic sulfur reservoirs. Carbon and oxygen isotopic compositions (δ13C and δ18O) of calcite revealed a progression from marine carbonate signatures in marble samples (from +1.89 to +2.23‰VPDB; from +21.61 to +21.73‰VSMOW) to depleted values in prograde (from −6.0 to +0.09‰VPDB; from +6.22 to +18.14‰VSMOW) and retrograde skarns (from −3.8 to −2.25‰VPDB; from +0.94 to +3.62‰VSMOW), reflecting interactions with high-temperature magmatic fluids and meteoric water mixing. The fluid inclusions in prograde minerals generated under the conditions of fluid boiling exhibited high temperatures, reaching up to 412 °C, and salinities up to 26 wt.% NaCl equivalent. Conversely, the fluid inclusions in retrograde minerals, which were generated due to fluid mixing, exhibited lower temperatures (with an average of 318 °C) and salinities with an average of 4.9 wt.% NaCl equivalent. This indicated that the cooler and more diluted fluids mix with meteoric waters and interact with organic materials in the host rocks. This suggests a multifaceted origin involving various sources and processes. Therefore, this study concluded that the skarn mineralization in the Yolindi area resulted from complex interactions between magmatic, metamorphic, and meteoric fluids, reflecting a dynamic ore-forming environment with implications for the regional metallogeny of Cu-Fe skarn deposits.

Quaternary fluvial carbonate deposits of the Almonda River Valley, Central Portugal

This paper discusses the formation and preservation of a fluvial tufa system influenced by Atlantic climate based on stratigraphical, chronological (amino-acid racemization, AAR), sedimentological and stable-isotope analyses. On the southwestern Iberian Peninsula, the tufas and associated deposits of the Almonda River valley occur as isolated terraced bodies and reach 25 m thick. AAR dated most deposits to within the warm Marine Isotope Stage 5 (MIS-5). Two Holocene ages were reset within MIS-5 based on diverse criteria. Widely varied carbonate and minor allochthonous coarse detrital facies occur arranged in four simple vertical associations. The deposit geometry and facies association distribution correspond to a low- to moderate-sloped fluvial valley consisting of several short knickpoints and extensive flat areas between them. The latter are occupied by slow-flowing water facies (carbonate sand, lime mud, phytoclast and oncoid rudstones, and up-growing stem boundstones). Facies that formed in moderate- to high-slope substrates were stromatolite, moss and down-growing stem boundstones. The homogeneous Miocene bedrock lithology and gentle structural deformation propitiated this depositional architecture. Calcite δ13C and δ18O values suggest that the aquifer water provided the outflowing Almonda water with (1) 18O-enriched water, compared with present precipitation and groundwater δ18O values, and (2) 13C-depleted CO2 from bituminous rocks and vegetation cover in the catchment. The proximity to the Atlantic coast favoured the Mesozoic-rock aquifer recharge with 18O-enriched water precipitation, assuring water availability during the formation of the studied tufas. No evidence of frequent intense erosion phases might indicate stable precipitation regimes, which would have allowed the preservation of loose fine-grained and palustrine deposits.

A simple but improved protocol for measuring carbon and oxygen isotope ratios of calcite in calcite-dolomite mixtures

The extraction of stable carbon and oxygen isotope ratios (δ13C and δ18O) of primarily precipitated calcite from partially dolomitized limestone is of prime interest because the δ13C and δ18O values of primary calcite are widely used in paleoclimate research. The differential acid extraction method (DAE) has been widely used to separate CO2 evolved during the calcite-orthophosphoric acid reaction from CO2 evolved from the dolomite-orthophosphoric acid reaction. However, the various laborious offline methods with inevitable uncertainties make DAE very challenging. We proposed a fully automatic-online DAE method in the present study, using an autosampler-GasBench II-Isotope Ratio Mass Spectrometer (IRMS). The results show that δ-values of calcite can be obtained from the mixture (grain size between 180 and 250 μm) having >50% calcite after ∼15–100 min of reaction with orthophosphoric acid at 30 °C. Further, both the precision and the accuracy of the measurement using the autosampler-GasBench II-IRMS can be improved by attaching micro-vibrators to the sample tray.

Clumped isotope analysis of zoned calcite cement, Carboniferous, Isle of Man

AbstractSequential analyses of δ13C, δ18O and Δ47 values of calcite and dolomite deposited in millimetre‐sized cavities are reported from the Ronaldsway Member packstones, Isle of Man. The Ronaldsway brachiopods have δ13C values of ca +2.3‰ and δ18O values of ca −7.2‰; carbon is like predicted Carboniferous values, while oxygen values are more negative. The brachiopods show preserved microstructure but have marginal alteration and a streaky cathodoluminescence pattern. Crinoid ossicles have δ13C values of ca +2.3‰ and one with a δ18O value of ca −3.1‰, compatible with Carboniferous marine precipitates; three samples have δ18O values of ca −6.5‰ and are 18O‐depleted. Calcite stages 1 and 2 have δ13C values ca +3.2‰ and δ18O values ca −2.5‰, compatible with Carboniferous sea water. Stage 1 and 2 have non‐luminescent to orange CL zones. Stage 1 and early stage 2 contain red luminescent dolomite micro crystals generated during Mg calcite stabilisation. The Δ47 values for stage 1 and 2 cements indicate temperatures of 86 and 105°C that occurred after the stabilisation of Mg calcite. Stage 3–8 zoned cements preserve their original growth surfaces and their δ13C and δ18O values suggest precipitation during burial and exhumation. The Δ47 values of the brachiopods and crinoids indicate temperatures between 85 and 140°C indicating they were either recrystallised at high temperatures or affected by solid state reordering. To evaluate these alternatives two quantitative models, water–rock reaction and reordering models are performed. The allochems and cements are progressively altered by porewater towards the fluid‐buffered behaviour. The quantitative evaluation of calcite and dolomite solid‐state reordering suggests the elevated clumped isotopic temperatures are produced by interaction with hydrothermal fluids. This study improves understanding by applying previously untried techniques; further Δ47 data and quantifying elemental variations would help further interpretation but the poorly documented post‐depositional history is a drawback.

Climatic implication of stalagmite δ13C in the middle reaches of the Yangtze River since the Last Glacial Maximum and coupling with δ18O

The relationship between monsoon circulation and regional hydrology in the Yangtze River Basin since the Last Glacial Maximum (LGM) remains unclear. In this study, we present speleothem (LS46) δ18O and δ13C records over the past 23.5 kyr from the Luoshui Cave in Central China. Stalagmite LS46 δ13C displayed a good similarity with variations in δDwax-derived monsoon precipitation from Lake TengchongQinghai (TCQH) and the extreme precipitation events identified by the IRMsoft-flux from Heshang Cave, thus indicating that speleothem calcite δ13C reflects the changes in regional hydrology. The ensemble empirical mode decomposition (EEMD) and wavelet spectrum analyses revealed that the regional hydrology was paced by ∼2000-year periodicity during the LGM and last deglaciation and ∼ 1000-year periodicity during the Holocene, respectively. Our results further indicated that the El Niño-Southern Oscillation (ENSO) plays an important role in regulating changes in the frequency and magnitude of regional hydrology in the Yangtze River Basin under different climatic conditions. Moreover, our results demonstrated that δ18O and δ13C were coupled on multiple timescales, thus potentially indicating that local hydrological variations in the middle reaches of the Yangtze River are regulated by large-scale monsoonal circulation. However, we also found that the δ18O and δ13C profiles decoupled during the last deglaciation, likely due to a decrease in evapotranspiration in combination with a decrease in monsoon intensity and temperature during this period. Consequently, the regional hydrological conditions did not experience any dramatic changes.

Formation of the Miaoan Au-Polymetallic Deposit in the Northern Taihang Mountain, North China Craton: Ore Geology, Geochronological and Geochemical Perspectives

Several gold ore-concentrated areas have been recognized in the destruction zone of the North China Craton (NCC). However, the deposits in the western part of the destruction zone have received less attention. Miaoan, a typical Au-polymetallic deposit in the northern Taihang Mountain, provides a good sample for deepening our understanding of the genesis of gold deposits in the western destruction zone. In this study, detailed ore geology, pyrite Rb-Sr age, trace element and S-C-O isotopes of Au-bearing ores were conducted to constrain the source of ore-forming materials and their tectonic setting. The pyrites obtain an Rb-Sr isochron age of 129.5 ± 2.5 Ma, consistent with those of magmatic rocks in this deposit, suggesting their genetic relationship. The δ34S values ranging from −5.5‰ to 1.6‰ and the high Co/Ni and Y/Ho ratios of pyrites indicate the mantle-crust mixing characteristics of ore-forming fluids. The δ13C (−6.3‰ to −2.0‰) and δ18O (9.3‰ to 17.6‰) values of Au-bearing ores and calcites suggest mixing characteristics as well. Geochronologically, the Miaoan Au-polymetallic deposit was formed during the destruction of the NCC. We propose that the Miaoan Au-polymetallic deposit is a decratonic gold deposit and that its ore-forming materials have a mixed source of mantle and crust.

Clumped isotope geothermometry in Archean mesothermal hydrothermal systems (Augmitto-Bouzan orogenic gold deposit, Abitibi, Québec, Canada): A note of caution and a look forward

This study evaluates the applicability of the clumped isotope thermometry to mesothermal hydrothermal systems (5–10 km depth; 250–450 °C). We measured Δ47, δ18O and δ13C of calcite as well as δ18O of cogenetic minerals from typical quartz-calcite ± tourmaline±chlorite orogenic veins from the Neoarchean Augmitto-Bouzan orogenic gold deposits (Abitibi, Canada). Our findings show that caution is required when utilizing the clumped isotope thermometry in the study of old mesothermal deposits. Temperatures calculated from Δ47 values are systematically and significantly shifted to low temperature, i.e., ∼150 °C rather than the ∼350 ± 50 °C expected for orogenic gold deposit formation and documented using oxygen isotope equilibrium between mineral pairs. We show that the low temperatures estimates resulted from solid-state reordering that occurred in calcite grains during the cooling history of the vein-hosting rocks. Because the fast cooling rates required to preserve the initial temperature of calcite formation in mesothermal hydrothermal systems are geologically unrealistic, we suggest that refractory minerals (i.e., minerals with higher blocking temperature such as magnesite, dolomite, ankerite) should be investigated to apply clumped isotope thermometry in such context.

Evaluation Methods and Indexes for Ultra‐deep Petroleum Reservoir Preservation with Case Studies

AbstractFollowing consideration of the characteristics of high temperature, high pressure and high in‐situ stress in ultra‐deep sedimentary basins, together with the existence of hydrocarbon phase state transformation, hydrocarbon‐water‐rock interaction and rock mechanical property transition at those depths, the evaluation index system for hydrocarbon preservation was established. The physical leakage evaluation indexes can be divided into three categories: the dynamic efficiency indexes of micro‐sealing, caprock integrity and natural gas diffusion. The chemical loss evaluation indexes can be divided into two categories: the thermochemical sulfate reduction (TSR) index in marine gypsum‐bearing carbonate strata and the thermochemical oxidation of hydrocarbons (TOH) index in clastic strata. The slippage angle and overconsolidation ratio (OCR) are the key evaluation indexes in the evaluation of the integrity of shale caprocks. TSR intensity can be quantitatively calculated by use of the ZnPVT state parameter method. The TOH strength can be used to estimate the degree of hydrocarbon chemical loss, based on the TOH‐related authigenic calcite cement content or the degree of negative δ13C of authigenic calcite. For the evaluation of ultra‐deep preservation in specific areas, key indexes can be selected according to the local geological conditions, instead of all indexes needing to be evaluated for every scenario.

Isotopic signatures of precent-day calcite and pyrite in low-temperature crystalline bedrock, Olkiluoto, SW Finland

Geochemical characteristics of precipitated fracture filling calcite and pyrite can provide much useful information about the deep bedrock environment at the time of their deposition. However, it has been difficult to identify fracture coatings precipitated from the present-day groundwater system. The aim of this study was to evaluate the relationship between the coexisting calcite and pyrite, and the groundwater present at the time of precipitation. Here we investigated fine-grained mineral precipitate deposited over a four-year period on the surface of groundwater monitoring equipment inserted into a drillhole at 530 m below sea level, at Olkiluoto, which is the planned site for a final repository of spent nuclear fuel. The experimental setting is also artificial in the sense that the drillholes have possibly affected groundwater circulation and a foreign object has been inserted into the drillhole. Combining the elemental and isotope geochemical composition of the precipitated calcite and pyrite with previously published compositional data on groundwater and evidence for microbial communities on this site, offered a possibility to get new insight of the precipitation and isotope fractionation processes taking place in deep crystalline bedrock. The concentration of the redox sensitive manganese in the precipitate gives supporting evidence for the influx of groundwater from overlying groundwater units. The δ13C (n = 13) and δ18O (n = 15) values of calcite vary from −13.2 to −9.7‰ and from −9.1 to −7.4‰, respectively. Comparison to the respective values in the local groundwater indicated that the precipitated calcite is in near isotopic equilibrium with its environment with respect to carbon and oxygen. The potential ultimate source of the carbon in the DIC and in the precipitate is likely in old fracture calcite coatings. The δ34S values of pyrite (n = 9) show relatively small variation from −5.7 to 8.3‰. This differs greatly from the huge span of δ34S values from −50 to 80‰ in fracture pyrites reported for the latest calcite fillings at Olkiluoto. The restricted range of δ34S values is interpreted to result from open system conditions during precipitation, with new dissolved sulfate entering from the large brackish SO4-type groundwater unit above. The isotopic fractionation of sulfur between dissolved sulfate and sulfide is estimated to be 25 ± 10‰, which is in agreement with the results reported in laboratory experiments for bacterial sulfate reduction.

Atmospheric pCO2 Reconstruction of Early Cretaceous Terrestrial Deposits in Texas and Oklahoma Using Pedogenic Carbonate and Occluded Organic Matter

Pedogenic carbonate samples collected from three Lower Cretaceous (Aptian–Albian) fossil localities in Texas and Oklahoma were analyzed to develop paleoatmospheric pCO2 estimates by measuring the stable carbon isotopes of pedogenic calcite and their co-existing occluded organic matter. Calcite δ13C values ranged from −10.9‰ to −4.4‰ while occluded organic matter δ13C values ranged from −27.3‰ to −21.1‰. These stable carbon isotope measurements combined with temperature (30 °C) and soil-respired CO2 concentration (839–6047 ppmV) values provided atmospheric pCO2 estimates ranging from 67 ppmV to over 1100 ppmV. These estimates show a significant increase in atmospheric pCO2 during the late Aptian followed by a decrease in atmospheric pCO2 during the late Aptian to early Albian transition period, roughly correlating with the OEA1b event. Given the lack of chronostratigraphic constraints of the Lower Cretaceous geologic units in the study area, these data provide further evidence for the approximate age of the units as well as pertinent paleoclimate insights into greenhouse climate conditions.

A newly identified Permian distal skarn deposit in the Western Tianshan, China: New evidence from geology, garnet U[sbnd]Pb geochronology and S[sbnd]Pb[sbnd]C[sbnd]H[sbnd]O isotopes of the Arqiale Pb[sbnd]Zn[sbnd]Cu deposit

The Arqiale PbZnCu deposit is located in the Wusun Range, Western Tianshan, China. Prograde and retrograde skarn minerals are abundant and associated with the PbZnCu mineralization. Given that the orebodies are stratabound and hosted in limestone and causative intrusions were not identified, the genetic relationship between mineralization and magmatic hydrothermal activity remains controversial. Geology, in-situ garnet LA-ICP-MS UPb dating and SPbCHO isotopes were carried out in this study, aiming to constrain the mineralization age, source of ore-forming components, and examine the link between mineralization and magmatism. In-situ garnet LA-ICP-MS UPb dating yielded a well-defined lower-intercept age of 268.6 ± 5.9 Ma, reflecting that the mineralization occurred much younger than that of ore hosting strata and formed in a post-collisional setting. In-situ δ34S values of sulfides (chalcopyrite, sphalerite and pyrite) range from −5.81‰ to −7.57‰ with an average of −6.37‰. The δ34S values of sulfide separates published previously vary from −7.1‰ to 1.3‰ (average −1.5‰). The in-situ206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios of galena vary from 18.262 to 18.269, 15.561 to 15.567 and 38.049 to 38.065, respectively. The aforementioned S-Pb isotopic compositions indicate that the metals and sulfur were sourced partially from causative intrusion and partially from hosing sedimentary rocks. The δ13C (-2.6 – −0.9‰), δ18OV-SMOW (3.2 – 7.7‰), δ18OH2O (-5.2 – −0.7‰) and δDH2O (-128.0 – −109.1‰) values of ore-bearing calcite suggest that the ore-forming fluids were initially sourced from magmatic water exsolved from the hidden causative intrusions, with increasing input of meteoric water in later time. These geological, geochemical and isotopic data confirm that Arqiale is a typical distal skarn PbZnCu deposit. Considering the chalcopyrite-garnet-ilvaite contents increasing and Zn/Pb rations decreasing from the shallow part in the south to the deeper part in the north, it is inferred that the hidden causative intrusions and Cu mineralization within contact zone may occur at depth in the northern part of Arqiale.

The effects of drip rate and geometry on the isotopic composition of speleothems: Evaluation with an advection-diffusion-reaction model

The curvature and slope of speleothem surfaces have been shown to affect the reaction rates in the aqueous carbonate system by altering the thickness of the CaCO3-precipitating solution. However, the effects of speleothem geometry and drip rate on the speleothem’s carbon and oxygen isotopic composition have yet to be investigated. Over more strongly sloping surfaces, solutions are thinner and flow faster. The effects of thinner and faster-flowing solutions on the isotopic composition of carbonate minerals precipitated from these solutions are of opposite sense. Thinner solutions enhance rates of CO2 degassing and mineral formation, increasing the degree of isotopic distillation of the dissolved inorganic carbon (DIC) reservoir and leading to larger isotopic fractionation between the carbonate mineral and the initial DIC. Concurrently, faster flow over the steeper surfaces results in shorter residence times of the solutions on the growing speleothem, thereby limiting the degree of isotopic distillation and CaCO3-DIC fractionation. Consequently, predicting the CaCO3-DIC isotopic fractionation as a function of drip rate, surface slope and flow distance is not trivial.Using an advection-diffusion-reaction model, we tested the sensitivity of the isotopic composition of calcite precipitated along inclined surfaces to the solution discharge (drip) rate and the surface slope. Calcite δ13C and δ18O values correlate well with the degree of prior calcite precipitation (PCP), which is identified as a major determinant of isotopic compositions in speleothems. Our results show that at low PCP, speleothem δ13C and δ18O values may initially decrease relative to calcite-DIC and calcite-water equilibrium due to expression of kinetic isotope effects of mineral precipitation. Upon progressive PCP, δ13C and δ18O values gradually increase due to continuous CO2(aq) formation and degassing. This shift in the isotopic composition of the calcite to lower-than-equilibrium and then higher-than-equilibrium values expands the regime of near-equilibrium compositions during the isotopic evolution. In turn, this may allow quantitative environmental reconstructions, even when the isotopic system is in disequilibrium. Under the simulated conditions, our model predicts maximal potential enrichments of 7 and 3‰ in the calcite δ13C and δ18O values, respectively. In addition, we found a strong dependence of the calcite δ13C and δ18O values on the drip rate and distance of flow, and a weak dependence on the surface slope. In fact, changes in drip rate alone may drive isotopic offsets of several permil, when all other environmental parameters are kept constant. According to our model, higher drip rates and shorter stalactites promote closer-to-equilibrium isotopic compositions of stalagmites, providing a higher signal-to-noise ratio, and minimizing variability that is unrelated to climate.

Organic matter removal for continuous flow isotope ratio mass spectrometry analysis of carbon and oxygen isotope compositions of calcite or dolomite in organic‐rich samples

Abstractδ13C and δ18O values of carbonate in organic‐rich samples such as soils, biofilms, and lake sediments have been scarcely used so far in paleo‐environmental, biomineralization, or diagenetic studies because organic matter in high proportions is suspected to alter carbonate isotope analysis. Yet, with the improvement of analytical capabilities and in particular the use of CF‐IRMS, this may not be an issue anymore. To evaluate this, δ13C and δ18O values of calcite or dolomite mixed in various proportions with yeast (used here as a model for immature organic matter) were measured. The results indicate that measurements of calcite or dolomite δ13C and δ18O by CF‐IRMS require organic matter removal only when its weight proportion exceeds that of carbonates. Yeast generated an unidentified molecule during phosphoric acid digestion at 25°C (none at 80°C), which shifted the carbonate δ18O values for yeast proportions higher than 50%. It also generated CO2, but with a noticeable shift in δ13C and δ18O values only at 80°C (none at 25°C) and for yeast proportions higher than 75%. Three methods of organic matter removal were tested: the well‐established NaOCl and H2O2 wet treatments as well as low temperature plasma ashing (LTA) so far seldom examined. LTA removed the isotope shifts, although imperfectly for yeast proportions of 95%, without carbonate dissolution. NaOCl efficiently removed the isotope shifts in all cases but dissolved part of the calcite and dolomite. H2O2 treatment caused severe dissolution of calcite and dolomite while worsening the δ13C and δ18O shifts and should thus be avoided.

Base metal mobility linked to brine and hydrocarbon migration at the Huincul High in the Neuquén Basin, Argentina: Implications for the formation of sediment-hosted base metal deposits

This contribution discusses the discovery of PbZn mineralization in hydrocarbon exploration drill holes hosted in siliciclastic Jurassic rocks below the Cretaceous sediment hosted Cu mineralization located north of the Huincul High. In the Early Cretaceous, hydrocarbon and basinal water expulsion took place from the oil source rocks (Los Molles Formation) into the reservoir rocks Lajas Formation (Middle Jurassic), after the formation of diagenetic quartz overgrowths. Marcasite, pyrite and illite + illite-smectite mixed layer minerals then formed together with hydrocarbons. Marcasite (δ34S −3.5 and −2.2‰) and pyrite (δ34S −11.6 to 18.1‰) precipitated via bacterial sulfate reduction from fluids showing temperatures <80 °C and fluctuating pH conditions. During the Paleogene, Andean tectonism triggered migration of oxidized basinal brine containing dissolved leached Zn and Pb from the Los Molles Formation source rocks and S from the evaporites of the basin. This brine entered in the hydrocarbon reservoir of the Lajas Formation, resulting in the precipitation of sphalerite (δ34S +10.4 to +10.8‰) and galena (δ34S +5.2‰) by TSR at temperatures of 119–123 °C together with siderite. The Andean orogeny may also have triggered the migration of hydrocarbons + brines from the shallowest source rocks (Vaca Muerta Formation) and reservoir rocks (Mulichinco, Lajas and Lotena formations) into the red beds of the upper Cretaceous Neuquén Group, which became bleached as a result. Marcasite (δ34S −36.4 to 18.2‰) and pyrite (δ34S −60.2 to −24‰) precipitated by BSR, while calcite (δ13C −12.3 to −5.6‰) formed due to redox reactions accompanying formation of quartz overgrowths, clay mineral coatings (δD −92.4‰ to −82.8‰ and δ18O 16.2‰ to 18.40‰), and barite (δ34S −5.9‰). Quartz overgrowths and barite precipitated from brines (1.5–10 wt% NaCl equiv.) at temperatures of 91–120 °C, with barite precipitating close to the feeder zones. Calcite cements are more widespread and generated from several pulses of brine and hydrocarbons up flow, evidenced by the wide range of homogenization temperatures (100–185 °C) and diversity of UV fluorescence colors of hydrocarbon-rich fluid inclusions. In subsequent Miocene tectonic events, basinal brines were able to leach Cu from the underlying thick red beds of the basin, entering the Neuquén Group oil reservoir traps or carrier beds where they became reduced. Chalcopyrite and bornite precipitated at temperatures >100 °C close to the feeder zones at the expense of barite as a local sulfur source. Chalcocite group minerals (δ34S −21.3‰ to −7.3‰) precipitated outwards in pore spaces of the sandstones at lower temperatures (<100 °C) through BSR of sulfate in the mineralizing brines. Final exhumation of the Neuquén Group (Upper Miocene-Pliocene) promoted the infiltration of the meteoric water, the oxidation of the sulfides and formation of supergene FeCu, V and U minerals. Isotope geochemistry and fluid inclusion results combined with alteration and ore mineralogy document the processes controlling the distribution of base metals in the Huincul High region that can be applied to evaluate the metal potential in other areas of the Neuquén Basin and further extrapolated to similar geological systems elsewhere.

Modern analogs reveal the origin of Carboniferous coal balls

Coal balls are calcareous peats with cellular permineralization invaluable for understanding the anatomy of Pennsylvanian and Permian fossil plants. Two distinct kinds of coal balls are here recognized in both Holocene and Pennsylvanian calcareous Histosols. Respirogenic calcite coal balls have arrays of calcite δ18O and δ13C like those of desert soil calcic horizons reflecting isotopic composition of CO2 gas from an aerobic microbiome. Methanogenic calcite coal balls in contrast have invariant δ18O for a range of δ13C, and formed with anaerobic microbiomes in soil solutions with bicarbonate formed by methane oxidation and sugar fermentation. Respirogenic coal balls are described from Holocene peats in Eight Mile Creek South Australia, and noted from Carboniferous coals near Penistone, Yorkshire. Methanogenic coal balls are described from Carboniferous coals at Berryville (Illinois) and Steubenville (Ohio), Paleocene lignites of Sutton (Alaska), Eocene lignites of Axel Heiberg Island (Nunavut), Pleistocene peats of Konya (Turkey), and Holocene peats of Gramigne di Bando (Italy). Soils and paleosols with coal balls are neither common nor extinct, but were formed by two distinct soil microbiomes.