Atmospheric palaeo-CO2 estimates based on the carbon isotope and stomatal data of Cheirolepidiaceae from the Lower Cretaceous of the Jiuquan Basin,Gansu Province

The stable carbon isotope compositions and the stomatal parameters (stomatal density and stomatal index) of four Cheirolepidiaceae species, Brachyphyllum ningxiaensis, Brachyphyllum obtusum, Pseudofrenelopsis dalatzensis and Pseudofrenelopsis gansuensis, were analyzed to recover the late Early Cretaceous atmospheric CO₂ levels. The fossil plants were collected from 5 consecutive sedimentary members of the uppermost Zhonggou Formation. Based on the stomatal data, the estimated palaeo-atmospheric CO₂ concentrations in the Jiuquan Basin during the late Early Cretaceous were 1060–882 ppmv based on the carboniferous standardization and were 641–531 ppmv based on the recent standardization; the pCO₂ values present at first a decreasing and then an increasing trend within the sedimentary time of the five members. The δ¹³Cp values based on the 21 Brachyphyllum specimens showed a large variation, which ranged from −20.98‰ to −25.69‰, with an average of −24.2‰. The values also identified a C3 photosynthetic pathway for the Brachyphyllum specimens. The predicted δ¹³Ca values varied from −2.1‰ to −6.38‰, with an average of −5.03‰. These two proxies were irregular within the different members; therefore, the correlation with the change in atmospheric CO₂ concentrations was not significant. Moreover, a water-stressed environment was proposed based on the δ¹³C values of the present fossil plants, a proposal that was also supported by the previous palaeobotanical, palynological and stratigraphical evidence. In the present study, an inconsistent relationship between the stable carbon isotope and the stomata values was apparent, which most likely indicated that the stomata numbers of the plant were more sensitive to the variation in the concentration of the atmospheric CO₂, whereas the δ¹³C values were sensitive to the moisture conditions.     

Nickel isotope fractionation during laterite Ni ore smelting and refining: Implications for tracing the sources of Ni in smelter-affected soils

Nickel isotope ratios were measured in ores, fly ash, slags and FeNi samples from two metallurgical plants located in the Goiás State, Brazil (Barro Alto, Niquelândia). This allowed investigating the mass-dependent fractionation of Ni isotopes during the Ni-laterite ore smelting and refining. Feeding material exhibits a large range of δ⁶⁰Ni values (from 0.02 ± 0.10‰ to 0.20 ± 0.05‰, n = 7), explained by the diversity of Ni-bearing phases, and the average of δ⁶⁰Ni_{feeding materials} was found equal to 0.08 ± 0.08‰ (2SD, n = 7). Both δ⁶⁰Ni values of fly ash (δ⁶⁰Ni = 0.07 ± 0.07‰, n = 10) and final FeNi produced (0.05 ± 0.02‰, n = 2) were not significantly different from the feeding materials ones. These values are consistent with the very high production yield of the factories. However, smelting slags present the heaviest δ⁶⁰Ni values of all the smelter samples, with δ⁶⁰Ni ranging from 0.11 ± 0.05‰ to 0.27 ± 0.05‰ (n = 8). Soils were also collected near and far from the Niquelândia metallurgical plant, to evaluate the potential of Ni isotopes for tracing the natural vs anthropogenic Ni in soils. The Ni isotopic composition of the non-impacted topsoils developed on ultramafic rocks ranges from −0.26 ± 0.09‰ to −0.04 ± 0.05‰ (n = 20). On the contrary, the Ni isotopic composition of the non-ultramafic topsoils, collected close to the plant, exhibit a large variation of δ⁶⁰Ni, ranging from −0.19 ± 0.13‰ up to 0.10 ± 0.05‰ (n = 4). This slight but significant enrichment in heavy isotopes highlights the potential impact of smelting activity in the surrounding area, as well as the potential of Ni isotopes for discerning anthropogenic samples (heavier δ⁶⁰Ni values) from natural ones (lighter δ⁶⁰Ni values). However, given the global range of published δ⁶⁰Ni values (from −1.03 to 2.5‰) and more particularly those associated to natural weathering of ultramafic rocks (from −0.61 to 0.32‰), the use of Ni isotopes for tracing environmental contamination from smelters will remain challenging.     

Stable isotopic signatures of the modern land snail Eremina desertorum from a low-latitude (hot) dry desert—A study from the Petrified Forest,New Cairo,Egypt

This study was conducted on recent desert samples—including (1) soils, (2) plants, (3) the shell, and (4) organic matter from modern specimens of the land snail Eremina desertorum—which were collected at several altitudes (316–360 m above sea level) from a site in the New Cairo Petrified Forest. The soils and shell_{E. desertorum} were analyzed for carbonate composition and isotopic composition (δ¹⁸O, δ¹³C). The plants and organic matter_{E. desertorum} were analyzed for organic carbon content and δ¹³C. The soil carbonate, consisting of calcite plus minor dolomite, has δ¹⁸O values from −3.19 to −1.78‰ and δ¹³C values −1.79 to −0.27‰; covariance between the two values accords with arid climatic conditions. The local plants include C3 and C4 types, with the latter being dominant. Each type has distinctive bulk organic carbon δ¹³C values: −26.51 to −25.36‰ for C3-type, and −13.74 to −12.43‰ for C4-type plants.The carbonate of the shell_{E. desertorum} is composed of aragonite plus minor calcite, with relatively homogenous isotopic compositions (δ¹⁸O_mean = −0.28 ± 0.22‰; δ¹³C_mean = −4.46 ± 0.58‰). Most of the δ¹⁸O values (based on a model for oxygen isotope fractionation in an aragonite-water system) are consistent with evaporated water signatures. The organic matter_{E. desertorum} varies only slightly in bulk organic carbon δ¹³C values (−21.78 ± 1.20‰) and these values suggest that the snail consumed more of C3-type than C4-type plants. The overall offset in δ¹³C values (−17.32‰) observed between shell_{E. desertorum} carbonate and organic matter_{E. desertorum} exceeds the value expected for vegetation input, and implies that 30% of carbon in the shell_{E. desertorum} carbonate comes from the consumption of limestone material.     

Stable isotopic insights into paleoclimatic conditions and alluvial depositional processes in the Kaiparowits Formation (Campanian,south-central Utah,U.S.A.)

The Kaiparowits Formation contains an exceptionally rich history of tectonic, climatic, and biologic conditions within the Western Interior of North America during the Campanian. Here we reconstruct aspects of the southern Cordilleran foreland basin's paleohydrology using δ¹⁸O and δ¹³C values determined from unionoid bivalve shells and pedogenic carbonate nodules derived from a suite of lithofacies associations. Unionoid shells derived from fluvial deposits display average water δ¹⁸O estimates of −13.7‰ ± 2.1 (1σ) (VSMOW) and shell δ¹³C values of −4.0‰ ± 1.5 (VPDB), whereas pedogenic carbonate nodules display average values of −6.0‰ ± 0.5 and −8.7‰ ± 0.8, respectively. Unionoid shells derived from pond deposits fall in between the two other environments with average values of −9.5‰ ± 1.8 and −5.7‰ ± 2.1, in δ¹⁸O and δ¹³C values respectively. Water δ¹⁸O estimates are interpreted to represent high altitude runoff within river systems, low elevation precipitation within the basin onto floodplain soils, and varying degrees of mixing between these two components within floodplain ponds. δ¹³C values track the isotopic composition of dissolved inorganic carbon within river, soil, and pond waters with high values likely reflecting greater contribution from chemically weathered marine carbonates exposed in the hinterland and lower values reflecting greater contributions from the in situ degradation of plant matter. Up-section there is a shift to lower δ¹⁸O values and higher δ¹³C values in fluvially-derived unionoid shells that post-dates an incursion of the Western Interior Seaway, but coincides with a shift in sediment provenance, an increase in basin sedimentation rates, and a change to a more anastomosed-style channel morphology within the basin foredeep depocentre. By combining the isotopic patterns with previously published sedimentologic, climate model, and paleofloral records we find: 1) additional evidence for humid, wet, and potentially monsoonal conditions within the region, 2) support for a tectonic uplift event, potentially related to Laramide deformation, and 3) greater aggradation and overbank flooding within the alluvial system in response to the uplift event.     

Ordovician low- to intermediate-Mg calcite marine cements from Sweden: marine alteration and implications for oxygen isotopes in Ordovician seawater

Petrography demonstrates the presence of three types of fibrous calcite cement in buildup deposits of the Kullsberg Limestone (middle Caradoc), central Sweden. Translucent fibrous calcite has intrinsic blue luminescence (CL) indicative of pure calcite. This cement has 2–5 mol% MgCO₃, low Mn and Fe (≤ 100 p.p.m.), and is considered to be slightly altered to unaltered, primary low- to intermediate-Mg calcite. Grey turbid fibrous calcite has variable but generally low MgCO₃ content (most analyses <2 mol%) and variable CL response, with Mn and Fe concentrations up to 1200 and 500 p.p.m., respectively. The heterogeneous characteristics of this variety of fibrous calcite are caused by diagenetic alteration of a translucent fibrous calcite precursor. Light-brown turbid fibrous calcite has low MgCO₃ (near 1 mol%) and variable Mn (up to 800 p.p.m.) and Fe (up to 500 p.p.m.) concentrations, with an abundance of bright luminescent patches, which formed during alteration caused by reducing diagenetic fluids. The δ¹³C and δ¹⁸O values of all fibrous calcite form a tight field (δ¹³C=1·7 to 3·1‰ PDB, δ¹⁸O= ? 2·6 to ? 4·1‰ PDB) compared with fibrous calcite isotope values from other units. Fibrous calcite δ¹⁸O values are larger than adjacent meteoric or burial cements, which have δ¹⁸O δ ? 8‰ PDB. Consequently, most diagenetic alteration of Kullsberg fibrous calcite is interpreted to have occurred in the marine diagenetic realm. First-generation equant and bladed calcite cements, which pre-date fibrous calcite, are interpreted as unaltered, low-Mg calcite marine cements based on δ¹³C and δ¹⁸O data (δ¹³C = 2·3 to 2·7‰ PDB, δ¹⁸O= ? 2·8 to ? 3·5‰ PDB). Unlike fibrous cement, which reflects global sea water chemistry, first-generation equant and bladed calcite are indicators of localized modification of seawater chemistry in restricted settings. Kullsberg abiotic marine cements have larger δ¹⁸O values than most Caradoc marine precipitates from equatorial Laurentia. Positive Kullsberg δ¹⁸O values are attributed to lower seawater temperatures and/or slightly elevated salinity on the Baltic platform relative to seawater from which other marine precipitates formed.     

The Carrancas Formation,Bambuí Group: A record of pre-Marinoan sedimentation on the southern São Francisco craton,Brazil

The Carrancas Formation outcrops in east-central Brazil on the southern margin of the São Francisco craton where it comprises the base of the late Neoproterozoic Bambuí Group. It is overlain by the basal Ediacaran cap carbonate Sete Lagoas Formation and was for a long time considered to be glacially influenced and correlative with the glaciogenic Jequitaí Formation. New stratigraphic, isotopic and geochronologic data imply that the Carrancas Formation was instead formed by the shedding of debris from basement highs uplifted during an episode of minor continental rifting. Reddish dolostones in the upper Carrancas Formation have δ¹³C values ranging from +7.1 to +9.6‰, which is a unique C isotopic composition for the lowermost Bambuí Group but similar to values found in the Tijucuçu sequence, a pre-glacial unit in the Araçuaí fold belt on the eastern margin of the São Francisco craton. The stratigraphic position below basal Ediacaran cap carbonates and the highly positive δ¹³C values together indicate a Cryogenian interglacial age for the Carrancas Formation, with the high δ¹³C values representing the so-called Keele peak, which precedes the pre-Marinoan Trezona negative δ¹³C excursion in other well characterized Cryogenian sequences. Hence, The Carrancas Formation pre-dates de Marinoan Jequitaí Formation and represents an interval of Cryogenian stratigraphy not previously known to occur on the southern margin of São Francicso craton. Documentation of Cryogenian interglacial strata on the São Francisco craton reinforces recent revisions to the age of Bambuí Group strata and has implications for the development of the Bambuí basin.     

Stable chlorine isotopes in arid non-marine basins: Instances and possible fractionation mechanisms

Stable chlorine isotopes are useful geochemical tracers in processes involving the formation and evolution of evaporitic halite. Halite and dissolved chloride in groundwater that has interacted with halite in arid non-marine basins has a δ³⁷Cl range of 0 ± 3‰, far greater than the range for marine evaporites. Basins characterized by high positive (+1 to +3‰), near-0‰, and negative (−0.3 to −2.6‰) are documented. Halite in weathered crusts of sedimentary rocks has δ³⁷Cl values as high as +5.6‰. Salt-excluding halophyte plants excrete salt with a δ³⁷Cl range of −2.1 to −0.8‰. Differentiated rock chloride sources exist, e.g. in granitoid micas, but cannot provide sufficient chloride to account for the observed data. Single-pass application of known fractionating mechanisms, equilibrium salt-crystal interaction and disequilibrium diffusive transport, cannot account for the large ranges of δ³⁷Cl. Cumulative fractionation as a result of multiple wetting-drying cycles in vadose playas that produce halite crusts can produce observed positive δ³⁷Cl values in hundreds to thousands of cycles. Diffusive isotope fractionation as a result of multiple wetting-drying cycles operating at a spatial scale of 1–10 cm can produce high δ³⁷Cl values in residual halite. Chloride in rainwater is subject to complex fractionation, but develops negative δ³⁷Cl values in certain situations; such may explain halite deposits with bulk negative δ³⁷Cl values. Future field studies will benefit from a better understanding of hydrology and rainwater chemistry, and systematic collection of data for both Cl and Br.     

Magma associations in Ediacaran granitoids of the Cachoeirinha‒Salgueiro and Alto Pajeú terranes,northeastern Brazil: Forty years of studies

Granitic magmatism in the Cachoeirinha‒Salgueiro and Alto Pajeú terranes in the Transversal Zone Domain of the Borborema Province, northeastern Brazil, occurred in three main time intervals: 650–620 Ma, 590–560 Ma and 545–520 Ma. The oldest one is characterized by intrusions of magmatic-epidote (mEp) bearing calc-alkalic (some with trondhjemitic affinities) and high-K calc-alkalic plutons, synkinematic to the main regional foliation, under contractional tectonic regime, and exhibits T_DM < 2.0 Ga and ƐNd (0.6 Ga) from −1 to −4, and δ¹⁸O (zircon) values from 7.1 to 10‰_VSMOW. O- and Nd-isotope data for the 650‒620 Ma group of plutons is compatible with partial fusion of subducted oceanic basaltic crust (mEp-bearing calc-alkalic tonalites/granodiorites, equivalent to adakites). Voluminous intrusions in the 590–560 Ma interval are represented by abundant mEp-free high-K calc-alkalic, peralkalic, ultrapotassic, mEp-bearing high-K calc-alkalic, and less abundant shoshonitic magmas. Nd-model ages for this group of plutons vary from 1.5 to 2.5 Ga and ƐNd (0.6 Ga) ranges from −8 to −20; δ¹⁸O (zircon) varies from 6.4 to 7.9‰_VSMOW. Values of δ¹⁸O (zircon) for the 590‒560 Ma old group of plutons coupled with Nd isotope data are compatible with remelting of crustal (negative ƐNd, 1.6 to 2.0 Ga old) source rocks. O- and Nd-isotope data for this group of plutons are compatible with underplating of basaltic magma in the base of the lower crust for the high-K calc-alkalic granitoids, coeval to transcurrent movements along sigmoidal shear zones. Intrusion of one shoshonitic (Serrote do Arapuá), one calc-alkalic (Riacho do Icó) plutons besides the peralkalic Manaíra-Princeza Isabel dike set have witnessed this transition from contractional to transcurrent movements along shear zones, around 610‒600 Ma.     

Carbon-oxygen isotopic geochemistry of the Yangla Cu skarn deposit,SW China: Implications for the source and evolution of hydrothermal fluids

The Yangla Cu deposit is the largest Cu skarn deposit in the Jinshajiang tectonic belt. Based on the detailed observation of crosscutting relationships, three mineralization stages (i.e., pre-ore, ore and supergene) have been identified in the Yangla deposit. The pre-ore stage is dominated by prograde skarn. The ore stage is characterized by the precipitation of hydrous silicate minerals, Fe-oxides, Fe-Cu-Mo-sulfides, quartz and calcite, whose mineral assemblages were formed in the early and late sub-ore stages. The early sub-ore stage is marked by retrograde alteration with the deposition of hydrous silicate minerals (e.g., actinolite, epidote and chlorite), Fe-oxides, abundant Fe-Cu-Mo-sulfides, quartz and minor calcite. Whilst, the late sub-ore stage, associated with silicic and carbonate alteration, is represented by widespread thick quartz or calcite veins with disseminated pyrite, chalcopyrite, galena and sphalerite. We present new carbon-oxygen (C-O) isotopic compositions of the ore-hosting marble and hydrothermal calcite of this deposit. The hydrothermal calcite in the Yangla deposit was precipitated from both the early and late sub-ore stages. Calcite I from the early sub-ore stage is anhedral, and occurs as spot in the skarn or locally replaces the skarn minerals. Calcite II from the late sub-ore stage is distinguished by being coarse-grained, subhedral to euhedral and its occurrence in thick veins. Calcite I contains lower δ¹³C_PDB (−7.0‰ to −5.0‰) and δ¹⁸O_SMOW (7.2‰ to 12.7‰) than Calcite II (δ¹³C_PDB = −4.5‰ to −2.3‰; δ¹⁸O_SMOW = 10.7‰ to 19.4‰). In the δ¹³C_PDB vs. δ¹⁸O_SMOW diagram, the Calcite I and Calcite II data fall close to the igneous carbonatite field and between the fields of igneous carbonatite and marine carbonates, respectively. This suggests a dominantly magmatic origin for the early sub-ore fluids, and there might have been increasing carbonate wall rock involvement towards the late sub-ore stage. The ore-hosting marble (δ¹³C_PDB = −4.8‰ to −0.3‰; δ¹⁸O_SMOW = 10.2‰ to 23.9‰) also shows a positive δ¹³C_PDB vs. δ¹⁸O_SMOW correlation, which is interpreted to reflect the decreasing alteration intensity during the interactions between the hydrothermal fluids and ore-hosting carbonates. Simulated calculation suggests that both the Calcite I and Calcite II precipitated at 350 °C to 250 °C and 250 °C to 150 °C, respectively. We proposed that CO₂ degassing and water/rock interactions were likely the two major processes that precipitated the calcite and led to the observed C-O isotopic features of the Yangla Cu deposit.     

Fibrous calcite from the Ordovician of Tennessee: preservation of marine oxygen isotopic composition and its implications

Three categories of fibrous calcite from early to middle Caradoc platform-marginal buildups in east Tennessee can be delineated using cathodoluminescent microscopy, minor element chemistry and stable C-O isotopic composition. Bright luminescent fibrous cement has elevated Mn (>1000 p.p.m.), negative δ¹³C and intermediate δ¹⁸O values relative to other types of fibrous calcite. This cement reflects fibrous calcite that interacted with reducing Mn-rich fluids. Dully luminescent fibrous cement has elevated Fe (>400 p.p.m.), positive δ¹³C and negative δ¹⁸O values relative to other fibrous cements. This cement was stabilized by burial fluids. Nonluminescent fibrous cement has low Mn and Fe (generally below 400 p.p.m.) and positive δ¹³C and δ¹⁸O values relative to other types of fibrous calcite. The latter cement is interpreted to be the best material for determining the isotopic composition of calcite precipitated in equilibrium with early to middle Caradoc seawater, which is δ¹³C=1% PDB and δ¹⁸O=?4 to ?5‰ PDB. Results from this study and Ashgillian brachiopods indicate that the average δ¹⁸O composition of the Ordovician ocean, during nonglacial periods, was probably never more negative than ?3‰ SMOW. Assuming an Ordovician seawater δ¹⁸O value of ?1‰ SMOW, Holston Formation fibrous cements would have precipitated at temperatures between 27 and 36 °C, which is near the upper temperature limit for metazoans. A seawater δ¹⁸O value of ?2‰ SMOW yields temperatures ranging from 23 to 31 °C, while a ?3‰ SMOW value yields temperatures of 18–26 °C.     

Upper Albian OAE 1d event in the Chihuahua Trough,New Mexico,U.S.A.

Oceanic anoxic events are clues to ocean processes and are correlation datums. In North America only OAE 1a and 2 are well documented. Based on a low-resolution sampling program, a multi-proxy geochemical approach constrained by a biostratigraphic framework was utilized to identify OAE 1d in the upper part of the upper Albian Mesilla Valley Formation near El Paso, Texas. Chronostratigraphic and biostratigraphic evidence indicate that the OAE 1d event in the Mesilla Valley section is located in the lower part of the upper Albian–Cenomanian Ovoidinium verrucosum zone, which correlates with the uppermost Albian Parathalmanninella appenninica and Stoliczkaia dispar zones. The chronostratigraphic age of the geochemical event in the Mesilla Valley Formation is uppermost Albian (97.39–97.30 Ma).The classic geochemical signatures for OAEs are enriched total organic carbon (TOC) concentrations and coupled positive δ¹³C excursions. OAE 1d at this location records TOC values ranging from 0.25 to 0.69 wt.% throughout the Mesilla Valley Formation, where TOC increases during the OAE (21.0–40.0 m) to more than 0.40 wt.%. Interestingly, the organic matter in the Mesilla Valley is dominantly type III, which indicates a pervasive terrigenous source. Although marine organic matter is abundant from the base into the middle of the proposed OAE interval, it is progressively replaced by terrestrial material above the OAE section during progradation. The δ¹³C_organic values record a positive δ¹³C shift of +1.6‰ from −26.41 to −24.80‰ across the stratigraphic interval from 21.0 to 40.0 m, which correlates with OAE 1d.Mn and Fe geochemistry suggest the depositional conditions of the Mesilla Valley Formation were dominated by anoxic and possibly Fe-rich bottom waters, specifically during the time period associated with the OAE 1d event. This interpretation is supported by the presence of Fe enrichment recorded by Fe_Total/Al and Fe_{Highly Reactive}/Fe_T with the lack of Fe_pyrite/Fe_{Highly Reactive} associated with Mn depletion.     

Abiotic methane seepage in the Ronda peridotite massif,southern Spain

Abiotic methane in serpentinized peridotites (MSP) has implications for energy resource exploration, planetary geology, subsurface microbiology and astrobiology. Once considered a rare occurrence on Earth, reports of MSP are increasing for numerous localities worldwide in low temperature, land-based springs and seeps. We report the discovery of six methane-rich water springs and two ponds with active gas bubbling in the Ronda peridotite massif, in southern Spain. Water is hyperalkaline with typical hydrochemical features of active serpentinization (pH: 10.7 to 11.7, T: 17.1 to 21.5 °C, Ca–OH facies). Dissolved CH₄ concentrations range from 0.1 to 3.2 mg/L. The methane stable C and H isotope ratios in the natural spring and bubbling sites (δ¹³C_CH4: −12.3 to −37‰ VPDB; δ²H_CH4: −280 to −333‰ VSMOW) indicate a predominant abiotic origin. In contrast, springs with manmade water systems, i.e., pipes or fountains, appear to have mixed biotic-abiotic origin (δ¹³C_CH4: −44 to −69‰; δ²H_CH4: −180 to −319‰). Radiocarbon (¹⁴C) analyses show that methane C in a natural spring is older than ca. 50,000 y BP, whereas dissolved inorganic carbon (DIC) analysed in all springs has an apparent ¹⁴C age ranging from modern to 2334 y BP. Therefore most, if not all, of the CH₄ is allochthonous, i.e., not generated from the carbon in the hyperalkaline water. Methane is also released as bubbles in natural ponds and as diffuse seepages (∼10¹–10² mg CH₄ m⁻²d⁻¹) from the ground up to several tens of metres from the seeps and springs, albeit with no overt visual evidence. These data suggest that the gas follows independent migration pathways, potentially along faults or fracture systems, physically isolated from the hyperalkaline springs. Methane does not seem to be genetically related to the hyperalkaline water, which may only act as a carrier of the gas. Gas-bearing springs, vents and invisible microseepage in land-based peridotites are more common than previously thought. In addition to other geological sources, MSP is potentially a natural source of methane for the troposphere and requires more worldwide flux measurements.     

Calcite fracture fillings as indicators of paleohydrology at Laxemar at the Äspö Hard Rock Laboratory,southern Sweden

Isotopic compositions of C (δ¹³C), O (δ¹⁸O) and Sr (δ⁸⁷Sr) were determined for calcite fracture fillings in the crystalline rock penetrated by a 1.6 km drill hole at Laxemar, near the Äspö Hard Rock Laboratory (ÄHRL) in southern Sweden. These calcites precipitated from groundwater some time in the past, and their δ¹³C, δ¹⁸O and δ⁸⁷Sr values reflect those of the source waters. The present-day groundwater system is hydrochemically stratified with highly saline water underlying more shallow brackish and fresh water. The origin of this stratified system is probably related to past glaciations although the ultimate origin of the deep, highly saline water is still problematical. None of the calcite fracture fillings sampled below 900 m could have precipitated from any of the present-day ground waters which in view of the glacial history of the region is not surprising. However, several shallow calcite fracture fillings are formed by precipitation from the present-day groundwater. Coupled variations in δ¹³C, δ¹⁸O and δ⁸⁷Sr isotopes at depths in excess of 900 m suggest that these isotope systems in calcite are recording a time-dependent evolution of groundwater composition.     

Veracity of Neoproterozoic negative C-isotope values: The termination of the Shuram negative excursion

There is widespread interest in the Neoproterozoic period of the Earth's history (1000 to 542 Ma) because of unprecedented δ¹³C fluctuations to < − 10‰ PDB through thick (> 1000 m) succession of stratigraphically complex sedimentary rocks deposited during tens of millions of years. In contrast, Phanerozoic large negative C-isotope excursions have been interpreted as the result of diagenetic fluid mixing during carbonate stabilization and burial and are less enigmatic due to the excellent biostratigraphic control on their timing and duration.The Ediacaran Nafun Group of Oman (part of the Huqf Supergroup spanning the Cryogenian–Early Cambrian) contains a large δ¹³C negative excursion (the Shuram excursion) reaching values as negative as − 12‰ at the base of the Shuram Formation. A steady recovery to positive values occurs over the entire Shuram and half through the overlying Buah Formation, suggesting a duration on the order of tens of My. Based on trace metal, chemostratigraphic and sedimentological analyses, the carbon isotope record obtained from the Buah Formation of northern Oman indicates a systematic and reproducible shift of δ¹³C values from − 6‰ to + 1‰ in 1 — a demonstrably diagenetic altered carbonate-cemented siliciclastic facies, and 2 — a least diagenetically altered stromatolitic facies. The identical reproducible isotopic pattern in these time-equivalent sections combined to the presence of exceptionally preserved δ¹⁸O values around − 2 to + 1‰ associated with the most negative δ¹³C values rules out isotopic resetting by diagenetic fluids as a mechanism to explain these values.It is concluded that it is possible to retain depositional δ¹³C values in demonstrably diagenetically altered carbonates. This raises the issue of the ability to recognize diagenetic alteration of C-isotopic values in Neoproterozoic rocks where a robust time frame to support reproducibility is not available. The results of this study provide strong support to a non diagenetic origin of the negative Shuram C-isotope excursion, believed to be the most profound (in terms of amplitude and duration) in the Earth's history.     

Carbon isotope records of the early Albian oceanic anoxic event (OAE) 1b from eastern Tethys (southern Tibet,China)

The early Albian Oceanic Anoxic Event (OAE), i.e., OAE1b, is well documented in western Tethys and in the primary North Atlantic Ocean, but has not yet been reported from eastern Tethys. In this paper, we present bulk carbon isotope data of hemipelagites to examine if it was recorded in eastern Tethys. Samples were taken from the upper Chuangdepu Member (nannofossil zone CC8) of the lower Gyabula (former Shadui) Formation at the Bangbu section, Qonggyai, southern Tibet of China. The δ¹³C values mainly range from −0.6‰ to 1.8‰ with a maximum of 1.87‰ and a minimum of −0.69‰. Three stages of carbon isotope evolution were distinguished with three boundaries. By the constraint of the stratigraphic sequence and nannofossil biostratigraphic zone CC8, the rapid δ¹³C change and correlation with western Tethys and Atlantic Ocean together suggest that these three boundaries of the carbon isotope evolution probably correspond to three subevents of the early Albian OAE1b, and the subevent levels of upper Kilian, Paquier, and Leenhardt are recorded in eastern Tethys (southern Tibet). The fact that the amount of δ¹³C shift is less by ∼1.5–2.0‰ in eastern Tethys than in western Tethys and Atlantic Ocean is interpreted as a result of possible cool sea surface (∼14–16 °C) of the southeastern Tethys (northern Indian passive margin of Greater India), which was probably located in a medium–high latitude during the Albian, leading to low primary productivity. The recognition of OAE-1b from Tethys Himalaya can improve our understanding of the Tethys and global paleoclimatic and paleoceanographic changes during the mid-Cretaceous.     

Carbon isotope stratigraphy using carbonate cements in the Triassic Sherwood Sandstone Group: Corrib Field,west of Ireland

Carbon stable isotopes from carbonate minerals (mainly dolomite) from six wells from the Lower Triassic Sherwood Sandstones of the Corrib Gas Field, Slyne Basin, west of Ireland, allow stratigraphic correlation. The results also provide information on palaeoenvironmental change during the deposition of these continental redbed sedimentary rocks. The Triassic reservoir rocks have been buried to > 4000 m and heated to > 165 °C and now contain methane-rich gas. Although the oxygen isotopic signal has been at least partially reset during burial and heating, a primary carbon isotopic signal appears to have survived diagenesis. The carbon isotope ratio varies from − 3.2‰ to + 2.1‰. All six wells show similar stratigraphic changes when all the carbon isotope data are plotted relative to a major playa horizon. δ¹³C increases from about − 3‰ at the base of the Sherwood to about + 2‰ 170 m above the base. δ¹³C then decreases to about − 2‰ for the next 70 m and remains steady for the following 50 m. The top 20 m of the Sherwood contains carbonate with a δ¹³C values decreasing to about − 3‰. The occurrence of a stratigraphically-correlatable carbon isotope pattern implies that the primary evolution signal has been preserved. The change in δ¹³C correlates with indicators of aridity and biological stress such that the highest δ¹³C values are in sedimentary rocks deposited in a playa lake (arid times); these rocks contain the greatest quantity of dolomite cement. Conversely, the lowest δ¹³C values correspond to sedimentary rocks deposited from well-developed rivers (relatively humid times) from the lowest quantity of dolomite cement. The same carbon isotope evolution has been found in another well in the Slyne basin and in Belgium, suggesting that the palaeoenvironmental isotope signal in the Triassic sedimentary rocks of the Corrib Field may have a regional significance.     

The recharge of glacial meltwater and its influence on the geochemical evolution of groundwater in the Ordovician-Cambrian aquifer system,northern part of the Baltic Artesian Basin

The geochemical evolution of groundwater in the Ordovician-Cambrian aquifer system in the northern part of the Baltic Artesian Basin (BAB) illustrates how continental glaciations have influenced groundwater systems in proglacial areas. The aquifer system contains water that has originated from various end-members: recent meteoric water, glacial meltwater and relict Na-Cl brine. The saline formation water that occupied the aquifer system prior to the glacial meltwater intrusion has been diluted by meltwaters of advancing-retreating ice sheets. The diversity in the origin of groundwater in the aquifer system is illustrated by a wide variety in δ¹⁸O values that range from −11‰ to −22.5‰. These values are mostly depleted with respect to values found in modern precipitation in the area. The chemical and isotopic composition of groundwater has been influenced by mixing between waters originating from different end-members. In addition, the freshening of a previously saline water aquifer due to glacial meltwater intrusion has initiated various types of water-rock interaction (e.g. ion exchange, carbonate mineral dissolution).     

Geology and geochemistry of the sediment-hosted Cheshmeh-Konan redbed-type copper deposit,NW Iran

The several-hundred-m-thick Miocene Upper Red Formation in northwestern Iran hosts stratiform and fault-controlled copper mineralization. Copper enrichment in the percent range occurs in dm-thick carbonaceous sandstone and shale units within the clastic redbed sequence and consists of fine-grained disseminated copper sulfides (chalcopyrite, bornite, chalcocite) and supergene alteration minerals (covellite, malachite and azurite). The copper mineralization formed after calcite cementation of the primary rock permeability. Copper sulfides occur mainly as replacement of diagenetic pyrite, which, in turn, replaced organic matter. Electron microprobe analysis on bornite, chalcocite and covellite identifies elevated silver contents in these minerals (up to 0.12, 0.72 and 1.21 wt%, respectively), whereas chalcopyrite and pyrite have only trace amounts of silver (<0.26 and 0.06 wt%, respectively). Microthermometric data on fluid inclusions in authigenic quartz and calcite indicate that the Cu mineralization is related to a diagenetic fluid of moderate-to low temperature (Th = 96–160 °C) but high salinity (25–38 wt% CaCl₂ equiv.). The range of δ³⁴S in pyrite is −41.9 to −16.4‰ (average −31.4‰), where framboidal pyrite shows the most negative values between −41.9 and −31.8‰, and fine-grained pyrite has relatively heavier δ³⁴S values (−29.2 to −16.4‰), consistent with a bacteriogenic derivation of the sulfur. The Cu-sulfides (chalcopyrite, bornite and chalcocite) show slightly heavier values from −14.6 to −9.0‰, and their sulfur sources may be both the precursor pyrite-S and the bacterial reduction of sulfate-bearing basinal brines. Carbonates related to the ore stage show isotopically light values of δ¹³C_V-PDB from −8.2 to −5.1‰ and δ¹⁸O_V-PDB from −10.3 to −7.2‰, indicating a mixed source of oxidation of organic carbon (ca. −20‰) and HCO₃⁻ from seawater/porewater (ca. 0‰). The copper mineralization is mainly controlled by organic matter content and paleopermeability (intragranular space to large fracture patterns), enhanced by feldspar and calcite dissolution. The Cheshmeh-Konan deposit can be classified as a redbed-type sediment-hosted stratiform copper (SSC) deposit.     

Oxygen,carbon and sulphur isotope studies in the Keban Pb–Zn deposits,eastern Turkey: An approach on the origin of hydrothermal fluids

Pb–Zn deposits are widespread and common in various parts of the Taurus Belt. Most of the deposits are of pyrometasomatic and hydrothermal origin. The Keban Pb–Zn deposits are located along the intrusive contact between the Paleozoic – Lower Triassic Keban Metamorphic Formation and the syenite porphyry of the Upper Cretaceous Keban igneous rocks. Various studies have already been carried out; using fluid inclusion studies on fluorite, calcite and quartz on the pyrite–chalcopyrite bearing Keban ore deposits. This study focuses on the interpretation of stable isotope compositions in connexion with fluid inclusion data. Sulphur isotope values (δ³⁴S) of pyrite are within the range of ?0.59 to +0.17‰_V-CDT (n = 10). Thus, the source of sulphur is considered to be magmatic, as evidenced by associated igneous rocks and δ³⁴S values around zero“0”. Oxygen isotope values δ¹⁸O of quartz vary between +10.5 and +19.9‰_(SMOW). However, δ¹⁸O and δ¹³C values of calcite related to re-crystallized limestone (Keban Metamorphic Formation) reach up to +27.3‰_(SMOW) and +1.6‰_(PDB), respectively. The δ³⁴S, δ¹³C and δ¹⁸O values demonstrate that skarn-type Pb–Zn deposits formed within syeno-monzonitic rocks and calc-schist contacts could have developed at low temperatures, by mixing metamorphic and meteoric waters in the final stages of magmatism.     

High-precision analysis of carbon isotopic composition for individual CO2 inclusions via Raman spectroscopy to reveal the multiple-stages evolution of CO2- bearing fluids and melts

The carbon isotopic composition of CO₂ inclusions trapped in minerals reflects the origin and evolution of CO₂-bearing fluids and melts, and records the multiple-stages carbon geodynamic cycle, as CO₂ took part in various geological processes widely. However, the practical method for determination isotope composition of individual CO₂ inclusion is still lacking. Developing a microanalytical technique with spatial resolution in micrometers to precisely determinate the δ¹³C value of individual CO₂ inclusion, will make it possible to analyze a tiny portion of a zoning mineral crystal, distinguish the differences in micro-scale, and possible to find many useful information that could not be obtained with the bulk extraction and analysis techniques. In this study, we systematically collected Raman spectra of CO₂ standards with different δ¹³C values (?34.9 ‰ to 3.58 ‰) at 32.0 °C and from ～7.0 MPa to 120.0 MPa, and developed a new procedure to precisely determinate the δ¹³C value of individual CO₂ inclusion. We investigated the relationship among the Raman peak intensity ratio, δ¹³C value, and CO₂ density, and established a calibration model with high accuracy (0.5 ‰?1.5 ‰), sufficient for geological application to distinguish different source of CO₂ with varying δ¹³CO₂. As a demonstration, we measured the δ¹³C values and the density of CO₂ inclusions in the growth zones of alkali basalt-hosted corundum megacrysts from Changle, Shandong Province. We found the significant differences of density and δ¹³C between the CO₂ inclusions in the core of corundum and those inclusions in the outer growth zones, the δ¹³C value decreases from core to rim with decreasing density: δ¹³C values are from ?7.5 ‰ to ?9.2 ‰ for the inclusions in the core, indicating the corundum core was crystallized from mantle-derived magmas; from ?13.5 ‰ to ?18.5 ‰ for CO₂ inclusions in zone 1 and from ?16.5 ‰ to –22.0 ‰ for inclusions in zone 2, indicating the outer zones of corundum grew in a low δ¹³C value environment, resulted from an infilling of low δ¹³C value fluid and/or degassing of the ascending basaltic magma.