Negative δ18O Values Research Articles

Formation temperature of microcrystalline dolomite in oil-rich black shale: Implications for hydrocarbon accumulation in a volcanic-lacustrine rift basin

Lacustrine microcrystalline dolostones in the ancient records have been commonly interpreted as of an evaporitic origin, on the basis of their numerous occurrences in modern evaporative shallow lakes. This interpretation obscures the forming mechanisms of dolostones formed in a deep lacustrine setting, where dolostones interbedded with shale become a focus of hydrocarbon source rocks in recent years. In this study, an alternative non-evaporitic origin of dolomite is interpreted for a Permian lacustrine laminated dolostone. The dolostones are thinly intercalated with tuffaceous shales and composed mainly of volumetrically abundant, low-ordered, subhedral to euhedral, microcrystalline dolomites with a variable amount of pyroclastics. Evidence for evaporation (e.g., the presence of halite, gypsum and shrinkage cracks) and typical methanogenic microfossils is absent. Instead, our dolostones are unevenly and locally distributed as thin beds or lenses and intercalated with tuffaceous shale and have a formation temperature ranging from 31.4 to 73.8 °C, as estimated from dolomite clumped oxygen? isotope thermometry. In addition, the dolostones have a87Sr/86Sr ratio similar to that of the mantle (0.705154 on average) and extremely negative δ18O (−2.9‰ to −24‰) and positive δ13C (5.1‰–10.8‰) values. A lateral trend of increasing formation temperature of the dolostone toward the volcanic center correlates with the trends of: 1) an increasing amount of pyroclastics, euhedral dolomite crystals, Fe, and TOC, and an increasingly positive δEu value, and 2) decreasing values of 87Sr/86Sr and δ18O. The correlation suggests that a local temperature increase and frequent elemental (Fe and Mg) cycling between the conditions of dolomite supersaturation and undersaturation, which are controlled by episodic volcanic-hydrothermal activities are the causes for dolomite nucleation and growth, resulting in the formation of massive dolostone during deposition and shallow burial. The process also affected organic matter accumulation and local transformation to immature or early mature hydrocarbon during deposition and early burial. The results establish a volcanism-controlled temperature range for primary dolomite nucleation and growth, as well as hydrocarbon generation in a deep lake environment during the period of deposition and early burial, and provide insights on shale oil exploration in petroliferous rift basins.

Lutetian–Bartonian (Middle Eocene) micropalaeontology, biostratigraphy and palaeoecology of the Mengen Coal Basin, Northwest Türkiye (Turkey)

This study focuses on the upper Lutetian–lower Bartonian Tokmaklar Formation in the Mengen Basin of Northwest Türkiye (Turkey), examining various aspects such as biostratigraphy, palaeoecology, and isotope data (δ18O and δ13C), providing insights into the geological history and environmental conditions during this interval. Moreover, the study incorporates coal petrography on four samples to explore a potential correlation between the coalification process and the preservation of palynomorphs. The formation is informally divided into two distinct categories: a coal-bearing sequence positioned at the base of the formation and a coal-free sequence above it. However due to dense vegetation and soil cover in the area, the availability of suitable outcrops for measured sections and obtaining samples is severely limited. Therefore, we relied on drilling data from Turkish Coal Enterprises (TCE) for the purpose of coal exploration, as well as two partial sections (Ender and Çorak) from underground mining. Microapalaeontological evidences involving benthic foraminiferans, ostracods, and palynomorphs, along with isotope data (δ18O and δ13C), suggest that the Tokmaklar Formation was deposited as a result of a local transgressive process during the late Lutetian–early Bartonian. Furthermore, palynological data, particularly the existence of mangroves such as Nypa, lepidocaryoid palm and Acrostichum aureum, coupled with quantitative palaeoclimate analysis, the negative δ18O values, and the lower δ13C values indicate a warm, probably tropical climate under high rainfall.

Diagenetic archives of the deeply-buried Cambrian Xiaoerbulake Formation microbialite reservoirs, Bachu-Tazhong area, Tarim Basin, China

The deep-burial Cambrian Xiaoerbulake Formation microbialites reservoir hosts significant hydrocarbon in the Tarim Basin. However, limited understandings of fluid-rock interactions from deposition to deep-burial regimes hamper petroleum exploration. Here, petrological observations, in-situ elemental contents and porosity-permeability analyses were performed to understand the complex interactions and the microbialites performance. Dolo-mudstone, crystalline dolostone, and four kinds of microbialites are distinguished as dolostones types. In the depositional stage, microbialites are characterized by (evaporated) seawater dolomitization with the mediation of microbial activity. The dolostone matrix shows seawater-like δ13C, δ18O and REY patterns. Thrombolitic and foam spongy dolostones from high-energy subtidal to intertidal zones show large framework pores compared to stratiform stromatolitic dolostones from low-energy intertidal zones. In near-surface settings, meteoric diagenesis generates secondary pores, while fine-crystalline dolomite cements partially fill pores. During the shallow to intermediate burial regimes, medium-to coarse-crystalline dolomite cements yield negative δ18O values and slightly flat REY patterns. The precipitation of this dolomite phase further decreases reservoir porosity. In deep burial settings, one type of saddle dolomite is likely to be formed by replacement from carbonate precursors, while the second type might be directly precipitated from hydrothermal fluids. These two types of saddle dolomites show different cathodoluminescent characteristics and geochemical data. Subsequently, two types of calcite cements are formed by the calcification of dolomite and yield significant negative δ13C values due to thermochemical sulfate reduction. Finally, the third calcite phase is likely to be a direct precipitate from burial brines. Hydrothermal activity and thermochemical sulfate reduction generate and/or re-distribute secondary pores. Based on the plethora of depositional environments and fluid-rock interactions, thrombolitic dolostone generally yields higher porosity-permeability than other types of microbialites. Thrombolite reservoir has high potential for petroleum exploration and is significant for those concerned with microbialite hydrocarbon fields.

Dipole Pattern of Holocene Hydroclimate Variations Across the Asian Drylands: Critical Evidence From West Asia

AbstractExploring the spatiotemporal differences of hydroclimate variations is crucial for managing future climate change. In the Asian drylands, West Asia (WA) and arid central Asia (ACA) are both climatically dominated by the westerlies and have shown a dipole pattern in precipitation variation during the past several decades. However, it is unclear whether such a difference exists during the Holocene, mainly because the dispute between the δ18O‐based early Holocene hydroclimate optimum and the pollen‐based mid‐Holocene optimum in WA. Here we present a precisely dated record based on lipid biomarkers from Almalou Peatland in the western Iranian Plateau. The chain length of n‐alkanoic acids was interpreted as a hydroclimate indicator based on a proxy validation study. Our record reveals a wetting trend during 9–7.5 cal ka BP, a mid‐Holocene hydroclimate optimum (7.5–3 cal ka BP), and a rapidly drying trend during 3–0 cal ka BP. The hydroclimate variation was supported by a water‐level reconstruction from the same core. The most negative δ18O values during the early Holocene could be partly attributed to the impacts of water vapor sources. Comparing our reconstruction from WA to those from ACA, we found a dipole pattern of hydroclimate variations on the millennial timescale during the Holocene. The simulation results revealed that, unlike the persistent wetting trend in ACA, the pivotal shift of spring insolation led to a transition from wetting to drying conditions in WA, ultimately leading to the generation of dipole pattern. This demonstrates that despite the consistent control by westerlies over the Asian drylands, there are distinct spatial differences in hydroclimate responses to natural forcings.

The stable isotope hydrology of Sable Island, Nova Scotia, Canada with implications for evaluating the water budget of wild horses

ABSTRACT We investigated the stable isotope hydrology of Sable Island, Nova Scotia, Canada over a five year period from September, 2017 to August, 2022. The δ 2H and δ 18O values of integrated monthly precipitation were weakly seasonal and ranged from –66 to –15 ‰ and from –9.7 to –1.9 ‰, respectively. Fitting these monthly precipitation data resulted in a local meteoric water line (LMWL) defined by: δ 2H = 7.22 ± 0.21 · δ 18O + 7.50 ± 1.22 ‰. Amount-weighted annual precipitation had δ 2H and δ 18O values of –36 ± 11 ‰ and –6.1 ± 1.4 ‰, respectively. Deep groundwater had more negative δ 2H and δ 18O values than mean annual precipitation, suggesting recharge occurs mainly in the winter, while shallow groundwater had δ 2H and δ 18O values more consistent with mean annual precipitation or mixing of freshwater with local seawater. Surface waters had more positive values and showed evidence of isolation from the groundwater system. The stable isotopic compositions of plant (leaf) water, on the other hand, indicate plants use groundwater as their source. Fog had δ 2H and δ 18O values that were significantly more positive than those of local precipitation, yet had similar 17O-excess values. δ 2H values of horsehair from 4 individuals lacked seasonality, but had variations typical to those of precipitation on the island. Differences in mean δ 2H values of horsehair were statistically significant and suggest variations in water use may exist between spatially disparate horse communities. Our results establish an important initial framework for ongoing isotope studies of feral horses and other wildlife on Sable Island.

Holocene savanna hydroclimate record from Kinrara Lake, north-east Queensland, Australia

We present a record of hydroclimatic change over the Holocene from Kinrara Lake, in a seasonally dry savanna location in north-eastern Australia. The record is derived from the oxygen (δ18O) and carbon stable isotope (δ13C) composition of endogenic and biogenic (gastropod) carbonate. The stable isotope proxy records are complemented by elemental geochemical (Itrax) and sedimentological proxy data providing a record of hydrologic and climate change, spanning 10.5 ka to the present day. Two main forms of endogenic carbonate occur in the lake sediments; (i) carbonate associated with biofilms during the early-Holocene, under drier-than-modern conditions, (ii) photosynthetic and evaporatively-enriched precipitates in the late-Holocene, associated with enhanced climate variability inducing drought periods. Strong relationships between negative δ18O values and increased Ti, Rb, Fe/Mn, inc/coh, are linked with strengthened monsoon conditions, while enhanced periods of dryness are inferred from more positive δ18O values, increased Ca/∑Fe, Ti, Al, and subsequent intensifications in lake productivity (higher Si/Ti, S/Ti, Mn/Ti). Three distinct phases can be identified in palaeohydrological history of the lake; (i) a relatively stable drier-than-modern phase during the early-Holocene (10.5 to 8.2 ka), (2) a significantly wetter-than-modern, monsoon-dominated phase through the mid-Holocene into the late-Holocene (8.2–2.8 cal yr BP), and (3) after 2.8 ka, increased intensity of ENSO-related rainfall variability during the late-Holocene, continuing into the present.

Summer insolation controlled movements of Intertropical Convergence Zone during last glacial cycle in northern South America

A paradigm in paleoclimatology holds that shifts in the mean position of the Intertropical Convergence Zone were the dominant climatic mechanism controlling rainfall in the tropics during the last glacial period. We present a new paleo-rainfall reconstruction based on speleothem stable oxygen isotopes record from Colombia, which spans most of the last glacial cycle. The strength and positioning of the Intertropical Convergence Zone over northern South America were more strongly affected by summer insolation at high northern latitudes than by local insolation during the last glacial cycle, resulting in an antiphased relationship with climate in the Cariaco Basin. Our data also provide new insight into how orbital forcing amplified/dampened Intertropical Convergence Zone precipitation during millennial-scale events. During Greenland Stadial events, the Intertropical Convergence Zone was positioned close to the latitude of El Peñon, as expressed by more negative δ18O values. Greenland Interstadial events are marked by relatively high stable oxygen isotope values and reduced rainfall in the El Peñon record, suggesting a northward withdrawal of the Intertropical Convergence Zone. During some Heinrich Stadial events, and especially Heinrich Stadial 1, the Intertropical Convergence Zone must have been displaced away from its modern location near El Peñon, as conditions were very dry at both El Peñon and Cariaco.

Diagenetic Evolution of Upper Cretaceous Kawagarh Carbonates from Attock Hazara Fold and Thrust Belt, Pakistan

A recent hydrocarbons discovery in 2021 in the Kawagarh Formation has brought attention to the significance of sedimentology and specifically diagenesis for understanding and characterizing the reservoir properties. The diagenetic history and multiscale processes that contributed to diagenesis were vaguely known. This study aimed to reconstruct various diagenetic phases, paragenetic sequences, and the interrelationship of these phases in the Kawagarh Formation. The diagenetic processes were identified and characterized through an integrated methodology utilizing the outcrop, petrographic, and geochemical analyses. Early calcite cementation was found to occur in the early stages of marine burial diagenesis involving pore fluid originating from the dissolution of aragonite in interlayer marl/mudstone beds and reprecipitating as microspar in adjacent limestone beds. The absence of mechanical compaction in wackstone and mudstone facies and the presence of late compaction in lithified packstones clearly imply that early calcite cementation occurred prior to compaction. Dolomitization with stylolites coupled with significant negative oxygen (δ18O) isotope values implies a fault-related hydrothermal dolomitization model. Uplift introduced the fractures and low Mg fresh fluids to the system which caused calcitisation in shallow burial settings. The depleted δ13C and negative δ18O values indicate the mixing of surface-derived waters with hot burial fluids during the calcitization. This study offers valuable insights into several aspects related to the formation and the basin itself, including burial depths, fluid influx, and geochemical gradients. It also sheds light on the evolution of reservoir properties such as porosity and permeability in dolomitization fronts. Such insights can be used to gain a deeper understanding about the burial history, basin evaluation, and reservoir characterization for hydrocarbon exploration.

Spatial characteristics of hydrochemistry and stable isotopes in river and groundwater, and runoff components in the Shule River Basin, Northeastern of Tibet Plateau

Water resources play a crucial role in constraining the high-quality development of the arid, necessitating an in-depth investigation and understanding of hydrological processes, hydrochemical characteristics, and their influencing factors amidst climate change. This study meticulously examined and analyzed the hydrochemistry and stable isotope composition (δ18O and δD) of river and groundwater within the Shule River Basin (SRB). Results showed that both river (mean: 8.01) and groundwater (mean: 7.92) had alkaline pH values, while average total dissolved solids were measured at 709.25 mg/L in river and 861.88 mg/L in groundwater, indicating predominance of fresh water sources. HCO3−, SO42−, Na+ and Ca2+ were the most abundant ions, influenced by evaporation-crystallization processes and rock weathering. The dominated hydrochemical facies in both river and groundwater were Ca–HCO3 type in the upper (UR) and the middle reaches (MR), while Ca–Mg–Cl type in the lower reaches (LR). The local meteoric water line (LMWL) was defined as δD = 8.01δ18O + 18.48 (R2 = 0.98, n = 163; P < 0 0.001). The more negative δ18O and δD values in river and groundwater were plotted nearby and lower right of the LMWL, implying that the important recharge source of those waters is from precipitation. The relationship between river δ18O and elevation showed an increase of 0.14‰/100 m in the UR, but a negative correlation with a rate of −0.47‰/100 m in the MR and LR. Precipitation, groundwater, baseflow and meltwater accounted for 62.5%, 19.8%, 11.9% and 5.8% of the UR river, respectively, during the observed period, according to the end-member mixing analysis. These runoff components displayed distinct seasonal variations, primarily driven by precipitation during the early and groundwater/baseflow during the rapid and end-stage ablation periods. The observed alterations in hydrological elements present both opportunities and challenges for water resource management across the SRB, and adaptive measures have been proposed based on our study. These findings provide valuable insights into efficient utilization of water resources from water chemistry and environmental isotopes.

PRE‐, SYN‐ AND POST‐TECTONIC DIAGENETIC EVOLUTION OF A CARBONATE RESERVOIR: A CASE STUDY OF THE LOWER CRETACEOUS FAHLIYAN FORMATION IN THE DEZFUL EMBAYMENT, ZAGROS FOLDBELT, SW IRAN

Lower Cretaceous carbonates of the Fahliyan Formation form prolific reservoir rocks at oilfields in the Dezful Embayment, central Zagros fold‐thrust belt, SW Iran. The carbonates have undergone significant diagenetic alteration in phases which can in general be linked to the pre‐, syn‐ and post‐tectonic evolution of the fold‐thrust belt. This paper investigates the impact of diagenetic processes on the reservoir quality of the carbonates using integrated petrographic, geochemical and sedimentological analyses of subsurface and outcrop samples of the formation. Diagenetic alterations include:(i) pre‐tectonic eogenesis in the marine and shallow‐burial realm, which resulted in micritization of allochems and cementation by equant and isopachous calcite rims and framboidal pyrite together with limited dolomitization and dissolution of metastable bioclasts. The isotopic compositions of micrite and early calcite cement depart from postulated values of Lower Cretaceous marine carbonates, signifying early stabilization of precursor metastable carbonate minerals and the possible effects of the incursion of meteoric waters and/or increasing burial temperatures;(ii) mesogenesis during the subsequent syn‐tectonic phase, which included Late Cretaceous ophiolite obduction at the northern margin of the Arabian Plate and the later Zagros orogeny in the Miocene‐Pliocene. Diagenetic modifications included the emplacement of hydrocarbons, the development of stylolites and fractures, and the precipitation of saddle dolomite, replacive rhombic dolomite, discrete pyrite, microcrystalline quartz, kaolin and anhydrite. The average stable isotope compositions of saddle dolomite (δ18O: ‐6.9 ‰ ± .9 and δ13C 0.5 ‰ ± 1.6, respectively) also reflects the influence of high temprature basinal fluids;and (iii) “late” (telogenetic, post‐tectonic) uplift‐related modification starting in the Pliocene, when the incursion of meteoric waters resulted in the formation of vugs, the calcitization of dolomite, and cementation by fracture‐filling blocky calcite. The negative δ18O and δ13C stable isotope values (average: ‐5.5 ‰ ± 1.5; and ‐3.6 ‰ ± 5.9, respectively) of late blocky calcite cement suggest the incursion of meteoric water into the system.This study demonstrates that diagenetic processes in carbonates in the Fahliyan Formation, which exerted a significant control on the distribution of secondary porosity, can be related to the tectonic evolution of the central Zagros fold‐thrust belt. Thus, constraining the diagenetic history of carbonate successions within the context of their wider tectonic evolution is important for the prediction of the spatial and temporal distribution of reservoir quality.

First record of Oceanic Anoxic Event 2 in the Eastern Carpathians: implications for chemostratigraphic and biostratigraphic correlations

This study aims to investigate a marlstone and claystone succession located at the southern end of the Eastern Carpathians, a region where oceanic anoxic event 2 (OAE2) has not been pointed out so far. Toward the upper half of this succession, a 17-cm-thick black shale was identified. The investigated depositional interval lies within the late Cenomanian–early Turonian, encompassing the UC3d up to UC7 nannofossil zones. The δ13C values fluctuated between 2.06‰ and 3.89‰, showing a positive isotope excursion that was assigned to OAE2. The δ13C isotope curve displays the following intervals: pre-excursion, first build-up, trough, second build-up, plateau, and post-excursion. Within the second build-up interval of OAE2, a substantial shift in CaCO3 values, accompanied by high concentrations of total organic carbon and a significant decline in the abundance and diversity of calcareous nannofossil assemblages, was observed. The nannofossil turnover related to OAE2 climax revealed predominance of Watznaueria barnesiae and temporary disappearance from the record of surface-water higher fertility taxa, such as Biscutum constans, Zeugrhabdotus erectus, and Discorhabdus ignotus. Above OAE2, peaks of Eprolithus floralis, followed by increased abundance of Eiffellithus turriseiffelii and Nannoconus spp., were identified. In the lower part of the studied succession (i.e., the upper Cenomanian UC3d nannofossil subzone), during the pre-excursion characterized by low δ13C values and less negative δ18O values, a small group of nannofossils more related to mid- and high-paleolatitudes, such as Crucibiscutum salebrosum, Repagulum parvidentatum, and Seribiscutum primitivum, is present, always showing a low abundance.

Seasonality and lake water temperature inferred from the geochemistry and sclerochronology of quaternary freshwater bivalves from the Turkana Basin, Ethiopia and Kenya

Reconstructing past environmental variability at short (annual-decadal) time scales is critical for understanding ecosystem change and ecological drivers of evolution. One promising approach to reconstructing that variability is through the use of stable isotope geochemistry and sclerochronology, the study of growth banding in organisms that undergo accretionary growth. We used a combination of sclerochronology, conventional stable isotope ratios and clumped isotope paleotemperatures to improve our understanding of past seasonality and climate variability in the Turkana Basin (Kenya, Ethiopia), which experiences a highly seasonal (tropical semi-desert) climate. In this case study, we apply these approaches to both Early Pleistocene and Holocene bivalve shells (Etheria and Pseudobovaria) to develop a model using various proxies of seasonal-interannual temporal variability in lake temperature and isotope chemistry. We leverage this model to better understand how lakes in the Turkana Basin have changed over short time-scales in the past. One modern (1979) river oyster has exclusively negative δ18O values through ∼1.5 yrs of growth and clumped isotope temperature reconstructions (30.1–31.5 °C) consistent with a river delta provenance. Late Holocene shells show a wider range of isotopic variability within each shell's growth history than the modern sample (∼2‰ for the modern sample vs. 5–7‰ for the Late Holocene samples) and near modern paleotemperatures, suggesting growth under both seasonal Omo flood pulse and lacustrine conditions. Middle Holocene shells exhibit less δ18O variability, consistent with growth in fresher Lake Turkana water at the end of the African Humid Period (12-5 ka), and with both surface water temperatures and water column temperature range similar to the Late Holocene. The Early Pleistocene shells have large seasonal δ18O cycles (4–7‰), with δ18O values comparable to modern and Holocene deltaic shells, and a large range of paleotemperatures (21.8–31.3 °C, including temperatures notably cooler than those measured in the modern lake: 25–31 °C), reflecting growth under significant seasonality in paleo-Omo River runoff. Oxygen isotope cycles suggest high degrees of seasonality of the paleo-Omo River runoff (or that of other major influents) into paleolake Lorenyang at ∼1.6 Ma, which may be similar to modern hydroclimate conditions. Comparison to prior datasets from nearby outcrops in the same basin suggests an increase in hydroclimate seasonality between 1.9 and 1.6 Ma. The combination of clumped isotope paleotemperature estimates from shallow water species such as E. elliptica with TEX86 measurements (derived here from previously published, contemporaneous sediment core studies from the south basin of Lake Turkana), which record temperatures near the oxycline, may provide a new approach to estimating past temperature variability along a vertical profile in lakes, thereby providing information on water column mixing regimes. Our approach greatly expands our toolkit for understanding coupled climate seasonality and variability in the Turkana Basin.

Mineralogy, geochemistry, and genesis of lithium-bearing argillaceous sediments associated with the Neogene Bigadiç borate deposits, Balıkesir, western Anatolia, Türkiye

The Li-bearing claystone and carbonate are sedimentary rocks deposited in the lacustrine environment hosting the Bigadiç borate deposits in western Anatolia. The purpose of this paper is to explain the mineralogical, geochemical, stable isotope characterizations and formation of Li-rich claystone (hectorite, saponite), and have strategic, technological, and economic importance for the country's economy, which have not been sufficiently studied previously. In the rhyolitic and dacitic tuffs, sanidine and plagioclase crystals were altered, biotite and hornblende, Fe-oxidized, locally opaque, and chloritized in a sericitized, Fe-oxidized, argillized, calcified, and zeolitized glassy matrix. The claystone consists mainly of smectite and minor illite, volcanogenic quartz, feldspar, mica, hornblende, and occasionally calcite, aragonite, dolomite, and gypsum/anhydrite. Hectorite and saponite were determined based on the expansion of their basal peaks following heating at 500 °C and solvation with ethylen-glycol; additionally, hectorite expanded, and saponite was not affected after glycerine-saturated Cs-smectite and heating at 100 °C for 20 h. Smectite shows webby to crenulated forms, and coexist with feldspar, volcanic glass, rhomboidal calcite, blocky gypsum/anhydrite, and Fe-oxide phases. The Li values increase up to 2650 ppm in the smectite-rich claystone and marl, and up to 449 ppm in the volcanic rocks. The positive correlation of REE with each of SiO2, Al2O3, and K2O; positive correlation of MgO vs. Li, and increase of MgO + CaO, Sr, Li, LREE relative to MREE and HREE; negative Eu anomaly and high values of As and S suggest that the feldspar, mica, and hornblende alteration originating from the Miocene volcanic and pyroclastic materials and presence of gypsum/anhydrite during the hydrothermal alteration activities were the sources for the smectite formation. The high negative δ18O values of calcite, the δD and δ18O values of smectite and δ34S‰ and δ18O‰ values of gypsum, and the 87Sr/86Sr isotope ratios range of calcite and gypsum suggest the contribution of mixing meteoric and hydrothermal environmental conditions during the depositional and diagenetic process(es) in the playa lake environment.

Secular change in the nature of mantle and tectonic evolution of northwestern margin of the Yangtze Block during Neoproterozoic: Constraints from the mafic intrusions and associated granitoids of the Hannan and Xiaomoling complexes

To reveal the Neoproterozoic tectonic evolution of the northwestern margin of the Yangtze Block, a petrological and geochemical study was carried out for the mafic intrusions and associated granitoids from the Hannan and Xiaomoling Complexes. The ca. 900–880 Ma Xiaomoling diorite and granodiorite have high K2O contents (2.29–3.57 wt%) and belong to the high-K calc-alkaline series. They display depleted whole-rock Sr–Nd–Hf isotope compositions (0.70151–0.70398, +0.6 to +2.5 and +4.4 to +11.2, respectively) and positive zircon εHf(t) (+3.6 to +9.9) with slightly elevated bulk zircon δ18O values (6.4–6.8 ‰) and minor Paleoproterozoic (∼2.2 Ga) inherited zircons, indicative of derivation from remelting of juvenile mafic crust with crustal contamination in a continental arc setting. The ca. 866 Ma Hannan gabbro-diorites show enrichments in LILEs and LREEs and depletions in HFSEs and display depleted Sr–Nd–Hf isotope compositions (0.70267, +5.4 and +17.8, respectively), positive zircon εHf(t) values (+8.6 to +12.0) and mantle-like zircon δ18O values (5.0–6.2 ‰), suggesting that they were generated through flux melting of a depleted mantle wedge. The ca. 850–840 Ma Xiaomoling hornblende gabbro and diabase display depleted Sr–Nd–Hf isotope compositions (0.70279–0.70288, +2.7 to +3.2 and +9.8 to +10.5, respectively) and are characterized by high Nb/U ratios and less enrichment in LREEs and LILEs, indicating that they were formed by decompression melting of a depleted mantle wedge in a back-arc setting. However, the coeval high-Mg diorite displays enriched whole-rock Sr–Nd–Hf isotopes (0.70477–0.70701, −4.0 to −6.0 and −7.2 to −7.4, respectively), negative zircon εHf(t) values (−1.6 to −9.2) and elevated zircon δ18O values (5.3–7.5 ‰), reflecting that the mantle-derived melts have underwent various degrees of crustal contamination. The ca. 780 Ma Hannan gabbro is characterized by earlier crystallization of plagioclase than clinopyroxene, implying that their parental magma is anhydrous. Additionally, the relatively shallow emplacement depth and tholeiitic affinities imply that they were generated by mantle decompression melting probably associated with a continental rift environment in response to Rodinia breakup. Taken together, the secular changes in the geochemical and isotopic compositions of these mafic rocks in the northwestern margin of the Yangtze Block record the evolution from a continental arc at ca. 900–880 Ma to continental rifting at ca. 780 Ma.

Two modes of gypsum replacement by carbonate and native sulfur in the Lorca Basin, SE Spain

Organoclastic sulfate reduction and bacterial sulfide oxidation have been suggested to explain the formation of authigenic carbonate and native sulfur replacing gypsum in the Lorca Basin, Spain. To gain more insight into the nature of this replacement, two types of sulfur-bearing carbonate (laminated and brecciated) from the late Miocene Lorca Basin were studied. Petrographic observations revealed that a sulfur-bearing laminated carbonate consists of clay-rich and dolomite-rich laminae with carbonate and native sulfur pseudomorphs after gypsum. Positive δ18Ocarbonate values in the laminae (δ18O = 2.6‰) and lipid biomarkers of halophilic archaea (e.g., extended archaeol) suggest formation under hypersaline conditions. Bacterial sulfate reduction, evidenced by biomarkers such as iso-C15, iso-C16, and iso-C17 fatty acids, produced hydrogen sulfide inducing the abiotic formation of organic sulfur compounds. Gypsum in the laminated carbonate likely dissolved due to undersaturation as evidenced by a low content of carbonate-associated sulfate (3,668 ppm) and 34S-enriched native sulfur (δ34S = 22.4‰), reflecting sulfate limitation. Such 34S-enrichment implies limited fluid flow, which probably restricted the supply of molecular oxygen required for native sulfur formation through oxidation of hydrogen sulfide. Alternatively, sulfate-reducing bacteria may have mediated native sulfur formation directly as a stress response to environmental conditions. The formation of sulfur-bearing calcite in brecciated carbonates is due to post-depositional alteration. Negative δ18O values of the calcite (δ18O = −1.5‰) and a tenfold decrease in carbonate-associated sulfate content (752 ppm) suggest gypsum dissolution and subsequent calcite precipitation from meteoric water. Relatively 34S-depleted native sulfur (δ34S = 13.1‰) leaves it ambiguous whether meteoric water influx could have supplied sufficient molecular oxygen for oxidation of hydrogen sulfide. In case of the brecciated carbonate, methanogenesis, anaerobic oxidation of methane, and bacterial sulfate reduction apparently mediated the formation of secondary minerals as indicated by 13C-depleted lipid biomarkers representative for the respective metabolisms. This study reveals that the conditions and timing of gypsum replacement are variable–taking place 1) during or shortly after gypsum deposition or 2) significantly after sedimentation–and suggests that methanogens in addition to anaerobic methanotrophic archaea and sulfate-reducing bacteria may be involved in the mineral-forming processes in the sedimentary subsurface.

Western South Atlantic seasonal variability recorded in a mid-deglacial bivalve from the outer Uruguayan continental shelf

The oceanographic dynamics on the continental shelf off southeastern South America are primarily controlled by the southward-flowing warm Brazil Current, converging with the northward-directed cold Malvinas (Falkland) Current, and interacting with the continental discharge of the Plata River. The seasonally reversing regional wind field together with the seasonal cycle of riverine discharge, determines which of these three components provides the dominant forcing. The Uruguayan shelf is thus located in a transitional zone that extends from the region influenced by the Brazil-Malvinas Confluence (BMC) in the open ocean to the Subtropical Shelf Front (STSF) on the continental shelf. Understanding how the resulting oceanic seasonal variability responded to different climatic boundary conditions may shed light on its future behavior. This study presents the first reconstruction of mid-deglacial seasonal hydrographic variability on the continental shelf off southeastern South America in seasonal resolution based on stable oxygen and carbon isotopes (δ18O, δ13C) from a thick-walled shell of a long-living bivalve. The mid-deglacial (14.3 cal ka BP; Bølling-Allerød interstadial) Retrotapes exalbidus bivalve shows a mean δ18O of 3.27 ± 0.42‰ (2.50 ± 0.42‰ when corrected for changes in global ice volume) and a seasonal δ18O amplitude of 1.69‰ for raw isotopic excursions. Moreover, the δ13C exhibits abrupt negative peaks coincident with more negative δ18O values that indicate seasons of elevated freshwater discharge. Finally, the growth rate of the bivalve suggests that the specimen was closer to the metabolically optimum than modern individual of this species from southern South America. Combining biogeographic and ecologic information with these isotopic data, the results point to colder waters and a slightly lower mid-deglacial seasonal amplitude in temperature compared with modern conditions at this shelf site. Because of the northward-displaced Plata River mouth during deglacial times, negative δ13C peaks are expected to reflect an influence of non-point freshwater sources in the form of small fluvial distributaries along the paleo-coast. Most of this signal may, however, be driven by seasonal metabolic effects associated with low ambient water temperatures related to a shallow-water environment located closer to the respective paleo-coastline due to the low sea level at those times.

Petrogenesis of Mantle-Hosted Granitoids from the Samail Ophiolite

Abstract Granitoids with evolved chemical signatures, intruding both oceanic crustal rocks and mantle peridotite, are well known in the Samail supra-subduction ophiolite of Oman and United Arab Emirates. The former are metaluminous tonalites and trondhjemites have positive εNd, relatively low δ18O values, resemble ridge ‘tholeiitic’ granitoids with MORB-like affinity, and formed by fractionation of basalt/gabbro or anatexis of oceanic crust. In contrast, the mantle-hosted granitoids are peraluminous, with negative εNd and high δ18O values. They can be modeled as having formed by mixing between partial melts of metabasalt and metasedimentary rocks with minimal mantle contribution. The mantle-hosted granitoids resemble typical peraluminous S-type granitoids (e.g. Himalaya, Variscan, Lachlan) but are compositionally distinct in having notably scattered data values of K2O, Na2O, CaO, Rb/Sr, relatively higher silica and, lower (Al2O3 + FeO + MgO + TiO2 wt%) and Th/Yb as compared to typical S-types. The mantle-hosted granitoids mainly originate from the subducted slab, and mostly intruded mantle peridotite in the lithospheric mantle, with no apparent association with the overriding oceanic plate and little interaction (e.g. assimilation) with the mantle. While the specific controls on geochemical variations remain speculative, results from this study show that the Samail mantle-hosted S-type granitoids are compositionally distinct from classic S-type granitoids formed in orogenic belts. While global S-type granitoids may be mineralogically similar, the Samail mantle-hosted granitoids preserve different geochemical signatures, reflecting their formation in distinct tectonic setting, including the mantle.

Hypogenic origin of paleocaves in the Ordovician carbonates of the southern Tahe oilfield, Tarim basin, northwest China

The Lower-Middle Ordovician paleocaves at the depths of over 6000 m in the southern Tahe Oilfield have been important objectives of petroleum production in the Tarim Basin. 3D seismic data, drilling well data, image logs, and cores were integrated to delineate the development characteristics, spatial distribution, and morphology of paleocave reservoirs in the Tahe Oilfield. The petrographic, geochemical features and fluid inclusion measurements of the cave and fracture-filling calcite in the Tahe Oilfield were subsequently performed. The formation mechanism of paleocaves in the southern Tahe Oilfield was revealed through the comparative analysis of paleocaves in the north and south of the Tahe Oilfield. The paleocaves in the northern and southern Tahe Oilfield are extensively distributed 0–150 m and 160–350 m away from the regional unconformity, respectively. Different from the diverse paleocave morphologies including single cave passages, anastomotic mazes, and branchwork passages in the northern Tahe Oilfield, the paleocaves in the southern Tahe Oilfield are dominated by isolated chambers and rising shafts. Additionally, almost all the cave and fracture-filling calcite cements in the northern Tahe Oilfield coexist with gray-green sand and clay. While, the cave-filling calcite cements are relatively clean, without any terrigenous minerals. Furthermore, the calcite samples in the northern Tahe Oilfield show δ13C and δ18O values varying from −5.90‰ to −0.39‰, and from −13.47‰ to −7.23‰, respectively. The calcite cements in the southern Tahe Oilfield present similar δ13C values with the Ordovician limestone samples and relatively more negative δ18O values in a range between −15.02‰ and −12.29‰. Compared with the calcite samples in the norther Tahe Oilfield, the cave-filling calcite in the southern Tahe Oilfield shows a narrower range of 87Sr/86Sr ratios varying from 0.709342 to 0.709689. In particular, large amount of two-phase aqueous inclusions observed in the calcite from the southern Tahe Oilfield display relatively higher homogenization temperatures ranging from 90.8 °C to 205.9 °C. These significant differences on the paleocaves between the north and south of the Tahe Oilfield suggest that the paleocaves in the south are overprinted by both gravity-driven deep circulating meteoric water during the early Hercynian and the ascending thermal water possibly occurring from the second episode of the middle Caledonian to the early Hercynian. The paleocaves in the southern Tahe Oilfield are interpreted to be generated by hypogene karst under the constraints of strike-slip fault system and lithostratigraphic sequence in the Ordovician in confined settings. This study is an important supplement to the previous Ordovician meteoric karst model in unconfined zones of the Tahe Oilfield. It indicates that the stratabound isolated paleocaves developed in the lower submember of the Upper Yingshan Formation in the southern Tahe Oilfield have significant exploration potentials.

Seasonal variations and controlling factors of speleothem multi-proxy in southeastern China: Implications for the reconstruction of precipitation seasonality

Precipitation in southeastern China exhibits strong seasonal variability, which significantly impacts local agricultural production and social development. However, the reconstruction of precipitation seasonality has been limited by the lack of precisely dated high-resolution paleoclimatic records. This study presents seasonal-scale multi-proxy records (trace elements: Mg/Ca, Sr/Ca Ba/Ca and stable isotopes: δ18O and δ13C) of a modern (1810–2009 AD) annually laminated stalagmite (EM1) from E’Mei Cave, Jiangxi Province in southeastern China. Comparative analysis of observation data with meteorological and simulation data shows that the seasonal variation of EM1 δ18O, derived from precipitation δ18O, is mainly controlled by the large-scale circulation and precipitation seasonality on an interannual timescale. The seasonal EM1 δ18O variation is controlled by the seasonal precipitation δ18O, however, the most negative values of EM1 δ18O are higher than those of simulated calcite δ18O and the average amplitude of the seasonal variation of EM1 δ18O (∼1.93‰) is much smaller than that of simulated calcite δ18O (∼9.72‰) because of evaporation and mixing of waters in the epikarst system. On the decadal timescales, variations of δ13C, Mg/Ca, Sr/Ca, and Ba/Ca were found to be strongly correlated, consistent with the variation of the local dry/flood index, indicating a common influencing factor of local hydroclimate change. However, their seasonal phase relationships vary between strong and weak summer monsoon conditions. We find a strong covariation between Mg/Ca and δ13C with Sr/Ca and Ba/Ca during the strong monsoon period (1951–1976), and they are in antiphase with seasonal δ18O variation. However, the seasonal variations of Sr/Ca and Ba/Ca transformed to dominantly antiphase with Mg/Ca and δ13C during the weak monsoon period (1977–1991 AD). Therefore, we suggest that Mg/Ca and δ13C are dominantly controlled by the local hydroclimate changes on seasonal timescales but Sr/Ca and Ba/Ca might have been affected by complex processes in the epikarst under different hydrothermal configuration conditions. The findings indicate the potential of the variation of the seasonal phase relationships between multi-proxy records in reconstructing precipitation seasonality changes under different hydrothermal backgrounds.

Variations of stable isotope in Typhoon Lupit (2021) rainfall and its response to upstream convective processes

AbstractTyphoons produce a large amount of rainfall with a highly depleted isotopic composition. However, the mechanisms of isotope fractionation during typhoons remain poorly understood. Here, we present the hourly resolution isotope composition of rainfall during Typhoon Lupit (2021) in Fuzhou, on the southeast coast of China, to better understand these processes. Our results showed that the rainfall of Typhoon Lupit had significant fluctuations in δ18O values, ranging from −20.1‰ to −6.3‰, and exhibited a three‐stage variation with distinctly negative δ18O values in the second stage. In the first stage of Lupit, water vapour originated primarily from the nearby sea area, which did not undergo sustained convective activity, resulting in relatively enriched δ18O values. In the second stage, the δ18O values were extremely negative mainly because of the accumulated convective activity and continuous precipitation as they travelled towards the centre of the typhoon. In the third stage, the mixing of more localized and nearby sea water vapour caused an increase in the δ18O values. In summary, the three‐stage characteristics of Typhoon Lupit were largely caused by the integration of accumulated convective activity and moisture sources. Our findings reveal how upstream rainout affects the isotopic behaviour of rainfall and may have implications for understanding the dynamics of typhoon rainfall isotopes.