Oxygen Isotope Analyses Research Articles

Isotopic evidence for human mobility in late antique Bulla Regia (Tunisia)

This paper represents the first isotopic study on late antique human mobility in North Africa, using the urban site of Bulla Regia in Tunisia as a case study. We also present the first values for bioavailable 87Sr/86Sr in northern Tunisia, analysing 63 plant and snail samples, as well as a simple method for the pre-processing of plants in the field to facilitate their export. Bulla Regia was a prominent Roman and late antique town situated on an important axis of transport and communication in North Africa and is therefore an ideal site to explore mobility in the region during this time period. Strontium (87Sr/86Sr) and oxygen (δ18OCarb) isotopic analysis of 22 late antique individuals from a Christian church and cemetery identified at least seven or eight non-locals, while comparative analysis of five Roman individuals from a funerary enclosure on the same site classified all but one of them as potential locals. Most non-local individuals exhibit 87Sr/86Sr values that match various areas of northern Tunisia, which supports regional mobility rather than long-distance migration, although when combined with the oxygen results, inter-regional mobility from an area with a warmer climate may be hypothesised for some individuals. Examination of the spatial distribution of non-local individuals in their cemetery setting reveals that they were privileged individuals, thus they may reflect the mobility of wealthier town-dwellers in late antiquity, particularly perhaps along the Carthage-Hippo route.

Post-depositional history of the lower Palaeocene interval using petrographic, CL and geochemical data in the East Tethys: Kopet-Dagh Basin, northeast Iran

AbstractThis study investigates the Danian siliciclastic successions in the East Tethys in the Kopet-Dagh Basin, NE Iran, which are composed of conglomerates, sandstones, shales and mudstones. The studied interval includes significant changes in sedimentary environments from alluvial to fluvial systems. The Danian siliciclastic formation is sandwiched between two marine carbonate sequences. The effects of the late Palaeocene sea transgression can be traced back to the precipitation of several types of carbonate cement in the studied siliciclastic formation. Several diagenetic features have been identified in the studied successions. The most observed features comprise physical and chemical compaction, cementation, alteration, dissolution, fractures and fillings. Some of the mentioned diagenetic processes, such as cementation, may be seen in a range of diagenetic environments and phases, such as early meteoric, low depth and deep burial, and late meteoric after the tectonic uplifting. The calcite cements considered in this study have been subdivided into four types. Some of the calcite cements, such as the rim, gravity pendant and meniscus, are classified as type one. They have formed around the rock grains and show no luminescence. The blocky and poikilotopic types have been grouped in type two. They are deposited between grains and exhibit dark luminescence. Type three cement consists of some of the blocky and poikilotopic cements that have formed amid grains and present a bright luminescence. Finally, type four comprises filled fractures which display a dark luminescence (blocky cement). Geochemical data revealed that the categorized cement types were precipitated in three diagenetic environments: early meteoric; burial; and late meteoric after the uplifting. The meteoric diagenetic environment is subdivided into vadose and phreatic meteoric. The burial diagenetic environment is subdivided into shallow burial and deeper burial. The qualitative petrographic method contributed to the initial recognition of the diagenetic features. The semi-quantitative cathodoluminescence method, the quantitative major and trace elements, and oxygen and carbon stable isotope analysis were utilized to evaluate the exact diagenetic processes and environments. Finally, the diagenetic sequence was reconstructed and depicted as diagenetic models and a paragenesis sequence. The data of this study can lay the foundation for future studies on the siliciclastic diagenesis in the studied basin.

宁夏河东沙区刺槐和丝绵木水分利用策略

PDF HTML阅读 XML下载 导出引用 引用提醒 宁夏河东沙区刺槐和丝绵木水分利用策略 DOI: 10.5846/stxb202202100330 作者: 作者单位: 作者简介: 通讯作者: 中图分类号: 基金项目: 国家自然科学基金项目（31760236，42161013）；宁夏自然科学基金项目（2022AAC03094） Water use strategies of Robinia pseudoacacia and Euonymus bungeanus in the east sandy land of the Yellow River in Ningxia, China Author: Affiliation: Fund Project: The National Natural Science Foundation of China (31760236,42161013);The National Natural Science Foundation of Ningxia,China(2022AAC03094) 摘要 | 图/表 | 访问统计 | 参考文献 | 相似文献 | 引证文献 | 资源附件 | 文章评论 摘要:刺槐和丝绵木混交林是宁夏河东沙区防护林建设的主要模式，了解刺槐和丝绵木的水分利用策略，能为区域植被恢复和防护林林分结构调整提供科学依据。以宁夏河东沙区刺槐（Robinia pseudoacacia）和丝绵木（Euonymus bungeanus）混交林为研究对象，通过监测微气象、树干液流和土壤质量含水量，结合大气降水、土壤水、植物木质部水同位素组成，采用Granier及其校正公式，运用贝叶斯混合模型（MixSIAR）和相似性比例指数（PS）研究2个树种的蒸腾耗水、水分来源和水分利用关系。结果表明：刺槐和丝绵木的蒸腾耗水量在生长季中期较高，前期和后期较小，刺槐的蒸腾耗水量是丝绵木的1.55倍；影响刺槐蒸腾耗水的主要环境因子为饱和水汽压差、太阳辐射、0-40 cm土壤质量含水量和40-120 cm土壤质量含水量；影响丝绵木蒸腾耗水的主要环境因子为饱和水汽压差、太阳辐射、平均气温、0-40 cm土壤质量含水量和40-120 cm土壤质量含水量；蒸腾耗水较高时，刺槐主要吸收利用中层土壤水，丝绵木主要吸收利用浅层土壤水，蒸腾耗水较低时，刺槐主要吸收利用浅层土壤水，丝绵木主要吸收利用中层土壤水；在土壤水分含量较小的月份，刺槐和丝绵木主要通过水分利用空间上的差异来应对干旱，维持自身的蒸腾耗水；土壤水分含量较高的月份，刺槐和丝绵木的相似性比例指数最大，存在较强的水分竞争关系；浅层土壤水分含量较高可能反映了沙区植物根系对土壤水分再分配作用下植物在水分和养分需求之间的平衡。 Abstract:The mixed forest of Robinia pseudoacacia and Euonymus bungeanus is the typical shelterbelt construction mode in the east sandy land of the Yellow River in Ningxia, China. Research on the water use strategies of Robinia pseudoacacia and Euonymus bungeanus could provide scientific basis for restoration regional vegetation and stand structure optimization allocation of shelter forest. In this study, the sap flow of Robinia pseudoacacia and Euonymus bungeanus was monitored continuously to clarify the characteristics of water consumption by transpiration which calculated by Granier and its correction formula, as well as simultaneous records of micro-meteorological factors and gravimetric soil water content. Combined with stable hydrogen and oxygen isotope analysis of rainfall, soil water and plant xylem water, the water source and water use relationship among symbiotic trees were quantitatively analyzed by Bayesian mixture model (MixSIAR) and the proportional similarity index (PS). The results showed that the water consumption of Robinia pseudoacacia and Euonymus bungeanus were higher in the middle growing season, but lower in the early and late growing season. The water consumption of Robinia pseudoacacia was 1.55 times larger than Euonymus bungeanus. The main environmental factors affecting water consumption of Robinia pseudoacacia were vapour pressure deficit, solar radiation, 0-40 cm gravimetric soil water content and 40-120 cm gravimetric soil water content. The main environmental factors affecting water consumption of Euonymus bungeanus were vapour pressure deficit, solar radiation, average temperature, 0-40 cm gravimetric soil water content and 40-120 cm gravimetric soil water content. Robinia pseudoacacia mainly used the middle layer soil water and Euonymus bungeanus mainly used the shallow layer soil water in the season with high water consumption. While the shallow layer soil water and the middle layer soil water were ultilized by Robinia pseudoacacia and Euonymus bungeanus separately in the season with lower tree water consumption. In addition, Robinia pseudoacacia and Euonymus bungeanus was able to deal with drought and maintain their own water consumption mainly through the spatial difference of water use strategy under drought seasons. In the seasons when gravimetric soil water content was higher, the proportional similarity index (PS) of Robinia pseudoacacia and Euonymus bungeanus was the highest, and there was a strong water competition relationship. The higher of shallow layer gravimetric soil water content might reflect a trade-off between water and nutrient requirements of plants under the effect of soil water redistribution by plant roots in the sandy land. 参考文献 相似文献 引证文献

Tissemouminites: A new group of primitive achondrites spanning the transition between acapulcoites and winonaites

AbstractThe Northwest Africa (NWA) 090 meteorite, initially classified as an acapulcoite, presents petrological, chemical, and isotopic characteristics comparable to a group of seven primitive winonaites: Dhofar 1222, NWA 725, NWA 1052, NWA 1054, NWA 1058, NWA 1463, and NWA 8614. Five of these samples were previously classified as acapulcoites or ungrouped achondrites before being reclassified as winonaites based on their oxygen isotopic compositions. These misclassifications are indicative of the particular compositional nature of these primitive achondrites. All contain relict chondrules and a lower closure temperature of metamorphism of 820 ± 20 °C compared to other typical winonaites, as well as mineral elemental compositions similar to those of acapulcoites. The oxygen isotopic signature of these samples, δ17O of 1.18 ± 0.17‰, δ18O of 3.18 ± 0.30‰, and Δ17O of −0.47 ± 0.02, is in fact resolvable from both acapulcoites and winonaites. We investigate the relationship between these eight primitive achondrites, typical winonaites, and acapulcoites, to redefine petrological, mineralogical, and geochemical criteria of primitive achondrite classification. Distinguishing between winonaites, acapulcoites, and this group of eight primitive achondrites can be unambiguously done using a combination of several mineralogical and chemical criteria. A combination of olivine fayalite content and FeO/MnO ratio, as well as plagioclase potassium content allow us to separate these three groups without the absolute necessity of oxygen isotope analyses. NWA 090 as well as the other seven primitive achondrites, although related to winonaites, are most likely derived from a parent body distinct from winonaites and acapulcoites–lodranites, and define a new group of primitive achondrites that can be referred to as tissemouminites.

Improving continuous-flow analysis of triple oxygen isotopes in ice cores: insights from replicate measurements

Abstract. Stable water isotope measurements from polar ice cores provide high-resolution information about past hydrologic conditions and are therefore important for understanding earth's climate system. Routine high-resolution measurements of δ18O, δD, and deuterium excess are made by continuous-flow analysis (CFA) methods that include laser spectrometers. Cavity ring-down laser spectroscopy (CRDS) allows for simultaneous measurements of all stable water isotopes, including δ17O and 17O excess (Δ17O); however, the limitations of CFA methodologies for Δ17O are not well understood. Here, we describe a measurement methodology for all stable water isotopes that uses a CFA system coupled with a CRDS instrument. We make repeated measurements of an ice-core section using this method to explore the reproducibility of CFA–CRDS measurements for Δ17O. Our data demonstrate that the CFA–CRDS method can make high-precision measurements of Δ17O (< 5 per meg at averaging times > 3000 s). We show that the variations within our CFA ice-core measurements are well matched in magnitude and timing by the variations within the discrete CRDS measurements; we find that calibration offsets generate most of the variability among the replicate datasets. When these offsets are accounted for, the precision of CFA–CRDS ice-core data for Δ17O is as good as the precision of Δ17O for continuous reference water measurements. We demonstrate that this method can detect seasonal variability in Δ17O in Greenland ice, and our work suggests that the measurement resolution of CFA–CRDS is largely defined by the melt and measurement rate. We suggest that CFA–CRDS has the potential to increase measurement resolution of δ17O and Δ17O in ice cores, but also highlight the importance of developing calibration strategies with attention to Δ17O.

Origin of Calcite Cements in Tight Sandstone Reservoirs of Chang 8 Member of the Yanchang Formation in Zhijing-Ansai Area, Ordos Basin, China

Calcite cement is a common type of cementation in tight sandstone reservoirs of the Upper Triassic Yanchang Formation Chang 8 Member in the Zhijing-Ansai area of the Ordos Basin, which has significant influence on reservoir densification and heterogeneity. Calcite cements affect the quality of the reservoir conspicuously. The characteristics and origins of calcite were investigated using a series of approaches from the perspective of petrography and geochemistry, including thin section observation and identification, cathode luminescence, scanning electron microscopy, AMICS analysis, LA-ICP-MS elements analysis, and carbon and oxygen isotopes analysis. The results of all analytical tests indicated that calcite cements can be divided into two types according to their occurrence and origins. Type-I calcite cements mainly occur in sandstone reservoirs near the sandstone–mudstone interface or the sandstone layers adjacent to mudstone. Generally, there is no chlorite coating around them, and they appear dark orange under cathode luminescence. The carbon source of Type-I calcite cements may be related to the compaction and drainage of mudstone. Type-II calcite cements are formed in the early stage, and their carbon source may be related to the compaction and drainage of the adjacent mudstone. Type-II calcite cements are surrounded by chlorite coating primarily present in the interior of fine-grained sandstone, showing as bright yellow under cathode luminescence. Decarboxylation of organic matter in the source rocks may provide a crucial source of carbon for Type-II calcite cements.

Cassiterite deposition induced by cooling of a single-phase magmatic fluid: Evidence from SEM-CL and fluid inclusion LA-ICP-MS analysis

Cassiterite (SnO2), the principal ore mineral of tin, is mainly formed in granite-related magmatic hydrothermal systems. The precipitation mechanism of this mineral in hydrothermal veins is still debated due to lack of direct constraints on this specific mineralization process. Here, we present a detailed reconstruction of fluid evolution history from a high-grade cassiterite-quartz vein in the Weilasituo Sn-polymetallic deposit, North China, based on combined SEM-CL imaging with fluid inclusion microthermometry, Raman and LA-ICP-MS analysis of intergrown cassiterite and gangue minerals.Formation of the cassiterite-quartz vein at Weilasituo started from early topazization and muscovite deposition along vein walls and was followed by crystallization of topaz, quartz (Q1) and cassiterite in a general sequential order. Cassiterite deposition occurred within a restricted time period before complete crystallization of topaz and quartz. Shortly after cassiterite precipitation, the vein was fractured and overprinted by later quartz generations (Q2 & Q3) and fluorite. In situ microanalysis on primary and/or pseudosecondary fluid inclusions from the different crystallization stages indicates that an acid and reduced single-phase magmatic fluid of gradually dropping temperature but very consistent salinity was responsible for vein formation. Mixing of this magmatic fluid with a biotite-plagioclase gneiss buffered, deep-cycled underground water of lower temperature and salinity occurred at the final stage, but it is not related to Sn mineralization. The physical and chemical changes of fluids bracketing cassiterite deposition demonstrate that cassiterite precipitation at Weilasituo was predominately induced by the cooling of the hydrothermal fluid by at least 50 °C, and it is accompanied by the oxidation of Sn(II)-Cl complexes with CO2 and/or As(III) species as potential oxidants. Early stage fluid-rock interaction with feldspathic host rocks and the formation of muscovite coverage on the vein walls are perhaps important for providing a fluid-buffered environment ideal for such mechanism. However, our result argues against meteoric water mixing or fluid boiling being the triggers of cassiterite deposition, and this conclusion has been further supported by cassiterite oxygen isotope analysis on the same set of samples.Additionally, the maximum base metal endowment (Pb and Zn) calculated from initial metal contents of the premineralization fluid at the Weilasituo Sn-polymetallic deposit are far less than proven reserves found in the two adjacent base metal deposits, and therefore a genetic link between these deposits is not suggested. This finding may have important implications for the ongoing exploration in the ore district.

The application of a CART model for forensic human geolocation using stable hydrogen and oxygen isotopes

The utility of stable hydrogen and oxygen isotope analysis of human tissues for geolocation is an important area of study within forensic science. This study aimed to first validate the latitudinal relationship between stable hydrogen and oxygen isotopes in drinking water and human keratinous tissues through the analysis of human samples with known geographical origin. And secondly, to explore the use of classification and regression tree (CART) models to geographically classify individuals based on the stable isotope values of tissues themselves. Human hair and toenails were collected from four distinct study sites across Canada. The comparison of stable isotope values in drinking water and human tissues produced low R2 values indicating that linear models may not fully explain the variation observed for both hydrogen and oxygen values. Additionally, large intrapopulation variations were observed for Canadian cities and highlights the importance of understanding the regional isotopic spread of human values. Further, this study demonstrated that a closed group of unknown individuals known to have originated from a limited number of geographically distinct regions may be classified into their respective groups through the use of CART models. The potential for the CART model approach for human geolocation presents a promising new tool.

Multiple fluid sources in skarn systems: Oxygen isotopic evidence from the Haobugao Zn-Fe-Sn deposit in the southern Great Xing’an Range, NE China

Abstract Diverse fluid sources and complex fluid flow paths in skarn systems appear to be well documented. Nevertheless, in situ microanalysis of oxygen isotopes by secondary ion microprobe (SIMS) in skarn minerals can provide further high spatial resolution information on this complexity and the formation of skarns and associated ore deposits. In this study, we investigated the Haobugao skarn Zn-Fe-Sn deposit (0.36 M tonnes Zn) in the southern Great Xing’an Range, northeast (NE) China, and the associated Early Cretaceous Wulanba biotite granite. Based on drill hole logging, four early skarn phases are recognized: proximal red-brown garnet-hedenbergite exoskarn, central green garnet exoskarn, light brown garnet-diopside exoskarn, and distal pyroxene skarn. Oxygen isotope analyses of garnet, pyroxene, and other minerals from skarn, oxide, and quartz-sulfide stages were carried out using SIMS to determine the origin and evolution of the skarn-forming hydrothermal system. Garnet from exoskarn has a much wider range in δ18OVSMOW, between –8.1 and +6.0‰, than other stages and minerals. The estimated δ18O values of fluids in equilibrium with the Haobugao skarn vary widely from –5.1‰ to +8.9‰, suggesting that the skarn formed via episodic flux of magmatic fluid and meteoric water. Low δ18O values of cassiterite and quartz from quartz-sulfide stage rocks are +1.2 to +3.6‰, and +5.7 to +5.9‰, respectively, indicating significant contributions of meteoric water during deposition of Pb-Zn sulphides. Therefore, meteoric fluids were periodically present throughout most of the stages of skarn formation at Haobugao.

Orogenic eclogites record relative magnitude of deep crustal flow and extent of migmatite-eclogite interaction

In exhumed orogens, refractory mafic rocks have the potential to preserve a record of petrogenesis and high-pressure (H P ) metamorphism that is commonly obliterated in quartzofeldspathic rocks owing to re-equilibration at high-temperature, low-pressure (L P –H T ) conditions. In the Montagne Noire (France) migmatite dome, located in the foreland of the Variscan orogen, eclogite is exposed in both the core and margin of the dome. In this study, we combine in situ U Pb petrochronology and oxygen-isotope analyses of key eclogite phases to demonstrate that eclogites from the two distinct domains had different protoliths and source regions, traveled relatively variable distances in the deep crust, and differentially interacted with surrounding migmatite prior to exhumation. Dome-margin eclogite zircons are small (~40 μm) with well-preserved inherited cores and thin (<15 μm) rims, compared to larger (40–120 μm) neo- and recrystallized dome-core zircons with small relict cores and wide (15–30 μm) recrystallized rims. Protolith and H P metamorphism ages were determined using in situ zircon and rutile petrochronology (LASS-ICP-MS). Both eclogites formed in a continental setting; dome margin protolith zircon cores formed at 442.5 ± 3.4 Ma (steep HREE slope, no Eu-anomaly) whereas zircon cores of the dome-core eclogites yielded scattered dates suggesting protolith crystallization between ~500–400 Ma (steep HREE slope, pronounced Eu-anomaly). Both eclogites experienced H P metamorphism at c. 320–310 Ma in garnet-stable, plagioclase-absent conditions. Most analyzed rutile yielded dates of 307–304 Ma associated with cooling. The record of H P fluid conditions was determined by O-isotope (SIMS) analyses of garnet and zircon. Dome-margin zircon cores and rims have δ 18 O of ~8.2–8.5 ‰, indistinguishable within uncertainty, in isotopic equilibrium with isotopically unzoned garnet (δ 18 O ~ 8.0–8.2 ‰). In contrast, zircons in dome-core eclogites have systematically lower zircon-core δ 18 O values compared to their rims and neocrystallized grains, and zircon cores were in equilibrium with major-cation zoned garnet with respect to oxygen. The two dome-core eclogite samples yielded zircon and garnet δ 18 O values of ~8.6–9.5 ‰ and ~ 9.7–10.5 ‰. Based on these results and existing H P fabric data for these eclogites, we propose that (1) gabbro protoliths for the two eclogites were emplaced at different depths in a Cambro-Ordovician continental crustal package; and (2) dome-core eclogites interacted extensively with surrounding gneiss during burial and foreland-vergent crustal flow, whereas the dome-margin eclogite was sourced proximally to the dome-emplacement location and had minimal chemical interaction with surrounding gneiss. At least parts of the Montagne Noire migmatite dome were deeply sourced, but rocks exhumed in the core had a more extensive and protracted history of deep-crustal flow than deep-crustal rocks exhumed at the margin. • Eclogites in migmatite dome retain memory of deep crust history. • Zircon (re)crystallization extent reveals distinct eclogite source, flow paths. • Petrochronology and O-isotopes record migmatite-eclogite interaction at depth. • Integrated garnet, zircon datasets reveal protolith, peak, exhumation histories. • Domes may exhume crust laterally-sourced >100 s of km from emplacement location.

Sedimentary model of the Ediacaran Doushantuo cap carbonates from the southeastern margin of the Yangtze Block: Evidence from carbon and oxygen isotopes and elemental geochemistry

Cap carbonate of the early Ediacaran period represents an abrupt climate shift from severe Marinoan glaciation to a post‐glacial warm environment. Some consensuses on the distinctive negative excursion of δ13Ccarb and the origin of its unique sedimentary structures have been reached over the past decades, but certain aspects such as the distribution and redox conditions of cap carbonate still remain controversial. To resolve these issues, we collected detailed samples of the Doushantuo cap carbonate from the Ganlong‐Fanyang section and the Poutoushang reservoir section in the Danzhai County, southeast Guizhou Province, respectively. We conducted carbon and oxygen isotope analysis and trace element analysis in this study. The Ganlong‐Fanyang section was possibly situated in a submarine highland because of its higher carbon isotope than that of the Potoushang section according to the carbon isotopic gradient. Negative carbon isotope excursions at the basal Doushantuo cap carbonate from the two sections correlate well with those from other equivalent cap carbonates and were corresponding to the first one (SN1 or EN1) of the carbon isotopic curve during the Ediacaran period, implying a remarkable global event after the post‐Marinoan glaciation. Geochemical features of trace elements and rare earth elements support an overall oxygen‐rich condition with syn‐depositional or pene‐contemporaneous hydrothermal activities and methane seeps during the deposition of cap carbonate. We reconstruct a new sedimentary model that the Doushantuo cap carbonates were mainly precipitated in relatively shallow‐ to deep‐water shelf environments without disturbance by abundant terrestrial materials, which may be on isolated platforms over the early developed grabens in a deep‐water basinal condition, rather than within the entire oceanic basin.

From Forests to the Coast - Multidisciplinary Investigation of Human Adaptations at the Mini-athiliya Shell Midden, Sri Lanka

Over the last three decades, Sri Lanka has risen to international prominence as a key area for exploring past forager adaptations. Much of this discussion has focused on the lowland rainforests of the Wet Zone of the island, and their preservation of the earliest fossils of our species, bone tools, and microlithic technologies in the region ca. 45,000 years ago. It has been recognized that the northern and southern coasts of Sri Lanka represent crucial locales for studying human occupation and adaptation through the Pleistocene and Holocene. Here, we revisit the important shell midden site of Mini-athiliya (dating to ca. 4,000 cal. years BP), on the southern coast of Sri Lanka, which has yielded human remains alongside microlithic stone tools and animal remains. We present a comparative analysis of body size variation of the human remains belonging to the HMA 6 adult skeleton from Mini-athiliya with a wider database of foragers to investigate local adaptations. We also apply stable carbon and oxygen isotope analysis to the tooth enamel of four other individuals documented at Mini-athiliya in order to determine their dietary reliance on forest, grassland, or coastal resources. Together, our results highlight that, rather than a clear distinction between earlier forest adaptations and later coastal specialisation, the Mini-athiliya individuals provide evidence for a plastic spectrum of ecological adaptation. We argue for continued research on how human populations in different parts of the island interacted and adapted to its diverse tropical settings across space and time.

Stable isotopic study of carbonatites from the Pakkanadu Alkaline Complex, southern India: Constraints on carbonatite melt evolution and sub-solidus, high temperature fluid-rock interaction

Carbonatites of the Pakkanadu Alkaline Complex (PAC) of the Dharmapuri Rift Zone (DRZ), in the Northern Granulite Terrain (NGT) of southern India, were intruded as small concordant and discordant bodies into pyroxenites and syenites during the Neoproterozoic (∼759‐–750 Ma). Carbonatite samples from the PAC were grouped into three major groups for oxygen and carbon isotope analysis: (A) calcite-dominated (88–100%), (B) dolomite-dominated (83–97%) and (C) admixtures of calcite and dolomite. End-member isotopic compositions were ẟ 13 C = −5.7 ± 0.1‰ and ẟ 18 O = +8.4 ± 0.2‰ for calcite and ẟ 13 C = −6.0‰ and ẟ 18 O = +6.9‰ for dolomite. The carbonatite isotopic compositions lie within the range known for primary igneous carbonatites (PIC), indicating their origin from a mantle source. The higher ẟ 18 O of the calcite end-member than the dolomite end-member indicates oxygen isotopic disequilibrium in the carbonatites. This disequilibrium was the product of sub-solidus oxygen isotope exchange with fluids derived from carbonatite melt during the brine-melt stage (600–400 °C). The narrow range of ẟ 13 C of the carbonatites and its similarity to the ẟ 13 C of depleted upper mantle (−6 ± 2‰) suggests that very little CO 2 was associated with the carbonatite melt. We infer that this type of carbonatite melt evolved from the upper asthenosphere or the base of the lithosphere (> 3 GPa, i.e., >100 km). Similar observations were made based on compiled ẟ 13 C and ẟ 18 O data for carbonatites from Salem-Attur fault, Sevathur, and Hogenakkal regions of the NGT. The ẟ 13 C and ẟ 18 O compositions of carbonatites from Samalpatti, India, however, are distinctly different and suggest two sources for carbonatite melts, one containing a significant amount of CO 2 and possibly evolved from somewhere in the middle of the lithospheric mantle (∼ 2–3 GPa, i.e., 60–100 km) and the other associated with crustal sedimentary or metasedimentary carbonates, which were possibly incorporated during emplacement of carbonatite melts originating from the lithospheric mantle. This study shows that carbonatite melts in the NGT mostly evolved from different levels of the upper mantle and were emplaced to crustal levels, perhaps via a rifting-induced fracture network. • Carbonatites of the Pakkanadu Alkaline Complex from southern India were investigated. • ẟ 13 C and ẟ 18 O of the carbonatites indicate their origin from a mantle source. • O isotope exchange occurred between the carbonatite and carbonatite-derived fluids. • CO 2 production was insignificant during partial melting of the mantle source. • The carbonatite was emplaced to crustal levels via a rift-related fracture system.

Diagenesis and Reservoir Evolution Model of the Ediacaran Dengying Formation in the Sichuan Basin: Evidence from Laser Ablation U-Pb Dating and In Situ Isotope Analysis

The microbial dolomite of the Ediacaran Dengying Fm., Sichuan Basin, SW China is endowed with abundant oil and gas resources. A complex diagenetic history greatly complicates the development of such microbial dolomite reservoirs, and has severely restrained hydrocarbon exploration. This study focused on key field profiles in Eastern Sichuan and aimed to decipher the origin and evolution of dolomites, using novel techniques, including elemental mapping, laser ablation U-Pb dating as well as carbon, oxygen, and strontium isotope analyses. Additionally, we compared the diagenesis and reservoir development model for the Dengying microbial dolomites of the Central Sichuan to other areas, with the aim to provide practical guidance for oil and gas exploration across the entire Sichuan Basin. Our results have shown that the Ediacaran microbial dolomite in Eastern Sichuan experienced four stages of diagenetic modification–specifically: (1) syn-sedimentary dolomitization; (2) penecontemporaneous cementation of fibrous dolomite cement; (3) bladed dolomite and brown-dark very fine crystalline dolomite cementation during the Ordovician; and (4) fine crystalline dolomite and medium-coarse crystalline dolomite cementation during the Silurian-Devonian. Petrology and geochemistry data imply that each diagenetic phase of dolomitization was mainly sourced from marine-dominated fluids. The influence of tectonically related fluids was rarely noted. Significantly, U-Pb ages of these dolomites reveal that the history of dolomite infill to pores within the Eastern Sichuan Basin clearly post-dated that in the Central Sichuan region, resulting in high porosities (6%–11%) that favored hydrocarbon accumulation. This study suggests that the platform margin at the eastern edge of the Xuanhan-Kaijiang paleo-uplift is favorable as the next key exploration target for microbial dolomites in the Sichuan Basin.

Petrogenesis of Jian forsterite jade solely composed of end-member forsterite (Fo 99.8): Constrained by trace element and oxygen isotope

The Jian forsterite jade, named for its enrichment of end-member forsterite, is a new type of jade discovered in Ji'an County (Jilin Province, Northeast China). The formation mechanism of this rare end-member forsterite remains unclear. In this study, we present the mineral chemistry and oxygen isotope analysis of end-member forsterite to elucidate the formation mechanism of the Jian forsterite jade. The Jian forsterite jade can be divided into three main types: yellowish-green, dark-green, and black. The Jian forsterite jade consists mainly of forsterite, serpentine, as well as minor brucite, spinel, phlogopite, dolomite, calcite, magnesite, and magnetite. The Fo% content (100 × Mg/[Mg + Fe], mol%) of forsterite varies from 96.69 to 99.82. All tested forsterite samples show low Ni, Mn, Cr, and Ca contents and very high B contents. The δ18O values of forsterite range from 13.79 ‰ to 18.57 ‰, which are significantly higher than those from the mantle and are similar to those from skarn, marble, and calc-silicate rocks. The oxygen isotope values of forsterite, coupled with a distinctive trace element signature, suggest that the genesis of end-member forsterite results from a siliceous fluid-mediated decarbonation of Mg-rich dolomite. The genesis of the Jian forsterite jade can be outlined in two main metamorphic stages: (1) high-temperature prograde stage related to the interaction of the gneiss-derived SiO2-rich fluids with overlying dolomite. High temperature leads to the formation of forsterite, spinel, and calcite mineral assemblage. (2) low-temperature retrograde stage characterized by the infiltration of hydrous fluids. Hydrous silicate minerals, mostly serpentine, phlogopite, and talc, are formed during this stage. Our work highlights and confirms the effectiveness of the trace element geochemistry of forsterite in identifying magnesian skarns, and classifies the forsterite in the Jian forsterite jade as an extreme example of this occurrence.

High-Precision Triple Oxygen Isotope Analysis of Carbon Dioxide by Tunable Infrared Laser Absorption Spectroscopy.

Precision measurements of the stable isotope ratios of oxygen (18O/16O and 17O/16O) in CO2 are critical to atmospheric monitoring and terrestrial climate research. High-precision 17O measurements by isotope ratio mass spectrometry (IRMS) are challenging because they require complicated sample preparation procedures, long measurement times, and relatively large samples sizes. Recently, tunable infrared laser direct absorption spectroscopy (TILDAS) has shown significant potential as an alternative technique for triple oxygen isotope analysis of CO2, although the ultimate level of reproducibility is unknown, partly because it is unclear how to relate TILDAS measurements to an internationally accepted isotope abundance scale (e.g., VSMOW2-SLAP2). Here, we present a method for high-precision triple oxygen isotope analysis of CO2 by TILDAS, requiring ∼8-9 μmol of CO2 (or 0.9 mg carbonate) in 50 min, plus ∼1.5 h for sample preparation and dilution of CO2 in N2 to a nominal 400 μmol mol-1. Overall reproducibility of Δ'17O (CO2) was 0.004‰ (4 per meg) for IAEA603 (SE, n = 6) and 10 per meg for NBS18 (SE, n = 4). Values corrected to the VSMOW2-SLAP2 scale are in good agreement with established techniques of high-precision IRMS, with the exception of Δ'17O measured by platinum-catalyzed exchange of CO2 with O2. Compared to high-precision IRMS, TILDAS offers the advantage of times less sample, and greater throughput, without loss of reproducibility. The flexibility of the technique should allow for many important applications to global biogeochemical monitoring and investigation of 17O anomalies in a range of geological materials.

Dating Coastal Archaeological Wood From Pingusugruk (15th–17th CE), Northern Alaska:

Abstract Along the coasts of northern Alaska, in a treeless tundra environment, the primary wood resource for coastal populations is driftwood, a seasonal and exogenous resource carried by the major rivers of western North America. The potential of Alaskan coastal archaeological wood for tree-ring research was first assessed in the 1940s by archaeologist and tree-ring research pioneer J. L. Giddings. Despite his success, the difficulties of dendrochronological studies on driftwood and the development of radiocarbon dating during the 1950s resulted in the near-abandonment of dendrochronology to precisely date archaeological sites and build long sequences using archaeological wood in Alaska. In this study, we explored the possibilities and limitations of standard ring-width dendrochronological methods for dating Alaskan coastal archaeological wood. We focus on the site of Pingusugruk, a late Thule site (15th–17th CE) located at Point Franklin, northern Alaska. The preliminary results have been obtained from the standard dendrochronological analyses of 40 timber cross-sections from two semi-subterranean houses at Pingusugruk. We cross-correlated individual ring-width series and built floating chronologies between houses before cross-dating them with existing regional 1000-year-long master chronologies from the Kobuk and Mackenzie rivers (available on the International Tree-Ring Databank, ITRDB). Additional work on various dendro-archaeological collections using an interdisciplinary approach (geochemical analyses of oxygen isotopes and radiocarbon dating) will help develop and expand regional tree-ring chronologies and climatic tree-ring sequences in Alaska.

A Neandertal dietary conundrum: Insights provided by tooth enamel Zn isotopes from Gabasa, Spain

The characterization of Neandertals' diets has mostly relied on nitrogen isotope analyses of bone and tooth collagen. However, few nitrogen isotope data have been recovered from bones or teeth from Iberia due to poor collagen preservation at Paleolithic sites in the region. Zinc isotopes have been shown to be a reliable method for reconstructing trophic levels in the absence of organic matter preservation. Here, we present the results of zinc (Zn), strontium (Sr), carbon (C), and oxygen (O) isotope and trace element ratio analysis measured in dental enamel on a Pleistocene food web in Gabasa, Spain, to characterize the diet and ecology of a Middle Paleolithic Neandertal individual. Based on the extremely low δ66Zn value observed in the Neandertal's tooth enamel, our results support the interpretation of Neandertals as carnivores as already suggested by δ15N isotope values of specimens from other regions. Further work could help identify if such isotopic peculiarities (lowest δ66Zn and highest δ15N of the food web) are due to a metabolic and/or dietary specificity of the Neandertals.

Measurements of Sulfur Isotope Composition on Ultrasmall (80 Nanomole) Sulfide and Sulfate Samples by a Modified EA‐IRMS

AbstractThe traditional method for sulfur isotope measurement using EA‐IRMS commonly requires sulfur content greater than 2 μmol. Such a large sample size limits its application to low‐S materials, the size mainly being due to ineffective utilization of sample gas, almost 99.7% of which is discarded with carrier gas through the split port of the continuous‐flow interface. A modified EA‐IRMS system with a gas chromatographic (GC) column and a custom‐built cryogenic concentration device is used in this study. We measured six reference materials to test the performance of this method. The results were consistent with those obtained through traditional EA‐IRMS. Precisions ranging from ±0.24‰ to ±0.76‰ (1σ) can be obtained with samples equivalent to ∼80 nmol sulfur, which were similar to results obtained from an alternative method using an absorption column. Our improved method is a powerful tool for sulfur isotope measurement in ultrasmall sulfide and sulfate samples, which can be further applied to carbon, nitrogen and oxygen isotope analyses of samples at about 100 nmol level.

A new method for phosphate purification for oxygen isotope ratio analysis in freshwater and soil extracts using solid-phase extraction with zirconium-loaded resin.

Phosphate (PO4 ) oxygen isotope (δ18 OPO4 ) analysis is increasingly applied to elucidate phosphorus cycling. Due to its usefulness, analytical methods continue to be developed and improved to increase processing efficiency and applicability to various sample types. A new pretreatment procedure to obtain clean Ag3 PO4 using solid-phase extraction (SPE) with zirconium-loaded resin (ZrME), which can selectively adsorb PO4 , is presented and evaluated here. Our method comprises (1) PO4 concentration, (2) PO4 separation by SPE, (3) cation removal, (4) Cl- removal, and (5) formation of Ag3 PO4 . The method was tested by comparing the resulting δ18 OPO4 of KH2 PO4 reagent, soil extracts (NaHCO3 , NaOH, and HCl), freshwater, and seawater with data obtained using a conventional pretreatment method. PO4 recovery of our method ranged from 79.2% to 97.8% for KH2 PO4 , soil extracts, and freshwater. Although the recovery rate indicated incomplete desorption of PO4 from the ZrME columns, our method produced high-purity Ag3 PO4 and accurate δ18 OPO4 values (i.e., consistent with those obtained using conventional pretreatment methods). However, for seawater, the PO4 recovery was low (1.1%), probably due to the high concentrations of F- and SO4 2- which interfere with PO4 adsorption on the columns. Experiments indicate that the ZrME columns could be regenerated and used repeatedly at least three times. We demonstrated the utility of ZrME for purification of PO4 from freshwater and soil extracts for δ18 OPO4 analysis. Multiple samples could be processed in three days using this method, increasing sample throughput and potentially facilitating more widespread use of δ18 OPO4 analysis to deepen our understanding of phosphorus cycling in natural environments.