Stable Oxygen Isotope Analyses Research Articles

Multistage selective diagenesis increasing poro-perm properties of Anisian sponge-microbial-coral patch reefs and adjacent facies in the Muschelkalk of Upper Silesia, southern Poland

Carbonate rocks, particularly reefs and circum-reef facies, are significant reservoir rocks whose reservoir properties depend on their primary composition and diagenetic history. This paper reconstructs the influence of multistage selective diagenesis on the pore system evolution and porosity-permeability properties of the Anisian tropical reef system (Karchowice and Diplopora Beds) in the Muschelkalk of Upper Silesia, southern Poland, using field and slab observations, standard and cathodoluminescence petrography, bulk and SIMS carbon and oxygen stable isotope analyses, porosity-permeability plug study, and computer image analysis of macroporosity (> 5 mm across). The reef system comprises two distinct levels of sponge-microbial(-coral) reef mounds surrounded by diverse bioclastic, peloidal, coated-grain, and micritic facies rich in Balanoglossites burrows. The strata experienced complex diagenetic alterations related to various fluids (marine, evaporitic, meteoric) and diagenetic environments (shallow substratal, burial, telogenetic), including (in chronological order): 1) early-marine precipitation of isopachous fibrous rims; 2) early dissolution during emersion; 3) brine-reflux dolomitization; 4) patchy silicification; 5) recrystallization; 6) burial calcite cementation by heated marine fluid; 7) deposition of vadose silt; 8) meteoric calcite cementation; 9) chemical compaction; 10) fracturing; and 11) final karstification, dedolomitization, FeO precipitation, and Liesegang ring formation by meteoric water during Cenozoic telogenesis. Many processes were selective and affected the same (more permeable) parts of the rocks. The strata exhibit porosities reaching 50% (combined plug porosity of 6–35% and macroporosity of up to 20%) and plug permeabilities of 0.07–70 mD, with the highest values occurring in the reefs and burrowed facies. The dominant late-stage telogenic dissolution pores originated from selective removal of dolomitized micrite within burrows and between sponge-microbial automicrite as well as dolomite crystals. The study illustrates the transition of the reef system from tight to porous due to multistage selective diagenesis and fluid flow, which enhanced subtle permeability differences between various types of micrite. This is the first case where four different fluids (dolomitizing, early dissolving, calcite-forming, and late dissolving) selectively migrated through the same rock parts at different times and modified them one after another.

Lithofacies and diagenetic controls on thrombolitic dolomite reservoir development from the Precambrian Dengying Formation in the central Sichuan Basin, SW China

Microbialite reservoirs are of great importance in oil and gas exploration. However, there is still a lack of comprehensive studies on the formation mechanisms of thrombolitic reservoirs, a specific type of microbialite. This research focuses on the oldest thrombolitic dolomite reservoir located within the Precambrian Dengying Formation in the central Sichuan Basin, southwestern China. A multi-disciplinary approach was employed to characterize different thrombolite facies and elucidate the formation mechanism of thrombolitic dolomite reservoirs and their controlling factors, involving core observation, thin-section analysis, cathodoluminescence, scanning electron microscope (SEM) microscopy, elemental analysis using LA-ICP-MS, and carbon and oxygen stable isotope analysis. Based on variations in texture, four types of thrombolite were identified: 1) distinct clotted thrombolite, 2) diffuse and regular clotted thrombolite, 3) diffuse and irregular clotted thrombolite, and 4) composite clotted thrombolite. Notably, the diffuse clotted thrombolitic dolomite is the prevalent lithology in the reservoir. Through modification by meteoric water, organic acid fluids, and hydrothermal fluids, a reservoir with dominant porosity in the form of primary growth-framework pores, dissolution pores, and vugs was formed. This resulted in the development of two high-quality reservoir intervals within the Second Member and at the top of the Fourth Member of the Dengying Formation. The growth-framework porosity of the thrombolites, epigenetic karstification, and tectonic fracturing were mainly conducive to reservoir development. However, various types of cementation have reduced porosity and connectivity within the reservoir. Overall, this study is a valuable example of the methodology required to understand meso- and microstructures of deep-buried thrombolitic dolomite reservoirs, including their heterogeneities and diagenesis, as the original structures influence diagenesis.

Sample preservation methods for nitrous oxide concentration and isotope ratio measurements in aquatic environments

AbstractThe nitrogen (N) and oxygen (O) stable isotope analysis of dissolved nitrous oxide (N2O) can provide important constraints on the sources and cycling of N2O in aquatic environments. The isotopic composition of aqueous N2O, both in field (natural abundance) or experimental (15N‐labeling) samples, however, may be altered by abiotic reactions involving nitrite () or hydroxylamine (NH2OH) and microbial activity during sample storage, if samples are not adequately preserved. Here we tested five different preservatives, mercuric chloride (HgCl2), copper sulfate (CuSO4), zinc chloride (ZnCl2), hydrochloric acid (HCl) mixed with sulfamic acid (SFA), and sodium hydroxide (NaOH), for fixing natural water samples from an estuary and a lake with different concentrations over a range of different storage times for N2O analyses. ZnCl2 and CuSO4 decreased the pH, and led to abiotic N2O production from , shifting the N2O isotopic composition significantly. Removal of with a mixture of SFA and HCl did not always prevent the alteration of the original N and O isotope composition of N2O, confirming the requirement for complete removal, and underscoring the biasing effects of at very low pH, even at trace levels. At low background, HgCl2 preservation led to robust and accurate results. However, in light of its toxicity and bioaccumulation potential in food webs, this fixative should be avoided. The addition of NaOH reduced abiotic side reactions involving , and yielded the most reliable and reproducible results for N2O concentration and isotope ratio measurements across tested settings and storage times.

Clumped and in situ carbon and oxygen isotopes of calcite as tracers for oxidation of hydrocarbons in deep siliciclastic strata

The oxidation of hydrocarbons, including methane, is part of interrelated hydrogeochemical reactions affecting the carbon budget in Earth’s crust. To investigate these processes in deep siliciclastic strata, we analyzed core samples from Lower Triassic red beds in the Mahu Sag (Junggar Basin, northwest China) by coupling petrological observations with high-resolution in situ secondary ion mass spectroscopy stable carbon and oxygen isotope analyses and clumped isotopes (Δ47) of authigenic calcite. The strata contain variable oil and gas content as well as abundant high-valence Fe and/or Mn oxides. Three sequential generations of cement occur, which are characterized as (1) non-luminescent, early diagenetic calcite (MnO <0.3%, δ13CVPDB [Vienna Peedee belemnite] = −5.6‰ to −4.1‰); (2) bright-orange luminescent late-stage I calcite (0.75%−5.23% MnO, δ13C = −51.4‰ to −25.8‰); and (3) dull-orange late-stage II calcite (4.10%−12.93% MnO, δ13C = −91.4‰ to −30.9‰). Clumped isotopic thermometry reveals that the calcite precipitation temperature increases successively from <40 °C, to 81−107 °C, to finally 107−132 °C, corresponding to three precipitation time periods: before the Late Triassic, from the Early Jurassic to the Early Cretaceous, and from the Early Cretaceous to the present, respectively. δ13C values of −55.7‰ to −25.8‰ indicate that late-stage I calcite is the final product of oxidation of both methane and C2+ hydrocarbons, whereas δ13C values as low as −91‰ indicate that late-stage II calcite is mainly derived from the thermochemical oxidation of methane (δ13C = −46.8‰ to −39.3‰) induced by high-valence Mn and/or Fe oxides. For late-stage I calcite, hydrocarbon oxidation was most likely promoted by high temperatures, although microbial oxidation cannot be completely ruled out. The higher precipitation temperature of late-stage II calcite demonstrates that the oxidation of methane requires higher activation energies than oxidation of C2+ hydrocarbons. We provide reliable geochemical evidence for thermally induced sequential oxidation of hydrocarbons within deep siliciclastic strata.

When the woolly rhinoceroses roamed East Asia: a review of isotopic paleoecology of the genus Coelodonta from the Tibetan Plateau to northern Eurasia

East Asia, being the evolutionary center of Coelodonta, offers a unique opportunity to explore the spatiotemporal paleoecologies of this genus. This study utilized bulk and serial stable carbon and oxygen isotope analyses on the Coelodonta nihowanensis and other ungulates from the Longdan fauna as well as two modern goats in the Linxia Basin, aiming to explore the paleoecology of C. nihowanensis at the periphery of the Tibetan Plateau during the Early Pleistocene. The isotopic results of these mammals indicated that C3 vegetation was possibly a major component of the local environment in the Linxia Basin, which was influenced by a seasonal summer monsoon. C. nihowanensis specimens in the Longdan fauna were possibly mixed feeders, as indicated by the wide distribution of their δ13C values and the intermediate δ18O values compared to other coexisting ungulates. Moreover, the comparison of the δ13C and δ18O values of similar taxa from the Linxia and Nihewan basins has revealed spatiotemporal differences in the paleoclimate and paleoenvironments of these two regions throughout the Early Pleistocene. This provides a holistic framework for understanding the paleoecology of the C. nihowanensis. The isotopic results of the C. nihowanensis in the Linxia and Nihewan basins suggested varied foraging ecologies across different sites and time spans during the Early Pleistocene. This underscores the adaptability of the C. nihowanensis to diverse environments from west to east in northern China. By scrutinizing the evolutionary ecological history of the woolly rhinoceroses from its ancestor, Coelodonta thibetana, to its final form, Coelodonta antiquitatis, this study sheds light on the ecological adaptation of this genus from the Pliocene to Late Pleistocene, spanning its migration from the Tibetan Plateau to northern Eurasia.

Shallow-water temperature seasonality in the middle Cretaceous mid-latitude northwestern Pacific

Temperature seasonality during the middle Cretaceous provides vital information about climate dynamics and ecological traits of organisms under the conditions of the “supergreenhouse” Earth. However, sub-annual scale paleotemperature records in the mid-latitude region remain limited. In this study, sclerochronological and stable oxygen isotope (δ18O) analyses of bivalve fossils from the northwestern Pacific (paleolatitude: 44°N) were used to estimate their life history and sub-annual scale temperature patterns of the middle Cretaceous. The materials studied included Cucullaea (Idonearca) delicatostriata and Aphrodina pseudoplana recovered from middle Turonian (middle Cretaceous) shallow marine deposits in Hokkaido, northern Japan. Growth increment width and shell δ18O of C. (I.) delicatostriata revealed that the growth rate was temporally maximized and then minimized, which can be interpreted as representing spring and winter growth, respectively. Approximately 25 fortnightly growth increments occurred within that cycle, suggesting that shell formation proceeded continuously throughout the year. Based on shell δ18O values, shallow-water temperatures from 28°C to 35°C with 7°C seasonality were estimated, under the assumption that seawater δ18O values were annually invariant at −1‰ relative to VSMOW. This temperature seasonality in the middle Cretaceous is more than 5°C smaller than the seasonality of modern shallow-water environments at the same latitudes. These findings, taken together with previous studies of other oceanic regions, suggest that the Northern Hemisphere had low seasonal shallow-water temperature variation of up to 10°C in the middle Cretaceous.

Multiproxy evidence for environmental stability in the Lesser Caucasus during the Late Pleistocene

The Lesser Caucasus, situated between Asia and Europe, has long been recognised as a key region for the study of human evolution in terms of the timing and routes of dispersal, as well as, ecological adaptations. In particular, scholars have argued whether stable environments persisted in the region throughout the last glaciation, serving as a refugium for temperate biota, likely attracting human settlement and use. Here, we present the results of a multidisciplinary study of Karin Tak Cave, which contains sediments that accumulated between 48,000 and 24,000 cal yr BP. We examined biostratigraphic changes at the site by looking at the composition of fauna, which we hypothesise to be naturally accumulated, in different stratigraphic phases using traditional zooarchaeological approaches combined with collagen fingerprinting (ZooMS, Zooarchaeology by Mass Spectrometry). To gain further insights into regional palaeoenvironmental conditions, we also applied stable carbon and oxygen isotope analyses to faunal tooth enamel. The obtained results suggest that the onset of the last glaciation did not cause dramatic changes in regional environments, indicating that the Lesser Caucasus was a climatically and ecologically stable region despite significant global climatic changes during this period.

Method to measure tree-ring width, density, elemental composition, and stable carbon and oxygen isotopes using one sample

Tree-ring width (RW), density, elemental composition, and stable carbon and oxygen isotope (δ13C, δ18O) are widely used as proxies to assess climate change, ecology, and environmental pollution; however, a specific pretreatment has been needed for each proxy. Here, we developed a method by which each proxy can be measured in the same sample. First, the sample is polished for ring width measurement. After obtaining the ring width data, the sample is cut to form a 1-mm-thick wood plate. The sample is then mounted in a vertical sample holder, and gradually scanned by an X-ray beam. Simultaneously, the count rates of the fluorescent photons of elements (for chemical characterization) and a radiographic grayscale image (for wood density) are obtained, i.e. the density and the element content are obtained. Then, cellulose is isolated from the 1-mm wood plate by removal of lignin, and hemicellulose. After producing this cellulose plate, cellulose subsamples are separated by knife under the microscope for inter-annual and intra-annual stable carbon and oxygen isotope (δ13C, δ18O) analysis. Based on this method, RW, density, elemental composition, δ13C, and δ18O can be measured from the same sample, which reduces sample amount and treatment time, and is helpful for multi-proxy comparison and combination research.

Hydraulic Relationship between Hulun Lake and Cretaceous Confined Aquifer Using Hydrochemistry and Isotopic Data

Hydraulic Relationship between Hulun Lake and Cretaceous Confined Aquifer Using Hydrochemistry and Isotopic Data

Marine resource exploitation and human settlement patterns during the Neolithic in SW Europe: stable oxygen isotope analyses (δ18O) on Phorcus lineatus (da Costa, 1778) from Campo de Hockey (San Fernando, Cádiz, Spain)

In recent decades, investigations in the southern Iberian Peninsula have increased our understanding of the socio-economic impact of the spread of the Neolithic in southwestern Europe, including changes in marine resources exploitation. Nevertheless, considerable uncertainty still exists around the seasonality of such subsistence systems and the putative role of marine fish and shellfish to the evolving agro-pastoral economies. Earlier studies on the European Atlantic coast (including Iberia) have shown that the stable oxygen isotope (δ18O) values from the topshell Phorcus lineatus (da Costa, 1778) can be reliably used to derive seasonal sea surface temperatures (SST) during its lifespan. This information can be used by archaeologists to estimate the seasonality of mollusc collection in the past, and to shed light into settlement and subsistence patterns. This paper presents the results of a stable isotope study on archaeological shells of P. lineatus recovered from the Neolithic settlement of Campo de Hockey (Cádiz, Spain). We analysed shells from both funerary and residential contexts and found that P. lineatus was consumed year-round, but with a stronger preference during winter. Our results therefore contribute to advance our understanding of the role of coastal environments in early farming societies of southwestern Europe.

Origin of the Yueguang gold deposit in Xinhua, Hunan Province, South China: insights from fluid inclusion and hydrogen–oxygen stable isotope analysis

Origin of the Yueguang gold deposit in Xinhua, Hunan Province, South China: insights from fluid inclusion and hydrogen–oxygen stable isotope analysis

Preservation of bone organic fraction is not predictive of the preservation of bone inorganic fraction when assessing stable isotope analysis sample quality control measures

Stable isotope analysis of carbon (C), nitrogen (N), hydrogen (H), and oxygen (O) of archaeological bone has become an increasingly common research method for interpreting human behavior in the past. However, diagenesis of skeletal material can invalidate stable isotope ratios, thereby compromising interpretations. We examine patterns of bone diagenesis using infrared spectroscopy of bone bioapatite samples in relation to indicators of organic preservation quality indicators. We assess crystallinity, an indicator of bioapatite preservation, using the infrared splitting factor (IR-SF) and carbonate content (carbonate to phosphate ratio, C/P) calculated from infrared spectra. We then test the assumption that if the organic fraction of bone is preserved, the mineral fraction will also be unaffected by postmortem chemical alteration. We analyzed 454 bone bioapatite and extracted bone organic sample pairs from modern, historic, and prehistoric humans. Consistent with previous studies, we observed a strong, statistically significant negative linear relationship between IR-SF and C/P (r = −0.855, p < 0.001). Modern bone bioapatite samples unaltered by diagenesis have low IR-SF and high C/P values. There was no significant association between the collagen yield or atomic C:N ratio and IR-SF or C/P values. The range of variation in IR-SF and C/P values for samples with organic yields between 0 and >20 percent spanned the range of modern bone bioapatite unaltered by diagenesis as well as bone bioapatite significantly affected by diagenesis. The lack of predictive patterning between bone inorganic and organic diagenesis suggests that the depositional context and site formation history play critical and independent roles in the organic and mineral fraction of bone. Thus, the preservation of the organic fraction of bone is not predictive of the preservation of the inorganic fraction (e.g., bioapatite).

Sensitivity of the thermohaline circulation during the Messinian: Toward constraining the dynamics of Mediterranean deoxygenation

During the Messinian, the sensitivity of the Mediterranean Basin to ecosystem perturbation was enhanced in response to the progressive restriction of water exchange with the Atlantic Ocean. The widespread deposition of organic-rich layers (i.e. sapropel) during the Messinian testifies the perturbation of the carbon and oxygen cycles; indeed, these sediments were deposited under conditions of oxygen starvation, presumably in response to a periodic deterioration of the thermohaline circulation strength. Disentangling the causes, the effect and magnitude of the thermohaline circulation weakening during the geological past is crucial for better constraining present and near-future deoxygenation dynamics in the Mediterranean region under the current climate warming. For this purpose, we investigate a Messinian sapropel-bearing succession cropping out at Monte dei Corvi (Ancona, central Italy) with mineralogical, petrographic, micropaleontological and stable Carbon and Oxygen isotopic analyses. We show that sapropel layers were deposited in response to an increase of the sea surface buoyancy, which hampered the thermohaline circulation and thus the oxygenation of bottom water, in turn affecting the bioturbating organisms. Within the lithological cycle, the recovery of an efficient thermohaline circulation is recorded by thin packstone layers underlying the marly limestone/marlstone, which record intense bottom currents. The marly limestone/marlstone accumulated during periods of intense primary productivity and organic carbon export to the sea bottom, which promoted bottom hypoxia but not organic matter preservation. We infer that these lithological changes resulted from variations in the Adriatic Deep Water formation system, controlled by precession-driven climatic and oceanographic changes.By integrating previously published Sea Surface Temperature (SST) with new isotopic and mineralogical data, we show that variations in Sea Surface Salinity (SSS) were the leading factor controlling sapropel deposition, minimizing the role of primary productivity. The SSTs characterizing the sapropel deposits are close to the range of those projected in the Eastern Mediterranean at the end of this century under climate warming. In this scenario, future warming will be coupled with SSS increase, which will counteract the density loss provided by temperature, making the bottom deoxygenation in the Eastern Mediterranean abysses unlikely. However, additional forcing, such as winter heat waves and eutrophication, could contribute to negatively affecting the Mediterranean oxygen balance and should be considered in model-based projections.

Isotopic evidence of an environmental shift at the fall of the Kushite kingdom of Meroë, Sudan

Between c. 300 BC and AD 350, the Meroitic kingdom dominated the Middle Nile Valley; following its breakdown, it was replaced by a series of smaller successor polities. Explanation for this change centres on socio-political and economic instability. Here, the authors investigate the role of climate and environment using stable carbon and oxygen isotope analyses of human and faunal dental enamel from 13 cemeteries. The results show increasing δ18O values towards the end of the Meroitic kingdom and in the post-Meroitic period, combined with less negative δ13C values. These trends suggest a shift towards more arid conditions associated with changes in agricultural practices and land use that may have contributed to the kingdom's dissolution.

A passive method for sampling water in the soil-plant-atmosphere continuum for stable hydrogen and oxygen isotope analyses.

Hydrogen and oxygen isotopes in water molecules are powerful tools to constrain the dynamics of water cycling within the soil-plant-atmosphere continuum (SPAC). However, the recovery of water from the SPAC requires logistical arrangements and implementation of different time- and cost-consuming techniques in either the field or the laboratory. We developed a passive method to sample water from the three compartments of the SPAC by using a hygroscopic salt of a high water absorbance capacity (CaCl2 ). This method allows either H2 O(V) -H2 O(L) isotope equilibration in the case of infinite water reservoir (atmospheric water vapor (WV)) or quantitative absorption of water from a finite water reservoir (e.g. soil and plants). The water absorbed by CaCl2 was distilled first and subsequently processed for hydrogen and triple oxygen isotope mass spectrometry analyses. The distillation step can be bypassed when employing isotope analytical techniques that are based on equilibration. Our experiments show that anhydrous CaCl2 absorbs WV of 210 ± 6% and 130 ± 6% of its dry weight from an infinite WV reservoir at relative humidity of 60% and 30%, respectively. Chemical and isotope equilibrations between WV and absorbed water were attained within 3 days at room temperature, enabling the back-calculation of the isotope composition of atmospheric WV. Preliminary experiments to extract water from plant and sand (i.e. finite WV reservoir) demonstrate a quasi-complete recovery of water in these matrices without significant isotope fractionation. The reproducibility of our method is better than 1.6‰, 0.32‰, 0.17‰ and 6‰ per meg for δ2 H, δ18 O, δ17 O and 17 O-excess. The CaCl2 -H2 O absorption (passive) method requires very limited logistics in the field facilitating spatial and temporal water vapor/water sampling from atmosphere and soil at low resolution (i.e. average of 3-5 days). Moreover, it allows high sample throughput for the extraction of plant water in the laboratory. The reproducibility of this method is similar to the analytical uncertainty in mass spectrometry analyses.

Investigation of Seasonal Settlement and Clam Harvest Pressure in the Sechelt Inlet System, British Columbia, Canada, Through Sclerochronology and Stable Oxygen Isotope Analyses

ABSTRACT The Sechelt inlet system (SIS), situated on the inner Sunshine Coast of British Columbia, lies within the territory of the shíshálh Nation. This study focuses on ∼1000 years of shíshálh shellfish harvesting from 930-0 cal. BP. Specifically, we investigated the seasonal timing of shellfish collection, relative shellfish harvesting pressure and paleo-temperature reconstruction at four archaeological sites. Thirty archaeological butter clam shells (Saxidomus gigantea) from the SIS underwent high-resolution shell oxygen isotope (δ18O) analysis and 662 individual archaeological shell fragments were analysed for growth stage determination. The δ18O results showed a pattern of year-round collection with an emphasis on spring collection at village sites. Results from shell growth stage analysis suggest an intensive pattern of shellfish harvesting in the region, regardless of the site type. Archaeological shells show a larger δ18Oshell range, possibly reflecting a greater sea surface temperature amplitude than modern shells (i.e. a difference of ∼6.5°C; modern range: ∼3.7–20.4°C; archaeological range: ∼ −0.8–22.4°C). We contextualise our results with previous studies of seasonal timing and intensity of shellfish harvesting from the Pacific Northwest Coast, while interpreting these new data in the context of shíshálh occupation and landscape use.

Isotopic insights into the Early Acheulean (1.95 Ma–1.66 Ma) high-elevation paleoenvironments at Melka Kunture (Upper Awash Valley, Ethiopia)

In this paper, we present stable carbon and oxygen isotope analyses of fauna tooth enamel from Garba IVD (1.95 Ma) and Gombore IB (1.66 Ma), two Early Acheulean sites of Melka Kunture (Upper Awash, Ethiopia), and discuss faunal taxonomy and fossil pollen. Our aim is to infer the diet and habitat of the fossil fauna, as well as the environment of both sites, in order to provide a broader paleoecological reconstruction. During the Pleistocene, the vegetation of the highlands of Ethiopia belonged to the Dry evergreen Afromontane Forest and grassland complex, which is distinct from the savanna of lower elevations in eastern Africa. Our carbon isotopic results indicate that all the analyzed faunal taxa were grazers consuming C4 plants, whereas oxygen isotopic results discriminate the taxa according to their semiaquatic or terrestrial habitats. These results are consistent with the taxonomic composition of the faunal assemblages and the palynological results, suggesting extended mountain grasslands in the landscape at Garba IVD. In contrast, the carbon isotopic results do not totally agree with the pollen paleoenvironmental reconstruction at Gombore IB, where the open vegetation was interrupted by forests and bushy vegetation. Stable isotope and pollen data provide different outcomes (feeding strategies vs. nearby plants) and have different temporal and spatial resolutions. This is relevant when reconstructing past environments by using independent proxies. Furthermore, isotopic comparisons with other Early Pleistocene paleontological and archaeological sites from eastern Africa indicate that all the analyzed taxa in common fed on C4 plants and that their dietary strategies were not affected by variations linked to the difference in elevations.

Triple oxygen stable isotope analysis of nitrite measured using continuous flow isotope ratio mass spectrometry

Oxygen stable isotopes (i.e., 16O, 17O, 18O) of nitrite (NO2−) are useful for investigating chemical processes and sources contributing to this important environmental contaminant and nutrient. However, it remains difficult to quantify the oxygen isotope compositions of NO2− due to the lack of internationally recognized NO2− reference materials with a well-known Δ(17O) value. Here we have adopted a combination of methodologies to develop a technique for measuring Δ(17O) of NO2− by reducing nitrate (NO3−) materials with internationally recognized Δ(17O) values to NO2− using activated cadmium catalyzed by chloride in a basic solution while conserving Δ(17O). The NO3− reference materials reduced to NO2− and sample NO2− unknowns are converted to N2O using sodium azide/acetic acid reagent and decomposed to O2 by passing through a heated gold tube and introduced into a continuous flow isotope ratio mass spectrometer for analysis at m/z 32, 33, and 34 for Δ(17O) quantification.The adapted method involves the following main points:•NO3− reference materials with internationally recognized oxygen isotope composition are reduced to NO2− under high pH conditions that conserve Δ(17O) values.•The NO3− reference materials reduced to NO2− and sample NO2− with unknown Δ(17O) values are reduced to N2O using chemical methods involving sodium azide/acetic acid.•The product N2O is extracted, purified, decomposed to O2, and analyzed for its isotope composition using a continuous flow isotope ratio mass spectrometer for Δ(17O) quantification. The Δ(17O) of NO2− samples are calibrated with respect to the NO3− reference materials with known Δ(17O) values.

Occurrence and Genesis of Cold‐Seep Authigenic Carbonates from the South‐Eastern Mediterranean Sea

AbstractMethane‐derived authigenic seep carbonates occur globally along continental margins. These carbonates are important archives to identify seep dynamics, the source of the ascending methane‐enriched fluids together with their timing, and are an important carbon sequestration mechanism. Recently, seep carbonates were discovered in the Levant Basin in the south‐eastern Mediterranean Sea. To elucidate past seepage activity and dynamics across the basin, different seep carbonate morphologies (chimneys, crusts and pavements) retrieved from the Levant Basin were mapped based on remotely operating vehicle data and analysed using standard sediment petrographic techniques, X‐ray diffraction and stable carbon and oxygen isotope analyses. Carbonate chimneys consist of micrite (δ13CVPDB of −10‰ to +5‰) with dispersed baryte and dolomite crystals, fan‐shaped aragonite (δ13CVPDB of −52‰ to −30‰) and high‐magnesium calcite cements, with the latter often growing from low‐magnesium calcite spherules. Botryoidal low‐magnesium calcite cements are forming in small cavities. Carbonate crusts consist of micrite with low‐magnesium calcite breccias, high‐magnesium calcite nodules (δ13CVPDB of −35‰ to −20‰) and cements, and partially replaced fan‐shaped aragonite cements. Carbonate pavements consist of low‐magnesium calcite microsparite, micritic dolomite and high‐magnesium calcite. Fan‐shaped aragonite is locally present as pore‐lining cement. Iron oxides are often seen coating the low‐magnesium calcite, high‐magnesium calcite and dolomite cements. Chimneys and crusts, characterised by high amounts of high‐magnesium calcite and aragonite, are interpreted to have formed through advective methane fluxes. Pavements, with high quantities of dolomite, are explained as the product of diffusive methane flux. Sediment petrographic and geochemical analysis of the different carbonate morphologies and cement phases therein witness distinct modes of ascending fluid fluxes and their mixing with marine pore water and/or sea water during precipitation of the individual phases.

Responses of Tree Growth and Intrinsic Water Use Efficiency to Climate Factors and Human Activities in Upper Reaches of Tarim River in Alaer, Xinjiang, China

With global warming and increasing human activities, exploring the impact of the rising atmospheric carbon dioxide concentration and climate change on forest ecosystems is crucial. In this study, we focus on Euphrates poplar (Populus euphratica Oliv.) in the upper reaches of the Tarim River in the Alaer region of Xinjiang. We use dendrochronological methods, tree-ring width, and stable carbon isotope series to explain basal area increment (BAI) and intrinsic water use efficiency (iWUE) changes. We further explore the influence of past climate change and human activities on the radial growth and iWUE of P. euphratica through stable oxygen isotope analysis combined with historical literature records. The results showed that relative humidity had an essential effect on Δ13C and δ18O fractionation in P. euphratica tree rings, whereas the vapor pressure deficit (VPD) was considered the main factor influencing the inter-annual variability of the iWUE and BAI. Since 1850, long-term variations in iWUE have exhibited an upward trajectory correlated with rising atmospheric CO2 levels. Approximately 13% of this iWUE increase can be attributed to changes in carbon-concentration-induced water use efficiency (cciWUE). Although Δ13C and δ18O were generally uncorrelated between 1850 and 2018, around 1918, their relationship changed from being weakly correlated to being significantly negatively correlated, which may record changes related to the upstream Tarim River diversion. During the period from 1850 to 2018, both the BAI and iWUE showed an increasing trend for P. euphratica growth; however, the relationship between them was not stable: during 1850–1958, both variables were mainly influenced by climatic factors, while during 1959–2018, the most important influence was due to human activities, specifically agricultural development and irrigation diversions. An abrupt surge in the BAI was observed from 1959 to 1982, reaching its peak around 1982. Surprisingly, post-1983, the escalating iWUE did not correspond with a continuation of this upward trajectory in the BAI, highlighting a divergence from the previous trend where the enhanced iWUE no longer facilitated the growth of P. euphratica. Despite P. euphratica having adapted to the continuously rising Ca, improving its iWUE and growth capacity, this adaptive ability is unstable and may easily be affected by human activities. Overall, the increase in Ca has increased the iWUE of P. euphratica and promoted its growth at a low frequency, while human activities have promoted its development at a high frequency.