Stable Carbon Isotope Composition Research Articles

Stable carbon isotope composition and intrinsic water use efficiency in plants along an altitudinal gradient on the eastern slope of Yulong Snow Mountain, China

BackgroundStable carbon isotope composition (δ13Cp) can be used to estimate the changes in intrinsic water use efficiency (iWUE) in plants, which helps us to better understand plants’ response strategies to climate change. This study focused on the variations in δ13Cp and iWUE for the different life-form plants (i.e., herbs, shrubs, and trees) along an altitudinal gradient (3300, 3600, 3900, 4100, 4300, and 4500 m) on the eastern slope of Yulong Snow Mountain, southeastern margin of the Qinghai-Tibet Plateau. The response mechanisms of δ13Cp and iWUE for different life-form plants to altitude were thoroughly analyzed in this mountain ecosystem.ResultsThe δ13Cp values of plants on the eastern slopes of Yulong Snow Mountain ranged from − 30.4‰ to − 26.55‰, with a mean of − 28.02‰, indicating a dominance of C3 plants. The δ13Cp and iWUE values varied among different life-form plants in the order of herbs > shrubs > trees, particularly in 3600, 3900, and 4300 m. The δ13Cp and iWUE values for herbs and shrubs increased with altitude and were mainly controlled by air temperature. The two parameters for trees exhibited a trend of initial decrease followed by an increase with altitude. Below 3900 m, the δ13Cp and iWUE values decreased with altitude, influenced by soil moisture. However, above 3900 m, the two parameters increased with altitude, mainly regulated by air temperature. In addition, iWUE was positively correlated with leaf P content but negatively correlated with leaf N:P ratio, especially for herbs and trees, suggesting that P plays a key role in modulating iWUE in this region.ConclusionsThe differentiated responses of water availability for different life-form plants to a higher altitudinal gradient are regulated by air temperature, soil moisture, and leaf P content in the Yulong Snow Mountain. These results provide valuable insights into understanding the water–carbon relationships in high-altitude ecosystems.

Transition from opportunistic to conservative water use strategy with the growth of Robinia pseudoacacia in a typical watershed in the semiarid Loess Plateau

Understanding water use strategy is essential to evaluate plant adaptability in water-limited regions, but whether this strategy changes with plant growth needs further investigation. Robinia pseudoacacia is an exotic pioneer plantation species widely planted in the semiarid Loess Plateau of China to restore degraded ecosystems. Plant water uptake proportion from different soil layers and the water uptake pattern calculated through soil water uptake niche breadth (B index) were determined for R. pseudoacacia in 11-, 25-, 33–, and 43-yr plantations. Leaf physiological parameters and carbon stable isotopic composition (δ13C) were measured concurrently to calculate short-term and long-time integrated water use efficiency (WUE). Then, the water use strategy for R. pseudoacacia at different plantation ages was assessed through water uptake patterns, stomatal conductance (gs), and WUE variation under varied soil water conditions. Results showed that R. pseudoacacia maintained high gs and low short-term WUE and δ13C through a relative equal water uptake pattern and absorbed water within 0 − 400 cm soil depths in 11- and 25-yr plantations. However, this species exhibited an exclusive water uptake pattern and absorbed water mainly from 50 − 400 cm soil depth, adopted low gs and high short-term WUE and δ13C in 33– and 43-yr plantations. Therefore, R. pseudoacacia transited from an opportunistic to a conservative water use strategy with plant growth. The short-term WUE and δ13C were mainly and significantly influenced by gs and specific leaf area, respectively. Furthermore, the significant influence of B index on gs, δ18OΔ, short-term WUE, and δ13C indicated that R. pseudoacacia coordinated both water uptake pattern and water use behavior to contend with varied soil water conditions. This study suggested that changes in age-related water use strategy were essential for the adaptability of R. pseudoacacia in water-limited conditions.

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

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

Stable isotope evidence for resource partitioning in extinct marine carnivores

Living pinnipeds play essential roles in marine ecosystems and display divergent lineage-specific foraging and habitat preferences. The origin of these ecological strategies remains unclear. We analyzed original (n = 22) and published (n = 93) stable carbon (δ13C) and oxygen (δ18O) isotope compositions of tooth enamel from fossil pinnipeds and coeval marine and terrestrial mammals from the late Early Miocene to early Middle Miocene Temblor Formation, the early Middle Miocene Round Mountain Silt Formation at Sharktooth Hill Bonebed, the Middle Miocene of lower levels of the Monterey Formation, and the late Middle Miocene Santa Margarita Formation from the eastern North Pacific Ocean; and original (n = 43) δ13C and δ18O values from the Early Pliocene Yorktown Formation in the western North Atlantic. As expected for aquatic mammals, pinnipeds and control marine mammals had low δ18O variability relative to coeval terrestrial mammals, indicating minimal diagenetic alteration. Among late Early Miocene and Middle Miocene pinnipeds, Allodesmus had lower δ13C values than coeval taxa indicating offshore foraging, in agreement with predictions based on skeletal morphology. However, Allodesmus from the late Middle Miocene Santa Margarita Formation had overlapping δ13C values with co-occurring cetaceans and pinnipeds suggesting preferential nearshore habitat. The stem otariid Pithanotaria had higher enamel δ13C values than co-occurring pinnipeds, indicating nearshore foraging. The stem odobenid Neotherium had intermediate δ13C values supporting foraging between nearshore and offshore predators. Conversely, the stem odobenid cf. Imagotaria had lower enamel δ18O but comparable δ13C values to coexisting pinnipeds, suggesting the exploitation of estuarine resources. At least two ecologically distinct pinniped groups also occurred in the Yorktown Formation. In this unit, the odobenid Ontocetus and some monachinae phocids were predominantly nearshore foragers, with higher enamel δ13C and δ18O values than simultaneously occurring marine mammals. The second group was exclusively integrated by phocids, which had comparatively low δ13C and δ18O values, compatible with northward foraging movements along the western North Atlantic coast. The paleoecological profiles of fossils bear strong similarities to the life modes of extant pinniped communities, implying that extant foraging modes appeared early in pinniped evolution and that resource partitioning contributed to their community structure over time.

Stable isotopic composition of Bothrops atrox (common lancehead) in four distinct land covers in eastern Amazonia

AbstractSince consumers reflect the isotopic composition of an assimilated diet, stable isotopes can be a useful tool to address the feeding ecology of tropical snakes. This is the first study reporting carbon and nitrogen stable isotopic composition of Bothrops atrox (Linnaeus, 1758) living in different landscapes located in the lower Amazon river, encompassing four main natural landscapes of the Amazon: old‐growth forests, várzeas (flooded forests), savannas, and pastures. Our null hypothesis is that the δ13C of forest specimens of B.atrox is more negative because forests are dominated by C3 plants, while C4 plants are common in the other landscapes. On the other hand, δ15N of forest specimens should be more positive, since the δ15N of old‐growth forests are higher than plants of savanna, várzea, and pastures. Confirming our hypothesis, the δ13C of B. atrox scales of the Tapajós National Forest was approximate −25‰ to −24‰, increased to approximately −23.5‰ to −23.0‰ in the savanna and pasture, and to −21‰ in the várzea, showing an increased contribution of C4‐derived carbon. Some specimens of B. atrox had δ15N as high as 18‰, which is much higher than the average δ15N of the snake's prey (7‰), confirming the apex position of B. atrox in the Amazon region. The δ15N values of the forest specimens were 5‰ higher than the savanna specimens, and this difference decreased to 3‰ between the forest and the pasture, and the várzea specimens. Finally, there were not large differences between δ15N values of livers and scales in any of the landscapes, suggesting a constant diet through time, and reinforcing the possibility of the use of snake's scale as a less invasive and non‐lethal tissue to analyze.Abstract in Portuguese is available with online material.

Silicate weathering linked with global climate change along the Mid-Pleistocene transition: A record from the Himalayan foreland Basin, India

Tectonic uplift and climate change play a pivotal role in controlling silicate weathering in the source region. Being adjacent to the hinterland, the sediments of the Himalayan foreland basin (HFB) hold an excellent archive to elucidate weathering link with climate and uplift. In this study, we present geochemical records of major, trace and rare earth elements, clay mineral compositions as well as the environmental magnetic and stable carbon isotope composition (δ13C) of siliciclastic sediments of the HFB over the past 2.0 Ma. These records have been used to link silicate weathering with global climate change along the Mid-Pleistocene Transition (MPT) period. The source rock compositions are characterized by selected elemental ratios, i.e., Cr/Th, Th/Sc, Th/Co and La/Sc as well as other geochemical proxies such as Al2O3/TiO2 and TiO2/Zr, suggesting a felsic source rock composition. The enriched LREE pattern of Chondrite-normalised REE with a negative Europium anomaly also attributes to felsic source rock composition. All these inferences suggest that most of the studied sediments were derived from mixed sources of the Higher Himalayan rocks and the Lesser Himalayan crystalline regions. A declining trend in kaolinite/(illite + chlorite) ratios, decreasing values of geochemical weathering indices (such as Rb/Sr and CIA), a decrease in magnetic susceptibility and gradual depleted value of δ13C indicate a decrease in chemical weathering of the siliciclastic rocks in the source region, which is most probably associated with the global climate change from warm-humid to cold-dry condition along the MPT. This suggests that variation in silicate weathering in the Himalayan region are mainly controlled by global climate and monsoon conditions.

Middle Eocene Climatic Optimum (MECO) and its imprint in the continental Escanilla Formation, Spain

Abstract. The Middle Eocene Climatic Optimum (MECO) is a global warming event mainly recognized in the marine domain and described less in the terrestrial environment. Here we present a comprehensive geochemical record of the MECO from the Escanilla Formation, a fluvial sedimentary succession in the southern Pyrenees, Spain, based on a suite of sampled paleosols, fluvial stromatolites, and pedogenic nodules. Our multiproxy approach involves using carbon and oxygen stable isotope compositions to identify the regional preservation of the MECO, calculate chemical weathering intensity and mean annual precipitation, perform clumped isotopes on carbonates, and identify clay mineralogy assemblages of paleosols. Results indicate that the Middle Eocene interval in the southern Pyrenees was characterized by low weathering rates under warm and arid climatic conditions. This is further supported by the presence of smectite, palygorskite, illite, and chlorite, which suggest seasonal rainfall but under generally dry conditions resulting in weak chemical weathering. Importantly, a negative organic carbon isotopic excursion indicates the regional, terrestrial impact of the MECO, highlighting that fluvial sedimentary successions even in active foreland basins can represent particularly interesting terrestrial archives of past changes in global climate.

Using Multi‐Homolog Plant‐Wax Carbon Isotope Compositions to Reconstruct Tropical Vegetation Types

AbstractThe stable carbon isotope composition (δ13C) of plant components such as plant wax biomarkers is an important tool for reconstructing past vegetation. Plant wax δ13C is mainly controlled by photosynthetic pathways, allowing for the differentiation of C4 tropical grasses and C3 forests. Proxy interpretations are however complicated by additional factors such as aridity, vegetation density, elevation, and the considerable δ13C variability found among C3 plant species. Moreover, studies on plant wax δ13C in tropical soils and plants have focused on Africa, while structurally different South American savannas, shrublands and rainforests remain understudied. Here, we analyze the δ13C composition of long‐chain n‐alkanes and fatty acids from tropical South American soils and leaf litter to assess the isotopic variability in each vegetation type and to investigate the influence of climatic features on δ13C. Rainforests and open vegetation types show distinct values, with rainforests having a narrow range of low δ13C values (n‐C29 alkane: ‰ ; Suess‐effect corrected). This allows for the detection of even minor incursions of savanna (δ13C n‐C29 alkane ‰) into rainforests. While Cerrado savannas and semi‐arid Caatinga shrublands grow under distinctly different climates, they can yield indistinct δ13C values for most compounds. Cerrado soils and litter show pronounced isotopic spreads between the n‐C33 and n‐C29 alkanes, while Caatinga shrublands show consistent values across the two homologs, thereby enabling the differentiation of these vegetation types. The same multi‐homolog isotope analysis can be extended to differentiate African shrublands from savannas.

The Pleistocene high-elevation environments between 2.02 and 0.6 Ma at Melka Kunture (Upper Awash Valley, Ethiopia) based upon stable isotope analysis

Pleistocene environments are among the most studied issues in paleoecology and human evolution research in eastern Africa. Many data have been recorded from archaeological sites located at low and medium elevations (≤ 1500 m), whereas few contexts are known at 2000 m and above. Here, we present a substantial isotopic study from Melka Kunture, a complex of prehistoric sites located at 2000—2200 m above sea level in the central Ethiopian highlands. We analyzed the stable carbon and oxygen isotopic composition of 308 faunal tooth enamel samples from sites dated between 2.02 and 0.6 Ma to investigate the animal diets and habitats. The carbon isotopic results indicate that the analyzed taxa had C4-dominated and mixed C3-C4 diets with no significant diachronic changes in feeding behavior with time. This is consistent with faunal and phytolith analyses, which suggested environments characterized by open grasslands (with both C3 and C4 grasses), patches of bushes and thickets, and aquatic vegetation. However, palynological data previously documented mountain forests, woodlands, and high-elevation grasslands. Additionally, the carbon isotopic comparison with other eastern African localities shows that differences in elevation did not influence animal feeding strategies and habitat partitioning, even though plant species vary according to altitudinal gradients. In contrast, the oxygen isotopic comparison suggests significant differences consistent with the altitude effect. Our approach allows us to detect diverse aspects of animal behavior, habitat, and vegetation that should be considered when reconstructing past environments.

Pyrogenic Carbon Degradation by Galvanic Coupling with Sprayed Seawater Microdroplets.

Surface waves are known for their mechanical role in coastal processes that influence the weather and climate. However, their chemical impact, particularly on the transformation of pyrogenic carbon, is poorly understood. Pyrogenic carbon is generally assumed to show negligible postformational alteration of its stable carbon isotope composition. Here we present an electrochemical interaction of pyrogenic carbon with the sprayed seawater microdroplets resulting from wave breaking, driven by the galvanic coupling between the microdroplet water-carbon interfaces and the microdroplet water-vapor interfaces. This enables refractory pyrogenic carbon to rapidly degrade via the oxygenation and mineralization reaction, which makes it ∼2.6‰ enriched in 13C, far exceeding the generally assumed postformation alteration values (<0.5‰) of pyrogenic carbon. The unique chemical dynamics of seawater microdroplets provide new insights into the discrepancy in carbon isotope signatures between riverine and marine black carbon, emphasizing the potential of coastal oceans for carbon sequestration in the global carbon cycle.

Organic Geochemical Evidence for the Formation of Condensate from Coaly Source Rocks in the Wumaying Buried Hill of the Huanghua Depression, Bohai Bay Basin.

Although oil and gas from coaly source rocks have been widely discovered worldwide, the role of oil generated from coal measures in marine-continental coaly deposits during the Carboniferous-Permian period in the Bohai Bay Basin has long been a subject of debate. The recent discovery of a condensate reservoir in the Wumaying buried hill within the Huanghua Depression of the Bohai Bay Basin offers new potential insights into this issue. In this study, we employed organic geochemical methods to explore the possibility of the Carboniferous-Permian coal deposit being a primary source of the condensate. The distribution of light hydrocarbons and the biomarker assemblage indicate that the condensate did not undergo significant secondary alterations such as thermal cracking, gas invasion fractionation, or biodegradation. The hydrocarbon generation potential of the Carboniferous-Permian coaly source rocks suggests that they could be an important contributor to the formation of condensate. High pristine/phytane ratios (1.0-7.5), an abundant presence of benzene series, and the dominance of C29 steranes (>50%) within the condensate could be indicative of coaly organic matter. These features are comparable to those found in coaly source rocks. Moreover, the stable carbon isotopic compositions of n-alkanes in the condensate, ranging from -26.0 to -30.0‰, correlate well with those from coaly mudstone (-25.4 to -30.0‰). This suggests that the condensate of the Wumaying buried hill may predominantly originate from the Carboniferous-Permian coaly mudstone. When integrated with the geological background, the results distinctly demonstrate that the Carboniferous-Permian coaly source rocks have significantly contributed to the formation of the condensate reservoir in the Wumaying buried hill. This provides an essential reference for future exploration of oil and gas resources derived from the carboniferous-Permian coaly source rocks in the Bohai Bay Basin.

Comprehensive molecular-isotopic characterization of archaeal lipids in the Black Sea water column and underlying sediments.

The Black Sea is a permanently anoxic, marine basin serving as model system for the deposition of organic-rich sediments in a highly stratified ocean. In such systems, archaeal lipids are widely used as paleoceanographic and biogeochemical proxies; however, the diverse planktonic and benthic sources as well as their potentially distinct diagenetic fate may complicate their application. To track the flux of archaeal lipids and to constrain their sources and turnover, we quantitatively examined the distributions and stable carbon isotopic compositions (δ13 C) of intact polar lipids (IPLs) and core lipids (CLs) from the upper oxic water column into the underlying sediments, reaching deposits from the last glacial. The distribution of IPLs responded more sensitively to the geochemical zonation than the CLs, with the latter being governed by the deposition from the chemocline. The isotopic composition of archaeal lipids indicates CLs and IPLs in the deep anoxic water column have negligible influence on the sedimentary pool. Archaeol substitutes tetraether lipids as the most abundant IPL in the deep anoxic water column and the lacustrine methanic zone. Its elevated IPL/CL ratios and negative δ13 C values indicate active methane metabolism. Sedimentary CL- and IPL-crenarchaeol were exclusively derived from the water column, as indicated by non-variable δ13 C values that are identical to those in the chemocline and by the low BIT (branched isoprenoid tetraether index). By contrast, insitu production accounts on average for 22% of the sedimentary IPL-GDGT-0 (glycerol dibiphytanyl glycerol tetraether) based on isotopic mass balance using the fermentation product lactate as an endmember for the dissolved substrate pool. Despite the structural similarity, glycosidic crenarchaeol appears to be more recalcitrant in comparison to its non-cycloalkylated counterpart GDGT-0, as indicated by its consistently higher IPL/CL ratio in sediments. The higher TEX86 , CCaT, and GDGT-2/-3 values in glacial sediments could plausibly result from selective turnover of archaeal lipids and/or an archaeal ecology shift during the transition from the glacial lacustrine to the Holocene marine setting. Our in-depth molecular-isotopic examination of archaeal core and intact polar lipids provided new constraints on the sources and fate of archaeal lipids and their applicability in paleoceanographic and biogeochemical studies.

Genetic variation in growth and leaf traits associated with local adaptation to climate in yellow birch (Betula alleghaniensis Britton)

Understanding patterns of variation in functional traits of hardwood trees is crucial for conserving and managing North American temperate forests under climate change. This study examined provenance variation of yellow birch ( Betula alleghaniensis Britton) in growth, biomass allocation, leaf morphology, and stable carbon isotope composition. Trees were grown from 10 seed sources originating from across Canada and the northern USA. Height and diameter were not significantly related to climate at seed origin, suggesting that variation may be better explained by site factors, such as soil pH and soil moisture. In contrast, carbon isotope composition and leaf morphological traits were significantly correlated to climate variables including temperature, precipitation, and solar radiation. Provenances from warmer, drier localities tended to have higher stable carbon isotope ratio (δ13C), greater specific leaf area, and narrower leaf width than their counterparts from cooler, wetter climates. Thus, variation in leaf morphological traits appears to be involved in adaptation of yellow birch to variation in temperature and moisture availability across the species’ range. Our results suggest that there may exist potential for selection and breeding of drought-resistant yellow birch genotypes to aid in reforestation under climate change.

Spatial distribution, environmental behavior, and health risk assessment of PAHs in soils at prototype coking plants in Shanxi, China: Stable carbon isotope and molecular composition analyses

To investigate the environmental behavior of and carcinogenic risk posed by 16 priority-controlled polycyclic aromatic hydrocarbons (PAHs), soil samples and air samples from the coke oven top were collected in two prototype coking plants (named PF and JD). The PF soils contained more PAHs than the JD soils because the PF plant employed the side-charging technique and had a lower coke oven height. The soils from both plants contained enough PAHs to pose a carcinogenic risk, and this risk was higher in the PF plant. Data were collected on the source characteristic spectrum of stable carbon isotopic composition (δ13C) of PAHs emitted from the coke oven top (δ13C values of −36.02‰ to −32.05‰ for gaseous PAHs and −34.09‰ to −25.28‰ for particulate PAHs), and these data fill a research gap and may be referenced for isotopic-technology-based source apportionment. Diagnostic ratios and isotopic technology revealed that the coking plant soils were mainly influenced by the coking process, followed by vehicle exhaust; the soils near the boundary of each plant were slightly affected by C3 plant burning. For most PAHs [excluding fluoranthene, benzo(k)fluoranthene, indeno(1,2,3-c,d)pyrene, and dibenzo(a,h)anthracene], the dominant migration process was the net volatilization of PAHs from soil to air. In the PF plant, 13C was depleted in gaseous PAHs during volatilization.

Molecular and Carbon Isotopic Compositions of Crude Oils from the Kekeya Area of the Southwest Depression, Tarim Basin: Implications for Oil Groups and Effective Sources

Molecular and stable carbon isotopic compositions of 32 crude oils from the Kekeya area of the Southwest Depression, Tarim Basin, were analyzed comprehensively to clarify oil groups and trace oil sources. The results indicate that lacustrine shale sequences within the Upper-Middle Permian Pusige Formation (P3–2p) are the major effective oil sources; the thermal maturation effects exert the crucial impact on geochemical compositions of crude oils. In the Kekeya structural belt, crude oils produced from the Lower-Neogene, Middle-Paleogene and Middle-Cretaceous sandstone reservoirs were generated mainly from deeply buried P3–2p at the late-to-high maturity stage. These condensates are depleted in terpanes, steranes and triaromatic steranes and enriched in adamantanes and diamantanes. The evaluated thermal maturity levels of crude oils by terpanoids and steranes are generally lower than that of diamondoids, implying at least two phases of oil charging. In the Fusha structural belt, oils produced from the Lower-Jurassic reservoirs (J1s) of Well FS8 were generated from the local P3–2p at the middle to late mature stage. On the contrary, these oils are relatively rich in molecular biomarkers such as terpanes and steranes and depleted in diamondoids with only adamantanes detectable. The P3–2p-associated oils can migrate laterally from the Kekeya to Fusha structural belt, but not to the location of Well FS8. The Middle-Lower Jurassic (J1–2) lacustrine shales as the major oil sources are limited to the area around Well KS101 in the Kekeya structural belt. Crude oils originated from J1–2 and P3–2p can mix together within the Cretaceous reservoirs of Well KS101 by presenting the concurrence of high concentrations of terpane and sterane biomarkers and diamondoids as well as 2–4% 13C-enriched n-alkanes than those of P3–2p derived oils. This study provides a better understanding of hydrocarbon sources and accumulation mechanisms and hence petroleum exploration in this region.

Controlling Factors of Vertical Geochemical Variations in Hydrate-Rich Sediments at the Site GMGS5-W08 in the Qiongdongnan Basin, Northern South China Sea

Large amounts of natural gas hydrates have been discovered in the Qiongdongnan Basin (QDNB), South China Sea. The chemical and stable carbon isotopic composition shows that the hydrate-bound gas was a mixture of thermogenic and microbial gases. It is estimated that microbial gas accounts for 40.96% to 60.58%, showing a trend of decrease with the increase in burial depth. A significant amount of gas hydrates is thought to be stored in the mass transport deposits (MTDs), exhibiting vertical superposition characteristics. The stable carbon isotopic values of methane (δ13C1) in the MTD1, located near the seabed, are less than −55‰, while those of the methane below the bottom boundary of MTD3 are all higher than −55‰. The pure structure I (sI) and structure II (sII) gas hydrates were discovered at the depths of 8 mbsf and 145.65 mbsf, respectively, with mixed sI and sII gas hydrates occurring in the depth range 58–144 mbsf. In addition, a series of indigenous organic matters and allochthonous hydrocarbons were extracted from the hydrate-bearing sediments, which were characterized by the origin of immature terrigenous organic matter and low-moderate mature marine algal/bacterial materials, respectively. More allochthonous (migrated) hydrocarbons were also discovered in the sediments below the bottom boundary of MTD3. The gas hydrated is “wet gas” characterized by a low C1/(C2 + C3) ratio, from 2.55 to 43.33, which was mainly derived from a deeply buried source kitchen at a mature stage. There is change in the heterogeneity between the compositions of gas and biomarkers at the site GMGS5-W08 along the depth and there is generally a higher proportion of thermogenic hydrocarbons at the bottom boundary of each MTDs, which indicates a varying contribution of deeply buried thermogenic hydrocarbons. Our results indicate that the MTDs played a blocking role in regulating the vertical transportation of hydrate-related gases and affect the distribution of gas hydrate accumulation in the QDNB.

A laser–laser method for carbonate C and O isotope measurement, metrology assessment, and stratigraphic applications

The stable isotopic compositions of carbon and oxygen (δ13Ccarb and δ18Ocarb) measured from carbonates are widely used in geology, notably to reconstruct paleotemperatures and the secular evolution of the biogeochemical carbon cycle, to characterize limestone sediment diagenesis, and to provide chemostratigraphy records. The standard technique used since the mid-20th century to measure C and O isotopic ratios is based on a wet chemical acid digestion protocol in order to evolve CO2 from carbonates—the latter being analyzed by mass spectrometry and, more recently, infrared spectroscopy. A newly developed laser-based method aims to circumvent this chemical preparation step by producing CO2 via an instant and spatially resolved calcination reaction. We describe an evolution of the laser calcination benchtop system previously described and used as a proof of concept toward a portable system, and we present the efficiency of this tool for performing carbon and oxygen isotope measurements from carbonate matrixes following standard evaluation metrology protocol. This metrological study explores the following: i) the use of internal standards; ii) inter-calibration with the traditional acid chemical preparation method; iii) analysis of the uncertainties of using GUM and ANOVA. Using 15 different types of carbonate minerals encompassing a range of isotopic VPDB compositions between −18.6‰ and +16.06‰ and between −14.80‰ and −1.72‰ for δ13Ccarb and δ18Ocarb, we show that isotopic cross-calibration is verified for both carbon and oxygen, respectively, and we demonstrate that the uncertainties (1σ) of the δ13Ccarb and δ18Ocarb measurements of laser–laser isotopic analysis are within 0.41‰ and 0.68‰, respectively. The advantages of this method in saving time and spatially resolved and automated analysis in situ are demonstrated by high-resolution chemostratigraphic analysis of a laminated lacustrine travertine sample.

Gas exchange and 13C-based estimates of intrinsic water-use efficiency show different responses to CO2 enrichment: a global meta-analysis of experimental studies

ABSTRACT Tree intrinsic water-use efficiency (iWUE) is a key characteristic of ecosystem functions central to the global cycles of carbon, water, and energy. Gas exchange and stable carbon isotope compositions have been widely used to assess iWUE. However, it remains unclear to what extent the iWUE estimates obtained using different approaches are comparable, particularly in combination with changes in temperature, precipitation, and experimental duration. Herein, the responses of different estimators of iWUE (as A/g s or through isotopic composition of leaves or tree rings) to elevated CO2 concentrations (eCO2) were assessed through a meta-analysis of 361 observations from 98 independent experiments. Our results show that (1) different proxies for iWUE provide inconsistent estimates of the response of iWUE to eCO2. (2) Throughout the growing season, the average response of g s to eCO2 was smaller than the single-point values estimated by gas exchange and the eCO2-induced reduction in g s was stronger for evergreen species than for deciduous species. (3) Precipitation, rather than temperature, significantly affected the responses of 13C-based estimates of iWUE to eCO2. (4) There was no significant response of leaf 13C-based iWUE estimates to eCO2. (5) The importance of photorespiration in elevated CO2 enhancement responses may be overestimated in evergreen species.

Systematic characterization of the influence of petroleum spill on terpene metabolism in Suaeda salsa (L.) Pall from coastal wetland: Implication by compound-specific stable isotope

With the increasing industrialization and urbanization, the ecological environment is suffering from severe deterioration in Liaohe coastal wetland, and petroleum spill is one of the pollution sources. Suaeda salsa (L.) Pall (S. salsa), one of the predominant plants in Liaohe coastal wetland, is facing the increasing degradation. Terpenes are a class of inherent compounds in plants, and play key role in maintain the growth of plants. However, the environmental stress on the terpene metabolism remained unclear in the plants. In the present study, the influence of petroleum spill on terpene metabolism in S. salsa was systematically investigated by analysis of concentrations, compositions and stable carbon isotope. Under the stress of petroleum spill, terpene concentrations showed the decreasing trend, indicating the inhibition effect of petroleum spill on terpene synthesis in S. salsa. The proportions of Sabinene and A-humulene showed the obviously increased with the influence of petroleum spill, implying that these congeners were more sensitive to petroleum spills. The significant changes in stable carbon isotope compositions were observed for Borneol, Dl-menthol, A-humulene and (-) -@-bisabolol, with the enrichment in heavier isotopes in residual fractions. This result indicated that the heavier 13C was preferentially fixed on terpene by S. salsa under the petroleum stress. The similar change trends along the incubation time was observed for A-humulene and (-) - trans caryophyllene, which might imply that A-humulene was one of the products of (-) - trans caryophyllene in S. salsa. Overall, the findings of present study verified the influence of petroleum spill on terpene metabolism in S. salsa, and were meaningful for protecting the plants in the petroleum-pollution wetlands.

Indian summer monsoon variability during the past ~75 ka based on stable isotope records of sediments from NW India

Here we report continuous and chronologically well-constrained records of stable oxygen (δ18O) and carbon (δ13C) isotope compositions of carbonate nodules (nodular calcretes), and δ13C of sediment organic matters (δ13CSOM) in samples from two (~48 m deep) drill-sediment cores, collected from a paleo-Yamuna channel in the NW Indo-Gangetic Plain in north Haryana. The results were used to reconstruct Indian summer monsoon (ISM) precipitation variability and paleovegetation pattern during the past ~75 ka and present a longer record of ISM variability in the Indo-Gangetic Plain. The δ18O of carbonate nodules (−7.80‰ to −4.04‰, average −6.01‰) shows a good negative covariation with variability in the model-derived intensity of ISM precipitation, indicating it to be a good proxy for ISM variability. We infer intense ISM precipitation during late marine isotope stage (MIS) 5, early and late MIS 3, and early MIS 1 periods, marked by relatively lower δ18O of carbonates. These changes in the ISM intensity are in-phase with the precession-induced changes in the Northern Hemisphere summer insolation. The δ13CSOM (−27.4‰ to −22.3‰, average −25.3‰) indicates C3-dominated vegetation in the Himalayan catchment with a noticeable increase in δ13CSOM during late MIS 4 to early MIS 3, late MIS 3, and early MIS 1 periods, which are characterized by the intense ISM (warm and moist condition). This suggests an increased abundance of C4 plants during the periods of intensified ISM precipitation. The δ13C of carbonate nodules varies from −3.63‰ to 1.56‰ (average −1.55‰). The enrichment in 13C of the carbonates is most likely due to the influence of dissolved inorganic carbon derived from the Himalayan source and/or atmospheric CO2 on the carbonate nodules. Therefore, we suggest that the δ13C of carbonate nodules from the Indo-Gangetic Plain requires a careful evaluation.