Fractionation of hydrogen,oxygen and carbon isotopes in n-alkanes and cellulose of three Sphagnum species

Compound-specific isotope measurements of organic compounds are increasingly important in palaeoclimate reconstruction. Searching for more accurate peat-based palaeoenvironmental proxies, compound-specific fractionation of stable C, H and O isotopes of organic compounds synthesized by Sphagnum were determined in a greenhouse study. Three Sphagnum species were grown under controlled climate conditions. Stable isotope ratios of cellulose, bulk organic matter (OM) and C₂₁–C₂₅ n-alkanes were measured to explore whether fractionation in Sphagnum is species-specific, as a result of either environmental conditions or genetic variation. The oxygen isotopic composition (δ¹⁸O) of cellulose was equal for all species and all treatments. The hydrogen isotopic composition (δD) of the n-alkanes displayed an unexpected variation among the species, with values between −154‰ for Sphagnum rubellum and −184‰ for Sphagnum fallax for the C₂₃ n-alkane, irrespective of groundwater level. The stable carbon isotopic composition (δ¹³C) of the latter also showed a species-specific pattern. The pattern was similar for the carbon isotope fractionation of bulk OM, although the C₂₃ n-alkane was >10‰ more depleted than the bulk OM. The variation in H fractionation may originate in the lipid biosynthesis, whereas C fractionation is also related to humidity conditions. Our findings clearly emphasize the importance of species identification in palaeoclimate studies based on stable isotopes from peat cores.     

徐州地区下古生界碳酸盐岩的碳、氧同位素研究

在已有的对徐州地区下古生界碳酸盐岩详细岩石学研究基础上，系统测试了碳酸盐岩方解石和白云石的碳、氧同位素组成特征；地球化学和岩石学研究相结合，综合提取了碳酸盐岩碳、氧同位素组成的沉积、成岩地质信息；初步探讨了同位素组成的地层变化及其意义。研究结果表明：碳酸盐岩碳同位素组成特征可以指示沉积环境及其演化，开阔陆表海、灰质障壁砂坝、局限陆表海、潮下带、潮渠、藻坪诸沉积相间碳酸盐岩的δ^13C值表现出规律性变化，碳同位素组成变化曲线上的显著正偏移与海侵有关；碳酸盐岩氧同位素组成对成岩环境及其演化有明显响应，淡水成岩环境、潮上成岩环境、潮间成岩环境、潮下成岩环境和埋藏成岩环境具有不同的碳酸盐岩氧同位素组成特征；徐州地区大北望寒武系剖面地层界线附近都有碳、氧同位素组成变化的特征显示，研究工作证实了徐州地区下古生界同位素地层划分的可行性。     

Analysis of carbon and oxygen stable isotopes in carbonate rocks by the laser micro-sampling technique

The analysis of stable isotopes of carbon and oxygen in different carbonate rocks by the phosphoric acid method is not easier than that by the laser sampling method developed in recent years, which optically focuses laser beams with sufficient energy on a micro area of a thin section in a vacuum sample box via microscope. CO 2 produced by heating decomposition of carbonate was purified by the vacuum system, and the stable isotopic values of carbon and oxygen were calculated and analyzed on a mass spectrometer. This paper adopted the laser micro-sampling technique to analyze the stable isotopes of carbon and oxygen in dolomite, carbonate cement, stromatolite and different forms of dawsonite (donbassite). Results indicated that the laser micro-sampling method is effective in analyzing carbonate composition and could be a convincing proof for justification on carbonate composition analysis.     

The genesis of calcite in carbonate rocks of the sedimentary basins: Evidence from the stable carbon and oxygen isotopes composition

The distributions of stable carbon and oxygen isotopes in modern and ancient limestones of various types were studied. Carbonate samples from modern sediments were collected in the Black and Barents Seas. Ancient carbonates were represented by Upper Jurassic (Kimmeridgian-Tithonian) limestones from the central part of the West Siberian basin. Carbonate samples include remains of modern and Upper Jurassic fauna, carbonate crust from sediments of the Black Sea, carbonate tube from sediments of the Barents Sea, and Upper Jurassic limestone from the carbonate layer found at top of Abalak, bottom of Bazhenov deposits in the central part of the West Siberian basin. According to the results of the isotope analysis and comparison with modern carbonates, Upper Jurassic limestones of the West Siberian basin belong to the group of methane-derived carbonates and precipitated as a result of anaerobic oxidation of methane (AOM). Fractures in limestones are filled with secondary calcite.     

The stable carbon isotopes in enstatite chondrites and Cumberland Falls

The carbon isotopic composition of the total carbon in the enstatite chondrites Indarch, Abee, St. Marks, Pillistfer, Hvittis and Daniel's Kuil and the enstatite achondrite Cumberland Falls has been measured. The empirical relationhip between carbon isotopic composition and total carbon content is distinct from that of carbonaceous and ordinary chondrites. Within the enstatite chondrite group the average ¹³C content increases with petrographic type: E4 < E5 < E6. Daniel's Kuil shows the largest ¹³C enrichment in the bulk carbon of any meteorite. The carbon isotopic composition is most clearly correlated with the abundance of the elements Zn, Cd and In. Insofar as these elements may hold the key to the understanding of enstatite chondrites, more detailed combined carbon isotope and trace element studies of these meteorites will play an important role in the deciphering of their history.     

Sulfur and oxygen isotopes of sulfate in precipitation and lakewater,Quebec, Canada

Stable isotope ratios of sulfur and oxygen of sulfate ion in precipitation and lakewater were monitored in six headwater lakes in Québec, Canada. The lakes studied are oligotrophic and located over a wide area (350 km) on the Canadian Shield, which is known to be sensitive to acidification.The δ³⁴S of the sulfate ion in precipitation ranges from 3.1 to 6.7‰ for all locations during the sampling period, which is very close to the values found for the lakes, from 3.5 to 6.7‰. Moreover, the δ³⁴S of sulfate showed seasonal variations which are parallel in time for all stations. This strongly suggests that precipitation is a major source of sulfate in the lakes that were investigated. However, the δ¹⁸Ovalues of precipitation sulfate are close to each other between stations and are consistently higher (+ 8.3 to 13.5‰) than that of the lakes (+ 1.7 to 8.5‰). In addition, there is no spatial or temporal trend in lake δ¹⁸O sulfate, suggesting that a transformation occurs to sulfate in the watersheds. We suggest the hypothesis that sulfate ion is reduced and reoxidized in the runoff and lake waters so that it acquires an oxygen isotopic label different from precipitation.     

Seasonal variability of soil phosphate stable oxygen isotopes in rainfall manipulation experiments

Phosphorus (P) availability limits productivity in many ecosystems worldwide. As a result, improved understanding of P cycling through soil and plants is much desirable. The use of the oxygen isotopes associated to phosphate can be used to study the cycle of P in terrestrial systems. However, changes with time in the oxygen isotopes associated to available P have not yet been evaluated under field conditions. Here we present the variations in available-P oxygen isotopes, based on resin extractions, in a semi-arid site that included plots in which the amount of rainfall reaching the soil was modified. In addition, the oxygen isotopes in the less dynamic fraction which is extractable by HCl, were also measured. The δ¹⁸O of the HCl-extractable phosphate shows no seasonal pattern and corresponds to the average value of the available phosphate of 16.5‰. This value is in the expected range for equilibration with soil water at the prevailing temperatures in the site. The δ¹⁸O values of resin-extractable P showed a range of 14.5-19.1‰ (SMOW), and evidence of seasonal variability, as well as variability induced by rainfall manipulation experiments. We present a framework for analyzing the isotopic ratios in soil phosphate and explain the variability as mainly driven by phosphate equilibration with soil water, and by the isotopic effects associated with extracellular mineralization. Additional isotopic effects result from fractionation in uptake, and the input to the soil of phosphate equilibrated in leaves. These results suggest that the δ¹⁸O of resin-extractable P is an interesting marker for the rate of biological P transformations in soil systems.     

Stable carbon and oxygen isotopes distribution in carbonates from the Central Barents Sea shelf sediments

Carbonate macrofaunal remains and diagenetic tubes collected from a number of structures in the Central Barents Sea area during the 18th TTR (Training Through Research) cruise were subdivided into three groups according to the results of stable carbon and oxygen isotopes analysis. The first group includes carbonates that were formed from bicarbonate only from surrounding sea waters. The carbonates of the second group were formed during diagenesis with use of mixed sources of bicarbonate. The fourth group includes methane-derived carbonates that were formed as a result of anaerobic oxidation of methane (AOM).     

A 16-Ma record of paleodiet using carbon and oxygen isotopes in fossil teeth from Pakistan

The Siwalik Sequence of northern Pakistan contains a 16-Ma record of paleosol carbonate and fossil teeth from which a record of paleovegetation can potentially be reconstructed and compared. The carbon isotopic composition of paleosol carbonate and organic matter from Siwalik strata reflects a major paleoecological change on the floodplains of major rivers beginning7.3 Ma ago. By 6 Ma C₃-dominated plant communities, probably composed of mostly trees and shrubs, were displaced by nearly continuous C₄ grassland. We find that the carbon isotopic ratios in herbivore tooth enamel reflect this dramatic ecologic shift. Carbonate in enamel older than 7 Ma averages −11‰ in δ¹³C_PDB, consistent with a largely C₃ diet. Enamel from the Plio-PIeistocene averages +1.9‰ in δ¹³C, similar to the value displayed by modern C₄ grazers. Analysis of post-burial carbonate cements, and the concordance with isotopic evidence from paleosols argues strongly against major isotopic alteration of the enamel, while coexisting bone may have been altered early in burial. This study confirms that enamel apatite is useful for paleodietary reconstruction much further back in the geologic record than was previously thought.     

The suitability of annual tree growth rings as environmental archives: Evidence from Sr,Nd, Pb and Ca isotopes in spruce growth rings from the Strengbach watershed

The combination of the Sr, Nd and Pb isotope systems, recognized as tracers of sources, with the Ca isotope system, known to reveal biology-related fractionations, allowed us to test the reliability of spruce (Picea abies) growth rings as environmental archives through time (from 1916 to 1983) in a forest ecosystem affected by acid atmospheric deposition. Sr and Pb isotopes have already been applied in former tree-ring studies, whereas the suitability of Nd and Ca isotope systems is checked in the present article. Our Sr and Nd isotope data indicate an evolution in the cation origin with a geogenic origin for the oldest rings and an atmospheric origin for the youngest rings. Ca isotopes show, for their part, an isotopic homogeneity which could be linked to the very low weathering flux of Ca. Since this flux is weak the spruces’ root systems have pumped the Ca mainly from the organic matter-rich top-soil over the past century. In contrast, the annual growth rings studied are not reliable and suitable archives of past Pb pollution.     

Mantle-derived fluids in the basement of the Deccan Trap: evidence from stable carbon and oxygen isotopes of carbonates from the Killari borehole basement, Maharashtra, India

We report here for the first time geochemical, mineralogical and stable carbon and oxygen isotopic data on the crystalline basement rocks of the 1993 Killari earthquake region of Maharashtra (India), which is covered by a thick suite of Deccan volcanics. Our results revealed the hitherto unknown amphibolite–granulite nature of the 2.5?Ga basement, which contains 2.00–2.28?wt% of CO₂. The stable carbon (δ¹³C) and oxygen (δ¹⁸O) isotopic measurements on carbonates separated from two basement samples KIL-13 (440.5?m depth) and KIL-20 (499.6?m depth) collected from the KLR-1 borehole drilled in the epicentral region showed the respective values of ?6.23 and ?6.22‰ versus PDB for δ¹³C and 7.94 and 8.11‰ versus SMOW for δ¹⁸O. The samples plot in the primary igneous carbonatite field, indicating the mantle origin of the carbonates, derived through the process of mantle metasomatism from the deep mantle carbon reservoir. This would suggest large-scale crust-mantle thermal fluid interaction beneath the Killari seismogenic region, which is characterized by massive upwarping of the high-velocity mafic crust and retrograde metamorphism.     

苏皖地区石炭纪海相碳酸盐岩碳和氧同位素演化规律

对江苏南京孔山和安徽巢湖凤凰山石炭系碳酸盐岩C、O稳定同位素进行了测定。结果表明，苏皖地区石炭系δ^13C,δ^18O记录是以4个同位素演化阶段为特征，前3个同位素演化阶段与同时代的北美石炭纪相似，仅仅是内部演化特征略有不同，这反映了区域性的沉积环境的不同变化。在金陵组下部、和州组下部、黄龙组中下部和船山组层段，δ^13C表现出明显的正漂移，这可能是受植物和生物量增长、有机碳储藏量增加所引起的。δ^18O记录总体上与δ^13C值呈相似的变化趋势。δ^18O增加记录了气候变冷和冰川作用的结果。δ^18O负漂移与气候变暖和冰川消融是一致的。在浅水潮坪环境，大气淡水的淋滤作用使δ^13C和δ^18O值明显降低。     

Oil-source correlation of the pre-Tertiary in the Huanghua Depression： Insights from stable carbon isotopes and molecular markers

Stable carbon isotopes were used together with molecular markers to constrain genetic relationships between sandstone extracts and potential source rocks in the pre-Tertiary in the Huanghua Depression, North China. Comparison of the extracts from Permo-Carboniferous terrigenous mudstones and Ordovician marine carbonates indicated that their prominent differences are in stable carbon isotopes, molecular markers and thermal maturity. Although the extracts of the Mesozoic and Lower Permian Xiashihezi Formation sandstones have some similar iso-topic characteristics, molecular markers data provide a good correlation between the Upper Jurassic-Lower Cretaceous oils and the Upper Carboniferous Taiyuan Formation mudstones, and between the Lower Permian Xiashihezi Formation oils and the Lower Permian mudstones. The results showed that the Upper Jurassic-Lower Cretaceous sandstone oils were derived chiefly from the Upper Carboniferous Taiyuan Formation terrigenous mudstones and that the Lower Permian Xiashihezi Formation oils were sourced from the Lower Permian Shanxi Formation and Xiashihezi Formation terrigenous mudstones.     

贺兰山地区树轮碳氧同位素与夏季风降水的相关性讨论

分析了贺兰山地区油松树轮的稳定碳氧同位素组成对环境因素的响应关系 , 发现树轮碳氧同位素组成均与当年 5～ 9月总降水量具有较好的响应关系 , 碳同位素组成与 5～ 9月总降水量呈负相关关系 ,而氧同位素组成与 5～ 9月总降水量呈正相关关系 ,二者都可较好地反映该地区夏季风降水量的变化.同时 ,碳氧同位素的相关性分析表明二者具有一定程度的负相关性.树轮碳氧同位素的分馏机理十分复杂,其同位素组成不仅与降水量有关,同时还受其他环境因素的影响,单纯利用一种同位素指标来提取相应的气候信息,存在很大的不确定性.在本研究中 ,同时采用两种同位素指标来研究其气候意义 ,使得出的结论更加可靠.因此 ,夏季风降水量是控制该地区树轮稳定碳氧同位素组成的主要因素.     

The Darasun gold deposit,Eastern Transbaikal region: Chemical composition,REE patterns,and stable carbon and oxygen isotopes of carbonates from ore veins

The chemistry, REE patterns, and carbon and oxygen isotopic compositions of carbonates from ore veins of the Darasun deposit are discussed. In addition to the earlier described siderite, calcite, and carbonates of the dolomite-ankerite series, kutnahorite is identified. The total REE content in Fe-Mg carbonates of the dolomite-ankerite series (2.8–73 ppm) is much lower than in later calcite (18–390 ppm). δ¹³C of Fe-Mg carbonates and calcite varies from +1.1 to −6.7‰ and from −0.9 to −4.9‰, respectively. δ¹⁸O of Fe-Mg carbonates and calcite varies from +17.6 to 3.6‰ and from +15.7 to −0.5‰, respectively. The REE sum and carbon and oxygen isotopic compositions reveal zonal distribution relative to the central granodiorite porphyry stock. The correlation between the carbon and oxygen isotopic compositions and REE sum reflects variations in the physicochemical formation conditions and composition of ore-forming fluid. The isotopic composition of fluid is calculated, and possible sources of its components are considered. Earlier established evidence for a magmatic source of ore-forming fluid and participation of meteoric water in ore formation is confirmed. Geochemical evidence for interaction of ore-forming fluid with host rocks is furnished. The relationships between the REE sum, on the one hand, and carbon and oxygen isotopic compositions of hydrothermal ore-forming fluid, on the other, are established.     

Seasonal variation in kangaroo tooth enamel oxygen and carbon isotopes in southern Australia

Serial sampling of tooth enamel growth increments for carbon and oxygen isotopic analyses of Macropus (kangaroo) teeth was performed to assess the potential for reconstructing paleoseasonality. The carbon isotope composition of tooth enamel apatite carbonate reflects the proportional intake of C₃ and C₄ vegetation. The oxygen isotopic composition of enamel reflects that of ingested and metabolic water. Tooth enamel forms sequentially from the tip of the crown to the base, so dietary and environmental changes during the tooth's formation can be detected. δ¹³C and δ¹⁸O values were determined for a series of enamel samples drilled from the 3rd and 4th molars of kangaroos that were collected along a 900 km north–south transect in southern Australia. The serial sampling method did not yield pronounced seasonal isotopic variation patterns in Macropus enamel. The full extent of dietary isotopic variation may be obscured by attenuation of the isotopic signal during enamel mineralisation. Brachydont (low-crowned) Macropus teeth may be less sensitive to seasonal variation in isotopic composition due to time-averaging during mineralisation. However, geographic variations observed suggest that there may be potential for tracking latitudinal shifts in vegetation zones and seasonal environmental patterns in response to climate change.