Separating soil and leaf water O isotopic signals in plant stem cellulose

The oxygen-18 signal of soil and leaf water are both recorded in heterotrophically synthesized plant stem cellulose. Presently, these signals can only be teased apart with modeling and assumptions on the nature of the isotopic enrichment of leaf water. A method by which these two signals are chemically separated and analyzed is tested here. Heterotrophically synthesized cellulose from germinating seeds having a mixture of isotopic signals from the reserve carbohydrate (starch) and that of the water during cellulose synthesis was hydrolyzed and the resulting glucose converted to glucose phenylosazone. The analysis of the ¹⁸O/¹⁶O ratios of cellulose and of glucose phenylosazone were used to calculate the oxygen isotope ratio of the oxygen attached to the second carbon of the glucose moieties of the cellulose molecule. The calculated δ¹⁸O value of this oxygen was highly correlated with that of the water available for cellulose synthesis showing a nearly one-to-one relationship (slope = 1.027) and leading to the conclusion that it completely exchanges with water during heterotrophic cellulose synthesis. Once this method is refined so as to increase precision, it will be possible to derive the δ¹⁸O values of soil water available to plants from the oxygen isotope analysis of stem cellulose and its derivative.     

Oxygen isotope heterogeneity in chondrules from the Mokoia CV3 carbonaceous chondrite

We report a study of the oxygen isotope ratios of chondrules and their constituent mineral grains from the Mokoia, oxidized CV3 chondrite. Bulk oxygen isotope ratios of 23 individual chondrules were determined by laser ablation fluorination, and oxygen isotope ratios of individual grains, mostly olivine, were obtained in situ on polished mounts using secondary ion mass spectrometry (SIMS). Our results can be compared with data obtained previously for the oxidized CV3 chondrite, Allende. Bulk oxygen isotope ratios of Mokoia chondrules form an array on an oxygen three-isotope plot that is subparallel to, and slightly displaced from, the CCAM (carbonaceous chondrite anhydrous minerals) line. The best-fit line for all CV3 chondrite chondrules has a slope of 0.99, and is displaced significantly (by δ¹⁷O ∼ −2.5‰) from the Young and Russell slope-one line for unaltered calcium-aluminum-rich inclusion (CAI) minerals. Oxygen isotope ratios of many bulk CAIs also lie on the CV-chondrule line, which is the most relevant oxygen isotope array for most CV chondrite components. Bulk oxygen isotope ratios of most chondrules in Mokoia have δ¹⁸O values around 0‰, and olivine grains in these chondrules have similar oxygen isotope ratios to their bulk values. In general, it appears that chondrule mesostases have higher δ¹⁸O values than olivines in the same chondrules. Our bulk chondrule data spread to lower δ¹⁸O values than any ferromagnesian chondrules that have been measured previously. Two chondrules with the lowest bulk δ¹⁸O values (−7.5‰ and −11.7‰) contain olivine grains that display an extremely wide range of oxygen isotope ratios, down to δ¹⁷O, δ¹⁸O around -50‰ in one chondrule. In these chondrules, there are no apparent relict grains, and essentially no relationships between olivine compositions, which are homogeneous, and oxygen isotopic compositions of individual grains. Heterogeneity of oxygen isotope ratios within these chondrules may be the result of incorporation of relict grains from objects such as amoeboid olivine aggregates, followed by solid-state chemical diffusion without concomitant oxygen equilibration. Alternatively, oxygen isotope exchange between an ¹⁶O-rich precursor and an ¹⁶O-poor gas may have taken place during chondrule formation, and these chondrules may represent partially equilibrated systems in which isotopic heterogeneities became frozen into the crystallizing olivine grains. If this is the case, we can infer that the earliest nebular solids from which chondrules formed had δ¹⁷O and δ¹⁸O values around -50‰, similar to those observed in refractory inclusions.     

Oxygen isotopic compositions of IVA iron meteorites: implications for the thermal evolution derived from in situ ultraviolet laser microprobe analyses

Oxygen isotopic compositions of silicate inclusions in IVA iron meteorites have been measured with an in situ UV laser microprobe technique. The homogeneity of oxygen isotopic compositions within and among individual mineral grains has also been examined. Oxygen isotope fractionations between coexisting mineral pairs were utilized in oxygen isotope thermometry. Our measured Δ¹⁷O values, ranging from 0.97 to 1.25‰, are characteristic of a single reservoir and fully confirm the oxygen isotopic similarity between IVA irons and L/LL chondrites. Steinbach and São João Nepomuceno, containing inclusions of two silicate minerals in mutual contact, exhibit a mass-dependent fractionation of ¹⁸O/¹⁶O between tridymite and bronzite with apparent oxygen isotopic heterogeneity. The SiO₂-bearing member, Gibeon, gives homogeneous oxygen isotopic compositions without detectable fractionation of ¹⁸O/¹⁶O between tridymite and quartz. Oxygen isotope equilibrium temperatures are estimated for coexisting tridymite and bronzite in the same sample slabs or clusters in Steinbach and São João Nepomuceno. The fractionations of ¹⁸O/¹⁶O between bronzite and tridymite range from 1.6 to 2.3‰ in different sample slabs or clusters. On the basis of the closure temperature concept, cooling rates are estimated at approximately 20 to 1000°C/Myr between 800 and 1000°C, a range of temperatures not accessible to other cooling rate methods. Using the Fast Grain Boundary diffusion model, we have demonstrated that significant oxygen heterogeneity both in tridymite and bronzite is probably due to isotope exchange during cooling between minerals with various grain sizes and mineral abundances in different regions of the samples. The new estimates of cooling rate by oxygen isotope thermometry refine previous cooling curves of IVA irons and support the breakup-reassembly model for the IVA parent body.     

Antiphase hydrogen and oxygen isotope periodicity in chert nodules

Oxygen and hydrogen isotope analyses were made of Jurassic-age chert nodules from the Holy Cross Mountains, SE Poland, along radial transects at high spatial resolution. There is a radial “sigmoidal” periodicity for both isotope ratios, but the two are out of phase, with high δD values corresponding to low δ¹⁸O values. Periodicity for a 100- to 120-mm diameter nodule is approximately 16 mm, increasing slightly toward the rim, with amplitudes approaching 20 and 3.0‰ for hydrogen and oxygen, respectively. The combined hydrogen-oxygen isotope data for one nodule fall on a published curve for chert forming in equilibrium with seawater (Knauth and Epstein, 1976); the range of delta values corresponds to temperature variations of ∼10°C. Data for a second chert fall on a subparallel δD-δ¹⁸O line with δD values that are almost 50‰ lower. The δD-δ¹⁸O patterns for the nodules cannot be explained by periodic mixing of meteoric and ocean water because the hydrogen and oxygen isotope data are out of phase. Two possible explanations for the antiphase periodicity are (a) cyclical temperature variations, perhaps related to an unstable convection system (e.g., Bolton et al., 1999), and (b) self-organizing catalytic precipitation (e.g., Wang and Merino, 1990). The systematic isotopic variations are difficult to explain by diagenesis and strongly suggest that primary isotopic compositions are preserved. The isotopic data provide important information on the thermal history of the sedimentary basin, if temperature variations are the cause of the isotopic periodicity.     

Relative humidity recorded in tree rings: A study along a precipitation gradient in the Olympic Mountains, Washington, USA

Humidity is one of the fundamental variables controlling the energy balance of the climate, and thus its reconstruction represents a significant aspect of paleoclimate studies. We here report a study of oxygen and hydrogen isotopic compositions of tree-ring cellulose along a precipitation gradient in the Olympic Mountains of Washington, USA, to examine whether and how the relative humidity is recorded in the cellulose. According to the physically-based model described in this paper, the relationship between δD and δ¹⁸O of cellulose should have the same slope as that in the relationship between δD and δ¹⁸O in the source water (∼8.8 for the local meteoric water) if there is no systematic variation in the mean relative humidity among study sites and no physiologic differences among trees. However, our isotopic analyses of cellulose yielded a slope of 17.4, significantly greater than the slope of the Local Meteoric Water Line. We show that to produce such a slope, a positive covariation between the relative humidity and the δD and δ¹⁸O in the source water is required across the precipitation gradient. This work suggests that the δD vs. δ¹⁸O relationship in tree rings can be a useful tool for paleohumidity reconstruction.     

The isotopic composition of Tertiary carbonates from the Mainz Basin: an example of isotopic fractionations in 'closed basins'

The carbon and oxygen isotopic composition of seventy-nine samples of biogenic carbonates from the Mainz Basin Tertiary (Oligocene and Lower Miocene) was analysed. Most samples were mollusc shells still consisting of aragonite. Assuming only small temperature effects, salinity trends derived from isotope data are consistent with palaeontological results from the region: a salinity cycle ranging from fresh water-brackish (Lower Oligocene) towards marine (Middle Oligocene) and brackish-fresh water (Upper Oligocene) was found. Within the Lower Miocene, a trend of decreasing salinities is suggested. Though the isotopic salinity trends coincide rather well with palaeontological salinities, the absolute oxygen isotope ratios indicate an unusual isotopic environment enriched in ¹⁸O. Isotope fractionation is explained by evaporation of a closed basin (Rupelton excluded) with fresh water influx from surrounding land areas in a subtropical climate. Enrichment in ¹⁸O by repeated evaporation processes is paralleled by increasing concentration of Sr. Increasing fresh water influx during the Oligocene is due to climatic changes with a trend of more humid conditions towards the younger rock strata.     

Stable isotopes in the ostracod shell: a preliminary study

Oxygen and carbon isotope ratios of Recent ostracods from six localities are presented. The δO¹⁸ data are consistent with precipitation of the shells in isotopic equilibrium with seawater. although additional data are necessary to confirm equilibrium precipitation. No strong correlation between carbon isotope ratios and temperature or salinity were observed for ostracods.     

Low δ18O eclogites from the Kokchetav massif, northern Kazakhstan

Oxygen isotopic compositions of silicates in eclogites and whiteschists from the Kokchetav massif were analyzed by whole‐grain CO₂‐laser fluorination methods. Systematic analyses yield extremely low δ¹⁸O for eclogites, as low as ?3.9‰ for garnet; these values are comparable with those reported for the Dabie‐Sulu UHP eclogites. Oxygen isotopic compositions are heterogeneous in samples of eclogite, even on an outcrop scale. Schists have rather uniform oxygen isotope values compared to eclogites, and low δ¹⁸O is not observed. Isotope thermometry indicates that both eclogites and schists achieved high‐temperature isotopic equilibration at 500–800 °C. This implies that retrograde metamorphic recrystallization barely modified the peak‐metamorphic oxygen isotopic signatures. A possible geological environment to account for the low‐δ¹⁸O basaltic protolith is a continental rift, most likely subjected to the conditions of a cold climate. After the basalt interacted with low δ¹⁸O meteoric water, it was tectonically inserted into the surrounding sedimentary units prior to, or during subduction and UHP metamorphism.     

Comparison of stable carbon and oxygen isotopes in Picea glauca tree rings and Sphagnum fuscum moss remains from subarctic Canada

Stable isotope ratios from tree rings and peatland mosses have become important proxies of past climate variations. We here compare recent stable carbon and oxygen isotope ratios in cellulose of tree rings from white spruce (Picea glauca), growing near the arctic tree line; and cellulose of Sphagnum fuscum stems, growing in a hummock of a subarctic peatland, in west-central Canada. Results show that carbon isotopes in S. fuscum correlate significantly with July temperatures over the past ~20 yr. The oxygen isotopes correlate with both summer temperature and precipitation. Analyses of the tree-ring isotopes revealed summer temperatures to be the main controlling factor for carbon isotope variations, whereas tree-ring oxygen isotope ratios are controlled by a combination of spring temperatures and precipitation totals. We also explore the potential of combining high-frequency (annual) climate signals derived from long tree-ring series with low-frequency (decadal to centennial) climate signals derived from the moss remains in peat deposits. This cross-archive comparison revealed no association between the oxygen isotopes, which likely results from the varying sensitivity of the archives to different seasons. For the carbon isotopes, common variance could be achieved through adjustments of the Sphagnum age model within dating error.     

Stable isotopic compositions of Recent freshwater cyanobacterial carbonates from the British Isles: local and regional environmental controls

Recent (<50 years old) freshwater cyanobacterial carbonates from diverse environments (streams, lakes, waterfalls) throughout Britain and Ireland were analysed for their stable carbon and oxygen isotope compositions. The mean δ¹⁸O value of ?5–9‰ PDB for river and stream data represents calcite precipitation in equilibrium with the mean oxygen isotopic composition of precipitation in central Britain (?7–5‰SMOW) assuming a mean water temperature of 9°C. The mean δ¹⁸O of lake data, ?4–5‰ PDB, is statistically different, reflecting the effects of residence time and/or variations in the oxygen isotopic composition of rainfall. Carbon isotopes have wide variations in both fluviatile and lake data sets (+ 3 to ?12‰ PDB). These variations are principally controlled in the fluviatile samples by contribution of isotopically light ‘soil zone’ carbon relative to isotopically heavier carbon from limestone aquifer rock dissolution. Lake samples have the heaviest carbon isotope values, reflecting a trend toward isotopic equilibrium between atmospheric CO₂ and aqueous HCO^?₃. We infer that isotopic compositions of ancient cyanobacterial carbonates should also record environmental information, although the effects of stabilization and diagenesis on primary δ¹⁸O values will need careful consideration. Primary carbon isotope compositions should be well preserved, although in marine samples values will be buffered by the isotopic composition of aqueous marine bicarbonate.     

Climatic significance of tree-ring δO in the Qilian Mountains, northwestern China and its relationship to atmospheric circulation patterns

It is important to understand the history and dynamics of climate in a transitional region between areas with different atmospheric circulation patterns, where the vegetation and ecosystems are vulnerable to environmental change. We investigated variations in the long-term oxygen isotope composition (δ¹⁸O) in tree rings of Qinghai spruce (Picea crassifolia) and their relationships to climatic parameters in the arid Qilian Mountains of northwestern China from 1870 to 2006. We found that the mean temperature from the previous November to the current February was significantly and positively correlated with the tree-ring δ¹⁸O values. The temperature effect, (the positive relationship between the temperature and the precipitation δ¹⁸O value) can explain the connection between temperature and the tree-ring δ¹⁸O values. Due to pooling of the earlywood and latewood into yearly tree-ring samples, it appears that the cellulose δ¹⁸O may be influenced by isotopically nonhomogeneous water sources and climatic conditions during the previous and current growing seasons. Subtle shifts and amplitude deviations in cellulose δ¹⁸O, which abruptly became more positive around 1977–1978, may be attributed to the shifting climatic regime in China and to temperature variations, respectively. Our results illustrated the potential for investigating climatic or atmospheric circulation patterns based on oxygen isotope records in tree rings in regions near the interface between different large-scale synoptic circulations.     

Identifying the δO signature of precipitation in grass cellulose and phytoliths: Refining the paleoclimate model

Cellulose and silica phytoliths were extracted from the leaves and stems of Calamovilfa longifolia, a C₄ grass, grown under varying climatic conditions across the North American prairies. The oxygen-isotope compositions of both cellulose and silica record a complex signal of the isotopic composition of the soil water that feeds the plants and the relative humidity conditions that influence transpiration rates, stomatal conductance, and ultimately the ¹⁸O-enrichment of leaf water. As the initial stages of cellulose formation occur in the leaves, cellulose in both the leaves and stems forms primarily from leaf water and does not differ greatly in its oxygen-isotope composition between these locations. In contrast, the δ¹⁸O values of leaf phytoliths are significantly enriched in ¹⁸O relative to stem phytoliths, reflecting the varying isotopic composition of the water in these tissues. The oxygen-isotope compositions of leaf cellulose may be used as a proxy for the isotopic composition of water involved in leaf phytolith formation, while the δ¹⁸O values of stem phytoliths can be used to determine the δ¹⁸O values of stem water involved in partial exchange reactions during the transport of carbohydrates through the plant. A comparison of the isotopic compositions of phytoliths with cellulose allows for the deduction of soil and leaf water δ¹⁸O values as well as temperature and relative humidity conditions during plant growth. This approach has application in paleoclimate studies that traditionally have required estimations of one or more of these variables because direct measurements were unavailable.     

A study of oxygen isotopic fractionation during bio-induced calcite precipitation in eutrophic Baldeggersee,Switzerland

In order to better understand environmental factors controlling oxygen isotope shifts in autochthonous lacustrine carbonate sequences, we undertook an extensive one-year study (March, 1995 to February, 1996) of water-column chemistry and daily sediment trap material from a small lake in Central Switzerland. Comparisons between calculated equilibrium isotope values, using the fractionation equation of Friedman and O’Neil, (1977) and measured oxygen isotope ratios of calcite in the sediment-traps reveal that oxygen isotopic values of autochthonous calcite (δ¹⁸O) are in isotopic equilibrium with ambient water during most of the spring and summer, when the majority of the calcite precipitates. In contrast, small amounts of calcite precipitated in early-spring and again in late-autumn are isotopically depleted in ¹⁸O relative to the calculated equilibrium values, by as much as 0.8‰. This seasonally occurring apparent isotopic nonequilibrium is associated with times of high phosphorous concentrations, elevated pH (∼8.6) and increased [CO₃²⁻] (∼50 μmol/l) in the surface waters. The resulting weighted average δ¹⁸O value for the studied period is −9.6‰, compared with a calculated equilibrium δ¹⁸O value of −9.4‰. These data convincingly demonstrate that δ¹⁸O of calcite are, for the most part, a very reliable proxy for temperature and δ¹⁸O of the water.     

Climatic dependence of stable carbon and oxygen isotope signals recorded in speleothems: From soil water to speleothem calcite

Understanding the relationship between stable isotope signals recorded in speleothems (δ¹³C and δ¹⁸O) and the isotopic composition of the carbonate species in the soil water is of great importance for their interpretation in terms of past climate variability. Here the evolution of the carbon isotope composition of soil water on its way down to the cave during dissolution of limestone is studied for both closed and open-closed conditions with respect to CO₂.The water entering the cave flows as a thin film towards the drip site. CO₂ degasses from this film within approx. 10 s by molecular diffusion. Subsequently, chemical and isotopic equilibrium is established on a time scale of several 10-100 s. The δ¹³C value of the drip water is mainly determined by the isotopic composition of soil CO₂. The evolution of the δ¹⁸O value of the carbonate species is determined by the long exchange time T_ex, between oxygen in carbonate and water of several 10,000 s. Even if the oxygen of the CO₂ in soil water is in isotopic equilibrium with that of the water, dissolution of limestone delivers oxygen with a different isotopic composition changing the δ¹⁸O value of the carbonate species. Consequently, the δ¹⁸O value of the rainwater will only be reflected in the drip water if it has stayed in the rock for a sufficiently long time.After the water has entered the cave, the carbon and oxygen isotope composition of the drip water may be altered by CO₂-exchange with the cave air. Exchange times, , of about 3000 s are derived. Thus, only drip water, which drips in less than 3000 s onto the stalagmite surface, is suitable to imprint climatic signals into speleothem calcite deposited from it.Precipitation of calcite proceeds with time constants, τ_p, of several 100 s. Different rate constants and equilibrium concentrations for the heavy and light isotopes, respectively, result in isotope fractionation during calcite precipitation. Since T_ex ? τ_p, exchange with the oxygen in the water can be neglected, and the isotopic evolution of carbon and oxygen proceed analogously. For drip intervals T_d < 0.1τ_p the isotopic compositions of both carbon and oxygen in the solution evolve linearly in time. The calcite precipitated at the apex of the stalagmite reflects the isotopic signal of the drip water.For long drip intervals, when calcite is deposited from a stagnant water film, long drip intervals may have a significant effect on the isotopic composition of the DIC. In this case, the isotopic composition of the calcite deposited at the apex must be determined by averaging over the drip interval. Such processes must be considered when speleothems are used as proxies of past climate variability.     

Controls on ostracod valve geochemistry: Part 2. Carbon and oxygen isotope compositions

The stable carbon and oxygen isotope compositions of fossil ostracods are powerful tools to estimate past environmental and climatic conditions. The basis for such interpretations is that the calcite of the valves reflects the isotopic composition of water and its temperature of formation. However, calcite of ostracods is known not to form in isotopic equilibrium with water and different species may have different offsets from inorganic precipitates of calcite formed under the same conditions. To estimate the fractionation during ostracod valve calcification, the oxygen and carbon isotope compositions of 15 species living in Lake Geneva were related to their autoecology and the environmental parameters measured during their growth. The results indicate that: (1) Oxygen isotope fractionation is similar for all species of Candoninae with an enrichment in ¹⁸O of more than 3‰ relative to equilibrium values for inorganic calcite. Oxygen isotope fractionation for Cytheroidea is less discriminative relative to the heavy oxygen, with enrichments in ¹⁸O for these species of 1.7 to 2.3‰. Oxygen isotope fractionations for Cyprididae are in-between those of Candoninae and Cytheroidea. The difference in oxygen isotope fractionation between ostracods and inorganic calcite has been interpreted as resulting from a vital effect. (2) Comparison with previous work suggests that oxygen isotope fractionation may depend on the total and relative ion content of water. (3) Carbon isotope compositions of ostracod valves are generally in equilibrium with DIC. The specimens’ δ¹³C values are mainly controlled by seasonal variations in δ¹³C_DIC of bottom water or variation thereof in sediment pore water. (4) Incomplete valve calcification has an effect on carbon and oxygen isotope compositions of ostracod valves. Preferential incorporation of at the beginning of valve calcification may explain this effect. (5) Results presented here as well as results from synthetic carbonate growth indicate that different growth rates or low pH within the calcification site cannot be the cause of oxygen isotope ‘vital effects’ in ostracods. Two mechanisms that might enrich the ¹⁸O of ostracod valves are deprotonation of that may also contribute to valve calcification, and effects comparable to salt effects with high concentrations of Ca and/or Mg within the calcification site that may also cause a higher temperature dependency of oxygen isotope fractionation.     

Ion microprobe measurements of O/O ratios of phosphate minerals in the Martian meteorites ALH84001 and Los Angeles

Oxygen isotope ratios of merrillite and chlorapatite in the Martian meteorites ALH84001 and Los Angeles have been measured by ion microprobe in multicollector mode. δ¹⁸O values of phosphate minerals measured in situ range from ∼3 to 6‰, and are similar to Martian meteorite whole-rock values, as well as the δ¹⁸O of igneous phosphate on Earth. These results suggest that the primary, abiotic, igneous phosphate reservoir on Mars is similar in oxygen isotopic composition to the basaltic phosphate reservoir on Earth. This is an important first step in the characterization of Martian phosphate reservoirs for the use of δ¹⁸O of phosphate minerals as a biomarker for life on Mars. Cumulative textural, major-element, and isotopic evidence presented here suggest a primary, igneous origin for the phosphates in Los Angeles and ALH84001; textural and chemical evidence suggests that phosphates in ALH84001 were subsequently shock-melted in a later event.     

Carbon and Oxygen Isotopic Composition of Surface‐Sediment Carbonate in Bosten Lake (Xinjiang,China) and its Controlling Factors

Bosten Lake is a mid-latitude lake with water mainly supplied by melting ice and snow in the Tianshan Mountains. The depositional environment of the lake is spatially not uniform due to the proximity of the major inlet and the single outlet in the western part of the lake. The analytical results show that the carbon and oxygen isotopic composition of recent lake sediments is related to this specific lacustrine depositional environment and to the resulting carbonate mineralogy. In the southwestern lake region between the Kaidu River inlet and the Kongqi River outlet, carbon isotope composition (δ13C) values of the carbonate sediment (?1‰ to ?2‰) have no relation to the oxygen isotope composition of the carbonate (δ18O) values (?7‰ to ?8‰), with both isotopes showing a low variability. The carbonate content is low (<20%). Carbonate minerals analyzed by X-ray diffraction are mainly composed of calcite, while aragonite was not recorded. The salinity of the lake water is low in the estuary region as a result of the Kaidu River inflow. In comparison, the carbon and oxygen isotope values are higher in the middle and eastern parts of the lake, with δ13C values between approximately +0.5‰ and +3‰, and δ18O values between ?1‰ and ?5‰. There is a moderate correlation between the stable oxygen and carbon isotopes, with a coefficient of correlation r of approximately 0.63. This implies that the lake water has a relatively short residence time. Carbonate minerals constitute calcite and aragonite in the middle and eastern region of the lake. Aragonite and Mg–calcite are formed at higher lake water salinity and temperatures, and larger evaporation effects. More saline lake water in the middle and eastern region of the lake and the enhanced isotopic equilibrium between water and atmospheric CO2 cause the correlating carbon and oxygen isotope values determined for aragonite and Mg–calcite. Evaporation and biological processes are the main reasons for the salinity and carbonate mineralogy influence of the surface-sediment carbonate in Bosten Lake. The lake water residence time and the CO2 exchange between the atmosphere and the water body control the carbon and oxygen isotope composition of the carbonate sediment. In addition, organic matter pollution and decomposition result in the abnormally low carbon isotope values of the lake surface-sediment carbonate.     

Modelling δC and δO in the solution layer on stalagmite surfaces

We derive equations describing the evolution of the carbon and oxygen isotope composition of the bicarbonate in a calcite precipitating solution on the surface of a stalagmite using a classical Rayleigh approach. The combined effects of calcite precipitation, degassing of CO₂ and the buffering effect of the water reservoir are taken into account. Whereas δ¹³C shows a progressive increase to a final constant value, δ¹⁸O shows an initial isotopic enrichment, which exponentially decays due to the buffering effect of the water reservoir. The calculated evolution is significantly different for both carbon and oxygen isotopes than derived in a recent paper [Dreybrodt W. (2008) Evolution of the isotopic composition of carbon and oxygen in a calcite precipitating H₂O-CO₂-CaCO₃ solution and the related isotopic composition of calcite in stalagmites. Geochim. Cosmochim. Acta72, 4712-4724.].Furthermore, we discuss the isotopic evolution of the bicarbonate in the solution for long residence times on the stalagmite surface, i.e., for t→∞. The equilibrium isotope ratio of the bicarbonate is then determined by isotopic exchange between the cave atmosphere and the bicarbonate in the solution and can be calculated by equilibrium isotope fractionation. For strongly ventilated caves exchange with the cave atmosphere will result in higher δ¹³C and δ¹⁸O values than those observed in a pure Rayleigh distillation scenario, for sparsely ventilated caves it will result in lower δ¹³C and δ¹⁸O values.     

Stable isotopic studies on chitin. III. The D/H and 18O/16O ratios in arthropod chitin

Stable hydrogen and oxygen isotope ratios are presented for carbon-bound hydrogen and for oxygen in chitin-derived substrates from 57 arthropod species collected in 50 different locations or grown under controlled conditions in the laboratory. No systematic isotopic differences were found among Insecta, Crustacea, and Merostomata. The determination of infra- and interindividual isotopic variabilities in a lobster and among individuals of crustacean populations yielded small variances of about ±3 per mil for δD values and ±0.3 per mil for δ¹⁸O values. Molting stage and sex of crustaceans showed no systematic effects on isotopic composition. The δD and δ¹⁸O values of ambient water showed only weak correlations with the respective δ values of chitin-derived substrates. Positive correlation was observed between δD values and trophic level. No temperature effects on δ¹⁸O and δD values from marine crustaceans were found that exceed the natural isotopic noise level. Taken together, these observations indicate that reconstruction of water isotopic composition from arthropod chitin δD and δ¹⁸O values will require specific information about the habits and habitats of the species involved in the analysis.     

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.