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Carbon isotopic composition and oxygen isotopic enrichment in phloem and total leaf organic matter of European beech (Fagus sylvatica L.) along a climate gradient.

This study investigated the influence of climate on the carbon isotopic composition (sigma13C) and oxygen isotopic enrichment (delta18O) above the source water of different organic matter pools in European beech. In July and September 2002, sigma13C and delta18O were determined in phloem carbohydrates and in bulk foliage of adult beech trees along a transect from central Germany to southern France, where beech reaches its southernmost distributional limit. The data were related to meteorological and physiological parameters. The climate along the transect stretches from temperate [subcontinental (SC)] to submediterranean (SM). Both sigma13Cleaf and delta18Oleaf were representative of site-specific long-term environmental conditions. sigma13C of leaves collected in September was indicative of stomatal conductance, vapour pressure deficit (VPD) and radiation availability of the current growing season. delta18O was mainly correlated to mean growing season relative humidity (RH) and VPD. In contrast to the leaves, sigma13Cphloem varied considerably between July and September and was well correlated with canopy stomatal conductance (Gs) in a 2 d integral prior to phloem sampling. The relationship between sigma13C and delta18O in both leaves and phloem sap points, however, to a combined influence of stomatal conductance and photosynthetic capacity on the variation of sigma13C along the transect. delta18Ophloem could be described by applying a model that included 18O fractionation associated with water exchange between the leaf and the atmosphere and with the production of organic matter. Hence, isotope signatures can be used as effective tools to assess the water balance of beech, and thus, help predict the effects of climatic change on one of the ecologically and economically most important tree species in Central Europe.

Carbon Isotopes↗

Carbon isotope discrimination and oxygen isotope composition in clones of the F(1) hybrid between slash pine and Caribbean pine in relation to tree growth, water-use efficiency and foliar nutrient concentration.

The objectives of this study were: (1) to examine how foliar carbon isotope discrimination (Delta) and oxygen isotope composition (delta(18)O) are related to tree growth, ash mineral nutrient concentration and foliar nutrient concentration in 7-year-old clones of the F(1) hybrid between slash pine (Pinus elliottii Engelm.) and Caribbean pine (P. caribaea var. hondurensis Barr. et Golf.) in subtropical Australia; and (2) to evaluate the potential of using foliar Delta, ash mineral nutrient concentration and delta(18)O measurements for selecting F(1) hybrid pine clones with high water-use efficiency (WUE) and growth potential. There were significant differences in tree growth, foliar Delta, delta(18)O and ash mineral nutrient concentration among the eight clones tested. Significant negative linear relationships existed between tree growth and Delta, extrapolating to zero growth at Delta = 24-30 per thousand. There were strong genetic correlations (r = -0.83 to -0.96) between Delta and tree growth, particularly tree height. Significant non-genetic correlations (r = -0.62 to -0.80) existed between Delta and foliar K concentration. Foliar delta(18)O, ash mineral nutrient concentration and foliar nutrient concentration were unrelated to tree growth. In the F(1) hybrid pine clones, variation in tree WUE, as reflected by Delta, was largely attributed to a genetic effect on leaf photosynthetic capacity rather than on stomatal conductance, as reflected by foliar delta(18)O.

Journal Article↗

Fractionation of the three stable oxygen isotopes by oxygen-producing and oxygen-consuming reactions in photosynthetic organisms.

The triple isotope composition (delta17O and delta18O) of dissolved O2 in the ocean and in ice cores was recently used to assess the primary productivity over broad spatial and temporal scales. However, assessment of the productivity with the aid of this method must rely on accurate measurements of the 17O/16O versus 18O/16O relationship in each of the main oxygen-producing and -consuming reactions. Data obtained here showed that cleavage of water in photosystem II did not fractionate oxygen isotopes; the delta18O and delta17O of the O2 evolved were essentially identical to those of the substrate water. The fractionation slopes for the oxygenase reaction of Rubisco and respiration were identical (0.518 +/- 0.001) and that of glycolate oxidation was 0.503 +/- 0.002. There was a considerable difference in the slopes of O2 photoreduction (the Mehler reaction) in the cyanobacterium Synechocystis sp. strain PCC 6803 (0.497 +/- 0.004) and that of pea (Pisum sativum) thylakoids (0.526 +/- 0.001). These values provided clear and independent evidence that the mechanism of O2 photoreduction differs between higher plants and cyanobacteria. We used our method to assess the magnitude of O2 photoreduction in cyanobacterial cells maintained under conditions where photorespiration was negligible. It was found that electron flow to O2 can be as high as 40% that leaving photosystem II, whereas respiratory activity in the light is only 6%. The implications of our findings to the evaluation of specific O2-producing or -consuming reactions, in vivo, are discussed.

Alcohol Oxidoreductases↗

Effect of increased metabolic rate on oxygen isotopic fractionation.

16O16O is preferentially used over 18O16O (a stable isotope of oxygen comprising about 0.2% of atmospheric O2) as oxygen is consumed during respiration in humans (Epstein and Zeiri, 1988, Proc. Natl. Acad. Sci. USA 85: 1727-1731). To test the hypothesis that oxygen isotopic fractionation is related to the metabolic rate, 8 healthy adults performed 5 min of constant work rate cycle ergometer exercise below and above their anaerobic threshold. Moreover, 3 subjects performed an incremental exercise to the limit of tolerance. Oxygen uptake (VO2) was measured breath by breath. Samples of the exhaled breath for oxygen isotope measurement were obtained at rest and at various times during exercise and recovery. Oxygen isotopic fractionation was determined by isotope ratio mass spectrometry and calculated as the ratio of the degree of fractionation to the oxygen consumed in the breath sample (Z value). For the constant work rate protocol, both low and high intensity exercise resulted in a significant decrease in Z compared to the rest values (P less than 0.01). However, for the high intensity exercise the reduction in fractionation was greater compared to the low intensity protocol (P less than 0.05). For the incremental test, there was a significant negative correlation between oxygen isotopic fractionation and VO2 expressed as percent of the maximal oxygen uptake (r = -0.91, P less than 0.0001). These data suggest that during exercise low-fractionating processes become more important as limiting steps for O2 transport.

Adult↗

Neolithic trade routes re-aligned by oxygen isotope analyses.

Oxygen isotope analyses of Spondylus shells from neolithic sites suggest that the source for the shells used as ornaments in the Balkans and central Europe during the fourth millennium BC was the Aegean and not the Black Sea. The trade in Spondylus may have taken the form of an exchange of gifts.

Journal Article↗

A new method to determine the 17O isotopic abundance in CO2 using oxygen isotope exchange with a solid oxide.

This paper discusses a simple method to determine 17O isotope excess or deficiency ('mass-independent isotopic composition') in CO2 gas. When applying conventional mass spectrometry of CO2 (m/z 44, 45 and 46) to determine the 17O/16O ratio, the 13C/12C ratio has to be established separately. This can be achieved by analysing an aliquot of sample CO2 before and after subjecting it to oxygen isotope exchange with a pool of oxygen with 'normal' 17O/16O ratio, i.e. with Delta17O approximately equal to delta17O-0.516 x delta18O = 0. Cerium oxide has been shown to be practically well suited for the exchange of CO2 oxygen; the reagent is safe and does not produce any contamination. The CO2-CeO2 exchange reaction has 99.8 +/- 0.7% recovery yield. At 650 degrees C this reaction reaches equilibrium in 30 min and, as tested, results in complete oxygen replacement. Delta17O determinations depend on accuracy of CO2 delta measurements: the repeatability of +/-0.015 per thousand (1sigma) in delta(45)R and delta(46)R determination relative to the working reference results in an error of Delta17O as small as +/-0.33 per thousand. Such a precision is sufficient for Delta17O determination in stratospheric CO2. The calculated Delta17O value systematically depends on absolute 17R and 13R ratios in isotopic reference materials, which are presently not yet known with certainty (the 17R value is most important), and may be inadequate for 17O-correction with a = 0.516. Within the present uncertainty, Delta17O determined in 17O-enriched CO2 agrees with the value directly measured in the enriched O2 from which this CO2 was produced. Besides Delta17O determination, investigated CO2-CeO2 equilibration may have several other implications. Fast, complete isotopic exchange of CO2 by reaction with CeO2 may also be employed to get reproducible 17O-correction and, hence, to better monitor small delta13C shifts and to isotopically equilibrate mixtures of CO2 gases.

Journal Article↗

Continuous shipboard sampling system for determination of triple oxygen isotopes and O2/Ar ratio by dual-inlet mass spectrometry.

A continuous shipboard sampling system was developed for the determination of the isotopic composition of the triple oxygen isotopes and oxygen to argon (O(2)/Ar) ratios in dissolved air. In this system, dissolved air is separated by a hollow fiber membrane degassing module. This system collects dissolved air quantitatively and rapidly. The sample flow rate through the membrane is critical for the fractionation of the oxygen isotopes and the O(2)/Ar ratio and should be < 2 mL/min. Fractionation of oxygen between the liquid and gas phase of the air-saturated water was found to be similar to that of earlier reports. The advantages of this method over existing techniques include rapid collection of samples (30 min/sample), high efficiency in extraction of gases from the liquid phase, and the lack of a sample preparation step (e.g. degassing).

Argon↗

Oxygen isotope corrections for online delta(34)S analysis.

Elemental analyzers have been successfully coupled to stable-isotope-ratio mass spectrometers for online measurements of the delta(34)S isotopic composition of plants, animals and soils. We found that the online technology for automated delta(34)S isotopic determinations did not yield reproducible oxygen isotopic compositions in the SO(2) produced, and as a result calculated delta(34)S values were often 1-3 per thousand too high versus their correct values, particularly for plant and animal samples with high C/S ratio. Here we provide empirical and analytical methods for correcting the S isotope values for oxygen isotope variations, and further detail a new SO(2)-SiO(2) buffering method that minimizes detrimental oxygen isotope variations in SO(2).

Animals↗

Aqueous alteration of the Bali CV3 chondrite: evidence from mineralogy, mineral chemistry, and oxygen isotopic compositions.

A petrographic, geochemical, and oxygen isotopic study of the Bali CV3 carbonaceous chondrite revealed that the meteorite has undergone extensive deformation and aqueous alteration on its parent body. Deformation textures are common and include flattened chondrules, a well-developed foliation, and the presence of distinctive (100) planar defects in olivine. The occurrence of alteration products associated with the planar defects indicates that the deformation features formed prior to the episode of aqueous alteration. The secondary minerals produced during the alteration event include well-crystallized Mg-rich saponite, framboidal magnetite, and Ca-phosphates. The alteration products are not homogeneously distributed throughout the meteorite, but occur in regions adjacent to relatively unaltered material, such as veins of altered material following the foliation. The alteration assemblage formed under oxidizing conditions at relatively low temperatures (<100 degrees C). Altered regions in Bali have higher Na, Ca, and P contents than unaltered regions which suggests that the fluid phase carried significant dissolved solids. Oxygen isotopic compositions for unaltered regions in Bali fall within the field for other CV3 whole-rocks, however, the oxygen isotopic compositions of the heavily altered material lie in the region for the CM and CR chondrites. The heavy-isotope enrichment of the altered regions in Bali suggest alteration conditions similar to those for the petrographic type-2 carbonaceous chondrites.

Calcium Phosphates↗

Variation in oxygen isotope fractionation during cellulose synthesis: intramolecular and biosynthetic effects.

The oxygen isotopic composition of plant cellulose is commonly used for the interpretations of climate, ecophysiology and dendrochronology in both modern and palaeoenvironments. Further applications of this analytical tool depends on our in-depth knowledge of the isotopic fractionations associated with the biochemical pathways leading to cellulose. Here, we test two important assumptions regarding isotopic effects resulting from the location of oxygen in the carbohydrate moiety and the biosynthetic pathway towards cellulose synthesis. We show that the oxygen isotopic fractionation of the oxygen attached to carbon 2 of the glucose moieties differs from the average fractionation of the oxygens attached to carbons 3-6 from cellulose by at least 9%, for cellulose synthesized within seedlings of two different species (Triticum aestivum L. and Ricinus communis L.). The fractionation for a given oxygen in cellulose synthesized by the Triticum seedlings, which have starch as their primary carbon source, is different than the corresponding fractionation in Ricinus seedlings, within which lipids are the primary carbon source. This observation shows that the biosynthetic pathway towards cellulose affects oxygen isotope partitioning, a fact heretofore undemonstrated. Our findings may explain the species-dependent variability in the overall oxygen isotope fractionation during cellulose synthesis, and may provide much-needed insight for palaeoclimate reconstruction using fossil cellulose.

Cellulose↗

The influence of climate on the oxygen isotopes in tree rings.

Natural variations in the oxygen isotope ratio 18O/16O are occurring in the hydrological cycle as a result of isotope fractionations during evaporation and condensation. These processes imprint a valuable climatic signal in the precipitation, which is stored in ice caps as well as in the cellulose of trees. Recent developments in the continuous-flow analysis of 18O/16O of organic matter now enable a systematic application of this method in tree rings. It becomes possible to build maps of the past oxygen isotope distribution in continental areas, yielding important information on regional climate changes. In this paper, the factors influencing the isotope composition of tree rings are discussed with an example from trees in northern Eurasia. Oxygen isotope values of Larix, Picea and Pinus trees were measured over a large climatic gradient extending from Norway to Siberia. The spatial isotope variations were highly correlated to the annual mean temperature (r2 = 0.84), whereby the slope of the corresponding regression line was 0.35%/degrees C. When considering the changes in 18O/16O during the 20th century, not only the temperature, but also changes in the precipitation patterns have to be considered, in particular the observed increase in the amount of winter precipitation.

Asia↗

Oxygen isotope exchange between refractory inclusion in Allende and solar nebula gas.

A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope composition (approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16). Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs. The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI. Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula.

Crystallization↗

Fractionation of oxygen isotopes due to equilibration of oxygen with hemoglobin.

The aim of the study was to answer the question as to whether the chemical reaction of oxygen with hemoglobin exhibits a source of isotopic fractionation, which could be of significance in forming the overall fractionation effect of respiration recently determined in man. Investigations were performed on bovine hemoglobin solutions adjusted to normal values of Hb concentration and pH. After degassing in vacuo, the hemoglobin solution was equilibrated in a closed system with pure oxygen of suitable pressure so that oxygen saturation levels of 30, 50 and 100% were achieved. After complete equilibration, isotope analysis of oxygen by mass spectrometry resulted in 16O18O/16O2 ratios which were 0.35 +/- 0.02% lower in the oxygen bound to hemoglobin than that of the gas phase during all levels of oxygenation. Model calculations suggest the following: (1) the fractionation during oxygen uptake in the lung at rest is primarily determined by the reaction with hemoglobin, (2) the overall fractionation effect of respiration can be explained as due to single effects of the constituent processes when assuming the oxygen transport to be limited by utilization.

Animals↗

Oxygen isotope exchange between refractory inclusion in allende and solar nebula Gas

A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope compositions ( approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16). Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs. The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI. Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula.

Journal Article↗

The oxygen isotope composition of dissolved anthropogenic phosphates: a new tool for eutrophication research?

High-precision oxygen isotope analyses were carried out on dissolved phosphate extracted from discharge waters from three wastewater treatment plants (WTP) located in western France, as well as on the different phosphate-based fertilizers applied by farmers in the same region. Measured delta(18)O values of phosphate from chemical fertilizers range from 19.6 to 23.1 per thousand, while those of phosphate from WTP discharge waters are more tightly grouped between 17.7 and 18.1 per thousand. The variability in delta(18)O values of phosphate fertilizers is attributed to oxygen isotope variations of the phosphorite deposits from which France's fertilizers are manufactured. The significance of the delta(18)O values of phosphate from WTP discharge waters is less straightforward. At present, it is not clear whether these values are primary isotopic compositions corresponding, e.g., to the oxygen isotope composition of phosphate builders included in detergents (delta(18)O(P)=17.9 per thousand), or represent secondary values reflecting biological recycling of the phosphate in equilibrium with ambient WTP water The restricted difference in isotopic composition obtained between phosphate from fertilizers and phosphate from WTP discharge waters (<2 per thousand), as well as the fairly large internal isotopic variability observed in both end-members (>/=1.5 per thousand), cast doubt about the possibility that the oxygen isotope composition could serve as a tracer for the source of anthropogenic phosphates in waters.

Agriculture↗

Extreme crustal oxygen isotope signatures preserved in coesite in diamond.

The anomalously high and low oxygen isotope values observed in eclogite xenoliths from the upper mantle beneath cratons have been interpreted as indicating that the parent rock of the eclogites experienced alteration on the ancient sea floor. Recognition of this genetic lineage has provided the foundation for a model of the evolution of the continents whereby imbricated slabs of oceanic lithosphere underpin and promote stabilization of early cratons. Early crustal growth is thought to have been enhanced by the addition of slab-derived magmas, leaving an eclogite residuum in the upper mantle beneath the cratons. But the oxygen isotope anomalies observed in eclogite xenoliths are small relative to those in altered ocean-floor basalt and intermediate-stage subduction-zone eclogites, and this has hindered acceptance of the hypothesis that the eclogite xenoliths represent subducted and metamorphosed ocean-floor basalts. We present here the oxygen isotope composition of eclogitic mineral inclusions, analysed in situ in diamonds using an ion microprobe/secondary ion mass spectrometer. The oxygen isotope values of coesite (a polymorph of SiO2) inclusions are substantially higher than previously reported for xenoliths from the subcratonic mantle, but are typical of subduction-zone meta-basalts, and accordingly provide strong support for the link between altered ocean-floor basalts and mantle eclogite xenoliths.

Journal Article↗

Exchange of oxygen isotopes in carbon dioxide-phosphoric [correction of phosporic] acid systems.

The rate of exchange of isotopes of oxygen between solutions of concentrated phosphoric acid and CO2 was measured as a function of temperature, acid strength (pressure of water in equilibrium with the solution), pressure of CO2, and surface area of the reaction vessel. At 75 degrees C, significant exchange was found to occur even for the "anhydrous" phosphoric acids, those in which the nominal percentage of H3PO4 in solution is equal to or exceeds 100%. Exchange is much slower at 25 degrees C, but isotopic shifts as large as 0.1% can be observed in 95% H3PO4 at equilibration times approaching 1000 hr. Rates of exchange were found to be dependent upon the vapor pressure of water in equilibrium with the acid solutions. Exchange was found to occur primarily on the surface of the reaction vessel above the solution, with no dependence on total CO2 pressure. These observations indicate that phosphoric acids with nominal concentrations of H3PO4 approaching 105% are preferable for the minimization of exchange between CO2 samples and acid solutions during phosphorolyses of carbonate materials. Moreover, with such acids, significant time--temperature trade-offs are possible, allowing rapid preparation of CO2 at elevated temperatures.

Carbon Dioxide↗

Measurement of the oxygen isotopic composition of nitrate in seawater and freshwater using the denitrifier method.

We report a novel method for measurement of the oxygen isotopic composition (18O/16O) of nitrate (NO3-) from both seawater and freshwater. The denitrifier method, based on the isotope ratio analysis of nitrous oxide generated from sample nitrate by cultured denitrifying bacteria, has been described elsewhere for its use in nitrogen isotope ratio (15N/14N) analysis of nitrate. (1) Here, we address the additional issues associated with 18O/16O analysis of nitrate by this approach, which include (1) the oxygen isotopic difference between the nitrate sample and the N20 analyte due to isotopic fractionation associated with the loss of oxygen atoms from nitrate and (2) the exchange of oxygen atoms with water during the conversion of nitrate to N2O. Experiments with 18O-labeled water indicate that water exchange contributes less than 10%, and frequently less than 3%, of the oxygen atoms in the N20 product for Pseudomonas aureofaciens. In addition, both oxygen isotope fractionation and oxygen atom exchange are consistent within a given batch of analyses. The analysis of appropriate isotopic reference materials can thus be used to correct the measured 18O/16O ratios of samples for both effects. This is the first method tested for 18O/16O analysis of nitrate in seawater. Benefits of this method, relative to published freshwater methods, include higher sensitivity (tested down to 10 nmol and 1 microM NO3-), lack of interference by other solutes, and ease of sample preparation.

Algorithms↗