Oxygen Isotope Enrichment Research Articles

Environmental effects on oxygen isotope enrichment of leaf water in cotton leaves.

The oxygen isotope enrichment of bulk leaf water (Delta(b)) was measured in cotton (Gossypium hirsutum) leaves to test the Craig-Gordon and Farquhar-Gan models under different environmental conditions. Delta(b) increased with increasing leaf-to-air vapor pressure difference (VPd) as an overall result of the responses to the ratio of ambient to intercellular vapor pressures (e(a)/e(i)) and to stomatal conductance (g(s)). The oxygen isotope enrichment of lamina water relative to source water (Delta(1)), which increased with increasing VPd, was estimated by mass balance between less enriched water in primary veins and enriched water in the leaf. The Craig-Gordon model overestimated Delta(b) (and Delta(1)), as expected. Such discrepancies increased with increase in transpiration rate (E), supporting the Farquhar-Gan model, which gave reasonable predictions of Delta(b) and Delta(1) with an L of 7.9 mm, much less than the total radial effective length L(r) of 43 mm. The fitted values of L for Delta(1) of individual leaves showed little dependence on VPd and temperature, supporting the assumption that the Farquhar-Gan formulation is relevant and useful in describing leaf water isotopic enrichment.

Hydrogeochemical characteristics of the River Sava watershed in Slovenia

The River Sava is a typical HCO3- - Ca2+ - Mg2+ River. Total alkalinity increases in the part of the watershed composed of carbonate and clastic rocks, which are less resistant to weathering processes. Ca2/Mg2+ ratios are around 2 in the carbonate part of the watershed and increase in the watershed composed of carbonate and clastic rocks, indicating dissolution of calcite with magnesium. According to PHREEQC for Windows calculations, the River Sava and its tributaries are oversaturated with respect to calcite and dolomite. δ18OH2O and δDH2O are related to the meteorological patterns in the drainage basin. River water temperatures fluctuate annually following air temperatures. The relationship between the temperature and δ18OH2O and δDH2O values primarily reflects the strong dependence of δ18O and δD on precipitation and evaporative enrichment in heavy oxygen and hydrogen isotopes of infiltrating water recharging the River Sava from its slopes. The δ13DIC values are controlled by processes in the terrestrial ecosystem and stream processes such as: (1) dissolution of carbonates, (2) soil derived CO2, and (3) equilibration with atmospheric CO2. Lower δ13DIC values are observed in the spring sampling season due to abundant precipitation related to soil leaching of CO2 in the river system. From discharge and concentration measurements of sulphate and according to the drainage area of the River Sava basin, the annual sulphur flux at the border with Croatia was estimated to be 1.4 x 107 g SO4/km2. Assuming that the sources of SO42- to the Sava are its tributaries, precipitation and other sources, the contributions of these inputs were calculated according to steady state equations and estimated to be 52 : 8 : 40 %, respectively. Other sources are attributed to human influences such as industrial pollution and oxidation of sulphides.

Origin of salt-enriched pore fluids in the northern Gulf of Mexico

Pore fluids from the Green Canyon Block in the northern Gulf of Mexico show distinct differences with respect to element concentrations and oxygen, hydrogen, and strontium isotope signatures. The shallowest of the three investigated sites (GC185 or Bush Hill at 540 m water depth) is interpreted as a seafloor piercing mud mound and the two deeper areas (GC415 East and West at 950 and 1050 m water depth) as gas vent and oil seep sites. All three locations accommodate near-surface gas hydrates and the sediment surface is populated with chemosynthetic communities. They are characterized by a distinct increase in salinity with depth. However, the origin of this increasing salinity is different for the GC415 sites and Bush Hill and the depth source of the fluids is considerably different for all sites. The more saline fluids of the GC415 sites result from the dissolution of halite by formation water from two different sources. The fluids of GC415 East have most likely a deeper origin (early Cenozoic or even Mesozoic) and experienced elevated temperatures leading to mineral/water reactions including mineral transformations (e.g. smectite to illite transformation) and dissolution (e.g. feldspar dissolution). This process is expressed by the heavier oxygen isotope values and distinct Li, Sr, and Ca enrichments. The fluids of GC415 West have a shallower origin which is expressed by a smaller enrichment in Li, Sr, and Ca and lighter oxygen isotopes. The fluids from Bush Hill are less saline and its fluid signature indicates intensive water/mineral interaction. Oxygen and hydrogen isotope values as well as Na/Cl and Br/Cl molar ratios suggest that the salt enrichment was caused by phase separation under sub-critical conditions. A simple heat flow model simulation suggests that sub-critical phase separation may have occurred at a depth of ∼ 1650 m at ∼ 350 °C.

Oxygen isotope enrichment of organic matter in Ricinus communis during the diel course and as affected by assimilate transport

The oxygen isotope composition in leaf water and organic compounds in different plant tissues is useful for assessing the physiological performance of plants in their environment, but more information is needed on Delta(18)O variation during a diel course. Here, we assessed Delta(18)O of the organic matter in leaves, phloem and xylem in stem segments, and fine roots of Ricinus communis during a full diel cycle. Enrichment of newly assimilated organic matter in equilibrium with leaf water was calculated by applying a nonsteady-state evaporative enrichment model. During the light period, Delta(18)O of the water soluble organic matter pool in leaves and phloem could be explained by a 27 per thousand enrichment compared with leaf water enrichment. Leaf water enrichment influenced Delta(18)O of phloem organic matter during the night via daytime starch synthesis and night-time starch remobilization. Phloem transport did not affect Delta(18)O of phloem organic matter. Diel variation in Delta(18)O in organic matter pools can be modeled, and oxygen isotopic information is not biased during transport through the plant. These findings will aid field studies that characterize environmental influences on plant water balance using Delta(18)O in phloem organic matter or tree rings.

Assessing environmental and physiological controls over water relations in a Scots pine (Pinus sylvestris L.) stand through analyses of stable isotope composition of water and organic matter

This study investigated the influence of meteorological, pedospheric and physiological factors on the water relations of Scots pine, as characterized by the origin of water taken up, by xylem transport as well as by carbon isotope discrimination (Delta13C) and oxygen isotope enrichment (Delta18O) of newly assimilated organic matter. For more than 1 year, we quantified delta2H and delta18O of potential water sources and xylem water as well as Delta13C and Delta18O in twig and trunk phloem organic matter biweekly, and related these values to continuously measured or modelled meteorological parameters, soil water content, stand transpiration (ST) and canopy stomatal conductance (G(s)). During the growing season, delta18O and delta2H of xylem water were generally in a range comparable to soil water from a depth of 2-20 cm. Long residence time of water in the tracheids uncoupled the isotopic signals of xylem and soil water in winter. Delta18O but not Delta13C in phloem organic matter was directly indicative of recent environmental conditions during the whole year. Delta18O could be described applying a model that included 18O fractionation associated with water exchange between leaf and atmosphere, and with the production of organic matter as well as the influence of transpiration. Phloem Delta13C was assumed to be concertedly influenced by G(s) and photosynthetically active radiation (PAR) (as a proxy for photosynthetic capacity). We conclude that isotope signatures can be used as effective tools (1) to characterize the seasonal dynamics in source and xylem water, and (2) to assess environmental effects on transpiration and G(s) of Scots pine, thus helping to understand and predict potential impacts of climate change on trees and forest ecosystems.

Large variation in whole‐plant water‐use efficiency among tropical tree species

It is well known that whole-plant water-use efficiency (transpiration efficiency of carbon gain, TE(C)) varies among plant species with different photosynthetic pathways. However, less is known of such variation among tree species within the C(3) group. Here we measured the TE(C) of seven C(3) tropical tree species. Isotopic analyses (delta(13)C, delta(18)O, and delta(15)N) and elemental analyses (carbon and nitrogen) were undertaken to provide insight into sources of variation in TE(C). Plants were grown over several months in approx. 80% full sunlight in individual 38-l containers in the Republic of Panama. Soil moisture content was nonlimiting. Significant variation was observed in TE(C) among the C(3) tree species. Values ranged from 1.6 mmol C mol(-1) H(2)O for teak (Tectona grandis) to 4.0 mmol C mol(-1) H(2)O for a legume, Platymiscium pinnatum. Variation in TE(C) was correlated with both leaf N concentration, a proxy for photosynthetic capacity, and oxygen-isotope enrichment, a proxy for stomatal conductance. The TE(C) varied with C-isotope discrimination within species, but the relationship broke down among species, reflecting the existence of species-specific offsets.

Erratum: “Anomalous oxygen isotope enrichment in CO2 produced from O+CO: Estimates based on experimental results and model predictions” [J. Chem. Phys. 124, 234301 (2006)

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Anomalous oxygen isotope enrichment in CO2 produced from O+CO: Estimates based on experimental results and model predictions

The oxygen isotope fractionation associated with O+CO-->CO(2) reaction was investigated experimentally where the oxygen atom was derived from ozone or oxygen photolysis. The isotopic composition of the product CO(2) was analyzed by mass spectrometry. A kinetic model was used to calculate the expected CO(2) composition based on available reaction rates and their modifications for isotopic variants of the participating molecules. A comparison of the two (experimental data and model predictions) shows that the product CO(2) is endowed with an anomalous enrichment of heavy oxygen isotopes. The enrichment is similar to that observed earlier in case of O(3) produced by O+O(2) reaction and varies from 70 0/00 to 136 0/00 for (18)O and 41 0/00 to 83 0/00 for (17)O. Cross plot of delta (17)O and delta (18)O of CO(2) shows a linear relation with slope of approximately 0.90 for different experimental configurations. The enrichment observed in CO(2) does not depend on the isotopic composition of the O atom or the sources from which it is produced. A plot of Delta(delta (17)O) versus Delta(delta (18)O) (two enrichments) shows linear correlation with the best fit line having a slope of approximately 0.8. As in case of ozone, this anomalous enrichment can be explained by invoking the concept of differential randomization/stabilization time scale for two types of intermediate transition complex which forms symmetric ((16)O(12)C(16)O) molecule in one case and asymmetric ((16)O(12)C(18)O and (16)O(12)C(17)O) molecules in the other. The delta (13)C value of CO(2) is also found to be different from that of the initial CO due to the mass dependent fractionation processes that occur in the O+CO-->CO(2) reaction. Negative values of Delta(delta (13)C) ( approximately 12.1 0/00) occur due to the preference of (12)C in CO(2)* formation and stabilization. By contrast, at lower pressures (approximately 100 torr) surface induced deactivation makes Delta(delta (13)C) zero or slightly positive.

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.

Stable isotope composition of Late Cretaceous benthic foraminifera from the southern South Atlantic: Biological and environmental effects

The stable carbon and oxygen isotope composition of different benthic foraminiferal species of the latest Campanian and earliest Maastrichtian from Ocean Drilling Project Hole 690C (Weddell Sea, southern South Atlantic, ∼1800 m paleowater depth) have been investigated. The total range of measured isotope values of all samples exceeds ∼4‰ for δ 13C and 1.1‰ for δ 18O. Carbon isotope values of proposed deep infaunal species are generally similar or only slightly lower when compared to proposed epifaunal to shallow infaunal species. Interspecific differences vary between samples probably reflecting temporal changes in organic carbon fluxes to the sea floor. Constantly lower δ 13C values for Pullenia marssoni and Pullenia reussi suggest the deepest habitat for these species. The strong depletion of δ 13C values by up to 3‰ within lenticulinids may be attributed to a deep infaunal microhabitat, strong vital effects, or different feeding strategy when compared to other species or modern lenticulinids. The mean δ 18O values reveal a strong separation of epifaunal to shallow infaunal and deep infaunal species. Epifaunal to shallow infaunal species are characterized by low δ 18O values, deep infaunal species by higher values. This result possibly reflects lower metabolic rates and longer life cycles of deep infaunal species or the operating of a pore water [CO 3 2−] effect on the benthic foraminiferal stable isotopes. Pyramidina szajnochae shows an enrichment of oxygen isotopes with test size comprising a total of 0.6‰ between 250 and 1250 μm shell size. Although δ 13C lacks a corresponding trend these data likely represent the presence of changes in metabolic rates during ontogenesis. These results demonstrate the general applicability of multi-species stable isotope measurements of pristine Cretaceous benthic foraminifera to reconstruct past microhabitats and to evaluate biological and environmental effects on the stable isotope composition.

Long‐period orbital control on middle Miocene global cooling: Integrated stratigraphy and astronomical tuning of the Blue Clay Formation on Malta

Application of an astronomical age model to a bulk carbonate oxygen isotope record in the Ras il Pellegrin section on Malta indicates that the major step in the middle Miocene global cooling (13.82 Ma ± 0.03) coincides with minimum eccentricity values associated with the 400‐kyr cycle and minimum obliquity amplitudes associated with the 1.2‐Myr cycle. This orbital configuration is very similar to that found for comparable oxygen isotope enrichment events in the late Paleogene and Neogene. The stepwise character of the middle Miocene cooling event appears to be controlled by the combined influence of the 100‐kyr eccentricity cycle and the 172‐kyr cycle in obliquity amplitude. The integrated stratigraphy further allows extension of the astronomical polarity timescale to the top of chron C5ACn. The boundary between the Globigerina Limestone and the Blue Clay Formation coincides with the major step in middle Miocene global cooling and provides a level suitable for placing the physical reference point for the Langhian/Serravallian boundary.

Oxygen isotope enrichment (Δ18O) as a measure of time-averaged transpiration rate

Experimental evidence is presented to show that the 18O enrichment in the leaf biomass and the mean (time-averaged) transpiration rate are positively correlated in groundnut and rice genotypes. The relationship between oxygen isotope enrichment and stomatal conductance (g(s)) was determined by altering g(s) through ABA and subsequently using contrasting genotypes of cowpea and groundnut. The Peclet model for the 18O enrichment of leaf water relative to the source water is able to predict the mean observed values well, while it cannot reproduce the full range of measured isotopic values. Further, it fails to explain the observed positive correlation between transpiration rate and 18O enrichment in leaf biomass. Transpiration rate is influenced by the prevailing environmental conditions besides the intrinsic genetic variability. As all the genotypes of both species experienced similar environmental conditions, the differences in transpiration rate could mostly be dependent on intrinsic g(s). Therefore, it appears that the delta18O of leaf biomass can be used as an effective surrogate for mean transpiration rate. Further, at a given vapour pressure difference, delta18O can serve as a measure of stomatal conductance as well.

Hydrochemical and isotopic effects associated with petroleum fuel biodegradation pathways in a chalk aquifer

Hydrochemical data, compound specific carbon isotope analysis and isotopic enrichment trends in dissolved hydrocarbons and residual electron acceptors have been used to deduce BTEX and MTBE degradation pathways in a fractured chalk aquifer. BTEX compounds are mineralised sequentially within specific redox environments, with changes in electron acceptor utilisation being defined by the exhaustion of specific BTEX components. A zone of oxygen and nitrate exhaustion extends approximately 100 m downstream from the plume source, with residual sulphate, toluene, ethylbenzene and xylene. Within this zone complete removal of the TEX components occurs by bacterial sulphate reduction, with sulphur and oxygen isotopic enrichment of residual sulphate ( ε s=− 14.4‰ to − 16.0‰). Towards the plume margins and at greater distance along the plume flow path nitrate concentrations increase with δ 15N values of up to + 40‰ indicating extensive denitrification. Benzene and MTBE persist into the denitrification zone, with carbon isotope enrichment of benzene indicating biodegradation along the flow path. A Rayleigh kinetic isotope enrichment model for 13C-enrichment of residual benzene gives an apparent ε value of − 0.66‰. MTBE shows no significant isotopic enrichment ( δ 13C = − 29.3‰ to − 30.7‰) and is isotopically similar to a refinery sample ( δ 13C = − 30.1‰). No significant isotopic variation in dissolved MTBE implies that either the magnitude of any biodegradation-induced isotopic fractionation is small, or that relatively little degradation has taken place in the presence of BTEX hydrocarbons. It is possible, however, that MTBE degradation occurs under aerobic conditions in the absence of BTEX since no groundwater samples were taken with co-existing MTBE and oxygen. Low benzene δ 13C values are correlated with high sulphate δ 34S, indicating that little benzene degradation has occurred in the sulphate reduction zone. Benzene degradation may be associated with denitrification since increased benzene δ 13C is associated with increased δ 15N in residual nitrate. Re-supply of electron acceptors by diffusion from the matrix into fractures and dispersive mixing is an important constraint on degradation rates and natural attenuation capacity in this dual-porosity aquifer.

Triple oxygen isotope composition of tropospheric carbon dioxide as a tracer of terrestrial gross carbon fluxes

Stratospheric photochemistry leads to anomalous oxygen isotope enrichments in CO2 (for which Δ17O = δ17O − 0.516 × δ18O ≠ 0). This isotope anomaly is not lost until air returns to the troposphere and CO2 undergoes isotope exchange with water primarily in the terrestrial biosphere and oceans. A two‐box model is used to investigate the contribution of stratospheric production and contemporary surface carbon fluxes to tropospheric Δ17OCO2. The predicted magnitude of ∼0.15‰ is large enough that measurement of a globally averaged tropospheric Δ17OCO2 should provide a new constraint for gross carbon exchanges between the biosphere and atmosphere in terrestrial carbon cycle models. Importantly, Δ17OCO2 should be complementary to the primary isotopic tracer of gross carbon exchanges, δ18OCO2, but is not dependent on numerous hydrologic variables. Furthermore, with improved measurement precision, Δ17OCO2 could serve as a direct tracer of gross carbon exchanges and their variations.

Experimentally-controlled carbon and oxygen isotope exchange between bioapatites and water under inorganic and microbially-mediated conditions

Modern bone and enamel powders have reacted at 301 K with 13C- and 18O-labelled waters under inorganic and microbial conditions. The aim of the study is to investigate the resistance of stable isotope compositions of bioapatite carbonate (δ 13C, δ 18Oc) and phosphate (δ 18Op) to isotopic alteration during early diagenesis. Rapid and significant carbon and oxygen isotope changes were observed in the carbonate and phosphate fractions of bone apatite before any detectable change occurred in the crystallinity or organic matter content. These observations indicate that chemical alterations of bone apatite are likely to start within days of death. Enamel crystallites are much more resistant than bone crystallites, but are not exempt of alteration. Non removable carbon and oxygen isotope enrichments were measured in the carbonate phase of bone (50–90%) and enamel (40%) after the acetic acid treatment. This result indicates that a significant part of 13C and 18O-labelled coming from the aqueous fluid has been durably incorporated into the apatite structure, probably through isotopic exchange or secondary carbonate apatite precipitation. As a result, acetic acid pre-treatments that are currently used to remove exogenous material by selective dissolution, are not adequate to restore pristine δ 13C and δ 18Oc values of fossil apatites. Under inorganic conditions, kinetics of oxygen isotope exchange are 10 times faster in carbonate than in phosphate. On the opposite, during biologically-mediated reactions, the kinetics of oxygen isotope exchange between phosphate and water is, at least, from 2 to 15 times faster than between carbonate and water. Enamel is a more suitable material than bone for paleoenvironmental or paleoclimatical reconstructions, but interpretations of δ 18Op or δ 13C values must be restricted to specimens for which no or very limited trace of microbial activity can be detected.

Do pathways of water movement and leaf anatomical dimensions allow development of gradients in H218O between veins and the sites of evaporation within leaves?

ABSTRACTThe oxygen isotope enrichment of bulk leaf water (ΔL) is often observed to be poorly predicted by the Craig–Gordon‐type models developed for evaporative enrichment from a body of water (Δe). The discrepancy between ΔL and Δe may be explained by gradients in enrichment within the leaf as a result of convection of unenriched water to the sites of evaporation opposing the diffusion of enrichment away from the sites; a Péclet effect. However, this effect is difficult to quantify because the velocities of water movement within the leaf are unknown. This paper attempts to model the complex anatomy of a leaf, and hence such velocities, to assess if the gradients in H218O required for a significant Péclet effect between the vein and the evaporation sites are possible within a leaf. Published dimensions of cells in wheat leaves are used to calculate the cross‐sectional areas perpendicular to the flow velocities of water through assumed pathways. By combining the ratio of actual to ‘slab’ velocities with anatomical lengths, equivalent lengths (L) emerge. In this way, it is concluded that if water moves only through the cell walls, or from cell to cell via either aquaporins or plasmodesmata, and evaporates from mesophyll cells, or the substomatal cells, or from the peristomatal region (a total of 15 combinations of assumptions), then the 15 central estimates of the values of L are between 9 and 200 mm. Each of these central estimates is subject to uncertainty, but overall their magnitude is important and estimates of L are comparable with those made from fitting to isotopic data (8 mm for wheat). It is concluded that significant gradients in enrichment between the vein and the evaporation sites are likely.

Microbial respiration and diffusive transport of O2, 16O2, and 18O15O in unsaturated soils and geologic sediments.

Molecular oxygen (O2) in unsaturated geologic sediments plays an important role in soil respiration, biodegradation of organic contaminants, metal oxidation, and global oxygen and carbon cycling, yet little is known about oxygen isotope fractionation during the consumption and transport of O2 in unsaturated zones. We used a laboratory kinetic cell technique to quantify isotope fractionation due to respiration and a numerical model to quantify both consumptive and diffusive fractionation of O2 isotopes at a field site comprised of unsaturated lacustrine sandy materials. The combined use of laboratory-based kinetic cell experiments and field-based isotope transport modeling provided an effective tool to characterize microbial respiration in unsaturated media. Based on results from the closed-system kinetic cells, O2 consumption and isotope fractionation were attributed to the alternative cyanide-resistant respiration pathway. At the field site, the modeled depth profiles for O2 and delta18O matched the measured in situ data and confirmed that the consumption of O2 was via the alternative respiration pathway. If the cyanide-resistant respiration pathway is indeed widespread in soils, its high oxygen isotope enrichment factor could help to explain the discrepancy between the predicted present-day Dole effect (+20.8/1000) and the observed Dole effect (+23.5/1000). Thus, further soil O2 isotope studies are needed to better characterize and model the fractionation of oxygen isotopes during subsurface respiration and the potential impact on the isotopic content of atmospheric O2.

Water relations link carbon and oxygen isotope discrimination to phloem sap sugar concentration in Eucalyptus globulus.

A strong correlation was previously observed between carbon isotope discrimination (Delta(13)C) of phloem sap sugars and phloem sap sugar concentration in the phloem-bleeding tree Eucalyptus globulus Labill. (J. Pate, E. Shedley, D. Arthur, M. Adams [1998] Oecologia 117: 312-322). We hypothesized that correspondence between these two parameters results from covarying responses to plant water potential. We expected Delta(13)C to decrease with decreasing plant water potential and phloem sap sugar concentration to increase, thereby maintaining turgor within sieve tubes. The hypothesis was tested with analyses of E. globulus trees growing on opposite ends of a rainfall gradient in southwestern Australia. The Delta(13)C of phloem sap sugars was closely related to phloem sap sugar concentration (r = -0.90, P < 0.0001, n = 40). As predicted, daytime shoot water potential was positively related to Delta(13)C (r = 0.70, P < 0.0001, n = 40) and negatively related to phloem sap sugar concentration (r = -0.86, P < 0.0001, n = 40). Additional measurements showed a strong correspondence between predawn shoot water potential and phloem sap sugar concentration measured at midday (r = -0.87, P < 0.0001, n = 30). The Delta(13)C of phloem sap sugars collected from the stem agreed well with that predicted from instantaneous measurements of the ratio of intercellular to ambient carbon dioxide concentrations on subtending donor leaves. In accordance, instantaneous ratio of intercellular to ambient carbon dioxide concentrations correlated negatively with phloem sap sugar concentration (r = -0.91, P < 0.0001, n = 27). Oxygen isotope enrichment (Delta(18)O) in phloem sap sugars also varied with phloem sap sugar concentration (r = 0.91, P < 0.0001, n = 39), consistent with predictions from a theoretical model of Delta(18)O. We conclude that drought induces correlated variation in the concentration of phloem sap sugars and their isotopic composition in E. globulus.

A stable sulfur and oxygen isotopic investigation of sulfur cycling in an anoxic marine basin, Framvaren Fjord, Norway

In 1993 we measured the δ 34S values of total dissolved sulfide ( δ 34S ∑H 2S ) and sulfate ( δ 34S SO 4 − ) and the δ 18O of sulfate ( δ 18O SO 4 − ) from water samples collected across the oxic–anoxic interface and in the deep permanently anoxic waters of the stratified Framvaren fjord in southern Norway. Near the chemocline, variations in the δ 34S SO 4 − and δ 18O SO 4 − values were generally less than 1‰ from ambient seawater values. However, a minimum δ 34S SO 4 − value of +19.7‰ was detected at 20 m depth, which coincided with the depth that sulfide first appeared and may reflect sulfide oxidation. Small increases in δ 34S SO 4 − and δ 18O SO 4 − values 3 m below this depth are consistent with a zone of sulfur disproportionation. The δ 34S ∑H 2S value near the interface at 22 m was −19.8‰, which is 41.2‰ depleted in 34S relative to the sulfate collected at that depth. In close agreement with earlier measurements made at Framvaren in 1982, the δ 34S SO 4 − values collected from the deeper anoxic waters showed a marked 34S enrichment with depth, which corresponded with a decrease in the sulfate concentration. These results are interpreted to be the result of active dissimilatory sulfate reduction. A Rayleigh plot for the sulfate data measured in 1993 provides estimates for the sulfur and oxygen isotope enrichment factors ( ε s and ε o, respectively) for sulfate reduction of −41.5‰ and −9.8‰, respectively, with the former value matching closely the observed difference in δ 34S between the dissolved sulfide and sulfate near the interface. Our results from 1993, however, contrast with δ 34S SO 4 − and δ 34S ∑H 2S data in the water column made in 1983 by Anderson et al. [Mar. Chem. 23 (1988) 283). We conclude that the results of 1983 may be anomalous, and as a result this may offer additional interpretations than what was previously provided for the origin of reduced inorganic sulfur in the sediments of Framvaren based on their measured δ 34S values. We hypothesize that the lower δ 34S trs values in the sediments relative to δ 34S ∑H 2S values in the water column could also result from different rates of sulfate reduction, or in shallower sediments just beneath the chemocline, also from disproportionation of S∘, S 2O 3 −, or SO 3 −. We hypothesize that the observed ratio of 4.4:1 for the measured changes in δ 34S SO 4 − versus δ 18O SO 4 − within the anoxic waters approximates the 4:1 atom ratio of oxygen to sulfur in the residual sulfate as a result of dissimilatory sulfate reduction and reflects little oxygen isotope exchange between intermediates of sulfur metabolism and water either during bacterial sulfate reduction or from sulfide reoxidation processes. Based on comparisons with other studies, we further propose that this lack of isotopic exchange with water, and the subsequent ∼4:1 ratio of δ 34S SO 4 − versus δ 18O SO 4 − , occurs under conditions that promote a unidirectional biochemical reaction for sulfate reduction during which kinetic isotope effects are fully expressed and are consequently reflected in the δ 34S SO 4 − and δ 18O SO 4 − values.

Oxygen isotope composition of stratospheric carbon dioxide

Heavy oxygen isotope enrichment in stratospheric CO2 has been identified in the past as a direct result of the large O3 isotope anomaly though no simultaneous measurements are known. Results from 8 stratospheric balloon flights at two latitudes are reported that provide now a complete oxygen isotope analysis of both gases. An unambiguous, very tight correlation between enrichments of 17O and 18O in CO2 has been found. The large ratio δ17O/δ18O of 1.71 ± 0.03 shows a faster transfer of 17O than of 18O into CO2 and establishes a standard throughout the lower and middle stratosphere between midlatitudes and high northern latitudes. Ozone isotope transfer can now be treated in models with reliable atmospheric data.