Oxygen Isotope Enrichment Research Articles

Stable isotopic evidence for increased terrestrial productivity through geological time

Marine life on Earth is known back to the Archean Eon, when life on land is assumed to have been less pervasive than now. Precambrian life on land can now be tested with stable isotopes because living soil CO2 is isotopically distinct for both carbon and oxygen from both marine and volcanic CO2. Our novel compilation of previously published oxygen and carbon isotopic compositions of pedogenic and paleokarst carbonate can be compared with the coeval marine record. Long-term enrichment (to heavier isotopic composition) of oxygen, but no significant trend in carbon through time, long apparent from marine carbonate, is now demonstrated also for pedogenic and paleokarst carbonate. Oxygen isotopic enrichment is not due to changing global temperature or hypsometry, but to increased evapotranspiration and photosynthesis on larger continents. Differences in isotopic composition between land and sea have increased in an episodic fashion, peaking at times of major evolutionary innovations for life on land, and also at times of ice ages. The δ13C and δ18O divergences between land and sea correspond to terrestrial productivity spikes including evolution of Neoproterozoic (635 Ma) lichens, middle Ordovician (470 Ma) non-vascular land plants, middle Devonian (385 Ma) forests, early Cretaceous (125 Ma) angiosperms, and middle Miocene (20 Ma) sod grasslands.

Material aspects of oxygen isotope effect studies in high-temperature superconductors

The article discusses issues related to the material aspects of the study of the oxygen isotope effect in High-temperature superconductors. These studies were initiated by Prof. K.A. Müller shortly after he and Dr. G. Bednorz discovered high-temperature superconductivity. Research on the isotope effect was carried out in the years 1991–1995, and then continued for various classes of superconductors and other strongly correlated electron systems. The paper presents methods of synthesis of complex oxide superconductors doped with isotopic oxygen-18. Methods for the determination of oxygen content and isotopic enrichment are also discussed.

Leaf cell wall properties and stomatal density influence oxygen isotope enrichment of leaf water.

Measurements of oxygen isotope enrichment of leaf water above source water (Δ18 OLW ) can improve our understanding of the interaction between leaf anatomy and physiology on leaf water transport. Models have been developed to predict Δ18 OLW such as the string-of-lakes model, which describes the mixing of leaf water pools, and the Péclet effect model, which incorporates transpiration rate and the mixing length between unenriched xylem and enriched mesophyll water in the mesophyll (Lm ) or veins (Lv ). Here we compare measurements and models of Δ18 OLW on two cell wall composition mutants grown under two light intensities and relative humidities to evaluate cell wall properties on leaf water transport. In maize (Zea mays), the compromised ultrastructure of the suberin lamellae in the bundle sheath of the ALIPHATIC SUBERIN FERULOYL TRANSFERASE mutant (Zmasft) reduced barriers to apoplastic water movement, resulting in higher E and, potentially, Lv and, consequently, lower Δ18 OLW . The difference in Δ18 OLW in cellulose synthase-like F6 (CslF6) mutants and wild-type of rice (Oryza sativa) grown under two light intensities co-varied with stomatal density. These results show that cell wall composition and stomatal density influence Δ18 OLW and that stable isotopes can facilitate the development of a physiologically and anatomically explicit water transport model.

Warm pool ocean heat content regulates ocean-continent moisture transport.

The Indo-Pacific Warm Pool (IPWP) exerts a dominant role in global climate by releasing huge amounts of water vapour and latent heat to the atmosphere and modulating upper ocean heat content (OHC), which has been implicated in modern climate change1. The long-term variations of IPWP OHC and their effect on monsoonal hydroclimate are, however, not fully explored. Here, by combining geochemical proxies and transient climate simulations, we show that changes of IPWP upper (0-200 m) OHC over the past 360,000 years exhibit dominant precession and weaker obliquity cycles and follow changes in meridional insolation gradients, and that only 30%-40% of the deglacial increases are related to changes in ice volume. On the precessional band, higher upper OHC correlates with oxygen isotope enrichments in IPWP surface water and concomitant depletion in East Asian precipitation as recorded in Chinese speleothems. Using an isotope-enabled air-sea coupled model, we suggest that on precessional timescales, variations in IPWP upper OHC, more than surface temperature, act to amplify the ocean-continent hydrological cycle via the convergence of moisture and latent heat. From an energetic viewpoint, the coupling of upper OHC and monsoon variations, both coordinated by insolation changes on orbital timescales, is critical for regulating the global hydroclimate.

Sources and Biogeochemical Processes of Nitrate in the Laolongdong Karst Underground River Basin, Chongqing

Samples of sewage, well water, and underground river water of the urbanized Laolongdong karst underground river basin in Chongqing, China were collected during July 2019 and October 2020 and measured to determine the nitrate origin and biogeochemical processes based on geochemistry and dual nitrate isotope (δ15N-NO3- and δ18O-NO3-) data. The results showed that:① the isotopic nitrate compositions of sewage ranged from -3.3‰ to 14.6‰ for δ15N-NO3- and from -5.2‰ to 20.6‰ for δ18O-NO3-, which indicated that nitrate originated from manure and sewage, fertilizer, and soil organic nitrogen. The δ15N-NO3- and δ18O-NO3- of well water varied from 3.1‰ to 12.6‰ and 2.9‰ to 8.9‰, respectively, suggesting nitrate was mainly from soil organic nitrogen and manure and sewage. For the underground river water, the δ15N-NO3- and δ18O-NO3- ranged from 5.6‰ to 28.6‰ and from -2.0‰ to 15.7‰, respectively, suggesting that municipal sewage and manure were the dominate nitrate sources. ② Based on the MixSIAR model, manure and sewage were the primary nitrate source of the underground river water, accounting for 89.1% of the total contribution, whereas the contributions of soil organic nitrogen, fertilizer, and atmospheric precipitation were 4.4%, 3.4%, and 3.1%, respectively. ③ In the basin, the concentration ratios of COD:ρ(NO3-) from low to high were as follows:well water (0.14-5.15), underground river water (0.50-9.36), and sewage (4.08-89.50). Only 50% of well water samples with COD:ρ(NO3-) were slightly higher than 0.65, which is the minimum stoichiometric ratio for denitrification occurrence. This indicated that there were insufficient COD concentrations to support that denitrification occurred in the well water. This was further verified by no significant enrichment of nitrogen and oxygen isotopes. As much as 90% of underground river water samples had a COD:ρ(NO3-) higher than 0.65, and the dual nitrate isotopes were simultaneously enriched with a δ15N:δ18O of 1.8, which is within the ratios ranging from 1.3 to 2.1, indicating that denitrification occurred. The COD:ρ(NO3-) for all wastewater samples was much higher than 0.65, of which 25% were higher than the stoichiometric ratio (29.34) for the occurrence of dissimilation reduction nitrate to ammonium (DNRA). The δ15N-NO3- and ρ(NH4+):ρ(NO3-) of sewage increased simultaneously, indicating that DNRA may have occurred in the sewage.

Stable isotopes of nitrate record effects of the 2015–2016 El Niño and diatom iron limitation on nitrogen cycling in the eastern North Pacific Ocean

AbstractIn eastern boundary current systems, strong coastal upwelling brings deep, nutrient‐rich waters to the surface ocean, supporting a productive food web. The nitrate load in water masses that supply the region can be impacted by a variety of climate‐related processes that subsequently modulate primary productivity. In this study, two coastal upwelling regimes along central and southern California were sampled seasonally for nitrogen and oxygen stable isotopes of nitrate (i.e., nitrate isotopes) over several years (2010–2016) on 14 California Cooperative Oceanic Fisheries Investigations (CalCOFI) cruises. Seasonal, interannual, and spatial variations in euphotic zone nitrate isotopes were largely driven by the extent of nitrate utilization, sometimes linked to iron limitation of diatom productivity. Pronounced isotopic enrichment developed with the El Niño conditions in late 2015 and early 2016 which likely resulted from increased nitrate utilization linked to reduced nitrate supply to the euphotic zone. Differential enrichment of nitrogen and oxygen isotopes was observed in the surface ocean, suggesting that phytoplankton increased their reliance on locally nitrified (recycled) nitrate during warmer and more stratified periods. Overall, nitrate isotopes effectively differentiated important euphotic zone processes such as nitrate assimilation and nitrification, while archiving the influence of disparate controls such as iron limitation and climatic events through their effects on nitrate utilization and isotopic fractionation.

Differentiation of Hydrogen and Oxygen Isotopes in the Water Source Treatment Wetlands of Stream Networks

To explore the isotopic distribution and differentiation of water along the hydraulic flow gradients and plant-bed/ditch systems in constructed root-channel wetlands, surface and subsurface water samples were collected from four ecological wetlands, namely Shijiuyang and Guanjinggang in Jiaxing, as well as Changshuitang and Taishangang in Haining. All samples were collected along water flow pathways during the wet and rainy summer season in August 2019, except for those from Taishangang, which were collected within the plant-bed/ditch system during the dry and cold winter season in January 2020. The abundance of deuterium (δD) and δ18 O was determined in each functional area of the wetlands to assess the influence of wetlands on water differentiation. Stable isotope technology and mathematical statistics were used to analyze the distribution of δD and δ18 O in constructed root-channel wetlands and to reveal the influence of plant-bed/ditch systems on stable isotopes of water. A variety of data mining methods were used to examine the differentiation of stable isotopes of water, at various dimensions and scales, including nonparametric Kendall's tau-b correlation, stepwise regression, gray relational analysis, and machine learning (random forest) combined with scatter diagrams and model hypothesis diagnosis analysis. The main results were as follows:① The spatiotemporal variations in water isotopes of stream networks were largely affected by different water supply and evaporation enrichment effects. The slope and intercept of the wetland water line in Jiaxing were both significantly lower than the regional precipitation line of the adjacent Changshu Station (CHNIP). This showed that the wetlands area had undergone hydrogen and oxygen isotope enrichment. The δD values in Shijiuyang wetland water ranged from -52.2‰ to -49.4‰, and δ18 O values ranged from -7.6‰ to -6.9‰. In Guanjinggang wetland water samples, δD ranged from -48.1‰ to -45.1‰, and δ18 O ranged from -6.8‰ to -5.8‰. The δD values in Changshuitang wetland water ranged from -49.8‰ to -48.4‰, and δ18 O ranged from -7.2‰ to -6.6‰. The δD values in Taishangang wetland water ranged from -55.3‰ to -51.6‰, and δ18 O ranged from -7.8‰ to -7.2‰. ② Hydrogen and oxygen isotope abundance and composition of water showed complex nonlinear changes in the vertical and horizontal dimensions at different scales. At the regional scale, water level elevation in the vertical dimension had a greater impact on water isotope distribution than the length of the hydraulic flow pathway in the horizontal dimension. Water isotopes tended to be enriched in low-lying areas with low water levels. At the local scale, the influence of hydraulic process often played a greater role in determining water isotope distributions. The spatial variations of water isotopes were comprehensively determined by the evaporation of regional water and meandering hydraulic processes inside the wetland. ③ Compared with other wetland functional areas, the central constructed root-channel area (middle treatment zone) was more enriched in water isotopes. ④ The underground macropore network formed by plants with developed rhizomes or roots (e.g., Phragmites communis Trin. and Typha orientalis Presl), mineral-rich substrate soil, and aquatic plants in the plant bed had a significant influence on the abundance of hydrogen and oxygen isotopes in the plant-bed/ditch system. Therefore, when water passed through the plant-bed/ditch system, the values of δD and δ18 O in the lower ditch (outlet) were lower than those in the higher ditch (inlet). ⑤ The abrupt change in isotopic contents of the plant-bed/ditch system might indicate an inflection point in water quality purification. ⑥ The deuterium excess (d-excess) in subsurface water of the plant-bed/ditch system was significantly higher than that in ditch water, and the coefficient of variation in subsurface water was considerably greater than that in ditch water. The d-excess in the wetland root-channel ecological purification zone showed significant temporal differences and was negative in the summer and positive in the winter, which reflected the seasonal variation in water vapor sources and the spatial variation in isotope fractionation behavior in wetlands. These results provide some understanding of the distribution of water isotopes in constructed wetlands, which will strengthen their operation and management. This study also provides some ideas regarding new technologies for water quality improvement and shows that water isotope technology may be a reliable method for analyzing wetland hydrology.

SIMS oxygen isotope matrix effects in silicate glasses: Quantifying the role of chemical composition

Instrumental mass fractionation (IMF) associated with Secondary Ion Mass Spectrometry (SIMS) measurements of oxygen isotope compositions in silicate glasses was studied using a set of 27 synthesized glasses spanning a compositionally broad range of six major oxides: SiO2, TiO2, Al2O3, total FeO (FeOt), MgO and CaO. The impact of chemical composition on the IMF values was investigated using a Cameca 1280-HR during a single SIMS analytical session operated under constant instrumental conditions. The data measured were compared with the δ18O values obtained by laser fluorination gas source mass-spectrometry (LF). The offset between the δ18O(LF) and δ18O(SIMS) was found to reach up to 5‰. Our data document that SIMS oxygen isotope matrix effects in silicate glasses strongly depend on the chemical composition of silicate glasses, here the cation‑oxygen bond strength was found to have a strong influence on the IMF value. We tested a variety of models based on single oxide contents and various composition-dependent parameters, but none were fully satisfactory for predicting IMF. Neither mean atomic mass nor NBO/T (the ratio of non-bridging oxygens per tetrahedrally coordinated cation) show a strong correlation with the IMF values (R2 of 0.45 and 0.46, respectively). Among the single oxides, only the model based on the SiO2 content is useful for prediction of the IMF in silicate glasses, but this model has a large standard error (1σ = ± 0.90‰) and was also found to break down for glasses with high Na and K contents. We propose an empirical model based on the correlation of six major element oxides that shows a strong correlation with IMF (R2 = 0.98, 1σ = ± 0.40‰). This model describes the experimental data with uncertainties that are roughly a factor of two better than the correction methods proposed in earlier studies. We also investigated using the correlation between IMF and isotope I-18O index, which describes the correlation between atomic bond strength and relative oxygen isotope enrichment in silicate substances (R2 = 0.87). Although our efforts provide refinements to the SIMS determination of δ18O in natural silicate glasses, truly accurate IMF corrections will need further refinements related to the impact of alkali elements.

Can hydraulic design explain patterns of leaf water isotopic enrichment in C3 plants?

H2 18 O enrichment develops when leaves transpire, but an accurate generalized mechanistic model has proven elusive. We hypothesized that leaf hydraulic architecture may affect the degree to which gradients in H2 18 O develop within leaves, influencing bulk leaf stable oxygen isotope enrichment (ΔL ) and the degree to which the Péclet effect is relevant in leaves. Leaf hydraulic design predicted the relevance of a Péclet effect to ΔL in 19 of the 21 species tested. Leaves with well-developed hydraulic connections between the vascular tissue and the epidermal cells through bundle sheath extensions and clear distinctions between palisade and spongy mesophyll layers (while the mesophyll is hydraulically disconnected) may have velocities of the transpiration stream such that gradients in H2 18 O develop and are expressed in the mesophyll. In contrast, in leaves where the vascular tissue is hydraulically disconnected from the epidermal layers, or where all mesophyll cells are well connected to the transpiration stream, velocities within the liquid transport pathways may be low enough that gradients in H2 18 O are very small. Prior knowledge of leaf hydraulic design allows informed selection of the appropriate ΔL modelling framework.

Drying in the Middle East During Northern Hemisphere Cold Events of the Early Glacial Period

AbstractFew paleoclimate records exist to assess the central Middle East's response to natural forcing beyond the instrumental record. Here, we present a multiproxy stalagmite‐based climate reconstruction from Iran's semiarid northeast that spans 100–70,000 years before present. During severe cold (stadial) events in the North Atlantic at ≈88, 77, and 73 ka, stalagmite trace‐element data indicate anomalously dry periods at this location. Stadial event increases in the stalagmite oxygen isotopes mirror those in a published Iranian stalagmite 800 km to the west. A global climate model simulates drying across the Middle East region in response to stadial event forcing, in agreement with oxygen isotope enrichments in both Iranian records, caused by a smaller fractional loss of moisture on the trajectory upstream. The paleoproxies and model experiments are consistent in indicating a drier Middle East climate during the cold North Atlantic stadials.

Multiproxy ecosystem response of abrupt Holocene climatic changes in the northeastern Mediterranean sedimentary archive and hydrologic regime

AbstractAspects of paleoclimatic and paleoceanographic evolution of the north Aegean Sea through the Holocene are revealed by the study of quantitative variations in planktonic foraminiferal, pteropodal, and palynomorph assemblages; the isotopic composition of planktonic foraminifera; and hydrographic-related indices, extracted from two high-sedimentation rate cores from the North Aegean Trough. Focusing on the last ~10 cal ka BP, the current Holocene subdivision (Greenlandian, Northgrippian, and Meghalayan) confirms the traditional understanding of an evolution from wetter (Greenlandian) to gradually drier (Northgrippian and Meghalayan) climatic conditions and further highlights the role of changing seasonality during this time. The most warm and humid phase corresponds to the time of the sapropel S1 deposition (9.6–6.1 cal ka BP). The Holocene climatic instability of the study area is further supported by six episodes of brief cooling (North Aegean cooling; NAEGC6–NAEGC1) centered at 9.30, 8.05, 7.05, 4.55, 3.55, and 2.05 cal ka BP, reflected by significant faunal changes and oxygen isotope enrichments. These cold/arid events are coeval with equivalent cooling events that have been described in different basins of the Mediterranean Sea, while signal similarities with equivalent changes in the intensity of the Siberian high suggest a climatic link between the studied area and the high-latitude areas.

Extreme 13C,15N and 17O isotopic enrichment in the young planetary nebula K4-47.

Carbon, nitrogen and oxygen are the three most abundant elements in the Galaxy after hydrogen and helium. Whereas hydrogen and helium were created in the Big Bang, carbon, nitrogen and oxygen arise from nucleosynthesis in stars. Of particular interest1,2 are the isotopic ratios 12C/13C, 14N/15N and 16O/17O because they are effective tracers of nucleosynthesis and help to benchmark the chemical processes that occurred in primitive interstellar material as it evolved into our Solar System3. However, the origins of the rare isotopes 15N and 17O remain uncertain, although novae and very massive stars that explode as supernovae are postulated4-6 to be the main sources of 15N. Here we report millimetre-wavelength observations of the young bipolar planetary nebula K4-47 that indicate another possible source for these isotopes. We identify various carbon-bearing molecules in K4-47 that show that this object is carbon-rich, and find unusually high enrichment in rare carbon (13C), oxygen (17O) and nitrogen (15N) isotopes: 12C/13C=2.2±0.8, 16O/17O=21.4±10.3 and 14N/15N=13.6±6.5 (uncertainties are three standard deviations); for comparison, the corresponding solar ratios7 are 89.4±0.2, 2,632±7 and 435±57. One possible interpretation of these results is that K4-47 arose from a J-type asymptotic giant branch star that underwent a helium-shell flash (an explosive nucleosynthetic event that converts large quantities of helium to carbon and other elements), enriching the resulting planetary nebula in 15N and 17O and creating its bipolar geometry. Other possible explanations are that K4-47 is a binary system or that it resulted from a white dwarf merger, as has been suggested for object CKVul8. These results suggest that nucleosynthesis of carbon, nitrogen and oxygen is not well understood and that the classification of certain stardust grains must be reconsidered.

Nitrogen and oxygen isotope enrichment factors of nitrate at different denitrification rates in an agricultural soil

ABSTRACTQuantitative evaluation of denitrification by the dual isotope approach, which measures the stable isotope ratios of nitrogen (δ15N) and oxygen (δ18O) in nitrate, has been hampered by the wide range of values reported for the ratio of enrichment factors for 15N and 18O (15ε and 18ε, respectively) during denitrification. The objectives of this study were to determine 15ε and 18ε values at different denitrification rates under controlled conditions, and to infer possible mechanisms by which the 18ε/15ε ratio is influenced under different conditions. Column experiments were conducted at 25, 15, and 10°C, which enabled determination of 15ε and 18ε at different denitrification rates, in the absence of nitrate replenishment from ammonium oxidation and other sources. The values of 15ε and 18ε ranged from −11.8 to −14.9‰ and from −8.4 to −15.9‰, respectively, with 15ε less sensitive to changes in the denitrification rates. The resultant 18ε/15ε ratio, ranging from 0.70 to 1.17, was close to the values reported for sediment incubations, and larger than those for groundwater systems. These results are consistent with the explanations that 18ε/15ε value itself is close to unity during denitrification, and that at smaller denitrification rates, concurrent reactions including re-oxidation of nitrite to nitrate lead to smaller apparent fractionation of 18O and smaller 18ε/15ε ratios. This suggests that while linear relationships between δ18O and δ15N give a strong evidence of denitrification, apparent 18ε/15ε values are site specific and depend on the ambient conditions. In evaluating denitrification in such systems, we suggest the use of 15ε in preference to 18ε because 15ε is less sensitive to denitrification rates.

Identifying evaporation fractionation and streamflow components based on stable isotopes in the Kaidu River Basin with mountain–oasis system in north‐west China

AbstractBased on stable isotopes in stream water, groundwater, and meltwater in the Kaidu River Basin, NW China, we estimated the evaporation enrichment of stable oxygen isotopes in different types of water and separated the contribution of each streamflow component in river run‐off. Our results indicated that δ18O and δ2H in stream water did not vary with altitude regularly but with seasons, with low concentrations in spring and high concentrations in summer. However, the seasonal variations of δ18O and δ2H in groundwater were not as obvious. The mean evaporation enrichment was between 26% and 44% for δ18O. Of the various water types under investigation, we found glaciers were influenced the most, showing an evaporation enrichment of 44%, followed by oasis groundwater (37%), stream water (36%), and mountain groundwater (26%). Overall, meltwater and groundwater were the predominant streamflow components, with their contributions were governed by temperature, and varied both temporally and specially. In the oasis region, groundwater was the predominant contributor (64% in spring, 50% in summer, and 66% in autumn), whereas in the mountains, groundwater was the dominant in spring (53%) and autumn (51%), and meltwater contributed the most in summer (52%). Precipitation contributed less than 15% to the streamflow.

Oxygen isotope enrichment in rice (Oryza sativa L.) grain organic matter captures signature of relative humidity

The oxygen isotopic composition (δ18O) of plant organic matter (OM) is primarily governed by the δ18O of source water (δ18OSW) and climatic factor of relative humidity (RH). Among the cereals, the growth of rice plants is critically dependent on the water availability in the growth-environment. In the present study, we investigated the sensitivity of δ18O in the bulk organic matter of rice grains to RH of their growth-environment. Our experimental setup consisted of both glasshouse and field experiments, where eight genotypes were grown at RH levels ranging from 67% to 87%. The δ18O measured in bulk grain OM and source water was used to calculate the net oxygen isotopic enrichment (Δ18OOM). Regression analysis of Δ18OOM with RH demonstrated a significant relationship (r2 = 0.96; p < 0.0001), thereby implying that the isotopic signature of evaporative conditions gets recorded in the rice grain OM. In addition, our study involved a separate experiment that monitored the degree of oxygen isotope enrichment in water samples extracted from different parts of the rice plant. For this purpose, we sampled four of the above eight genotypes along with three other rice genotypes that were grown in both open cultivation fields and glasshouse. Water present in the culms, leaves, and grains were extracted quantitatively. Isotopic analyses revealed progressive 18O enrichment of the water in the culms and leaves and intermediate enrichment values of that in the grains. Based on the isotope data, we validated mechanistic models for prediction of δ18O of the leaf water and that of the plant carbohydrates. The model predictions were in close agreement with the experimental observations. The study provides insights into the rice plant’s oxygen isotope systematics that build the foundation for future applications of the stable isotope technique to study the interactions between rice and environment.

High nitrogen isotope fractionation of nitrate during denitrification in four forest soils and its implications for denitrification rate estimates

Denitrification is a major process contributing to the removal of nitrogen (N) from ecosystems, but its rate is difficult to quantify. The natural abundance of isotopes can be used to identify the occurrence of denitrification and has recently been used to quantify denitrification rates at the ecosystem level. However, the technique requires an understanding of the isotopic enrichment factor associated with denitrification, which few studies have investigated in forest soils. Here, soils collected from two tropical and two temperate forests in China were incubated under anaerobic or aerobic laboratory conditions for two weeks to determine the N and oxygen (O) isotope enrichment factors during denitrification. We found that at room temperature (20°C), NO3− was reduced at a rate of 0.17 to 0.35μgNg−1h−1, accompanied by the isotope fractionation of N (15ε) and O (18ε) of 31‰ to 65‰ (48.3±2.0‰ on average) and 11‰ to 39‰ (18.9±1.7‰ on average), respectively. The N isotope effects were, unexpectedly, much higher than reported in the literature for heterotrophic denitrification (typically ranging from 5‰ to 30‰) and in other environmental settings (e.g., groundwater, marine sediments and agricultural soils). In addition, the ratios of Δδ18O:Δδ15N ranged from 0.28 to 0.60 (0.38±0.02 on average), which were lower than the canonical ratios of 0.5 to 1 for denitrification reported in other terrestrial and freshwater systems. We suggest that the isotope effects of denitrification for soils may vary greatly among regions and soil types and that gaseous N losses may have been overestimated for terrestrial ecosystems in previous studies in which lower fractionation factors were applied.

Multiple stable isotope fronts during non-isothermal fluid flow

Stable isotope signatures of oxygen, hydrogen and other elements in minerals from hydrothermal veins and metasomatized host rocks are widely used to investigate fluid sources and paths. Previous theoretical studies mostly focused on analyzing stable isotope fronts developing during single-phase, isothermal fluid flow. In this study, numerical simulations were performed to assess how temperature changes, transport phenomena, kinetic vs. equilibrium isotope exchange, and isotopic source signals determine mineral oxygen isotopic compositions during fluid-rock interaction. The simulations focus on one-dimensional scenarios, with non-isothermal single- and two-phase fluid flow, and include the effects of quartz precipitation and dissolution.If isotope exchange between fluid and mineral is fast, a previously unrecognized, significant enrichment in heavy oxygen isotopes of fluids and minerals occurs at the thermal front. The maximum enrichment depends on the initial isotopic composition of fluid and mineral, the fluid-rock ratio and the maximum change in temperature, but is independent of the isotopic composition of the incoming fluid. This thermally induced isotope front propagates faster than the signal related to the initial isotopic composition of the incoming fluid, which forms a trailing front behind the zone of transient heavy oxygen isotope enrichment. Temperature-dependent kinetic rates of isotope exchange between fluid and rock strongly influence the degree of enrichment at the thermal front. In systems where initial isotope values of fluids and rocks are far from equilibrium and isotope fractionation is controlled by kinetics, the temperature increase accelerates the approach of the fluid to equilibrium conditions with the host rock. Consequently, the increase at the thermal front can be less dominant and can even generate fluid values below the initial isotopic composition of the input fluid. As kinetics limit the degree of isotope exchange, a third front may develop in kinetically limited systems, which propagates with the advection speed of the incoming fluid and is, therefore, traveling fastest. The results show that oxygen isotope signatures at thermal fronts recorded in rocks and veins that experienced isotope exchange with fluids can easily be misinterpreted, namely if bulk analytical techniques are applied. However, stable isotope microanalysis on precipitated minerals may – if later isotope exchange is kinetically limited – provide a valuable archive of the transient thermal and hydrological evolution of a system.

Diurnal variation of oxygen isotopic enrichment in asymmetric‐18 ozone observed by the SMILES from space

AbstractAtomic oxygen is a key oxidant for greenhouse gases such as H2O, CH4, and N2O whose amounts are currently increasing in the stratosphere. Ozone photolysis is a major source of atomic oxygen generation. We found, for the first time, that the ozone photolysis of 48O3 and 18O16O16O generated a sharp diurnal variation of δ18OOO in the middle stratosphere (37 km), in contrast to the temporal variation of 48O3. The average isotopic enrichment δ18OOO derived from the Superconducting Submillimeter‐Wave Limb‐Emission Sounder (SMILES) observation was higher during daytime (16.2 ± 3.3%) than at night (13.7 ± 3.6%). Isotopic fractionation effects were simulated for both ozone formation reaction and ozone photolysis with the ozone photolysis contribution estimated to be 80% of the daytime δ18OOO enhancement. Significant solar radiation dependence was observed in the isotopic fractionation of ozone photolysis derived from the SMILES observation and theoretical calculations. These results show that δ18O can be a powerful tool to investigate oxidant chemistry.

Reduced crown root number improves water acquisition under water deficit stress in maize (Zea mays L.).

In this study we test the hypothesis that maize genotypes with reduced crown root number (CN) will have greater root depth and improved water acquisition from drying soil. Maize recombinant inbred lines with contrasting CN were evaluated under water stress in greenhouse mesocosms and field rainout shelters. CN varied from 25 to 62 among genotypes. Under water stress in the mesocosms, genotypes with low CN had 31% fewer crown roots, 30% deeper rooting, 56% greater stomatal conductance, 45% greater leaf CO2 assimilation, 61% net canopy CO2 assimilation, and 55% greater shoot biomass than genotypes with high CN at 35 days after planting. Under water stress in the field, genotypes with low CN had 21% fewer crown roots, 41% deeper rooting, 48% lighter stem water oxygen isotope enrichment (δ(18)O) signature signifying deeper water capture, 13% greater leaf relative water content, 33% greater shoot biomass at anthesis, and 57% greater yield than genotypes with high CN. These results support the hypothesis that low CN improves drought tolerance by increasing rooting depth and water acquisition from the subsoil.

Evaporation induced 18O and 13C enrichment in lake systems: A global perspective on hydrologic balance effects

Growing pressure on sustainable water resource allocation in the context of global development and rapid environmental change demands rigorous knowledge of how regional water cycles change through time. One of the most attractive and widely utilized approaches for gaining this knowledge is the analysis of lake carbonate stable isotopic compositions. However, endogenic carbonate archives are sensitive to a variety of natural processes and conditions leaving isotopic datasets largely underdetermined. As a consequence, isotopic researchers are often required to assume values for multiple parameters, including temperature of carbonate formation or lake water δ18O, in order to interpret changes in hydrologic conditions. Here, we review and analyze a global compilation of 57 lacustrine dual carbon and oxygen stable isotope records with a topical focus on the effects of shifting hydrologic balance on endogenic carbonate isotopic compositions.Through integration of multiple large datasets we show that lake carbonate δ18O values and the lake waters from which they are derived are often shifted by >+10‰ relative to source waters discharging into the lake. The global pattern of δ18O and δ13C covariation observed in >70% of the records studied and in several evaporation experiments demonstrates that isotopic fractionations associated with lake water evaporation cause the heavy carbon and oxygen isotope enrichments observed in most lakes and lake carbonate records. Modeled endogenic calcite compositions in isotopic equilibrium with lake source waters further demonstrate that evaporation effects can be extreme even in lake records where δ18O and δ13C covariation is absent. Aridisol pedogenic carbonates show similar isotopic responses to evaporation, and the relevance of evaporative modification to paleoclimatic and paleotopographic research using endogenic carbonate proxies are discussed.Recent advances in stable isotope research techniques present unprecedented opportunities to overcome the underdetermined nature of stable isotopic data through integration of multiple isotopic proxies, including dual element 13C-excess values and clumped isotope temperature estimates. We demonstrate the utility of applying these multi-proxy approaches to the interpretation of paleohydroclimatic conditions in ancient lake systems. Understanding past, present, and future hydroclimatic systems is a global imperative. Significant progress should be expected as these modern research techniques become more widely applied and integrated with traditional stable isotopic proxies.