Oxygen Isotope Exchange Reactions Research Articles

An experimental simulation of oxygen isotope exchange reaction between amorphous silicate dust and carbon monoxide gas in the early Solar System

The reaction mechanism and kinetics of oxygen isotope exchange between tens of nanometer-sized amorphous silicate grains with forsterite composition (amorphous forsterite) and low-pressure carbon monoxide (CO) gas (PCO) of 0.05–1 Pa at 643–883 K were examined to investigate oxygen isotopic evolution in the protosolar disk that led to the mass-independent oxygen isotopic variation of planetary materials. Both CO gas supply- and diffusion-controlled isotope exchange reactions were observed. At 753–883 K and PCO of 0.05–1 Pa, the supply of CO gas controls the isotope exchange reaction, and its rate is 2–3 orders of magnitude smaller than that of the H2O supply-controlled isotope exchange reaction. The diffusion-controlled isotope exchange occurred at 643–703 K and PCO of 0.3 Pa, and the reaction rate of D (m2/s) = (3.1 ± 2.3) × 10−23 exp[−41.7 ± 9.6 (kJ mol−1) R−1 (1/T − 1/1200)] was obtained.We found that the oxygen isotope exchange rates of amorphous forsterite with CO and H2O gases are larger than those of gaseous isotope exchange between CO and H2O gases at a wide range of temperatures, wherein amorphous forsterite crystallization does not precede the isotope exchange reaction of amorphous forsterite with these gases. The most sluggish isotope exchange rate between H2O and CO in the gas phase suggests that amorphous forsterite would play a role in accelerating gaseous isotopic equilibrium through the isotope exchange of amorphous forsterite with both CO and H2O. We found that the oxygen isotopic equilibrium between 0.1 μm-sized amorphous forsterite, CO, and H2O would be accomplished through the isotope exchange of amorphous forsterite at temperatures as low as ∼600–700 K in the dynamically accreting protosolar disk, which is significantly lower than expected for the case of gaseous isotope exchange (>∼800 K).

Oxygen isotope exchange between molten silicate spherules and ambient water vapor with nonzero relative velocity: Implication for chondrule formation environment

Oxygen isotope compositions of chondrules reflect the environment of chondrule formation and its spatial and temporal variations. Here, we present a theoretical model of oxygen isotope exchange reaction between molten silicate spherules and ambient water vapor with finite relative velocity. We found a new phenomenon, that is, mass-dependent fractionation caused by isotope exchange with ambient vapor moving with nonzero relative velocity. We also discussed the plausible condition for chondrule formation from the point of view of oxygen isotope compositions. Our findings indicate that the relative velocity between chondrules and ambient vapor would be lower than several 100ms−1 when chondrules crystallized.

Oxygen isotope exchange kinetics between CAI melt and carbon monoxide gas: Implication for CAI formation in the earliest Solar System

Coarse-grained igneous calcium-aluminum-rich inclusions (CAIs) are suggested to have experienced gas–melt isotope exchange of oxygen during the melting events of their precursors. Therefore, their oxygen isotope variation would preserve information about the high-temperature processes in the earliest Solar System. We experimentally determined oxygen isotope exchange kinetics between CAI analog melt and carbon monoxide (CO) gas at 1420 °C and 1460 °C under CO gas partial pressures of 0.1, 0.5, and 1 Pa to understand the role of CO gas on the oxygen isotope exchange. We observed oxygen isotope zoning profiles inside the reacted samples that formed through the oxygen isotope exchange reaction at the melt surface and oxygen diffusion in the melt. The zoning profiles were fitted using a three-dimensional spherical diffusion model with time-dependent surface concentration. The oxygen isotope exchange efficiency for colliding CO molecules is estimated to be ∼3.3 × 10–4, which is much smaller than that for H2O (0.28). The oxygen diffusion coefficient obtained in this study is similar to that obtained in the oxygen isotope exchange experiments between the CAI melt and H2O, suggesting that the diffusion species in the melt is O2–, despite the surrounding atmospheres.A comparison of the isotope exchange reaction kinetics between (1) CAI melt and CO gas, (2) CAI melt and H2O gas, and (3) CO and H2O gases shows that the reaction rate decreases in the order of (3), (2), and (1). The rapid isotope exchange of the reaction (1) indicates that the oxygen isotopic compositions of H2O and CO should have been equilibrated during the melting and crystallization processes of igneous CAIs. Both H2O and CO change the oxygen isotope compositions of molten CAI in the same direction, although reaction (2) controls the isotope exchange timescale between the CAI melt and surrounding gas. Our dataset demonstrates that type B CAIs having melilite with homogeneous oxygen isotope composition should have been heated for 2–3 days at PH2 > 100 Pa above the melilite liquidus (∼1400 °C) in the solar protoplanetary disk.

Spectral dependence of UV light penetration into powder TiO2 anatase

The penetration depth of UV monochromatic light into deposited TiO2 anatase powder was investigated. The light penetration depth was considered in units of numbers of surface hole, Ns, and electron, NO2, centers activated during irradiation. The numbers of hole centers Ns were obtained from photostimulated oxygen isotope exchange reaction registered by means of mass spectrometry. The numbers of electron centers NO2 were obtained from subsequent thermo-programmed desorption spectroscopy of photoadsorbed oxygen O2-. It was shown that the depth D of UV light penetration into UV absorbing TiO2 powder coat depends on the wavelength and intensity I0 of incident UV light and obeys to the equation DI0=1kefflg(I0/Im) obtained from the Beer–Lambert–Bouguer law with effective extinction coefficient keff and minimal value of light intensity Im, below which the photoactivation is considered negligible. Commonly, the value Im has an order of a few microwatts/cm2 for activation of electron and hole type centers except for a case of 334 nm falling into the band of the first direct band-to-band transition of anatase, where relatively high threshold value Im=0.063 mW/cm2 for photoactivation of hole centers was revealed. Effective extinction coefficient keff may be considered proportional to the absorption coefficient of TiO2 in the region of fundamental absorption, whereas, in the non-fundamental absorption region, keff exceeds significantly that of TiO2 due to, probably, dominating scattering processes. At small intensities of the incident light, there is a strong sensitivity of the penetration depth (and activated surface) to the intensity.

Increasing the reliability of compound identification in biological samples using 16O/18O-exchange mass spectrometry.

The task of multipurpose analysis of biological samples and identification of individual compounds in them is actual for many organizations in various fields; the results of such analyses can affect lives. The most frequently used, most accurate, and highly sensitive method used for this kind of analysis is the combination of gas/liquid chromatography and high-resolution mass spectrometry. However, in some areas, it is necessary to increase the reliability of compound identification. In this paper, we present a method that combines the reaction of oxygen isotope exchange with mass spectrometry; the method allows to increase the reliability of identification of individual compounds. Oxygen isotope exchange reaction is a "selective" one, which means that not all oxygen present in the molecule can exchange, but only in certain functional groups. Thus, by the number of isotope exchanges that have occurred in this molecule, the right structural formula might be more accurately chosen. The method was tested both on pure pharmaceutical substances and on real human urine samples. In both cases, the effectiveness of the method was shown: the number of expected exchanges in known substances coincided with the experimental one, and from several possible structures of unknown substances, the correct one was chosen based on the number of isotope exchanges.

Oxygen Isotope Exchange Reaction for Untargeted LC-MS Analysis.

LC-MS is a key technique for the identification of small molecules in complex samples. Accurate mass, retention time, and fragmentation spectra from LC-MS experiments are compared to reference values for pure chemical standards. However, this information is often unavailable or insufficient, leading to an assignment to a list of candidates instead of a single hit; therefore, additional features are desired to filter candidates. One such promising feature is the number of specific functional groups of a molecule that can be counted via derivatization or isotope-exchange techniques. Hydrogen/deuterium exchange (HDX) is the most widespread implementation of isotope exchange for mass spectrometry, while oxygen 16O/18O exchange is not applied as frequently as HDX. Nevertheless, it is known that some functional groups may be selectively exchanged in 18O enriched media. Here, we propose an implementation of 16O/18O isotope exchange to highlight various functional groups. We evaluated the possibility of using the number of exchanged oxygen atoms as a descriptor to filter database candidates in untargeted LC-MS-based workflows. It was shown that 16O/18O exchange provides 62% (median, n = 45) search space reduction for a panel of drug molecules. Additionally, it was demonstrated that studying the fragmentation spectra after 16O/18O can aid in eliminating false positives and, in some cases, help to annotate fragments formed with water traces in the collisional cell.

An experimental study on oxygen isotope exchange reaction between CAI melt and low-pressure water vapor under simulated Solar nebular conditions

Calcium-aluminum-rich inclusions (CAIs) are known as the oldest high-temperature mineral assemblages of the Solar System. The CAIs record thermal events that occurred during the earliest epochs of the Solar System formation in the form of heterogeneous oxygen isotopic distributions between and within their constituent minerals. Here, we explored the kinetics of oxygen isotope exchange during partial melting events of CAIs by conducting oxygen isotope exchange experiments between type B CAI-like silicate melt and 18O-enriched water vapor (PH2O = 5 × 10−2 Pa) at 1420 °C. We found that the oxygen isotope exchange between CAI melt and water vapor proceeds at competing rates with surface isotope exchange and self-diffusion of oxygen in the melt under the experimental conditions. The 18O concentration profiles were well fitted with the three-dimensional spherical diffusion model with a time-dependent surface concentration. We determined the self-diffusion coefficient of oxygen to be ∼1.62 × 10−11 m2 s−1, and the oxygen isotope exchange efficiency on the melt surface was found to be ∼0.28 in colliding water molecules. These kinetic parameters suggest that oxygen isotope exchange rate between cm-sized CAI melt droplets and water vapor is dominantly controlled by the supply of water molecules to the melt surface at PH2O < ∼10−2 Pa and by self-diffusion of oxygen in the melt at PH2O > ∼1 Pa at temperatures above the melilite liquidus (1420–1540 °C). To form type B CAIs containing 16O-poor melilite by oxygen isotope exchange between CAI melt and disk water vapor, the CAIs should have been heated for at least a few days at PH2O > 10−2 Pa above temperatures of the melilite liquidus in the protosolar disk. The larger timescale of oxygen isotopic equilibrium between CAI melt and H2O compared to that between H2O and CO in the gas phase suggests that the bulk oxygen isotopic compositions of ambient gas at ∼1400 °C in the type B CAI-forming region is preserved in the oxygen isotopic compositions of type B CAI melilite. Based on the observed oxygen isotopic composition, we suggest that a typical type B1 CAI (TS34) from Allende was cooled at a rate of ∼0.1–0.5 K h−1 during fassaite crystallization.

Improving the extraction and purification of leaf and phloem sugars for oxygen isotope analyses.

The oxygen isotopic composition (here shown as the δ18 O value) of soluble sugars in leaves and phloem tissue holds valuable information about plant functions in response to climatic changes. However, δ18 O analysis of sugars is prone to error, and thoroughly tested methods are lacking. We performed three experiments to test if sample preparation modifies the δ18 O values of sugars. In experiment 1, we tested the effects of oven-drying versus freeze-drying, whereas in experiment 2 we focused on the extraction and purification of leaf sugars. In experiment 3, we investigated the exudation and purification of twig phloem sugars as a function of exudation time and different ethylenediaminetetraacetic acid (EDTA) exudation media. Freeze-drying produced more consistent δ18 O values than oven-drying for sucrose but not for phloem sugars. The extraction and purification of leaf sugars can be performed without a significant modification of their δ18 O values; yet the purified leaf and phloem sugars possessed higher δ18 O values than the fraction of water-soluble compounds. Moreover, the exudation time significantly modulated the δ18 O values of phloem sugars, which is probably related to changes in the sugar composition. The addition of EDTA did not improve the determination of the δ18 O values of phloem sugars. We show that the sample preparation of plant sugars for the reliable determination of δ18 O values requires a strict protocol, which is described in this paper. For phloem sugar, we recommend a maximum exudation time of 1 h to reduce the degradation of sucrose and minimise oxygen isotope exchange reactions between the resulting hexoses and water.

Original composition and formation process of slab-derived deep brine from Kashio mineral spring in central Japan

Brine samples from the wells in the Kashio mineral spring (an “Arima-type” hot spring at Ooshika-Mura, central Japan) were analyzed to determine the original chemical and isotopic compositions of the deep brine end-member before its dilution by meteoric water and to elucidate the origin of the end-member. The trends of variation between Cl, δD, and δ18O indicated the existence of a two-component mixing system and a systematic variation in the mixing ratio, which were mentioned in previous studies. By carefully tracking the variation in tritium (3H) and atmospheric noble gas in the brine, the Cl concentration in the end-member was determined to be 24,000 mg/L. This value is consistent with the result of previous studies. Based on the estimated composition and other related data, we inferred that the end-member originated from slab-derived fluid, which in turn may have undergone oxygen isotope exchange reactions with minerals. Although both the Arima and Kashio brines are considered to be derived from fluid dehydrated from the Philippine Sea slab, the chemical and isotopic compositions of the Kashio end-member are different from those of the Arima end-member. In particular, the Kashio end-member is characterized by low Cl concentration (~ 40% lower than that in the Arima end-member), low hydrogen isotope ratio, and low 3He/4He ratio (1.4 Ra). These results indicate that the chemical and isotopic compositions of the slab-derived fluid are different for each location. The significant difference in δD could reflect the difference in the dehydration depth. Finally, the low temperature and relatively low 3He/4He ratio of the brine end-member could be explained by its long residence time within the crust.

A method for isotope exchange kinetics in mineral-water system-an in-situ study on oxygen isotope exchange in Na2CO3-H2O system.

The experiments on the exchange reaction rate of the oxygen isotopes in the mineral-water system with initial conditions of 100°C and 240MPa, 100°C and 924MPa, 118°C and 170MPa are taken. The oxygen isotope 18O exchange reactions between aqueous C16O32- and H218O are mainly traced by measuring the Raman peak intensity of oxygen-containing elements (CO32-) in sodium carbonate solution. The inconsistent trends between the molar fraction and the concentration of C18O216O2- indicate oxygen isotope exchange between sodium carbonate and heavy water accompanied by dissolution and recrystallization between supersaturated sodium carbonate solution and solid sodium carbonate. In the heterogeneous experimental systems the order of oxygen isotope exchange reactions are more than 1 and the dynamics of oxygen isotope exchange conform to JMAK kinetics model with the nucleation and growth processes of sodium carbonate crystal.

Oxygen Isotopic Exchange between Amorphous Silicate and Water Vapor and Its Implications for Oxygen Isotopic Evolution in the Early Solar System

Abstract Meteoritic evidence suggests that oxygen isotopic exchange between 16O-rich amorphous silicate dust and 16O-poor water vapor occurred in the early solar system. In this study, we experimentally investigated the kinetics of oxygen isotopic exchange between submicron-sized amorphous forsterite grains and water vapor at protoplanetary disk-like low pressures of water vapor. The isotopic exchange reaction rate is controlled either by diffusive isotopic exchange in the amorphous structure or by the supply of water molecules from the vapor phase. The diffusive oxygen isotopic exchange occurred with a rate constant D (m2 s−1) = (1.5 ± 1.0) × 10−19 exp[−(161.5 ± 14.1 (kJ mol−1))R −1(1/T−1/1200)] at temperatures below ∼800–900 K, and the supply of water molecules from the vapor phase could determine the rate of oxygen isotopic exchange at higher temperatures in the protosolar disk. On the other hand, the oxygen isotopic exchange rate dramatically decreases if the crystallization of amorphous forsterite precedes the oxygen isotopic exchange reaction with amorphous forsterite. According to the kinetics for oxygen isotopic exchange in protoplanetary disks, original isotopic compositions of amorphous forsterite dust could be preserved only if the dust was kept at temperatures below 500–600 K in the early solar system. The 16O-poor signatures for the most pristine silicate dust observed in cometary materials implies that the cometary silicate dust experienced oxygen isotopic exchange with 16O-poor water vapor through thermal annealing at temperatures higher than 500–600 K prior to their accretion into comets in the solar system.

First-Principles Computed Rate Constant for the O + O2 Isotopic Exchange Reaction Now Matches Experiment.

We show, by performing exact time-independent quantum molecular scattering calculations, that the quality of the ground electronic state global potential energy surface appears to be of utmost importance in accurately obtaining even as strongly averaged quantities as kinetic rate constants. The oxygen isotope exchange reaction, 18O + 32O2, motivated by the understanding of a complex long-standing problem of isotopic ozone anomalies in the stratosphere and laboratory experiments, is explored in this context. The thermal rate constant for this key reaction is now in quantitative agreement with all experimental data available to date. A significant recent progress at the frontier of three research domains, advanced electronic structure calculations, ultrasensitive spectroscopy, and quantum scattering calculations, has therefore permitted a breakthrough in the theoretical modeling of this crucial collision process from first principles.

Investigation of the ozone formation reaction pathway: Comparisons of full configuration interaction quantum Monte Carlo and fixed-node diffusion Monte Carlo with contracted and uncontracted MRCI.

The association/dissociation reaction path for ozone (O2 + O ↔ O3) is notoriously difficult to describe accurately using ab initio electronic structure theory, due to the importance of both strong and dynamic electron correlations. Experimentally, spectroscopic studies of the highest lying recorded vibrational states combined with the observed negative temperature dependence of the kinetics of oxygen isotope exchange reactions confirm that the reaction is barrierless, consistent with the latest potential energy surfaces. Previously reported potentials based on Davidson-corrected internally contracted multireference configuration interaction (MRCI) suffer from a spurious reef feature in the entrance channel even when extrapolated towards the complete basis set limit. Here, we report an analysis of comparisons between a variety of electronic structure methods including internally contracted and uncontracted MRCI (with and without Davidson corrections), as well as full configuration interaction quantum Monte Carlo, fixed-node diffusion Monte Carlo, and density matrix renormalization group.

New evidence on the correlation between lattice fringe with catalytic performance for suprafacial CO and intrafacial CH4 oxidations over Co3O4 by isotopic 18O2 exchange

Tricobalt tetroxide (Co3O4) with a typical spinel-type crystal structure using as oxidation catalyst has attracted considerable attention. In this study, series of Co3O4 samples with diverse morphologies including nanoslice (NS), nanoparticle (NP), nanoflower (NF), and nanopolyhedron (NPL) crystals faceted with (3 1 1), (2 2 0), and (1 1 1) surfaces have been synthesized. Physicochemical properties of these materials were characterized by means of numerous techniques [XRD, N2 sorption, SEM, HRTEM, XPS, H2-TPR, and oxygen isotopic exchange (OIE) reaction] as well as DFT calculation. Furthermore, their catalytic activities for CO and CH4 oxidation were comparatively evaluated. The NS and NP samples (respective SBET of 137 and 90m2/g) possess much higher adsorbed oxygen and better low-temperature reducibility with respect to the other samples. In 18O2 exchange reaction, the NS sample showed the best transfer ability for surface as well as bulk oxygen among the investigated samples. Accordingly, the excellent catalytic performance towards CO and CH4 oxidation over NS-Co3O4 samples was associated with the abundant surface oxygen species, good low-temperature reducibility, especially the best mobility for both surface and bulk oxygen.

Ab initio R1 mechanism of photostimulated oxygen isotope exchange reaction on a defect TiO2 surface: The case of terminal oxygen atom exchange

Based on density functional theory we propose R1 mechanism of photostimulated oxygen isotope exchange (POIEx) reaction between 16O18O and terminal oxygen atom of a defect TiO2 surface, which is modeled by amorphous Ti8O16 nanocluster in excited S1 electronic state. The proposed mechanism involves four adsorption intermediates and five transition states. The computed activation energy of the POIEx equals 0.24eV. The computed g-tensors of the predicted ozonide O3− chemisorption species match well EPR data on O2 adsorption on UV-irradiated nanocrystalline TiO2. This match serves a mean of justification of the proposed R1 mechanism of the POIEx reaction. In addition, it is found that the proposed R1 POIEx reaction’s mechanism differs from R1 mechanism of thermo-assisted OIEx reaction on a surface of supported vanadium oxide catalyst VOx/TiO2 reported earlier.

Kinetics of enzyme‐catalysed oxygen isotope exchange between phosphate and water revealed by Raman spectroscopy

Pyrophosphatases (EC 3.6.1.1) are ubiquitous enzymes that catalyse the hydrolysis of pyrophosphate, a byproduct of many biochemical reactions. The hydrolysis leads to an oxygen isotope exchange between the newly formed phosphate molecules and water. Here, we applied Raman spectroscopy to monitor the oxygen isotope exchange reaction in presence of pyrophosphatase from baker's yeast. For this purpose, enzymatic assays consisting of 0.8 m 18O‐enriched phosphate were prepared under pH‐buffered conditions. Upon addition of pyrophosphatase, the Raman spectrum of the solution immediately started to shift to higher wavenumbers, indicating the progressive substitution of 18O in phosphate by 16O from water. The analytical results were quantified by fitting a Voigt function to the measured Raman spectra that allowed to determine the relative contribution of each phosphate isotopologue in solution over time. Based on the relative contribution of the different phosphate species, the apparent overall oxygen exchange rate could be calculated assuming a first‐order kinetic. The progressive formation and disappearance of the different phosphate isotopologues were then modelled by applying a consecutive reaction scheme with first‐order steps. The results of our experiments show that Raman spectroscopy can be used to study the kinetics of enzyme‐catalysed oxygen isotope exchange in the phosphate–water system. Copyright © 2016 John Wiley &amp; Sons, Ltd.

Ligand- and oxygen-isotope-exchange pathways of geochemical interest

Environmental context Most chemical processes in water are either ligand- or electron-exchange reactions. Here the general reactivity trends for ligand-exchange reactions in aqueous solutions are reviewed and it is shown that simple rules dominate the chemistry. These simple rules shed light on most molecular processes in water, including the uptake and degradation of pesticides, the sequestration of toxic metals and the corrosion of minerals. Abstract It is through ligand-exchange kinetics that environmental geochemists establish an understanding of molecular processes, particularly for insulating oxides where there are not explicit electron exchanges. The substitution of ligands for terminal functional groups is relatively insensitive to small changes in structure but are sensitive to bond strengths and acid–base chemistry. Ligand exchanges involving chelating organic molecules are separable into two classes: (i) ligand substitutions that are enhanced by the presence of the chelating ligand, called a ‘spectator’ ligand and (ii) chelation reactions themselves, which are controlled by the Lewis basicity of the attacking functional group and the rates of ring closure. In contrast to this relatively simple chemistry at terminal functional groups, substitutions at bridging oxygens are exquisitely sensitive to details of structure. Included in this class are oxygen-isotope exchange and mineral-dissolution reactions. In large nanometer-sized ions, metastable structures form as intermediates by detachment of a surface metal atom, often from a underlying, highly coordinated oxygen, such as μ4-oxo, by solvation forces. A metastable equilibrium is then established by concerted motion of many atoms in the structure. The newly undercoordinated metal in the intermediate adds a water or ligand from solution, and protons transfer to other oxygens in the metastable structure, giving rise to a characteristic broad amphoteric chemistry. These metastable structures have an appreciable lifetime and require charge separation, which is why counterions affect the rates. The number and character of these intermediate structures reflect the symmetry of the starting structure.

A novel methodological approach for δ18O analysis of sugars using gas chromatography-pyrolysis-isotope ratio mass spectrometry

Although the instrumental coupling of gas chromatography-pyrolysis-isotope ratio mass spectrometry (GC-Py-IRMS) for compound-specific δ18O analysis has been commercially available for more than a decade, this method has been hardly applied so far. Here we present the first GC-Py-IRMS δ18O results for trimethylsilyl-derivatives of plant sap-relevant sugars and a polyalcohol (glucose, fructose, sucrose, raffinose and pinitol). Particularly, we focus on sucrose, which is assimilated in leaves and which is the most important transport sugar in plants and hence of utmost relevance in plant physiology and paleoclimate studies. Replication measurements of sucrose standards and concentration series indicate that the GC-Py-IRMS δ18O measurements are not stable over time and that they are amount (area) dependent. We, therefore, suggest running sample batch replication measurements in alternation with standard concentration series of reference material. This allows for carrying out (i) a drift correction, (ii) a calibration against reference material and (iii) an amount (area) correction. Tests with 18O-enriched water do not provide any evidence for oxygen isotope exchange reactions affecting sucrose and raffinose. We present the first application of GC-Py-IRMS δ18O analysis for sucrose from needle extract (soluble carbohydrate) samples. The obtained δ18Osucrose/ Vienna Standard Mean Ocean Water (VSMOW) values are more positive and vary in a wider range (32.1–40.1 ‰) than the δ18Obulk/ VSMOW values (24.6–27.2 ‰). Furthermore, they are shown to depend on the climate parameters maximum day temperature, relative air humidity and cloud cover. These findings suggest that δ18Osucrose of the investigated needles very sensitively reflects the climatically controlled evaporative 18O enrichment of leaf water and thus highlights the great potential of GC-Py-IRMS δ18Osucrose analysis for plant physiology and paleoclimate studies.

Scaling of extended defects in nano-sized Brownmillerite CaFeO2.5

We investigated the formation of extended defects in CaFeO2.5, predominantly appearing as antiphase boundaries (APBs), as a function of the synthesis method and temperature. While CaFeO2.5 is known to adopt an ordered oxygen defect structure showing long range order of the (FeO4)∞ chains in its bulk form, interestingly, we demonstrated that the length of these (FeO4)∞ chains can be considerably scaled down to few nanometers by adopting a modified sol–gel method (low temperature synthesis) while the grain size of the resulting nano-phase CaFeO2.5 is around 50 nm. We discuss the synthesis dependent modulation of the length of APBs, characterized by X-ray diffraction and high resolution TEM, to be at the origin of an amplified switching dynamics of the (FeO4)∞ chains. This can accordingly explain the reduction of the onset temperature for oxygen diffusion to set in from 450 °C for bulk-CaFeO2.5 to 320 °C for nano-CaFeO2.5, as determined by 18O/16O oxygen isotope exchange reactions.

Equilibrium mass-dependent fractionation relationships for triple oxygen isotopes

With a growing interest in small 17O-anomaly, there is a pressing need for the precise ratio, ln 17 α/ln 18 α, for a particular mass-dependent fractionation process (MDFP) (e.g., for an equilibrium isotope exchange reaction). This ratio (also denoted as “ θ”) can be determined experimentally, however, such efforts suffer from the demand of well-defined process or a set of processes in addition to high precision analytical capabilities. Here, we present a theoretical approach from which high-precision ratios for MDFPs can be obtained. This approach will complement and serve as a benchmark for experimental studies. We use oxygen isotope exchanges in equilibrium processes as an example. We propose that the ratio at equilibrium, θ E ≡ ln 17 α/ln 18 α, can be calculated through the equation below: θ a - b E = κ a + ( κ a - κ b ) ln 18 β b ln 18 α a - b where 18 β b is the fractionation factor between a compound “b” and the mono-atomic ideal reference material “O”, 18 α a−b is the fractionation factor between a and b and it equals to 18 β a/ 18 β b and κ is a new concept defined in this study as κ ≡ ln 17 β/ln 18 β. The relationship between θ and κ is similar to that between α and β. The advantages of using κ include the convenience in documenting a large number of θ values for MDFPs and in estimating any θ values using a small data set due to the fact that κ values are similar among O-bearing compounds with similar chemical groups. Frequency scaling factor, anharmonic corrections and clumped isotope effects are found insignificant to the κ value calculation. However, the employment of the rule of geometric mean (RGM) can significantly affect the κ value. There are only small differences in κ values among carbonates and the structural effect is smaller than that of chemical compositions. We provide κ values for most O-bearing compounds, and we argue that κ values for Mg-bearing and S-bearing compounds should be close to their high temperature limitation (i.e., 0.5210 for Mg and 0.5159 for S). We also provide θ values for CO 2(g)–water, quartz–water and calcite–water oxygen isotope exchange reactions at temperature from 0 to 100 °C.