Non-equilibrium Isotope Effects Research Articles

Covariation between oxygen and hydrogen stable isotopes declines along the path from xylem water to wood cellulose across an aridity gradient.

Oxygen and hydrogen isotopes of cellulose in plant biology are commonly used to infer environmental conditions, often from time series measurements of tree rings. However, the covariation (or the lack thereof) between δ18 O and δ2 H in plant cellulose is still poorly understood. We compared plant water, and leaf and branch cellulose from dominant tree species across an aridity gradient in Northern Australia, to examine how δ18 O and δ2 H relate to each other and to mean annual precipitation (MAP). We identified a decline in covariation from xylem to leaf water, and onwards from leaf to branch wood cellulose. Covariation in leaf water isotopic enrichment (Δ) was partially preserved in leaf cellulose but not branch wood cellulose. Furthermore, whilst δ2 H was well-correlated between leaf and branch, there was an offset in δ18 O between organs that increased with decreasing MAP. Our findings strongly suggest that postphotosynthetic isotope exchange with water is more apparent for oxygen isotopes, whereas variable kinetic and nonequilibrium isotope effects add complexity to interpreting metabolic-induced δ2 H patterns. Varying oxygen isotope exchange in wood and leaf cellulose must be accounted for when δ18 O is used to reconstruct climatic scenarios. Conversely, comparing δ2 H and δ18 O patterns may reveal environmentally induced shifts in metabolism.

Beyond Equilibrium: Kinetic Isotope Fractionation in High-Temperature Environments

Igneous and metamorphic rocks exhibit greater isotopic heterogeneity than expected from equilibrium. Large nonequilibrium isotope effects can arise from diffusion and chemical reactions, such as crystal growth and dissolution. The effects are time-dependent and can, therefore, be used to probe timescales of igneous and metamorphic processes that are inaccessible to direct observation. New discoveries of isotopic variability in nature, informed by diffusion and reaction modeling, can provide unique insights into the formation of rocks in the interiors of planetary bodies.

Carbon and oxygen isotope systematics in cave environments: Lessons from an artificial cave “McMaster Cave”

Understanding carbon and oxygen isotope systematics in cave environments is a prerequisite for the interpretation of stable isotopes in speleothem-based paleoclimate records. Here we present a series of experimental data collected under laboratory conditions with controlled temperature, relative humidity, drip water chemistry, flow rate and cave pCO2, simulating the growth of speleothems in natural cave settings. Drip water with high pCO2 and low calcium concentration (Ca2+ = 2 mmol/L) flowed along a three-step glass path, similar to a stalactite-stalagmite-pool route in natural caves, forming a thin water film that allowed CO2 degassing and CaCO3 precipitation as a result of the pCO2 gradient between the drip water and ambient cave atmosphere. The experiments were conducted at 15, 25 and 32 °C and flow rates of 700, 270 and 125 ml/d.The growth rate of calcite on the stalagmite-like settings increases linearly with increasing flow rate and/or temperature. The δ13CCc and δ18OCc of calcite formed on the stalagmite-like settings increases with decreasing flow rate (corresponding to increasing exposure time of water) at a given temperature, indicating non-equilibrium isotope effects between calcite, water and dissolved inorganic carbon (DIC). Nevertheless, these non-equilibrium isotope effects still display regular temperature dependence under a constant flow rate. This suggests that non-equilibrium isotope effects in natural stalagmites might be used to provide useful qualitative paleoclimate information (such as differentiating wet/dry and warm/cold climate conditions). The non-equilibrium carbon and oxygen isotope effects in the stalagmite-like settings were most likely caused by rapid CO2 degassing and CaCO3 precipitation that rapidly consume the available DIC pool in the thin water film. Furthermore, CO2 exchange between DIC and cave atmosphere quickly amplified the observed non-equilibrium carbon isotope effects in the precipitated calcite.In the pool-like settings, calcite was buffered by oxygen isotope exchange between DIC species and water, and slowly precipitated at or near to oxygen isotopic equilibrium with the temperature dependence of 1000ln18αCc-H2O = 18.33 (103/T) – 33.31 regardless of flow rate. This fractionation relation agrees with that determined by Kim and O’Neil (1997) when a newly recommended value for the acid fractionation factor for calcite is used (i.e., Kim et al., 2015). Carbon isotope fractionation between calcite and bicarbonate was temperature-independent between 15 and 32 °C and the average magnitude was 1000ln13αCc–HCO3− = 1.7 ± 0.7‰. Observed variability of 1000ln18αCc-H2O in modern calcite speleothems from natural cave settings lies in the range predicted by this study, between the predicted maximum non-equilibrium deviation at the stalagmite-like settings and the equilibrium 1000ln18αCc-H2O achieved in the pool-like settings.

Diverse origins of Arctic and Subarctic methane point source emissions identified with multiply-substituted isotopologues

Methane is a potent greenhouse gas, and there are concerns that its natural emissions from the Arctic could act as a substantial positive feedback to anthropogenic global warming. Determining the sources of methane emissions and the biogeochemical processes controlling them is important for understanding present and future Arctic contributions to atmospheric methane budgets. Here we apply measurements of multiply-substituted isotopologues, or clumped isotopes, of methane as a new tool to identify the origins of ebullitive fluxes in Alaska, Sweden and the Arctic Ocean. When methane forms in isotopic equilibrium, clumped isotope measurements indicate the formation temperature. In some microbial methane, however, non-equilibrium isotope effects, probably related to the kinetics of methanogenesis, lead to low clumped isotope values. We identify four categories of emissions in the studied samples: thermogenic methane, deep subsurface or marine microbial methane formed in isotopic equilibrium, freshwater microbial methane with non-equilibrium clumped isotope values, and mixtures of deep and shallow methane (i.e., combinations of the first three end members). Mixing between deep and shallow methane sources produces a non-linear variation in clumped isotope values with mixing proportion that provides new constraints for the formation environment of the mixing end-members. Analyses of microbial methane emitted from lakes, as well as a methanol-consuming methanogen pure culture, support the hypothesis that non-equilibrium clumped isotope values are controlled, in part, by kinetic isotope effects induced during enzymatic reactions involved in methanogenesis. Our results indicate that these kinetic isotope effects vary widely in microbial methane produced in Arctic lake sediments, with non-equilibrium Δ18 values spanning a range of more than 5‰.

Nonequilibrium H/D Isotope Effects from Trajectory-Based Nonadiabatic Dynamics

Ground-state equilibrium kinetic isotope effects can be treated well in the framework of transition state theory, whereas excited-state nonequilibrium isotope effects are theoretically less explored. In this article we show for the first time that trajectory-based nonadiabatic dynamics simulations are able to reproduce experimental values for nonequilibrium H/D isotope effects in excited-state processes. We use high-level electronic structure calculations (MS-CASPT2, DFT/MRCI, and TDDFT) and full-dimensional OM2/MRCI-based nonadiabatic dynamics simulations to study the ultrafast intramolecular excited-state proton transfer (ESIPT) and the subsequent deactivation of 7-(2-pyridyl)indole (7PyIn) and its deuterated analogue (7PyIn-D). We evaluate a total of 1367 surface-hopping trajectories to establish the differences in the dynamical behavior of 7PyIn and 7PyIn-D. The computed H/D isotope effects for ESIPT and excited-state decay are consistent with recent experimental results from femtosecond pump-probe resonance-enhanced multiphoton ionization spectroscopy. We also analyze the influence of temperature fluctuations in the initially prepared sample on the photodynamics of 7PyIn and 7PyIn-D.

Carbon isotope ratio of Cenozoic CO2: A comparative evaluation of available geochemical proxies

[1] The carbon isotope ratio (δ13C) of plant material is commonly used to reconstruct the relative distribution of C3 and C4 plants in ancient ecosystems. However, such estimates depend on the δ13C of atmospheric CO2 (δ13CCO2) at the time, which likely varied throughout Earth history. For this study, we use benthic and planktonic δ13C and δ18O records to reconstruct a long-term record of Cenozoic δ13CCO2. Confidence intervals for δ13CCO2 values are assigned after careful consideration of equilibrium and non-equilibrium isotope effects and processes, as well as resolution of the data. We find that benthic foraminifera better constrain δ13CCO2 compared to planktonic foraminiferal records, which are influenced by photosymbiotes, depth of production, seasonal variability, and preservation. Furthermore, sensitivity analyses designed to quantify the effects of temperature uncertainty and diagenesis on benthic foraminifera δ13C and δ18O values indicate that these factors act to offset one another. Our reconstruction suggests that Cenozoic δ13CCO2 averaged −6.1 ± 0.6‰ (1σ), while only 11.2 million of the last 65.5 million years correspond to the pre-Industrial value of −6.5‰ (with 90% confidence). Here δ13CCO2 also displays significant variations throughout the record, at times departing from the pre-Industrial value by more than 2‰. Thus, the observed variability in δ13CCO2 should be considered in isotopic reconstructions of ancient terrestrial-plant ecosystems, especially during the Late and Middle Miocene, times of presumed C4 grassland expansion.

Gas phase photolysis of 1-pentene and 1-pentene-d10 at 7.1 and 7.6 eV. Kinetic considerations

The gas phase photolysis of n-pentene was carried out in a static system using nitrogen resonance lines at [Formula: see text] and the bromine line at [Formula: see text] The mechanism for the photolysis was proposed and compared to what was concluded at 8.4 eV (147 nm, the xenon resonance line). The kinetics of the decomposition of the excited C3H5* radicals formed in the primary photochemical process and the C5H11* radicals formed by the addition of hydrogen atoms to the parent molecules were discussed. The investigations were extended to the n-C5D10 photolytic System. The observed decomposition rate constants of the excited pentyl radicals as well as the secondary non-equilibrium isotope effects agree with the data published earlier. It is concluded from these experiments that, at least at 7.6 eV, hot hydrogen atoms are produced.Only a small fraction of the C3H5* radicals décompose and yield aliène. At the same time the combined primary–secondary non-equilibrium isotope effects are much less than those calculated for the 'pure' primary isotope effects. To account for these observations, it is assumed that the C3H5* radicals are formed with a wide spread in the internal energies. Since the threshold of the decomposition of the excited C3H5* radical lies above its mean excess energy (calculated on the statistical basis), an analogy in the energy-distribution functions on the radicals activated photochemically and thermally may be suggested. If so, an inverse secondary isotope effect may contribute to the gross effect involved in the C3H5* radical decomposition.