Gregory A. Henkes

Because of its global abundance and reactivity with hydroxyl radicals (OH•), tropospheric carbon monoxide indirectly impacts the lifetimes of other OH•‐reactive gases, in particular methane and reactive hydrocarbons. The origin and chemistry of atmospheric CO have been studied using stable isotopes. Both ¹³CO and C¹⁸O undergo isotopic fractionation during its main chemical loss reaction, CO + OH•. The kinetic isotope effect (KIE) for ¹³CO is mass dependent, with a value of ∼5‰; ¹²CO reacts faster than ¹³CO with OH. Whereas C¹⁸O + OH• exhibits an inversely mass dependent KIE ∼−10‰. We hypothesize these KIEs result in a relative depletion of ¹³C¹⁸O, a CO clumped isotope. To test this, we collected CO from air samples on Long Island, NY, and discovered a −3 to −8‰ difference in the clumped isotope ratio, Δ₃₁, relative to a random distribution of ¹³C and ¹⁸O in CO. A clear negative trend between [CO] and Δ₃₁ is driven by two factors: (a) the atmospheric addition of CO from either a primary or secondary source with a Δ₃₁ of ∼0‰ and (b) the continuing reaction of CO with OH•, leaving the remaining CO pool relatively depleted in ¹³C¹⁸O. This is analogous to the mechanism that determines CO Δ¹⁷O values. This study is among the first to show clumped isotope fractionation resulting from atmospheric chemistry and not thermal equilibration, which may inform the identification of clumped isotope KIEs in other atmospheric trace gases. These first Δ₃₁ observations motivate future experimental and observational studies targeted at characterizing the clumped isotopes of CO sources, background CO, and experimentally fractionated CO.

Measurements of oxygen and hydrogen stable isotope ratios (δ¹⁸O and δD) in meteoric waters provide insight to overlapping effects of evaporation, precipitation, and mixing on basin scale hydrology. This study of waters collected between 2016 and 2021 in the Turkana Basin, northern Kenya, uses δ¹⁸O and δD to understand water balance in Lake Turkana, a large, low‐latitude, alkaline desert lake. The Omo River, a major river system in the Ethiopian Highlands, is historically understood to provide approximately 90% of the water input to Lake Turkana. Discharge of the Omo is prohibitively difficult to measure, but stable isotope ratios in the lake may provide a meaningful method for monitoring the lake's response to changes in input. Precipitation in the Turkana Basin is low (18O and δD yields results consistent with published water balance models. Continued sampling of lake and meteoric waters in the Turkana Basin will be a useful way to monitor the lake's response to regional and global climate change.

I- Biological processes in the Proterozoic Ocean are often inferred from modern oxygen-deficient environments (MODEs) or from stable isotopes in preserved sediment. To-date, few MODE studies have simultaneously quantified carbon fixation genes and attendant stable isotopic signatures. Consequently, how carbon isotope patterns reflect these pathways has not been thoroughly vetted. Addressing this, we profiled planktonic productivity and quantified carbon fixation pathway genes and associated carbon isotope values of size-fractionated (0.2 – 2.7 and > 2.7 μm) particulate organic carbon values (8 ¹³ C _POC ) from meromictic Fayetteville Green Lake, NY, USA. The high-O ₂ Calvin-Benson-Bassham (CBB) gene ( cbbL) was most abundant in the 2 CBB gene ( cbbM) was most abundant near the lower oxycline boundary in the larger size fraction, coincident with purple sulfur bacteria populations. The reverse citric acid cycle gene ( aclB) was equally abundant in both size fractions in the deepest photic zone, coinciding with green sulfur bacteria populations. Methane coenzyme reductase A ( mcrA ), of anaerobic methane cyclers, was most abundant at the lower oxycline boundary in both size fractions, coinciding with Methanoregula populations. 8 ¹³ C _POC values overlapped with the high-O ₂ CBB fixation range except for two negative excursions near the lower oxycline boundary, likely reflecting assimilation of isotopically-depleted groundwater-derived inorganic carbon by autotrophs and acetate oxidation by sulfate-reducers. Throughout aphotic waters, 8 ¹³ C _POC values of the large size fraction became 13C-enriched, likely reflecting abundant purple sulfur bacterial aggregates. Microalgal-like isotopic signatures corresponded with increases in cbbL , cbbM and aclB , and enrichment of exopolymer-rich prokaryotic photoautotrophs aggregates. Results suggest that 8 ¹³ C _POC values of preserved sediments from areas of the Proterozoic Ocean with sulfidic photic zones may reflect a mixture of alternate carbon-fixing populations exported from the deep photic zone, challenging the paradigm that sedimentary stable carbon isotope values predominantly reflect oxygenic photosynthesis from surface waters.

The Turkana Depression is located within the East African Rift system (EARs) si...

The terrestrial Lower Cretaceous Cedar Mountain Formation, Utah, is a critical archive of paleoclimate, tectonics, and vertebrate ecology and evolution. Early Cretaceous carbon cycle perturbations associated with ocean anoxia have been interpreted from this succession, as expressed in stable carbon isotopes. However, refining the timing of the observed stable isotope excursions remains a key challenge in understanding how marine anoxia affects the Earth system, and is ultimately recorded in the terrestrial realm. The geochronology and geochemistry of a terrestrial carbonate near the base of this succession, which potentially records the Ap7 global carbon isotope excursion, is studied here. Petrographic and geochemical analyses are used to test plausible mechanisms for U incorporation into the calcite lattice in this sample. Using these methods, the hypothesis that the incorporation of U was at or close to the timing of carbonate precipitation is evaluated. U–Pb geochronology of calcite indicates a plausible Early Cretaceous age. However, comparison of the new U–Pb ages of calcite with detrital zircon maximum depositional ages immediately beneath the studied sample indicates a disparity in the apparent sedimentation rates if both types of geochronologic information are interpreted as reflecting the timing of sediment deposition. The totality of data supports an early, and high-temperature, diagenetic timing of U incorporation, with potential for minor leaching of U in subsequent fluid–rock interaction. The most likely mechanism for U transport and immobilization in these samples is hydrothermal fluid–rock interaction. Therefore, the radiometric ages, and corresponding stable isotope composition of U-bearing carbonate domains in this sample, indicate early subsurface fluid–rock interactions and not a record of atmosphere–soil geochemical reactions.

Carbonate clumped isotopes (∆47) have become a widely applied method for paleothermometry, with applications spanning many environmental settings over hundreds of millions of years. However, ∆47-based paleothermometry can be complicated by closure temperature-like behavior whereby C–O bonds are reset at elevated diagenetic or metamorphic temperatures, sometimes without obvious mineral alteration. Laboratory studies have constrained this phenomenon by heating well-characterized materials at various temperatures, observing temporal ∆47 evolution, and fitting results to kinetic models with prescribed C–O bond reordering mechanisms. While informative, these models are inflexible regarding the nature of isotope exchange, leading to potential uncertainties when extrapolated to geologic timescales. Here, we instead propose that observed reordering rates arise naturally from random-walk 18O diffusion through the carbonate lattice, and we develop a “disordered” kinetic framework that treats C–O bond reordering as a continuum of first-order processes occurring in parallel at different rates. We show theoretically that all previous models are specific cases of disordered kinetics; thus, our approach reconciles the transient defect/equilibrium defect and paired reaction-diffusion models. We estimate the rate coefficient distributions from published heating experiment data by finding a regularized inverse solution that best fits each ∆47 timeseries without assuming a particular functional form a priori. Resulting distributions are well-approximated as lognormal for all experiments on calcite or dolomite; aragonite experiments require more complex distributions that are consistent with a change in oxygen bonding environment during the transition to calcite. Presuming lognormal rate coefficient distributions and Arrhenius-like temperature dependence yields an underlying activation energy, E, distribution that is Gaussian with a mean value of μE = 224.3 ± 27.6 kJ mol−1 and a standard deviation of σE = 17.4 ± 0.7 kJ mol−1 (±1σ uncertainty; n = 24) for calcite and μE = 230.3 ± 47.7 kJ mol−1 and σE = 14.8 ± 2.2 kJ mol−1 (n = 4) for dolomite. These model results are adaptable to other minerals and may provide a basis for future experiments whereby the nature of carbonate C–O bonds is altered (e.g., by inducing mechanical strain or cation substitution). Finally, we apply our results to geologically relevant heating/cooling histories and suggest that previous models underestimate low-temperature alteration but overestimate ∆47 blocking temperatures.