We report measurements of resolved 12 CH 2 D 2 and 13 CH 3 D at natural abundances in a variety of methane gases produced naturally and in the laboratory. The ability to resolve 12 CH 2 D 2 from 13 CH 3 D provides unprecedented insights into the origin and evolution of CH 4. The results identify conditions under which either isotopic bond order disequilibrium or equilibrium are expected. Where equilibrium obtains, concordant Δ 12 CH 2 D 2 and Δ 13 CH 3 D temperatures can be used reliably for thermometry. We find that concordant temperatures do not always match previous hypotheses based on indirect estimates of temperature of formation nor temperatures derived from CH 4/ H 2 D/H exchange, underscoring the importance of reliable thermometry based on the CH 4 molecules themselves. Where Δ 12 CH 2 D 2 and Δ 13 CH 3 D values are inconsistent with thermodynamic equilibrium, temperatures of formation derived from these species are spurious. In such situations, while formation temperatures are unavailable, disequilibrium isotopologue ratios nonetheless provide novel information about the formation mechanism of the gas and the presence or absence of multiple sources or sinks. In particular, disequilibrium isotopologue ratios may provide the means for differentiating between methane produced by abiotic synthesis versus biological processes. Deficits in 12 CH 2 D 2 compared with equilibrium values in CH 4 gas made by surface-catalyzed abiotic reactions are so large as to point towards a quantum tunneling origin. Tunneling also accounts for the more moderate depletions in 13 CH 3 D that accompany the low 12 CH 2 D 2 abundances produced by abiotic reactions. The tunneling signature may prove to be an important tracer of abiotic methane formation, especially where it is preserved by dissolution of gas in cool hydrothermal systems (e.g., Mars). Isotopologue signatures of abiotic methane production can be erased by infiltration of microbial communities, and Δ 12 CH 2 D 2 values are a key tracer of microbial recycling.

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The abundances of molecules containing more than one rare isotope have been applied broadly to determine formation temperatures of natural materials. These applications of "clumped" isotopes rely on the assumption that isotope-exchange equilibrium is reached, or at least approached, during the formation of those materials. In a closed-system terrarium experiment, we demonstrate that biological oxygen (O2) cycling drives the clumped-isotope composition of O2 away from isotopic equilibrium. Our model of the system suggests that unique biological signatures are present in clumped isotopes of O2—and not formation temperatures. Photosynthetic O2 is depleted in (18)O(18)O and (17)O(18)O relative to a stochastic distribution of isotopes, unlike at equilibrium, where heavy-isotope pairs are enriched. Similar signatures may be widespread in nature, offering new tracers of biological and geochemical cycling.

Oscillations in ice sheet extent during early and middle Miocene are intermittently preserved in the sedimentary record from the Antarctic continental shelf, with widespread erosion occurring during major ice sheet advances, and open marine deposition during times of ice sheet retreat. Data from seismic reflection surveys and drill sites from Deep Sea Drilling Project Leg 28 and International Ocean Discovery Program Expedition 374, located across the present-day middle continental shelf of the central Ross Sea (Antarctica), indicate the presence of expanded early to middle Miocene sedimentary sections. These include the Miocene climate optimum (MCO ca. 17−14.6 Ma) and the middle Miocene climate transition (MMCT ca. 14.6−13.9 Ma). Here, we correlate drill core records, wireline logs and reflection seismic data to elucidate the depositional architecture of the continental shelf and reconstruct the evolution and variability of dynamic ice sheets in the Ross Sea during the Miocene. Drill-site data are used to constrain seismic isopach maps that document the evolution of different ice sheets and ice caps which influenced sedimentary processes in the Ross Sea through the early to middle Miocene. In the early Miocene, periods of localized advance of the ice margin are revealed by the formation of thick sediment wedges prograding into the basins. At this time, morainal bank complexes are distinguished along the basin margins suggesting sediment supply derived from marine-terminating glaciers. During the MCO, biosiliceous-bearing sediments are regionally mapped within the depocenters of the major sedimentary basin across the Ross Sea, indicative of widespread open marine deposition with reduced glacimarine influence. At the MMCT, a distinct erosive surface is interpreted as representing large-scale marine-based ice sheet advance over most of the Ross Sea paleo-continental shelf. The regional mapping of the seismic stratigraphic architecture and its correlation to drilling data indicate a regional transition through the Miocene from growth of ice caps and inland ice sheets with marine-terminating margins, to widespread marine-based ice sheets extending across the outer continental shelf in the Ross Sea.

The distribution of isotopes within O2 molecules can be rapidly altered when they react with atomic oxygen. This mechanism is globally important: while other contributions to the global budget of O2 impart isotopic signatures, the O(3P) + O2 reaction resets all such signatures in the atmosphere on subdecadal timescales. Consequently, the isotopic distribution within O2 is determined by O3 photochemistry and the circulation patterns that control where that photochemistry occurs. The variability of isotopic ordering in O2 has not been established, however. We present new measurements of 18O18O in air (reported as Δ36 values) from the surface to 33 km altitude. They confirm the basic features of the clumped‐isotope budget of O2: Stratospheric air has higher Δ36 values than tropospheric air (i.e., more 18O18O), reflecting colder temperatures and fast photochemical cycling of O3. Lower Δ36 values in the troposphere arise from photochemistry at warmer temperatures balanced by the influx of high‐Δ36 air from the stratosphere. These observations agree with predictions derived from the GEOS‐Chem chemical transport model, which provides additional insight. We find a link between tropical circulation patterns and regions where Δ36 values are reset in the troposphere. The dynamics of these regions influences lapse rates, vertical and horizontal patterns of O2 reordering, and thus the isotopic distribution toward which O2 is driven in the troposphere. Temporal variations in Δ36 values at the surface should therefore reflect changes in tropospheric temperatures, photochemistry, and circulation. Our results suggest that the tropospheric O3 burden has remained within a ±10% range since 1978.

The precise mass dependence of respiratory O 2 consumption underpins the "oxygen triple-isotope" approach to quantifying gross primary productivity in modern and ancient environments. Yet, the physical-chemical origins of the key 18 O/ 16 O and 17 O/ 16 O covariations observed during respiration have not been tied to theory; thus, the approach remains empirical. Firstprinciples calculations on enzyme active-site models suggest that changes in the O−O bond strength upon electron transfer strongly influence respiratory isotopic fractionation. However, molecular diffusion may also be important.Here, we use measurements of the relative abundances of rare isotopologues 17 O 18 O and 18 O 18 O as additional tracers of mass dependence during dark respiration experiments of lacustrine water. We then compare the experimental results to first-principles calculations of O 2 interacting with heme-oxidase analogues. We find a significantly steeper mass dependence, supported by theory, than has been previously observed. Enrichments of 17 O 18 O and 18 O 18 O in the O 2 residue suggest that θ values are strongly influenced by chemical processes, rather than being dominated by physical processes (i.e., by bond alteration rather than diffusion). In contrast, earlier data are inconsistent with theory, implying that analytical artifacts may have biased those results. Implications for quantifying primary productivity are discussed.

The anaerobic oxidation of methane (AOM) is a crucial component of the methane cycle, but quantifying its role in situ under dynamic environmental conditions remains challenging. We use sediment samples collected during IODP Expedition 347 to the Baltic Sea to show that relative abundances of 12 CH 2 D 2 and 13 CH 3 D in methane remaining after microbial oxidation are in internal, thermodynamic isotopic equilibrium, and we attribute this phenomenon to the reversibility of the initial step of AOM. These data suggest that 12 CH 2 D 2 and 13 CH 3 D together can identify the influence of anaerobic methanotrophy in environments where conventional bulk isotope ratios are ambiguous, and these findings may lead to new insights regarding the global significance of enzymatic back reaction in the methane cycle.

[1] In this study we tested upland hillslope evolution models and constrained the rates of regolith production, colluvial transport, and eolian deposition over geologic time scales in a dated volcanic landscape in northern New Mexico using field measurements of regolith thickness; geochemical analyses of regolith, bedrock, and regional dust; numerical modeling of regolith production and transport; and quantitative analyses of airborne light detection and ranging (lidar) digital elevation models (DEMs). Within this volcanic landscape, many topographically closed basins exist as a result of compressional folding and explosion pitting during eruption. The landscape has evolved from an initial state of no regolith cover at 40 ± 5 ka to its modern state, which has highly weathered regolith ranging from 0 to 3+ m, with local thickness values controlled primarily by topographic position. Our models constrain the maximum rate of regolith production in the study area to be in the range of 0.02 to 0.12 m kyr −1 and the rate of colluvial transport per unit slope gradient to be in the range of 0.2 to 2.7 m 2 kyr −1, with higher values in areas with more aboveground biomass. We conclude that a depth-dependent colluvial transport model better predicts the observed spatial distribution of regolith thickness compared to a model that has no depth dependence. This study adds to the database of estimates for rates of regolith production and transport in the western United States and shows how dated landscapes can be used to improve our understanding of the coevolution of landscapes and regolith cover.