What controls clumped isotopes? Stable isotopes of a molecule can clump together in several combinations, depending on their mass. Even for simple molecules such as O 2 , which can contain 16 O, 17 O, and 18 O in various combinations, clumped isotopes can potentially reveal the temperatures at which molecules form. Away from equilibrium, however, the pattern of clumped isotopes may reflect a complex array of processes. Using high-resolution gas-phase mass spectrometry, Yeung et al. found that biological factors influence the clumped isotope signature of oxygen produced during photosynthesis (see the Perspective by Passey). Similarly, Wang et al. showed that away from equilibrium, kinetic effects causing isotope clumping can lead to overestimation of the temperature at which microbially produced methane forms. Science , this issue p. 431; p. 428; see also p. 394

Natural gas hydrates are a potential source of energy and may play a role in climate change and geological hazards. Most natural gas hydrate appears to be in the form of 'structure I', with methane as the trapped guest molecule, although 'structure II' hydrate has also been identified, with guest molecules such as isobutane and propane, as well as lighter hydrocarbons. A third hydrate structure, 'structure H', which is capable of trapping larger guest molecules, has been produced in the laboratory, but it has not been confirmed that it occurs in the natural environment. Here we characterize the structure, gas content and composition, and distribution of guest molecules in a complex natural hydrate sample recovered from Barkley canyon, on the northern Cascadia margin. We show that the sample contains structure H hydrate, and thus provides direct evidence for the natural occurrence of this hydrate structure. The structure H hydrate is intimately associated with structure II hydrate, and the two structures contain more than 13 different hydrocarbon guest molecules. We also demonstrate that the stability field of the complex gas hydrate lies between those of structure II and structure H hydrates, indicating that this form of hydrate is more stable than structure I and may thus potentially be found in a wider pressure-temperature regime than can methane hydrate deposits.

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Subterranean estuaries extend inland into density-stratified coastal carbonate aquifers containing a surprising diversity of endemic animals (mostly crustaceans) within a highly oligotrophic habitat. How complex ecosystems (termed anchialine) thrive in this globally distributed, cryptic environment is poorly understood. Here, we demonstrate that a microbial loop shuttles methane and dissolved organic carbon (DOC) to higher trophic levels of the anchialine food web in the Yucatan Peninsula (Mexico). Methane and DOC production and consumption within the coastal groundwater correspond with a microbial community capable of methanotrophy, heterotrophy, and chemoautotrophy, based on characterization by 16S rRNA gene amplicon sequencing and respiratory quinone composition. Fatty acid and bulk stable carbon isotope values of cave-adapted shrimp suggest that carbon from methanotrophic bacteria comprises 21% of their diet, on average. These findings reveal a heretofore unrecognized subterranean methane sink and contribute to our understanding of the carbon cycle and ecosystem function of karst subterranean estuaries.

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Atmospheric contributions of methane from Arctic wetlands during the Holocene are dynamic and linked to climate oscillations. However, long-term records linking climate variability to methane availability in Arctic wetlands are lacking. We present a multi-proxy *12,000 year paleoecological reconstruction of intermittent methane availability from a radiocarbon-dated sediment core (LQ-West) taken from a shallow tundra lake (Qalluuraq Lake) in Arctic Alaska. Specifically, stable carbon isotopic values of photosynthetic biomarkers and methane are utilized to estimate the proportional contribution of methane-derived carbon to lake-sediment-preserved benthic (chironomids) and pelagic (cladocerans) components over the last *12,000 years. These results were compared to temperature, hydrologic, and habitat reconstructions from the same site using chironomid assemblage data, oxygen isotopes of chironomid head capsules, and radiocarbon ages of plant macrofossils. Cladoceran ephippia from *4,000 cal year BP sediments have d 13 C values that range from *-39 to -31%, suggesting peak methane carbon assimilation at that time. These low d 13 C values coincide with an apparent decrease in effective moisture and development of a wetland that included Sphagnum subsecundum. Incorporation of methane-derived carbon by This is one of 18 papers published in a special issue edited by Darrell Kaufman and dedicated to reconstructing Holocene climate and environmental change from Arctic lake sediments. chironomids and cladocerans decreased from *2,500 to 1,500 cal year BP, coinciding with a temperature decrease. Live-collected chironomids with a radiocarbon age of 1,640 cal year BP, and fossil chironomids from 1,500 cal year BP in the core illustrate that 'old' carbon has also contributed to the development of the aquatic ecosystem since *1,500 cal year BP. The relatively low d 13 C values of aquatic invertebrates (as low as -40.5%) provide evidence of methane incorporation by lake invertebrates, and suggest intermittent climate-linked methane release from the lake throughout the Holocene.

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Dissolved methane concentrations in the ocean are close to equilibrium with the atmosphere. Because methane is only sparingly soluble in seawater, measuring it without contamination is challenging for samples collected and processed in the presence of air. Several methods for analyzing dissolved methane are described in the literature, yet none has conducted a thorough assessment of the method yield, contamination issues during collection, transport and storage, and the effect of temperature changes and preservative. Previous extraction methods transfer methane from water to gas by either a "sparge and trap" or a "headspace equilibration" technique. The gas is then analyzed for methane by gas chromatography. Here, we revisit the headspace equilibration technique and describe a simple, inexpensive, and reliable method to measure methane in fresh and seawater, regardless of concentration. Within the range of concentrations typically found in surface seawaters (2-1000 nmol L -1 ), the yield of the method nears 100% of what is expected from solubility calculation following the addition of known amount of methane. In addition to being sensitive (detection limit of 0.1 ppmv, or 0.74 nmol L -1 ), this method requires less than 10 min per sample, and does not use highly toxic chemicals. It can be conducted with minimum materials and does not require the use of a gas chromatograph at the collection site. It can therefore be used in various remote working environments and conditions.