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There is growing interest in developing spatially resolved methane (CH4) isotopic source signatures to aid in geographic source attribution of CH4 emissions. CH4 hydrogen isotope measurements (δ2H–CH4) have the potential to be a powerful tool for geographic differentiation of CH4 emissions from freshwater environments, as well as other microbial sources. This is because microbial δ2H–CH4 values are partially dependent on the δ2H of environmental water (δ2H–H2O), which exhibits large and well-characterized spatial variability globally. We have refined the existing global relationship between δ2H–CH4 and δ2H–H2O by compiling a more extensive global dataset of δ2H–CH4 from freshwater environments, including wetlands, inland waters, and rice paddies, comprising a total of 129 different sites, and compared these with measurements and estimates of δ2H–H2O, as well as δ13C-CH4 and δ13C–CO2 measurements. We found that estimates of δ2H–H2O explain approximately 42 % of the observed variation in δ2H–CH4, with a flatter slope than observed in previous studies. The inferred global δ2H–CH4 vs. δ2H–H2O regression relationship is not sensitive to using either modelled precipitation δ2H or measured δ2H–H2O as the predictor variable. The slope of the global freshwater relationship between δ2H–CH4 and δ2H–H2O is similar to observations from incubation experiments but is different from pure culture experiments. This result is consistent with previous suggestions that variation in the δ2H of acetate, controlled by environmental δ2H–H2O, is important in determining variation in δ2H–CH4. The relationship between δ2H–CH4 and δ2H–H2O leads to significant differences in the distribution of freshwater δ2H–CH4 between the northern high latitudes (60–90∘ N), relative to other global regions. We estimate a flux-weighted global freshwater δ2H–CH4 of −310 ± 15 ‰, which is higher than most previous estimates. Comparison with δ13C measurements of both CH4 and CO2 implies that residual δ2H–CH4 variation is the result of complex interactions between CH4 oxidation, variation in the dominant pathway of methanogenesis, and potentially other biogeochemical variables. We observe a significantly greater distribution of δ2H–CH4 values, corrected for δ2H–H2O, in inland waters relative to wetlands, and suggest this difference is caused by more prevalent CH4 oxidation in inland waters. We used the expanded freshwater CH4 isotopic dataset to calculate a bottom-up estimate of global source δ2H–CH4 and δ13C-CH4 that includes spatially resolved isotopic signatures for freshwater CH4 sources. Our bottom-up global source δ2H–CH4 estimate (−278 ± 15 ‰) is higher than a previous estimate using a similar approach, as a result of the more enriched global freshwater δ2H–CH4 signature derived from our dataset. However, it is in agreement with top-down estimates of global source δ2H–CH4 based on atmospheric measurements and estimated atmospheric sink fractionations. In contrast our bottom-up global source δ13C-CH4 estimate is lower than top-down estimates, partly as a result of a lack of δ13C-CH4 data from C4-plant-dominated ecosystems. In general, we find there is a particular need for more data to constrain isotopic signatures for low-latitude microbial CH4 sources.

Greenhouse gas (GHG) emissions from permafrost organic carbon decomposition in lakes and rivers can accelerate global warming. We used radiocarbon (14C) measurements to determine the predominant sources of dissolved organic carbon (DOC), particulate organic carbon (POC), dissolved inorganic carbon (DIC), and methane (CH4) in five thermokarst lakes and three rivers in an area of widespread permafrost degradation in Northern Quebec to assess contributions from thawing permafrost and other old carbon (fixed before CE 1950) reservoirs. We compared emission pathways (dissolved gas and ebullition), seasons (summer and winter), and surface soil type (mineral and peat soils). Modern carbon (fixed after CE 1950) was the dominant source of DOC, DIC, and CH4 of non‐peatland aquatic systems, while POC and sediment carbon were predominantly fixed in the last millennia. In the peatland systems, modern and permafrost carbon were important sources of DOC, lake DIC, lake ebullition CO2, and lake dissolved CH4. In contrast, POC, lake ebullition CH4, and river DIC were dominated by millennial‐old carbon. In winter, the 14C age of DOC, DIC, and POC in the peatland lakes increased, but the 14C age of dissolved CH4 did not change. Our results point to a clearly older overall carbon source for ebullition CH4 relative to dissolved CH4 in the peatland lakes, but not the non‐peatland lakes. The younger ages of diffusive CH4 and DIC relative to DOC and POC in all lakes suggest that recent primary productivity strongly influences the large total lake CH4 emissions in this area, as diffusion fluxes greatly exceed ebullition fluxes.

Lakes and ponds can be hotspots for CO₂ and CH₄ emissions, but Arctic studies remain scarce. Here we present diffusive and ebullition fluxes collected over several years from 30 ponds and 4 lakes formed on an organic‐rich polygonal tundra landscape. Water body morphology strongly affects the mixing regime—and thus the seasonal patterns in gas emissions—with ice‐out and autumnal turnover periods identified as hot moments in most cases. The studied thermokarst lake maintained relatively high ebullition rates of millennia‐old CH4 (up to 3405 ¹⁴C YBP). Larger and deeper kettle lakes maintained low fluxes of both gases (century to millennium‐old), slowly turning into a CO₂ sink over the summer. During winter, lakes accumulated CO₂, which was emitted during the ice‐out period. Coalescent polygonal ponds, influenced by photosynthesizing benthic mats, were continuous CO₂ sinks, yet important CH₄ emitters (modern carbon). The highest fluxes were recorded from ice‐wedge trough ponds (up to 96 mmol CO₂ equivalent m⁻² d⁻¹). However, despite clear signs of permafrost carbon inputs via active shore erosion, these sheltered ponds emitted modern to century‐old greenhouse gases. As the ice‐free period lengthens, scenarios of warmer and wetter conditions could favor both the production of CO₂ and CH₄ from thawing permafrost carbon, and CH₄ production from recently fixed carbon through an atmospheric CO₂₋to₋CH₄ shunt at sites in which primary production is stimulated. This must be carefully considered at the landscape scale, recognizing that older carbon stocks can be mineralized efficiently in specific locations, such as in thermokarst lakes.

There is growing interest in developing spatially resolved methane (CH4) isotopic source signatures to aid in geographic source attribution of CH4 emissions. CH4 hydrogen isotope measurements (δ2H-CH4) have the potential to be a powerful tool for spatial resolution of CH4 emissions from freshwater environments, as well as other microbial sources. This is because microbial δ2H-CH4 values are partially dependent on the δ2H of environmental water (δ2H-H2O), which exhibits large and well-characterized spatial variability globally. We compiled a comprehensive global dataset of paired CH4 δ2H and δ13C measurements from freshwater environments, including wetlands, inland waters, and rice paddies, comprising a total of 131 different ecosystems, and compared these with measurements and estimates of δ2H-H2O. We found that the estimated δ2H of annual precipitation (δ2Hp) explained approximately 35 % of the observed variation in δ2H-CH4, and that the relationship between δ2H-CH4 and δ2Hp led to significant differences in the distribution of freshwater δ2H-CH4 between the northern high latitudes (60–90º N) relative to other global regions. Residual variability in δ2H-CH4 is partially explained by differences in the dominant methanogenic pathway and CH4 oxidation, as inferred from carbon isotope fractionation between CH4 and carbon dioxide (αC). Our results imply that hydrogenotrophic methanogenesis is characterized by a steeper slope of δ2H-CH4 vs. δ2Hp than acetoclastic methanogenesis, a pattern that is consistent with previous predictions. Biogeochemical sources of variability in δ2H-CH4 are reflected in apparent differences between different freshwater ecosystems, with relatively high values in rivers and bogs, and low values in fens and rice paddies, although more data is needed to verify whether these differences are significant. To estimate how changes in the spatial distribution of freshwater emissions would influence global atmospheric CH4 isotopic measurements, we developed a bottom-up mixing model of global CH4 δ2H and δ13C sources, including spatially resolved signatures for freshwater CH4 sources. This model implies that changes in high-latitude freshwater CH4 emissions would have an especially strong influence on global source δ2H-CH4. We estimate that global CH4 emissions sources have a combined δ2H value of −277±8 ‰, which is consistent with top-down estimates based on atmospheric measurements. In contrast our estimated δ13C value of −56.4±1.4 ‰ is not consistent with atmospheric measurements, suggesting possible errors in either emissions inventories or estimates of sink fluxes and isotopic fractionations. Overall our results emphasize the value of δ2H-CH4 measurements to help constrain atmospheric CH4 budgets.

The release of long‐stored carbon from thawed permafrost could fuel increased methanogenesis in northern lakes, but it remains unclear whether old carbon substrates released from permafrost are metabolized as rapidly by methanogenic microbial communities as recently produced organic carbon. Here, we apply methane (CH₄) clumped isotope (Δ₁₈) and ¹⁴C measurements to test whether rates of methanogenesis are related to carbon substrate age. Results from culture experiments indicate that Δ₁₈ values are negatively correlated with CH₄ production rate. Measurements of ebullition samples from thermokarst lakes in Alaska and glacial lakes in Sweden indicate strong negative correlations between CH₄ Δ₁₈ and the fraction modern carbon. These correlations imply that CH₄ derived from older carbon substrates is produced relatively slowly. Relative rates of methanogenesis, as inferred from Δ₁₈ values, are not positively correlated with CH₄ flux estimates, highlighting the likely importance of environmental variables other than CH₄ production rates in controlling ebullition fluxes.

The long-term effects of deforestation on tropical forest soil carbon reservoirs are important for estimating the consequences of land use on the global carbon cycle, but are poorly understood. The Maya Lowlands of Mexico and Guatemala provide a unique opportunity to assess this question, given the widespread deforestation by the ancient Maya that began ~4,000 years ago. Here, we compare radiocarbon ages of plant waxes and macrofossils in sediment cores from three lakes in the Maya Lowlands to record past changes in the mean soil transit time of plant waxes (MTTwax). MTTwax indicates the average age of plant waxes that are transported from soils to lake sediments, and comparison of radiocarbon data from soils and lake sediments within the same catchment indicates that MTTwax reflects the age of carbon in deep soils. All three sediment cores showed a decrease in MTTwax, ranging from 2,300 to 800 years, over the past 3,500 years. This decrease in MTTwax, indicating shorter storage times for carbon in lake catchment soils, is associated with evidence for ancient Maya deforestation. MTTwax never recovered to pre-deforestation values, despite subsequent reforestation, implying that current tropical deforestation will have long-lasting effects on soil carbon sinks.

Investigation of the biology and biochemistry of the deep subsurface provides invaluable information regarding the limit of life in extreme environments and its role in the global carbon cycle. It has been observed that subsurface microbial CH4 can form in apparent isotopic equilibrium, both with respect to methane clumped isotopic species and D/H fractionation with respect to coexisting water. This observation fostered the suggestion that methanogenic metabolisms in energy-starved environments can operate through slow and reversible enzymatic reactions. Here we present isotopic data including a vertical profile of clumped isotopic indices of methane from Paleozoic-aged pore waters in an aquiclude system from the Michigan Basin. We show evidence of both internal isotopic equilibrium of methane and intermolecular H-isotopic equilibrium between methane and co-occurring non-gaseous n-alkanes. Various mixing and microbial metabolic models were tested and allowed us to identify the possibility of the production of methane at thermodynamic equilibrium from the syntrophic degradation of sedimentary n-alkanes at ultra-slow rates. Significance Statement The recent ability to measure the clumped isotopic composition of methane has fostered new ways of observing the deep subsurface biogeochemistry and has been proposed as a new independent geothermometer when methane is formed at or near isotopic equilibrium. In this manuscript, we present the first continuous Paleozoic sedimentary profile of clumped isotopes in pore methane (i.e. directly sampled from the pores of tight sedimentary rocks) from a paleo-bioreactor in the subsurface and show that a syntrophic metabolic network between fermentative bacteria and mainly acetotrophic methanogens can thrive in an energy limited environment.

The analysis of faecal stanols in lake sediment cores offers a novel opportunity to reconstruct human population change, assuming that variability in faecal stanol concentration is a reliable proxy for relative human populations. The ancient lowland Maya of Mesoamerica represents an important ancient society whose demographic dynamics in many locations remain uncertain. We apply the faecal stanol proxy to a sediment core retrieved from a lake adjacent to the archaeological site of Itzan, an ancient population centre in the southwestern Maya lowlands. The sedimentary faecal stanol record from Laguna Itzan implies substantial centennial- and millennial-scale changes in local human populations from 3300 cal years BP to the present. Variability in faecal stanol concentrations is broadly consistent with archaeological evidence for regional societal change across the Maya lowlands, but also implies an earlier presence of humans at this site than is currently indicated in the Itzan archaeological record. We find evidence for high-frequency variability in coprostanol concentrations during the Maya Preclassic period, which we infer represents centennial-scale shifts in settlement patterns associated with changes in agricultural and land use patterns. Given Preclassic-period faecal peak stanol concentrations, we observe lower-than-expected Classic-period faecal peak stanol concentrations, and these may partly be a result of either use of human waste for fertiliser or reduced soil erosion or both. Three periods of inferred population decline are associated with palaeoclimate evidence for a drying climate, specifically during the Terminal Classic (1220-1050 cal yr BP) and the Protoclassic 2 (1860-1670 cal yr BP), as well as the less well-studied drought between 3330 and 2900 cal yr BP during the Early to Middle Preclassic periods. An additional decline and hiatus in coprostanol input coincides with a period of anomalously wet climate in the Late Preclassic. These linkages suggest that climatic change and variability could have played a role in demographic change at multiple points in the evolution of Maya civilisation. Our work shows that faecal stanols are valuable proxies for past human population dynamics, and their relation to climatic change, in Mesoamerica.

Paleoclimatologists have discovered abundant evidence that droughts coincided with collapse of the Lowland Classic Maya civilization, and some argue that climate change contributed to societal disintegration. Many archaeologists, however, maintain that drought cannot explain the timing or complex nature of societal changes at the end of the Classic Period, between the eighth and eleventh centuries ce. This review presents a compilation of climate proxy data indicating that droughts in the ninth to eleventh century were the most severe and frequent in Maya prehistory. Comparison with recent archaeological evidence, however, indicates an earlier beginning for complex economic and political processes that led to the disintegration of states in the southern region of the Maya lowlands that precedes major droughts. Nonetheless, drought clearly contributed to the unusual severity of the Classic Maya collapse, and helped to inhibit the type of recovery seen in earlier periods of Maya prehistory. In the drier northern Maya Lowlands, a later political collapse at ca. 1000 ce appears to be related to ongoing extreme drought. Future interdisciplinary research should use more refined climatological and archaeological data to examine the relationship between climate and social processes throughout the entirety of Maya prehistory.

A growing body of paleoclimate data indicates that periods of severe drought affected the Maya Lowlands of southeastern Mexico and northern Central America, especially during the Terminal Classic period (ca. 800–950 CE), raising the possibility that climate change contributed to the widespread collapse of many Maya polities at that time. A broad range of paleoclimate proxy methods have been applied in the Maya Lowlands and the data derived from these methods are sometimes challenging for archeologists and other non-specialists to interpret. This paper reviews the principal methods used for paleoclimate inference in the region and the rationale for climate proxy interpretation to help researchers working in the Maya Lowlands make sense of paleoclimate datasets. In particular, we focus on analyses of speleothems and lake sediment cores. These two paleoclimate archives have been most widely applied in the Maya Lowlands and have the greatest potential to provide insights into climate change impacts on the ancient Maya. We discuss the development of chronologies for these climate archives, the proxies for past climate change found within them, and how these proxy variables are interpreted. Finally, we present strategies for improving our understanding of proxy paleoclimate data from the Maya Lowlands, including multi-proxy analyses, assessment of spatial variability in past climate change, combined analysis of climate models and proxy data, and the integration of paleoclimatology and archeology.

Changes in terrestrial environments across the Cretaceous-Paleogene boundary, including plant ecology and carbon and water-cycling, remain poorly defined. Fluvial sediments spanning the Cretaceous-Paleogene (K-Pg) boundary of southern Saskatchewan, Canada contain well preserved plant wax n-alkanes that provide a means of reconstructing changes to plant ecology and carbon and water cycling during this mass extinction event. We measured n-alkane carbon (δ13C) and hydrogen (δ2H) isotope ratios in two sedimentary sections and applied established fractionation factors to estimate the isotopic compositions of precipitation and bulk sedimentary organic matter sources. We also analyzed the distribution of n-alkanes as an indicator of the relative abundance of aquatic and terrestrial plants. We find a consistent shift towards a greater relative abundance of longer-chain n-alkanes across the boundary, implying a persistent increase in the relative abundance of terrestrial plants in the sedimentary basin. This is consistent with an increase in birch and elm palynomorphs immediately above the boundary. We hypothesize the extinction of all large herbivores at the boundary may have facilitated this transition to a terrestrial angiosperm dominated flora immediately after the boundary. We also find that the region was characterized by isotopically light precipitation, with δ2H values between −95‰ to −160‰, but do not observe evidence for major millennial-scale changes in regional precipitation isotopic composition spanning the boundary. n-Alkanes derived from both aquatic and terrestrial plants at one site display an upward trend in δ13C values of approximately 2‰ across the K-Pg boundary. This suggests millennial-scale local or global carbon-cycle variability altering either plant carbon isotope fractionation or the carbon isotope composition of dissolved inorganic carbon and atmospheric CO2. Overall our results suggest that carbon and water cycle changes associated with the K-Pg impact in terrestrial environments in western Canada were short-lived, but ecological shifts in plant communities were longer-lasting.

Abiotic hydrocarbon gas, typically generated in serpentinized ultramafic rocks and crystalline shields, has important implications for the deep biosphere, petroleum systems, the carbon cycle and astrobiology. Distinguishing abiotic gas (produced by chemical reactions like Sabatier synthesis) from biotic gas (produced from degradation of organic matter or microbial activity) is sometimes challenging because their isotopic and molecular composition may overlap. Abiotic gas has been recognized in numerous locations on the Earth, although there are no confirmed instances where it is the dominant source of commercially valuable quantities in reservoir rocks. The deep hydrocarbon reservoirs of the Xujiaweizi Depression in the Songliao Basin (China) have been considered to host significant amounts of abiotic methane. Here we report methane clumped-isotope values (Δ_(18)) and the isotopic composition of C_1–C_3 alkanes, CO_2 and helium of five gas samples collected from those Xujiaweizi deep reservoirs. Some geochemical features of these samples resemble previously suggested identifiers of abiotic gas (^(13)C-enriched CH_4; decrease in ^(13)C/^(12)C ratio with increasing carbon number for the C1–C4 alkanes; abundant, apparently non-biogenic CO_2; and mantle-derived helium). However, combining these constraints with new measurements of the clumped-isotope composition of methane and careful consideration of the geological context, suggests that the Xujiaweizi depression gas is dominantly, if not exclusively, thermogenic and derived from over-mature source rocks, i.e., from catagenesis of buried organic matter at high temperatures. Methane formation temperatures suggested by clumped-isotopes (167–213 °C) are lower than magmatic gas generation processes and consistent with the maturity of local source rocks. Also, there are no geological conditions (e.g., serpentinized ultramafic rocks) that may lead to high production of H_2 and thus abiotic production of CH_4 via CO_2 reduction. We propose that the Songliao gas is representative of an atypical type of thermogenic gas that can be mistaken for abiotic gas. Such gases may be encountered more frequently in future exploration of deep or over-mature petroleum systems.

© 2018 The Author(s). Methane clumped-isotope compositions provide a new approach to understanding the formational conditions of methane from both biogenic and thermogenic sources. Under some conditions, these compositions can be used to reconstruct the formational temperatures of the gas, and this capability can be applied to common subsets of both biogenic and thermogenic systems. Additionally, there are examples in which clumped-isotope compositions do not reflect gas-formation temperatures but instead mixing effects and kinetic phenomena; such kinetic effects also occur in common and recognizable subtypes of biogenic and thermogenic gases. Here we review the use of methane clumped-isotope measurements for understanding the origin of methane in the subsurface. We review methane clumped-isotope measurements from numerous biogenic and thermogenic natural gas reservoirs.We then place these measurements in the context of common frameworks for identifying the formational conditions of methane including the use of methane δ13C and δD values and C1/C2-3ratios. Finally, we propose a framework for how methane clumped isotopes can be used to identify the origin of methane accumulations.

© 2017 Elsevier Ltd The isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding petroleum systems, atmospheric greenhouse gas concentrations, the global carbon cycle, and life in extreme environments. Recent analytical developments focusing on multiply substituted isotopologues (‘clumped isotopes’) are opening a valuable new window into methane geochemistry. When methane forms in internal isotopic equilibrium, clumped isotopes can provide a direct record of formation temperature, making this property particularly valuable for identifying different methane origins. However, it has also become clear that in certain settings methane clumped isotope measurements record kinetic rather than equilibrium isotope effects. Here we present a substantially expanded dataset of methane clumped isotope analyses, and provide a synthesis of the current interpretive framework for this parameter. In general, clumped isotope measurements indicate plausible formation temperatures for abiotic, thermogenic, and microbial methane in many geological environments, which is encouraging for the further development of this measurement as a geothermometer, and as a tracer for the source of natural gas reservoirs and emissions. We also highlight, however, instances where clumped isotope derived temperatures are higher than expected, and discuss possible factors that could distort equilibrium formation temperature signals. In microbial methane from freshwater ecosystems, in particular, clumped isotope values appear to be controlled by kinetic effects, and may ultimately be useful to study methanogen metabolism.

© 2016 Elsevier Ltd. 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 δ18values spanning a range of more than 5‰.