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Highlights:-We present a review and an expanded dataset of methane clumped isotope measurements.-Methane clumped isotope values often indicate equilibrium formation temperature.-Kinetic effects during or after methane production can affect clumped isotope values.-The wide variability in clumped isotope values suggests it will be a useful tracer. AbstractThe isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding petroleum systems, atmospheric 3 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.

Noble gases are chemically inert and variably soluble in crustal fluids. They are primarily introduced into hydrocarbon reservoirs through exchange with formation waters, and can be used to assess migration pathways and mechanisms, as well as reservoir storage conditions. Of particular interest is the role groundwater plays in hydrocarbon transport, which is reflected in hydrocarbon-water volume ratios. Here, we present compositional, stable isotope and noble gas isotope and abundance data from the Sleipner Vest field, in the Norwegian North Sea.Sleipner Vest gases are generated from primary cracking of kerogen and the thermal cracking of oil. Gas was emplaced into the Sleipner Vest from the south and subsequently migrated to the east, filling and spilling into the Sleipner Ost fields. Gases principally consist of hydrocarbons (83-93%), CO 2 (5.4-15.3%) and N 2 (0.6-0.9%), as well as trace concentrations of noble gases. Helium isotopes ( 3He/

Microbially mediated reductive processes involving the oxidation of labile organic carbon are widely considered to be critical to the release of arsenic into shallow groundwaters in South and Southeast Asia. In areas where there is significant pumping of groundwater for irrigation the involvement of surface-derived organic carbon drawn down from ponds into the underlying aquifers has been proposed but remains highly controversial. Here we present isotopic data from two sites with contrasting groundwater pumping histories that unequivocally demonstrate the ingress of surface pond-derived organic carbon into arsenic-containing groundwaters. We show that pond-derived organic carbon is transported to depths of up to 50 m even in an arsenic-contaminated aquifer in Cambodia thought to be minimally disturbed by groundwater pumping. In contrast, in the extensively exploited groundwaters of West Bengal, we show that pond-derived organic carbon is transported in shallow groundwater to greater depths, in excess of 100 m in the aquifer. Intensive pumping of groundwaters may potentially drive secular increases in the groundwater arsenic hazard in this region by increasing the contribution of bioavailable pond-derived dissolved organic carbon drawn into these aquifer systems and transporting it to greater depths than would operate under natural flow conditions.

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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/C2–3 ratios. Finally, we propose a framework for how methane clumped isotopes can be used to identify the origin of methane accumulations.

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We utilize carbonate clumped isotope thermometry to explore the diagenetic and thermal histories of exhumed brachiopods, crinoids, cements, and host rock in the Permian Palmarito Formation, Venezuela, and the Carboniferous Bird Spring Formation, Nevada, USA. Carbonate components in the Palmarito Formation, buried to ~4 km depth, yield statistically indistinguishable clumped isotope temperatures [T(Δ 47 )] ranging from 86 to 122 °C. Clumped isotope temperatures of components in the more deeply buried Bird Spring Formation (>5 km) range from ~100 to 165 °C and differ by component type, with brachiopods and pore-filling cements yielding the highest T(Δ 47 ) (mean = 153 and 141 °C, respectively) and crinoids and host rock yielding significantly cooler T(Δ 47 ) (mean = 103 and 114 °C). New high-resolution thermal histories are coupled with kinetic models to predict the extent of solid-state C-O bond reordering during burial and exhumation for both sites. Application of these models, termed "THRMs" (thermal history reordering models), suggests that brachiopods in the Palmarito Formation experienced partial bond reordering without complete equilibration of clumped isotopes at maximum burial temperature. In contrast, clumped isotope bonds of brachiopods from the Bird Spring Formation completely equilibrated at maximum burial temperature, and now reflect blocking temperatures achieved during cooling. The 40-50-°C-cooler clumped isotope temperatures measured in Bird Spring Formation crinoids and host rock can be explained by recrystallization and cementa tion during shallow burial combined with a greater inherent resistance to solid-state reordering than brachiopods.