Controls on the isotopic composition of microbial methane

Microbial methane production (methanogenesis) is responsible for more than half of the annual emission of this major greenhouse gas to the atmosphere. Though the stable isotopic composition of methane is often used to characterize its sources and sinks, empirical descriptions of the isotopic signature of methanogenesis currently limit such attempts. We developed a biochemical-isotopic model of methanogenesis by CO2 reduction, which predicts carbon and hydrogen isotopic fractionations, and clumped isotopologue distributions, as functions of the cell’s environment. We mechanistically explain multiple-isotopic patterns in laboratory and natural settings and show that such patterns constrain the in-situ energetics of methanogenesis. Combining our model with environmental data, we infer that in almost all marine environments and gas deposits, energy-limited methanogenesis operates close to chemical and isotopic equilibrium.

Carbon and oxygen isotopic composition of fluid inclusion CO2 and CH4 within the Archean Junction gold deposit, Kambalda, Western Australia

ABSTRACT The Junction orogenic gold deposit in the St Ives district of Western Australia is characterized by a syn-gold mineral assemblage dominated by quartz-calcite-albite-biotite-chlorite-pyrrhotite. The deposit had a light hydrocarbon,CO2, and O2 soil-gas signature above known mineralization prior to mining and it has been proposed that the source of the light hydrocarbon gases in the soil was gas-rich fluid inclusions trapped in gold-related alteration minerals, particularly calcite, albite, quartz, and pyrrhotite. Linking the soil gases with those in the deposit is extremely difficult. However, establishing that the gases in the soil are indeed present within the deposit and that those gases are related to the syn-Au alteration minerals is achievable through stable-isotope studies. Carbon and O stable-isotope compositions of pre-gold, syn-gold, and post-gold quartz veins; syn-gold and post-gold calcite; and CO2 and CH4 in the fluid inclusions that each of these minerals host were investigated to establish if the various mineral and fluid-gas species in the deposit are in isotopic equilibrium with each other, an important first step to relate syn-ore minerals with the relevant gases. Pre-ore Mo-type quartz veins contain CO2 (δ13Cgas = –1‰) and CH4 (δ13Cgas = ca. –33‰) in fluid inclusions at a ratio of ca. 93:7. The paucity of Mo-type quartz veins in the deposit suggests that these veins were not the main source of the soil-gas signature. Syn-gold alteration post-dates the Mo-type quartz veins. Quartz and co-existing calcite in the Au-bearing Junction shear zone have δ18Omineral values around 12.0 and 10.5‰, respectively. Multiple co-existing quartz-calcite pairs indicate that gold deposition occurred at ∼400 °C. This temperature agrees with mineral equilibria temperature estimates, the entrapment temperatures of fluid inclusions, and temperature modelling of solid-solution mineral phases. The temperature dictates that the quartz and calcite are in isotopic equilibrium with each other. The calcite in the Junction shear zone has δ13Cmineral values from –7.4 to –2.5‰, indicating that the CO2-rich ore fluid had a δ13Cfluid value of –3.7 ± 0.9‰. CO2 and CH4 released from quartz-hosted fluid inclusions have δ13Cgas values from –4.3 to +3.5‰ (mean = –1.5 ± 1.9‰) and –50.5 to –35.2‰, respectively. The isotopic composition of the fluid inclusion CO2 is in disequilibrium with co-existing CH4 that was co-released from the same quartz vein and the calculated δ13Cfluid value from co-existing calcite. Isotopic mass balance calculations using the two co-released gases show that the CO2 was initially in equilibrium with the syn-ore calcite but has since re-equilibrated with CH4 at temperatures below 200 °C. The abundance of CH4 in some quartz veins suggests that the syn-gold vein assemblage could be the source for the soil-gas anomaly. Post-gold veins contain quartz and calcite that have δ18Omineral values of ca. 11.0 and 10.0‰, respectively. Individual mineral pairs indicate precipitation at ∼320 °C from a fluid with a δ18Ofluid value of 4.7 ± 0.9‰, distinct from that which formed the syn-gold quartz veins. The post-gold calcite has δ13Ccalcite values from –7.5 to –5.4‰, indicative of formation from a CO2-bearing fluid having a δ13Cfluid value of –4.6 ± 0.9‰. The δ13Cfluid values are indistinguishable from fluid inclusion CO2 values of –3.6 ± 0.9‰, indicating no post entrapment re-equilibration, which suggests that CH4 was at trace volumes or absent in the post-gold quartz veins. These data lead to the conclusion that post-entrapment reequilibration between fluid inclusion CO2 and CH4 has occurred, but that the two gases were likely in equilibrium at the time of entrapment. This has implications for the interpretation of C isotope studies that focus on fluid inclusion CO2 measured from other gold and base-metal deposits, especially when the isotopic value of that CO2 is assumed to represent a specific source for the ore-forming fluids. The data also lead to a model that proposes that the syn-gold alteration assemblage could have produced the soil-gas anomalies observed above the mineralization.

Most natural-forming calcites precipitate at isotopic equilibrium

Based on thermodynamic equilibrium isotope fractionation theory, this letter reasonably understands the clumping 13C-18O (Δ47 ), as well as carbon and oxygen isotope fractionation in calcites with extremely slow-growing rates from Devils Hole and Laghetto Basso (Corchia Cave) at atomic level with solid physical precipitation models and quantum-mechanical backgrounds. It is found that most calcites in nature precipitate in at equilibrium.

High-resolution carbon and oxygen isotope record in modern brachiopod Pictothyris picta collected off Okinoshima, Japan

<p>Carbon (δ<sup>13</sup>C) and oxygen (δ<sup>18</sup>O) isotope composition of Rhynchonelliformea brachiopods (hereafter, called ‘brachiopods’) have been regarded as useful paleoenvironmental indicators throughout the Phanerozoic. However, recent studies have revealed that the isotopic composition in modern brachiopod shells records not only environmental changes in ambient seawater but also is influenced by biological controls such as the chemical/isotopic composition of calcifying fluids and physiological processes (e.g., growth rates, metabolism). The latter is known as biological isotope fractionation effects, such as kinetic, metabolic, and pH effects. Recently, a new calcification mechanism in brachiopod shell formation, ion transport mechanism, was proposed. In this study, we measured δ<sup>13</sup>C and δ<sup>18</sup>O values of the primary (PL) and secondary (SL) shell layers of three <em>Pictothyris picta</em> (one male and two female specimens) collected at a water depth of~61 m off Okinoshima to improve our understanding of biological isotope fractionation effects during their shell secretion. We obtained ontogenetic-series δ<sup>13</sup>C and δ<sup>18</sup>O profiles from the PL (PL-Ont) and the uppermost SL (SL-Ont) at the sampling resolution of 3 days to 8 months per sample. We obtained inner-series δ<sup>13</sup>C and δ<sup>18</sup>O profiles from the innermost SL (SL-In) as well. The variations in the δ<sup>13</sup>C and δ<sup>18</sup>O profiles of the PL-Ont showed similar trends to those of the SL-Ont. However, the PL-Ont values mostly exhibited relatively lower δ<sup>18</sup>O values than those of the SL-Ont. Cross plots between the δ<sup>13</sup>C and δ<sup>18</sup>O values of the PL-Ont indicated a strong positive correlation and were lower than those of calcite precipitated in isotopic equilibrium with ambient seawater at the fast growth stage, suggesting the significant influence of the kinetic isotope fractionation effect. The SL was precipitated in oxygen isotopic equilibrium with ambient seawater regardless of the growth stage and/or the seasonal changes in living environments. Furthermore, the PL-Ont, SL-Ont, and SL-Inshowed similar δ<sup>18</sup>O values during the cold season, indicating negligible influences of the kinetic, pH, and magnesium effects on δ<sup>18</sup>O composition. The δ<sup>13</sup>C values of the PL-Ont formed at the cold season (= micro-portion formed under the least kinetic isotope fractionation effect) were lower than those of the SL, indicating the stronger metabolic effect on the PL secretion. Our isotopic data showed that the time lag of the PL and the SL formation varies among specimens.</p>

Carbon, oxygen and strontium isotope composition of Plattenkalk from the Upper Jurassic Wattendorf Konservat-Lagerstätte (Franconian Alb, Germany)

The oldest Jurassic (Kimmeridgian) Plattenkalk occurs in Wattendorf on the northern Franconian Alb (southern Germany). It is a 15 m thick alternation of laminated dolomite and limestone, interbedded with carbonate debris layers in a depression ~2 km across and a few tens of metres deeper than the surrounding microbial-sponge reefs. The Plattenkalk overlies a few tens of metres of microbial-sponge biostrome facies and bedded, micritic basinal limestone. The bulk-rock stable isotopes of the micritic basinal facies gradually change from normal marine (δ13C ~ +2‰, δ18O ~ –2‰ VPDB) to lower values (δ13C ~ 0‰, δ18O ~ –6‰) in a ~ 40 m thick interval including Plattenkalk and suggest ageing of the bottom waters. The surrounding reefs are isotopically nearly invariant (δ13C ~ +2‰, δ18O ~ –2‰ VPDB). An isotope anomaly (δ13C of > ~ –9‰) is restricted to the basinal facies and is most pronounced in the biostrome facies. This indicates methanogenesis, which is documented in negative δ13C in dedolomite, calcite-cemented dolomite and calcite concretions and occurred probably mainly below seabed. The Konservat-Lagerstätte was probably deposited near an oxygen minimum zone in a water column with low productivity of organic material. Dolomite is in isotopic equilibrium with Plattenkalk and was probably deposited as protodolomite from chemically modified, aged seawater. 87Sr/86Sr ratios of bulk carbonate are often slightly radiogenic, probably due to random analytical sample contamination by clay minerals. Belemnite and some matrix 87Sr/86Sr is slightly lower than that of Kimmeridgian seawater, either caused by basin restriction or by fluids derived from the diagenesis of Oxfordian rocks below. An equivalent Upper Kimmeridgian depression ~23 km distant and a somewhat younger Konservat-Lagerstätte in Poland show a δ13C isotope anomaly below the main fossil beds. Isotopic evidence for saline bottom waters, the current interpretation, is lacking. This study also shows that micritic carbonates can preserve their early diagenetic, marine δ18O signal, which is correlatable over tens of kilometres.