Identifying thermogenic and microbial methane in deep water Gulf of Mexico Reservoirs

The Gulf of Mexico (GOM) produces 5% of total U.S. dry gas production (USEIA, 2016). Despite this, the proportion of microbial and thermogenic methane in discovered and producing fields from this area is still not well understood. Understanding the relative contributions of these sources in subsurface environments is important to understanding how and where economically substantial amounts of methane form. In addition, this information will help identify sources of environmental emissions of hydrocarbons to the atmosphere. We apply stable isotopes including methane clumped-isotope measurements to solution and associated gases from several producing fields in the U.S. Gulf of Mexico to estimate the proportions, properties and origins of microbial and thermogenic endmembers. Clumped isotopes of methane are unique indicators of whether methane is at thermodynamic isotopic equilibrium or affected by kinetic processes. The clumped methane thermometer can provide insights into formation temperatures and/or into kinetic processes such as microbial methanogenesis, early catagenetic processes, mixing, combinatorial processes, and diffusion. In this data set, we find that some fluids have clumped isotope methane apparent temperatures consistent with the methane component being produced solely by the thermogenic breakdown of larger organic molecules at substantially greater temperatures than those reached in shallow reservoirs. A portion of these reservoirs with hot clumped isotope methane temperatures are consistent with exhibiting a kinetic isotope effect. Other reservoirs have clumped isotope methane apparent temperatures, and other isotopic and molecular proportions, consistent with mixtures of microbial and thermogenic methane. We show that in certain cases the evidence is most consistent with formation of the microbial methane in the current reservoir. However, in other cases the methane is produced at significantly shallower depths and is then transported to greater depths as a result of post generation burial of methane bearing sedimentary sequences to the current reservoir conditions. For the first time, we show that methane of an unambiguously purely microbial origin (i.e. those that do not contain obvious contributions of thermogenic methane) is dominantly generated at temperatures less than 60 °C, despite burial to greater depths. This finding suggests that, while microorganisms are able to generate methane at temperatures up to 105 °C under laboratory conditions (Brock, 1985), in the Gulf of Mexico, microbial methane is dominantly produced in the 20–60 °C window

Diagnóstico da área cultivada com uva fina de mesa (Vitis vinifera L.) sob cobertura plástica e do manejo de pragas.

Neste trabalho, foi realizado o censo das áreas cultivadas com uvas finas de mesa sob cultivo protegido e a identificação das principais espécies de pragas e estratégias de controle empregadas pelos produtores, no município de Caxias do Sul-RS. Na safra de 2007/2008, foram identificados os produtores envolvidos com a atividade no município e através de entrevista presencial e semiestruturada ao estabelecimento produtivo, registrou-se a área cultivada e variedades. Para produtores com cultivo de áreas superiores a 2.000m2 da cultivar Itália, com dois anos ou mais de produção, foi aplicado outro questionário na safra de 2008/2009 com o objetivo de levantar as informações referentes: a) espécies de insetos e ácarospraga que danificam as uvas finas de mesa na propriedade, segundo o viticultor; b) conhecer a realidade do manejo de insetos e ácaros-praga na cultura; c) verificar os parâmetros que o produtor utiliza para a aplicação de inseticidas; d) conhecer os produtos aplicados, e e) identificar o tipo de assistência técnica recebida pelo viticultor. Foram identificados 43 produtores de uvas finas de mesa sob cultivo protegido com área total cultivada de 30,36 ha, sendo 70,31% desta área da cultivar Itália. As pragas mais importantes mencionadas pelos produtores foram tripes - Frankliniella rodeos Moulton e a mosca-das-frutas-sul-americana Anastrepha fraterculus (Wied). O manejo realizado para controle destas pragas é através da aplicação de inseticidas com os ingredientes ativos acefato e fentiona, respectivamente, com base em calendário. Os principais problemas enfrentados para implementar estratégias de manejo de pragas no cultivo são a falta de assistência técnica, a ausência de metodologias confiáveis para o monitoramento e o reduzido número de inseticidas autorizados para a cultura

Isotopic evidence for quasi-equilibrium chemistry in thermally mature natural gases

Natural gas is a key energy resource, and understanding how it forms is important for predicting where it forms in economically important volumes. However, the origin of dry thermogenic natural gas is one of the most controversial topics in petroleum geochemistry, with several differing hypotheses proposed, including kinetic processes (such as thermal cleavage, phase partitioning during migration, and demethylation of aromatic rings) and equilibrium processes (such as transition metal catalysis). The dominant paradigm is that it is a product of kinetically controlled cracking of long-chain hydrocarbons. Here we show that C₂₊ n-alkane gases (ethane, propane, butane, and pentane) are initially produced by irreversible cracking chemistry, but, as thermal maturity increases, the isotopic distribution of these species approaches thermodynamic equilibrium, either at the conditions of gas formation or during reservoir storage, becoming indistinguishable from equilibrium in the most thermally mature gases. We also find that the pair of CO₂ and C₁ (methane) exhibit a separate pattern of mutual isotopic equilibrium (generally at reservoir conditions), suggesting that they form a second, quasi-equilibrated population, separate from the C₂ to C₅ compounds. This conclusion implies that new approaches should be taken to predicting the compositions of natural gases as functions of time, temperature, and source substrate. Additionally, an isotopically equilibrated state can serve as a reference frame for recognizing many secondary processes that may modify natural gases after their formation, such as biodegradation

Position-Specific Hydrogen Isotope Equilibrium in Propane

Intramolecular isotope distributions can constrain source attribution, mechanisms of formation and destruction, and temperature-time histories of molecules. In this study, we explore the D/H fractionation between central (-CH_2-) and terminal (-CH_3) positions of propane (C_3H_8)- a percent level component of natural gases. The temperature dependenceof position-specific D/H fractionation of propane could potentially work as a geo-thermometer for natural gas systems, and a forensic identifier of specific thermogenic sources of atmospheric or aquatic emissions. Moreover, kinetically controlled departures from temperature dependent equilibrium might constrain mechanisms of thermogenic production, or provide indicators of biological or photochemical destruction. We developed a method to measure position-specific D/H differences of propane with high-resolution gas source mass spectrometry. We performed laboratory exchange experiments to study the exchange ratesfor both terminal and central positions, and used catalysts to drive the hydrogen isotopedistribution of propane to thermodynamic equilibrium. Experimental results demonstrate that D/H exchange between propane and water happens easily in the presence of either Pd catalyst or Ni catalyst. Exchange rates are similar between the two positions catalyzed by Pd. However, the central position exchanges 2.2 times faster than the terminal position in the presence of Ni catalyst. At 200 °C in the presence of Pd catalyst, the e-folding time of propane-water exchange is 20 days and of homogeneous exchange (i.e., equilibrium between central and terminal positions) is 28 min. An equilibrated (bracketed and time-invariant) intramolecular hydrogen isotope distribution was attained for propane at three temperatures, 30 °C, 100 °C and 200 °C; these data serve as an initial experimental calibration of a new position-specific thermometer with a temperature sensitivity of 0.25‰ per °C at 100 °C. We use this calibration to test the validity of prior published theoretical predictions. Comparison of data with models suggest the most sophisticated of these discrepant models (Webb and Miller, 2014) is most accurate; this conclusion implies that there is a combined experimental and theoretical foundation for an ‘absolute reference frame’ for position-specific H isotope analysis of propane, following principles previously used for clumped isotope analysis of CO_2, CH_4 and O_2 (Eiler and Schauble, 2004; Yeung et al., 2014; Stolper et al., 2014)