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At least 325 records · Page 18

Mechanisms for Methane Transport and Hydrate Accumulation in Coarse-Grained Reservoirs

The distribution of natural methane hydrate within high saturation reservoirs and mechanisms that control the migration of methane are an active area of research. In this project, we studied methane migration mechanisms and associated hydrate accumulation rates in coarse-grained sands of the Terrebonne Basin, located in Walker Ridge Block 313 (WR313), northern Gulf of Mexico. Hydrate in this area is distributed heterogeneously within ~900 m of methane hydrate stability zone, in both thick (10-25 m) and thin (< 3 m) sand layers, and in units of subvertical hydrate-filled fractures. We investigated hydrate formation from diffusively and advectively supplied methane using one-, two-, and three-dimensional basin modeling with inputs from well log and seismic data. The hydrate accumulations at WR313 can mostly be explained by short, diffusive migration of methane as well as short-range advective transport of methane from clays into neighboring coarser-grained layers. This is likely enhanced by small-scale lithologic variations, including local microbial methanogenesis in interbedded clays. Furthermore, our work shows overpressure in clay sediments surrounding sand reservoirs may enhance short-range diffusive migration. Long-range migration of dissolved methane and gas mainly influence hydrate saturation right at the base of the hydrate stability zone, although the dissolved phase can be channeled upwards along sands by compaction-driven flow. Capillary effects can allow gas bubbles to migrate appreciable distances above the predicted base of gas hydrate stability, possibly reaching a few tens of meters into the hydrate stability zone. Recycling methane from hydrate buried beneath the base of the hydrate stability zone can concentrate hydrate at large saturations within a few tens of meters of the base of hydrate stability.

58 GEOSCIENCES↗

Highly Efficient Non-Oxidative Methane Conversion with Continuous Hydrogen Removal

A non-oxidative methane conversion catalytic system has been successfully developed. Ball-milling and annealing above 1973 K are necessary in order to synthesize the unique methane activation catalyst. Characterization and evaluation of catalysts shows that the surface area should be carefully controlled to minimize coke deposition. The influence of temperature, pressure, space velocity and hydrogen concentration on catalytic process was systematically studied. The reaction conditions were optimized to a combination of 1323 K, ambient pressure and a space velocity of 4900 ml/g·h. A process, using 0.5% Fe/SiO 2 catalyst under these conditions, yield a methane conversion of 15.62%, with product distribution of 40.05% C 2 , 26.48% BTX and 10.7% naphthalene and demonstrated stable operation of at least 50 hours. This result meets the milestone in the phase I proposal. A non-oxidative methane catalyst-integrated SOFC reactor was accomplished, using nickel-free cells of both ScSZ oxygen-ion conductor and BZY proton conductor. With in-situ hydrogen removal enabled by SOFC, hydrogen concentration in the reactor was effectively reduced, shifting reaction equilibrium and boosting methane conversion. However, due to the high temperature requirement of this reaction, most available proton-conducting SOFCs become oxygen-ion conducting, leading to side reactions and counteracting the benefits from hydrogen removal. To take advantage of the enhanced oxygen-ion conductance of SOFC at high temperatures, we have also paired the nickel-free SOFCs with high-performance oxidative coupling of methane (OCM) catalysts. The SOFC-OCM tubular membrane reactor, employing a Mn-Ce-Na 2 WO 4 /SiO 2 -based catalyst, demonstrates a remarkable performance of 60.7% methane conversion with 41.6% C 2 + selectivity, 5.8 ethylene-to-ethane ratio and 19.4% ethylene yield. The use of integrated SOFC-OCM reactor enables better hydrocarbon selectivity and higher ethylene-to-ethane ratio, eliminating the need of an expensive air separation unit and preventing the direct co-feed of explosive methane-oxygen mixture. We believe this presents a great promise towards commercialization as an advanced methane conversion technology.

02 PETROLEUM↗

Monitoring, Understanding, and Predicting the Growth of Methane Emissions in the Arctic

Concern over Arctic methane (CH 4 ) emissions has increased following recent discoveries of poorly understood sources and predictions that methane emissions from known sources will grow as Arctic temperatures increase. New efforts are required to detect increases and explain sources without being confounded by the multiple sources. Methods for distinguishing different sources are critical. We conducted measurements of atmospheric methane and source tracers and performed baseline global atmospheric modeling to begin assessing the climate impact of changes in atmospheric methane. The goal of this project was to address uncertainties in Arctic methane sources and their potential impact on climate by (1) deploying newly developed trace-gas analyzers for measurements of methane, methane isotopologues, ethane, and other tracers of methane sources in the Barrow, AK, (2) characterizing methane sources using high-resolution atmospheric chemical transport models and tracer measurements, and (3) modeling Arctic climate using the state-of-the-art high- resolution Spectral Element Community Atmosphere Model (CAM-SE).

54 ENVIRONMENTAL SCIENCES↗

Biological methane production and accumulation under sulfate-rich conditions at Cape Lookout Bight, NC

Introduction: Anaerobic oxidation of methane (AOM) is hypothesized to occur through reverse hydrogenotrophic methanogenesis in marine sediments because sulfate reducers pull hydrogen concentrations so low that reverse hydrogenotrophic methanogenesis is exergonic. If true, hydrogenotrophic methanogenesis can theoretically co-occur with sulfate reduction if the organic matter is so labile that fermenters produce more hydrogen than sulfate reducers can consume, causing hydrogen concentrations to rise. Finding accumulation of biologically-produced methane in sulfate-containing organic-rich sediments would therefore support the theory that AOM occurs through reverse hydrogenotrophic methanogenesis since it would signal the absence of net AOM in the presence of sulfate. Methods: 16S rRNA gene libraries were compared to geochemistry and incubations in high depth-resolution sediment cores collected from organic-rich Cape Lookout Bight, North Carolina. Results: We found that methane began to accumulate while sulfate is still abundant (6–8 mM). Methane-cycling archaea ANME-1, Methanosarciniales, and Methanomicrobiales also increased at these depths. Incubations showed that methane production in the upper 16 cm in sulfate-rich sediments was biotic since it could be inhibited by 2-bromoethanosulfonoic acid (BES). Discussion: We conclude that methanogens mediate biological methane production in these organic-rich sediments at sulfate concentrations that inhibit methanogenesis in sediments with less labile organic matter, and that methane accumulation and growth of methanogens can occur under these conditions as well. Our data supports the theory that H2 concentrations, rather than the cooccurrence of sulfate and methane, control whether methanogenesis or AOM via reverse hydrogenotrophic methanogenesis occurs. We hypothesize that the high amount of labile organic matter at this site prevents AOM, allowing methane accumulation when sulfate is low but still present in mM concentrations

59 BASIC BIOLOGICAL SCIENCES↗

A model of the methane cycle, permafrost, and hydrology of the Siberian continental margin

A two-dimensional model of a sediment column, with Darcy fluid flow, biological and thermal methane production, and permafrost and methane hydrate formation, is subjected to glacial–interglacial cycles in sea level, alternately exposing the continental shelf to the cold atmosphere during glacial times and immersing it in the ocean in interglacial times. The glacial cycles are followed by a "long-tail" 100 kyr warming due to fossil fuel combustion. The salinity of the sediment column in the interior of the shelf can be decreased by hydrological forcing to depths well below sea level when the sediment is exposed to the atmosphere. There is no analogous advective seawater-injecting mechanism upon resubmergence, only slower diffusive mechanisms. This hydrological ratchet is consistent with the existence of freshwater beneath the sea floor on continental shelves around the world, left over from the last glacial period. The salt content of the sediment column affects the relative proportions of the solid and fluid H 2 O-containing phases, but in the permafrost zone the salinity in the pore fluid brine is a function of temperature only, controlled by equilibrium with ice. Ice can tolerate a higher salinity in the pore fluid than methane hydrate can at low pressure and temperature, excluding methane hydrate from thermodynamic stability in the permafrost zone. The implication is that any methane hydrate existing today will be insulated from anthropogenic climate change by hundreds of meters of sediment, resulting in a response time of thousands of years. The strongest impact of the glacial–interglacial cycles on the atmospheric methane flux is due to bubbles dissolving in the ocean when sea level is high. When sea level is low and the sediment surface is exposed to the atmosphere, the atmospheric flux is sensitive to whether permafrost inhibits bubble migration in the model. If it does, the atmospheric flux is highest during the glaciating, sea level regression (soil-freezing) part of the cycle rather than during deglacial transgression (warming and thawing). The atmospheric flux response to a warming climate is small, relative to the rest of the methane sources to the atmosphere in the global budget, because of the ongoing flooding of the continental shelf. The increased methane flux due to ocean warming could be completely counteracted by a sea level rise of tens of meters on millennial timescales due to the loss of ice sheets, decreasing the efficiency of bubble transit through the water column. The model results give no indication of a mechanism by which methane emissions from the Siberian continental shelf could have a significant impact on the near-term evolution of Earth's climate, but on millennial timescales the release of carbon from hydrate and permafrost could contribute significantly to the fossil fuel carbon burden in the atmosphere–ocean–terrestrial carbon cycle.

Archer, D.↗

Environmental controls on ecosystem-scale cold-season methane and carbon dioxide fluxes in an Arctic tundra ecosystem

Abstract. Understanding the processes that influence and control carbon cycling in Arctic tundra ecosystems is essential for making accurate predictions about what role these ecosystems will play in potential future climate change scenarios. Particularly, air–surface fluxes of methane and carbon dioxide are of interest as recent observations suggest that the vast stores of soil carbon found in the Arctic tundra are becoming more available to release to the atmosphere in the form of these greenhouse gases. Further, harsh wintertime conditions and complex logistics have limited the number of year-round and cold-season studies and hence too our understanding of carbon cycle processes during these periods. We present here a two-year micrometeorological data set of methane and carbon dioxide fluxes, along with supporting soil pore gas profiles, that provide near-continuous data throughout the active summer and cold winter seasons. Net emission of methane and carbon dioxide in one of the study years totalled 3.7 and 89 g C m−2 a−1 respectively, with cold-season methane emission representing 54 % of the annual total. In the other year, net emission totals of methane and carbon dioxide were 4.9 and 485 g C m−2 a−1 respectively, with cold-season methane emission here representing 82 % of the annual total – a larger proportion than has been previously reported in the Arctic tundra. Regression tree analysis suggests that, due to relatively warmer air temperatures and deeper snow depths, deeper soil horizons – where most microbial methanogenic activity takes place – remained warm enough to maintain efficient methane production whilst surface soil temperatures were simultaneously cold enough to limit microbial methanotrophic activity. These results provide valuable insight into how a changing Arctic climate may impact methane emission, and highlight a need to focus on soil temperatures throughout the entire active soil profile, rather than rely on air temperature as a proxy for modelling temperature–methane flux dynamics.

54 ENVIRONMENTAL SCIENCES↗

Methane oxidation in Saanich Inlet during summer stratification

Saanich Inlet, British Columbia, an fjord on the southeast coast of Vancouver Island, typically stratifies in summer, leading to the formation of an oxic-anoxic interface in the water column and accumulation of methane in the deep water. The results of methane concentration measurements in the water column of the inlet at various times throughout the summer months in 1983 are presented. Methane gradients and calculated diffusive fluxes across the oxic-anoxic interface increased as the summer progressed. Methane distribution and consumption in Saanich Inlet were studied in more detail during August 1986. At this time, a typical summer stratification with an oxic-anoxic interface around 140 m was present. At the interface, steep gradients in nutrient concentrations, bacterial abundance and methane concentration were observed. Methane oxidation was detected in the aerobic surface waters and in the anaerobic deep layer, but highest rates occurred in a narrow layer at the oxic-anoxic interface. Estimated methane oxidation rates were suffcient to consume 100 percent of the methane provided by diffusive flux from the anoxic layer. Methane oxidation is thus a mechanism whereby atmospheric flux from anoxic waters is minimized.

Ward, B. B.↗

Methane Production and Transport within the Marsh Biome of Biosphere 2

In recent decades, the concentration of methane in the earth's atmosphere increased 1-2% annually. It's rate of increases, combined with methane's effectiveness as a greenhouse gas, has led to an intensive research effort to determine the sources and sinks of the gas in the environment. Biosphere 2 offers a unique opportunity to contribute to the effort because it lacks a major photochemical sink present in the Earth's atmosphere. Researchers can therefore concentrate on biological processes involved in methane cycles. Wetlands are a large source of atmospheric methane, due to anoxic conditions in the sediments and the abundance of organic materials. In order to determine if these conditions in Biosphere 2 also promote methane production, this study looked for the fluxes of methane and methods of transport of the gas from from the water and sediments to the atmosphere in the Marsh Biome. Fluxes of methane from the sediments and waters were measured using static chambers, peepers, and leaf bags. Fluxes and vertical profiles of methane in the sediments show that substantial amounts of methane are being produced in the marsh and are being transported into the Biosphere 2 environment.

Molnar, Jennifer↗

A Process-based, Climate-Sensitive Model to Derive Methane Emissions from Natural Wetlands: Application to 5 Wetland Sites, Sensitivity to Model Parameters and Climate

Methane emissions from natural wetlands constitutes the largest methane source at present and depends highly on the climate. In order to investigate the response of methane emissions from natural wetlands to climate variations, a 1-dimensional process-based climate-sensitive model to derive methane emissions from natural wetlands is developed. In the model the processes leading to methane emission are simulated within a 1-dimensional soil column and the three different transport mechanisms diffusion, plant-mediated transport and ebullition are modeled explicitly. The model forcing consists of daily values of soil temperature, water table and Net Primary Productivity, and at permafrost sites the thaw depth is included. The methane model is tested using observational data obtained at 5 wetland sites located in North America, Europe and Central America, representing a large variety of environmental conditions. It can be shown that in most cases seasonal variations in methane emissions can be explained by the combined effect of changes in soil temperature and the position of the water table. Our results also show that a process-based approach is needed, because there is no simple relationship between these controlling factors and methane emissions that applies to a variety of wetland sites. The sensitivity of the model to the choice of key model parameters is tested and further sensitivity tests are performed to demonstrate how methane emissions from wetlands respond to climate variations.

Walter, Bernadette P.↗

Modeling Modern Methane Emissions from Natural Wetlands: Model Description and Results - 1

Methane is an important greenhouse gas which contributes about 22 percent to the present greenhouse effect. Natural wetlands currently constitute the biggest methane source and were the major source in preindustrial times. Wetland emissions depend highly on the climate, i.e., on soil temperature and water table. To investigate the response of methane emissions from natural wetlands to climate variations, a process-based model that derives methane emissions from natural wetlands as a function of soil temperature, water table, and net primary productivity is used. For its application on the global scale, global data sets for all model parameters are generated. In addition, a simple hydrologic model is developed in order to simulate the position of the water table in wetlands. The hydrologic model is tested against data from different wetland sites, and the sensitivity of the hydrologic model to changes in precipitation is examined. The global methane­ hydrology model constitutes a tool to study temporal and spatial variations in methane emissions from natural wetlands. The model is applied using high-frequency atmospheric forcing fields from European Center for Medium-range Weather Forecasts (ECMWF) re-analyses of the period from 1982 to 1993. We calculate global annual methane emissions from wetlands to be 260 teragrams per year. Twenty-five percent of these methane emissions originate from wetlands north of 30 degrees North Latitude. Only 60 percent of the produced methane is emitted, while the rest is re-oxidized. A comparison of zonal integrals of simulated global wetland emissions and results obtained by an inverse modeling approach shows good agreement. In a test with data from two wetlands the seasonality of simulated and observed methane emissions agrees well.

Biogeochemical processes↗

The Global Methane Budget 2000-2012

The global methane (CH4) budget is becoming an increasingly important component for managing realistic pathways to mitigate climate change. This relevance, due to a shorter atmospheric lifetime and a stronger warming potential than carbon dioxide, is challenged by the still unexplained changes of atmospheric CH4 over the past decade. Emissions and concentrations of CH4 are continuing to increase, making CH4 the second most important human-induced greenhouse gas after carbon dioxide. Two major difficulties in reducing uncertainties come from the large variety of diffusive CH4 sources that overlap geographically, and from the destruction of CH4 by the very short-lived hydroxyl radical (OH). To address these difficulties, we have established a consortium of multi-disciplinary scientists under the umbrella of the Global Carbon Project to synthesize and stimulate research on the methane cycle, and producing regular (approximately biennial) updates of the global methane budget. This consortium includes atmospheric physicists and chemists, biogeochemists of surface and marine emissions, and socio-economists who study anthropogenic emissions. Following Kirschke et al. (2013), we propose here the first version of a living review paper that integrates results of top-down studies (exploiting atmospheric observations within an atmospheric inverse-modeling framework) and bottom-up models, inventories and data-driven approaches (including process-based models for estimating land surface emissions and atmospheric chemistry, and inventories for anthropogenic emissions, data-driven extrapolations).For the 2003-2012 decade, global methane emissions are estimated by top-down inversions at 558 TgCH4 yr(exp -1), range 540-568. About 60 of global emissions are anthropogenic (range 50-65%). Since 2010, the bottom-up global emission inventories have been closer to methane emissions in the most carbon-intensive Representative Concentrations Pathway (RCP8.5) and higher than all other RCP scenarios. Bottom-up approaches suggest larger global emissions (736 TgCH4 yr(exp -1), range 596-884) mostly because of larger natural emissions from individual sources such as inland waters, natural wetlands and geological sources. Considering the atmospheric constraints on the top-down budget, it is likely that some of the individual emissions reported by the bottom-up approaches are overestimated, leading to too large global emissions. Latitudinal data from top-down emissions indicate a predominance of tropical emissions (approximately 64% of the global budget, less than 30deg N) as compared to mid (approximately 32%, 30-60deg N) and high northern latitudes (approximately 4%, 60-90deg N). Top-down inversions consistently infer lower emissions in China (approximately 58 TgCH4 yr(exp -1), range 51-72, minus14% ) and higher emissions in Africa (86 TgCH4 yr(exp -1), range 73-108, plus 19% ) than bottom-up values used as prior estimates. Overall, uncertainties for anthropogenic emissions appear smaller than those from natural sources, and the uncertainties on source categories appear larger for top-down inversions than for bottom-up inventories and models. The most important source of uncertainty on the methane budget is attributable to emissions from wetland and other inland waters. We show that the wetland extent could contribute 30-40% on the estimated range for wetland emissions. Other priorities for improving the methane budget include the following: (i) the development of process-based models for inland-water emissions, (ii) the intensification of methane observations at local scale (flux measurements) to constrain bottom-up land surface models, and at regional scale (surface networks and satellites) to constrain top-down inversions, (iii) improvements in the estimation of atmospheric loss by OH, and (iv) improvements of the transport models integrated in top-down inversions. The data presented here can be downloaded from the Carbon Dioxide Information Analysis Center (http://doi.org/10.3334/CDIAC/GLOBAL_ METHANE_BUDGET_2016_V1.1) and the Global Carbon Project.

Saunois, Marielle↗

Cometary Origin of Atmospheric Methane Variations on Mars Unlikely

The detection of methane in the atmosphere of Mars was first reported in 2004. Since then a number of independent observations of methane have been reported, all showing temporal variability. Up until recently, the origin of methane was attributed to sources either indigenous to Mars or exogenous, where methane is a UV degradation byproduct of organics falling on to the surface. Most recently, a new hypothesis has been proposed that argues that the appearance and variation of methane are correlated with specific meteor events at Mars. Indeed, extraplanetary material can be brought to a planet when it passes through a meteoroid stream left behind by cometary bodies orbiting the Sun. This occurs repeatedly at specific times in a planet's year as streams tend to be fairly stable in space. In this paper, we revisit this latest hypothesis by carrying out a complete analysis of all available data on Mars atmospheric methane, including the very recent data not previously published, together with all published predicted meteor events for Mars. Whether we consider the collection of individual data points and predicted meteor events, whether we apply statistical analysis, or whether we consider different time spans between high methane measurements and the occurrence of meteor events, we find no compelling evidence for any correlation between atmospheric methane and predicted meteor events.

methane↗

Incentives for Methane Mitigation and Energy-Efficiency Improvements in Case of Ukraine’s Natural Gas Transmission System

Reducing methane losses is a concern for climate change policy and energy policy. The energy sector is the major source of methane emissions into the atmosphere. Reducing methane emissions and avoiding combustion can be very cost-effective, but various barriers prevent such energy-efficiency measures from taking place. To date, few examples of industry-wide improvements exist. One example of substantial investments into upgrading natural gas transmission system comes from Ukraine. The Ukrainian transmission company, Ukrtransgaz, reduced its own system’s natural gas consumption by 68 percent in 2011 compared to the level in 2005. Evaluating reductions in methane emissions is challenging because of lack of accurate data and gaps in accounting methodologies. At the same time, Ukraine’s transmission system has undergone improvements that, at the very least, have contained methane emissions, if not substantially reduced them. In this paper, we describe recent developments in Ukraine’s natural gas transmission system and analyze the incentives that forced the sector to pay close attention to its methane losses. Ukraine is one of most energy-intensive countries, among the largest natural gas consumers in the world, and a significant emitter of methane. The country is also dependent on imports of natural gas. A combination of steep increases in the price of imported natural gas, and comprehensive domestic environmental and energy policies, regional integration policy, and international environmental agreements has created conditions for successful methane emission and combustion reductions. Learning about such case studies can help us design better policies elsewhere.

Methane Mitigation, Energy Efficiency, Ukraine, Na↗

Methane emissions from pan-Arctic lakes during the 21st century: An analysis with process-based models of lake evolution and biogeochemistry

The importance of methane emissions from pan-Arctic lakes in the global carbon cycle has been suggested by recent studies. These studies indicated that climate change influences this methane source mainly in two ways: the warming of lake sediments and the evolution of thermokarst lakes. Few studies have been conducted to quantify the two impacts together in a unified modeling framework. Here we adapt a region-specific lake evolution model to the pan-Arctic scale and couple it with a lake methane biogeochemical model to quantify the change of this freshwater methane source in the 21st century. Our simulations show that the extent of thaw lakes will increase throughout the 21st century in the northern lowlands of the pan-Arctic where the reworking of epigenetic ice in drained lake basins will continue. The projected methane emissions by 2100 are 28.3 ± 4.5 Tg CH 4 yr -1 under a low warming scenario (Representative Concentration Pathways (RCPs) 2.6) and 32.7±5.2 Tg CH 4 yr -1 under a high warming scenario (RCP 8.5), which are about 2.5 and 2.9 times the simulated present-day emissions. Most of the emitted methane originates from nonpermafrost carbon stock. For permafrost carbon, the methanogenesis will mineralize a cumulative amount of 3.4 ± 0.8 Pg C under RCP 2.6 and 3.9 ± 0.9 Pg C under RCP 8.5 from 2006 to 2099. The projected emissions could increase atmospheric methane concentrations by 55.0–69.3 ppb. In conclusion, this study further indicates that the warming of lake sediments dominates the increase of methane emissions from pan-Arctic lakes in the future.

54 ENVIRONMENTAL SCIENCES↗

Data-Constrained Projections of Methane Fluxes in a Northern Minnesota Peatland in Response to Elevated CO 2 and Warming

Large uncertainties exist in predicting responses of wetland methane (CH 4 ) fluxes to future climate change. However, sources of the uncertainty have not been clearly identified despite the fact that methane production and emission processes have been extensively explored. In this study, we took advantage of manual CH 4 flux measurements under ambient environment from 2011 to 2014 at the Spruce and Peatland Responses Under Changing Environments (SPRUCE) experimental site and developed a data-informed process-based methane module. The module was incorporated into the Terrestrial ECOsystem (TECO) model before its parameters were constrained with multiple years of methane flux data for forecasting CH 4 emission under five warming and two elevated CO 2 treatments at SPRUCE. We found that 9°C warming treatments significantly increased methane emission by approximately 400%, and elevated CO 2 treatments stimulated methane emission by 10.4%–23.6% in comparison with ambient conditions. The relative contribution of plant-mediated transport to methane emission decreased from 96% at the control to 92% at the 9°C warming, largely to compensate for an increase in ebullition. The uncertainty in plant-mediated transportation and ebullition increased with warming and contributed to the overall changes of emissions uncertainties. At the same time, our modeling results indicated a significant increase in the emitted CH 4 :CO 2 ratio. This result, together with the larger warming potential of CH 4 , will lead to a strong positive feedback from terrestrial ecosystems to climate warming. In conclusion, the model-data fusion approach used in this study enabled parameter estimation and uncertainty quantification for forecasting methane fluxes.

58 GEOSCIENCES↗

Temporal variations of methane concentration and isotopic composition in groundwater of the St. Lawrence Lowlands, eastern Canada

Dissolved methane concentrations in shallow groundwater are known to vary both spatially and temporally. The extent of these variations is poorly documented although this knowledge is critical for distinguishing natural fluctuations from anthropogenic impacts stemming from oil and gas activities. This issue was addressed as part of a groundwater research project aiming to assess the risk of shale gas development for groundwater quality over a 500-km{sup 2} area in the St. Lawrence Lowlands (Quebec, Canada). A specific study was carried out to define the natural variability of methane concentrations and carbon and hydrogen isotope ratios in groundwater, as dissolved methane is naturally ubiquitous in aquifers of this area. Monitoring was carried out over a period of up to 2.5 years in seven monitoring wells. Results showed that for a given well, using the same sampling depth and technique, methane concentrations can vary over time from 2.5 to 6 times relative to the lowest recorded value. Methane isotopic composition, which is a useful tool to distinguish gas origin, was found to be stable for most wells, but varied significantly over time in the two wells where methane concentrations are the lowest. The use of concentration ratios, as well as isotopic composition of methane and dissolved inorganic carbon (DIC), helped unravel the processes responsible for these variations. This study indicates that both methane concentrations and isotopic composition, as well as DIC isotopes, should be regularly monitored over at least 1 year to establish their potential natural variations prior to hydrocarbon development.

54 ENVIRONMENTAL SCIENCES↗

Co-aromatization of methane with olefins: The role of inner pore and external surface catalytic sites

The co-aromatization of methane with olefins is investigated using Ag-Ga/HZSM-5 as the catalyst at 400 degrees C. The presence of methane has a pronounced effect on the product distribution in terms of increased average carbon number and substitution index and decreased aromatic carbon fraction compared with its N2 environment counterpart. The participation of methane during the co-aromatization over the Ag-Ga/HZSM-5 catalyst diminishes as the co-fed olefin feedstock molecule becomes larger, from 1-hexene to 1-octene and 1-decene, in diameter. The effect of suppressed methane participation with larger olefinic molecules is not as significant when Ag-Ga/HY is employed as the catalyst, which might be attributed to the larger pore size of HY that gives more room to hold olefin and methane molecules within the inner pores and reduces the diffusion limitation of olefin molecules. The effect of olefin feedstock on the methane participation during the co-aromatization over Ag-Ga/HZSM-5 is experimentally evidenced by 13C and 2D NMR. The incorporation of the methane carbon atoms into the phenyl ring of product molecules is reduced significantly with larger co-fed olefins, whereas its incorporation into the substitution groups of the formed aromatic molecules is not notably affected, suggesting that the methane participation in the phenyl ring formation might preferably occur within inner pores, while its incorporation into substitution groups may mainly take place on external catalytic sites. This hypothesis is well supported by the product selectivity obtained over Ag-Ga/HZSM-5 catalysts prepared using conventional ZSM-5, ZSM-5 with the external catalytic sites deactivated, nanosize ZSM-5, ZSM-5 with a micro/meso pore structure and ZSM-5 with the inner pores blocked, and further confirmed by the isotopic labeling studies.

09 BIOMASS FUELS↗

Pore accessibility and trapping of methane in Marcellus shale

Accessibility of pore space in unconventional reservoirs is an important factor influencing both methane storage capacity and the kinetics of methane desorption. The determination of open (accessible) versus closed (inaccessible) porosity is therefore vital for the prediction of gas production potential. This study investigates accessibility of pores to methane in overmature middle Devonian Marcellus shale samples (cut parallel and perpendicular to bedding) using small and ultra-small neutron scattering (SANS and USANS) with contrast matching (CM), supplemented by other complementary techniques, such as mercury injection capillary pressure (MICP) and low pressure gas (N2 and CO2) adsorption. Our results demonstrate that for the samples studied, only about 6 % of pores with diameter 25-500 nm are accessible to methane. The accessibility fraction for pores larger than 500 nm is 35%. For nanopores smaller than 25 nm, pore accessibility could not be quantitatively determined due to increased methane density and condensation effects in confinement. Our observations indicate that methane penetrates the accessible small mesopores and micropores down to at least 1 nm in diameter, and the density of confined deuterated methane (CD4) is 0.68 g/cm3 for pores of diameter 25 nm and gradually increases with the decreased pore size. Moreover, elevated gas pressure causes formation of additional high-density methane nano-clusters. These clusters have a form of slightly anisotropic polydisperse discs oriented along bedding plane, about 1-12 nm in diameter and with average thickness of 3.6 nm. Utilizing samples cut parallel and perpendicular to the bedding, this study also briefly addresses anisotropy of pores. Based on the iso-size intensity ratio R, our SANS and USANS results demonstrate anisotropy in the out-of-bedding direction and suggest that the degree of anisotropy depends on the pore size. Specifically, for pore diameters ~2.5 to 250 nm, the extent of anisotropy is smaller than for pores ~500 nm to 6 µm in diameter. Finally, comparison of pore size distribution results calculated from SANS/USANS to those obtained using MICP shows good agreement at low pressures, but large difference at pressures above 1000 bar. Here, this discrepancy requires further testing; it is possible that the high mercury pressure used in MICP alters the mesopore and micropore structure of shales.

03 NATURAL GAS↗