Anna M. Martini

Microbial production and modification of gases in sedimentary basins: A geochemical case study from a Devonian shale gas play, Michigan basin

An expanded data set for gases produced from the Antrim Shale, a Devonian black shale in the Michigan basin, United States, has allowed for a detailed examination of the related chemical and isotopic compositional changes in the solid-gas-liquid systems that discriminate between microbial and thermogenic gas origin. In the Antrim Shale, economic microbial gas deposits are located near the basin margins where the shale has a relatively low thermal maturity and fresh water infiltrates the permeable fracture network. The most compelling evidence for microbial generation is the correlation between deuterium in methane and coproduced water. Along the basin margins, there is also a systematic enrichment in 13C of ethane and propane with decreasing concentrations that suggests microbial oxidation of these thermogenic gas components. Microbial oxidation accounts not only for the shift in 13C values for ethane, but also, in part, for the geographic trend in gas composition as ethane and higher chain hydrocarbons are preferentially removed. This oxidation is likely an anaerobic process involving a syntrophic relationship between methanogens and sulfate-reducing bacteria.The results of this study are integrated into a predictive model for microbial gas exploration based on key geochemical indicators that are present in both gas and coproduced water. One unequivocal signature of microbial methanogenesis is the extremely positive carbon isotope values for both the dissolved inorganic carbon in the water and the coproduced CO2 gas. In contrast, the 13C value of methane is of limited use in these reservoirs as the values typically fall between the commonly accepted fields for thermogenic and microbial gas. In addition, the confounding isotopic and compositional overprint of microbial oxidation, increasing the values to typically thermogenic values, may obscure the distinction between methanogenic and thermogenic gas.

Pleistocene recharge to midcontinent basins: effects on salinity structure and microbial gas generation

The hydrogeochemistry of saline-meteoric water interface zones in sedimentary basins is important in constraining the fluid migration history, chemical evolution of basinal brines, and physical stability of saline formation waters during episodes of freshwater recharge. This is especially germane for interior cratonic basins, such as the Michigan and Illinois basins. Although there are large differences in formation water salinity and hydrostratigraphy in these basins, both are relatively quiescent tectonically and have experienced repeated cycles of glaciation during the Pleistocene. Exploration for unconventional microbial gas deposits, which began in the upper Devonian-age Antrim Shale at the northern margin of the Michigan Basin, has recently extended into the age-equivalent New Albany Shale of the neighboring Illinois Basin, providing access to heretofore unavailable fluid samples. These reveal an extensive regional recharge system that has profoundly changed the salinity structure and induced significant biogeochemical modification of formation water elemental and isotope geochemistry. New-formation water and gas samples were obtained from Devonian-Mississippian strata in the Illinois Basin. These included exploration wells in the New Albany Shale, an organic-rich black shale of upper Devonian age, and formation waters from over- and underlying regional aquifer systems (Siluro-Devonian and Mississippian age). The hydrostratigraphic relations of major aquifers and aquitards along the eastern margin of the Illinois Basin critically influenced fluid migration into the New Albany Shale. The New Albany Shale formation water chemistry indicates significant invasion of meteoric water, with δD values as low as −46.05‰, into the shale. The carbon stable isotope system (δ13C values as high as 29.4‰), coupled with δ18O, δD, and alkalinity of formation waters (alkalinity ≤24.08 meq/kg), identifies the presence of microbial gas associated with meteoric recharge. Regional geochemical patterns identify the underlying Siluro-Devonian carbonate aquifer system as the major conduit for freshwater recharge into the fractured New Albany Shale reservoirs. Recharge from overlying Mississippian carbonates is only significant in the southernmost portion of the basin margin where carbonates directly overlie the New Albany Shale. Recharge of dilute waters (Cl− <1000 mM) into the Siluro-Devonian section has suppressed formation water salinity to depths as great as 1 km across the entire eastern Illinois Basin margin. Taken together with salinity and stable isotope patterns in age-equivalent Michigan Basin formation waters, they suggest a regional impact of recharge of δ18O- and δD-depleted fluids related to Pleistocene glaciation. Devonian black shales at both basin margins have been affected by recharge and produced significant volumes of microbial methane. This recharge is also manifested in different salinity gradients in the two basins because of their large differences in original formation water salinity. Given the relatively quiet tectonic history and subdued current topography in the midcontinent region, it is likely that repeated cycles of glacial meltwater invasion across this region have induced a strong disequilibrium pattern in fluid salinity and produced a unique class of unconventional shale-hosted gas deposits.

Salinity Constraints on Subsurface Archaeal Diversity and Methanogenesis in Sedimentary Rock Rich in Organic Matter

ABSTRACT The diversity of microorganisms active within sedimentary rocks provides important controls on the geochemistry of many subsurface environments. In particular, biodegradation of organic matter in sedimentary rocks contributes to the biogeochemical cycling of carbon and other elements and strongly impacts the recovery and quality of fossil fuel resources. In this study, archaeal diversity was investigated along a salinity gradient spanning 8 to 3,490 mM Cl− in a subsurface shale rich in CH4 derived from biodegradation of sedimentary hydrocarbons. Shale pore waters collected from wells in the main CH4-producing zone lacked electron acceptors such as O2, NO3−, Fe3+, or SO42−. Acetate was detected only in high-salinity waters, suggesting that acetoclastic methanogenesis is inhibited at Cl− concentrations above ∼1,000 mM. Most-probable-number series revealed differences in methanogen substrate utilization (acetate, trimethylamine, or H2/CO2) associated with chlorinity. The greatest methane production in enrichment cultures was observed for incubations with salinity at or close to the native pore water salinity of the inoculum. Restriction fragment length polymorphism analyses of archaeal 16S rRNA genes from seven wells indicated that there were links between archaeal communities and pore water salinity. Archaeal clone libraries constructed from sequences from 16S rRNA genes isolated from two wells revealed phylotypes similar to a halophilic methylotrophic Methanohalophilus species and a hydrogenotrophic Methanoplanus species at high salinity and a single phylotype closely related to Methanocorpusculum bavaricum at low salinity. These results show that several distinct communities of methanogens persist in this subsurface, CH4-producing environment and that each community is adapted to particular conditions of salinity and preferential substrate use and each community induces distinct geochemical signatures in shale formation waters.

Formation temperatures of thermogenic and biogenic methane

Making of methane deep underground Technologies such as hydraulic fracturing, or “fracking,” can now extract natural gas from underground reservoirs. Within the gas, the ratio of certain isotopes holds clues to its origins. Stolper et al. analyzed a wide range of natural gas, including samples from some of the most active fracking sites in the United States. Using a “clumped isotope” technique, the authors could estimate the high temperatures at which methane formed deep underground, as well as the lower temperatures at which ancient microbes produced methane. The approach can help to distinguish the degree of mixing of gas from both sources. Science, this issue p. 1500 Isotopic analysis of methane indicates the timing and location of hydrocarbon gas formation in natural settings. Methane is an important greenhouse gas and energy resource generated dominantly by methanogens at low temperatures and through the breakdown of organic molecules at high temperatures. However, methane-formation temperatures in nature are often poorly constrained. We measured formation temperatures of thermogenic and biogenic methane using a “clumped isotope” technique. Thermogenic gases yield formation temperatures between 157° and 221°C, within the nominal gas window, and biogenic gases yield formation temperatures consistent with their comparatively lower-temperature formational environments (<50°C). In systems where gases have migrated and other proxies for gas-generation temperature yield ambiguous results, methane clumped-isotope temperatures distinguish among and allow for independent tests of possible gas-formation models.

Identification of microbial and thermogenic gas components from Upper Devonian black shale cores, Illinois and Michigan basins

Differentiation of microbial versus thermogenic methane in coalbed and black shale accumulations can affect strategies for exploration and may influence the total gas content in a given area. Early identification of these processes from crushed core materials, even before formation fluids and produced gas samples are available, could permit a more efficient and cost-effective exploration. Total gas contents and compositional and isotopic data from New Albany Shale core materials are presented, which delineate regional occurrence of microbial, thermogenic, and mixed gas generation in the Illinois Basin. These trends are consistent with those identified from detailed prior studies of produced gas and water chemistry from the same locations. The most useful markers for microbial gas in crushed core gases are elevated CO2 contents characterized by high values (5). Core gas analyses from wells in which microbial gas is identified commonly have significantly more total gas absorbed than do core samples from wells producing gases solely of thermogenic origin. These observations are independent of variations in sample depth and organic carbon content in a given core. Thus, this integrated case study of core and produced gases in the Illinois Basin illustrates that the areas containing microbial gas, in addition to early thermogenic gas, may be more productive than pure thermogenic zones for these early to immature unconventional gas deposits.

Sites of anomalous organic remineralization in the carbonate sediments of South Florida, USA: The sulfur cycle and carbonate-associated sulfate

The modern shallow-platform, calcium-carbonate–dominated sediments of the Florida Keys (Florida Bay and Atlantic reef tract) are diverse in their biological, sedimentological, and geochemical properties. Sites of intense bioturbation and thick seagrass cover are pervasive within Florida Bay and are often characterized by appreciable early diagenetic aragonite dissolution. Additional, less common sites show atypical diagenetic profi les that suggest strong reworking and/or very rapid deposition of the upper sediment layer extending to a depth of at least 20 cm. Diagenesis in these seagrass-free areas is dominated by rapid burial of labile organic matter that would otherwise be degraded aerobically under conditions of slower burial. Correspondingly, these oozy, water-rich sediments display anomalously high rates of microbial decomposition as recorded in S-sulfate reduction rates and patterns of sulfate depletion, high dissolved sulfi de concentrations in excess of several millimolar (mM), and elevated alkalinities. Unlike many sites in Florida Bay where solute concentrations suggest volumetrically signifi cant net dissolution of metastable carbonate phases, dramatic increases in carbonate alkalinity from organic matter oxidation during bacterial sulfate reduction support net precipitation of CaCO 3 in the highly reactive surface layer. This early carbonate mineralization is indicated by measured depletions in Ca approaching 4 mM relative to overlying seawater. Geochemical signatures of sediment reworking or rapid sedimentation are corroborated by porosity 162 T.W. Lyons et al.

Extensive microbial modification of formation water geochemistry: Case study from a Midcontinent sedimentary basin, United States

The Upper Devonian Antrim Shale in the Michigan Basin is an economically significant source of microbially produced methane along the basin margins where meteoric recharge has been focused. Oxygen and hydrogen stable isotope compositions of Antrim formation waters show that fresh waters, recharged from Pleistocene glaciation and modern precipitation, suppressed basinal brine salinity to great depths and enhanced methanogenesis. This paper presents results of integrated elemental and isotope analyses of Antrim Shale formation waters from the margins and center of the Michigan Basin, focusing on solute sources and geochemical modifications associated with regionally extensive microbial methanogenesis. Cl-Br-Na systematics reveal that salinity is controlled not only by mixing between variable amounts of basinal brine and meteoric water, but also by halite dissolution where fluids recharged through underlying Devonian carbonate aquifers with localized evaporite deposits. Divalent cations, carbonate system parameters, and carbon isotope compositions of dissolved inorganic carbon have been systematically and profoundly altered by microbial methanogenesis. Large decreases in formation water Ca/Mg and Ca/Sr ratios accompany increasing carbonate alkalinity values in areas with high rates of microbial gas production. Thermodynamic and reaction-path modeling show that these changes are consistent with calcite precipitation during progressive microbial methanogenesis. Similar variations in fluid chemistry are evident in databases from other sedimentary basins containing black shales and coal beds associated with microbial gas. Microbial methanogenesis may play an important role in the geochemical evolution of divalent cation relationships in crustal fluids and should be considered in models of formation water origin and evolution.

Oxygen isotope ratios of PO4: An inorganic indicator of enzymatic activity and P metabolism and a new biomarker in the search for life

The distinctive relations between biological activity and isotopic effect recorded in biomarkers (e.g., carbon and sulfur isotope ratios) have allowed scientists to suggest that life originated on this planet nearly 3.8 billion years ago. The existence of life on other planets may be similarly identified by geochemical biomarkers, including the oxygen isotope ratio of phosphate (δ18Op) presented here. At low near-surface temperatures, the exchange of oxygen isotopes between phosphate and water requires enzymatic catalysis. Because enzymes are indicative of cellular activity, the demonstration of enzyme-catalyzed PO4–H2O exchange is indicative of the presence of life. Results of laboratory experiments are presented that clearly show that δ18OP values of inorganic phosphate can be used to detect enzymatic activity and microbial metabolism of phosphate. Applications of δ18Op as a biomarker are presented for two Earth environments relevant to the search for extraterrestrial life: a shallow groundwater reservoir and a marine hydrothermal vent system. With the development of in situ analytical techniques and future planned sample return strategies, δ18Op may provide an important biosignature of the presence of life in extraterrestrial systems such as that on Mars.

Coupled hydrology and biogeochemistry of Paleocene–Eocene coal beds, northern Gulf of Mexico

Thirty-six formation waters, gas, and microbial samples were collected and analyzed from natural gas and oil wells producing from the Paleocene to Eocene Wilcox Group coal beds and adjacent sandstones in north-central Louisiana, USA, to investigate the role hydrology plays on the generation and distribution of microbial methane. Major ion chemistry and Cl−Br relations of Wilcox Group formation waters suggest mixing of freshwater with halite-derived brines. High alkalinities (up to 47.8 meq/L), no detectable SO4, and elevated δ13C values of dissolved inorganic carbon (up to 20.5‰ Vienna Peedee belemnite [VPDB]) and CO2 (up to 17.67‰ VPDB) in the Wilcox Group coals and adjacent sandstones indicate the dominance of microbial methanogenesis. The δ13C and δD values of CH4, and carbon isotope fractionation of CO2 and CH4, suggest CO2 reduction is the major methanogenic pathway. Geochemical indicators for methanogenesis drop off significantly at chloride concentrations above ∼1.7 mol/L, suggesting that high salinities inhibit microbial activity at depths greater than ∼1.6 km. Formation waters in the Wilcox Group contain up to 1.6% modern carbon (A14C) to at least 1690 m depth; the covariance of δD values of co-produced H2O and CH4 indicate that the microbial methane was generated in situ with these Late Pleistocene or younger waters. The most enriched carbon isotope values for dissolved inorganic carbon (DIC) and CO2, and highest alkalinities, were detected in Wilcox Group sandstone reservoirs that were CO2 flooded in the 1980s for enhanced oil recovery, leading to the intriguing hypothesis that CO2 sequestration may actually enhance methanogenesis in organic-rich formations.

Mg-smectite authigenesis in a marine evaporative environment, Salina Ometepec, Baja California

Formation of authigenic trioctahedral Mg-rich smectite is common in evaporative lake sediments, but was not described previously in modern marine evaporative environments. This study documents formation of authigenic K-rich, Mg-smectite during very early diagenesis in the dominantly sili-ciclastic Salina Ometepec (Baja California), a large supratidal evaporative sabkha complex near the mouth of the Colorado River. Here, sediment pore waters are exceptionally Mg2+-rich relative to other marine evaporative environments due to suppressed sulfate reduction which limits production of carbonate alkalinity and, hence, carbonate (particularly dolomite) precipitation. Sediment cores were obtained along a five km transect seaward across the hypersaline mud flat to evaluate how these atypical geochemical conditions would affect the clay mineral compositions.Scanning transmission electron microscopy (STEM) observations show that the smectite from the marine Inlet, near the sediment source, consists of grains of irregular shape that give selected area diffraction (SAED) patterns reflecting dominant turbostratic stacking. Analytical electron microscopy (AEM) analyses indicate that K+ is the dominant interlayer cation; the mean composition is approximately K0.7(Al3.3Fe(III)0.3Mg0.5)(Al0.5Si7.5)O20(OH)4. Such smectite is implied to be detrital in part because it is similar to smectite known to be deposited by the Colorado River.Smectite from the hypersaline mud flat occurs as aggregates of small subhedral pseudohexagonal plate or lath-shaped crystals ≤250 nm in diameter, with thicknesses varying between three and ten layers. The SAED patterns reflect substantial turbostratic stacking, but with a greater frequency of interlayer coherency as compared with detrital smectite. Crystals from greater sediment depths are larger and more nearly euhedral. This smectite is dominantly trioctahedral, with mean composition approximately K0.7(Al0.7Fe(III)0.5Mg4.45)(Al1.2Si6.8)O20(OH)4 (saponitic). This smectite is inferred to be dominantly authigenic in origin.The X-ray diffraction (XRD) and STEM/AEM data collectively imply that detrital aluminous diocta-hedral smectite reacts to form authigenic Mg-rich trioctahedral smectite, driven in part by the high Mg2+/ Ca2+ ratio of pore waters. Such early-formed Mg-rich smectite may be the precursor for the trioctahedral mixed-layer smectite, corrensite, and chlorite assemblages found in ancient marine evaporative sequences. These results also add to the accumulating evidence that interlayer K+ in marine smectite is fixed during the earliest stages of marine diagenesis near the sediment water interface.