Lynn M. Walter

Depletion of 13C in seawater ΣC02 on modern carbonate platforms: Significance for the carbon isotopic record of carbonates

Seawater ΣCO2 from modern carbonate platforms (Bahama Banks and Florida) is depleted in 13C by as much as 4‰ relative to open-ocean water. Depletion in 13C is caused by isotopically light CO2 input from respiration of marine and terrestrial organic matter during water-mass residence on the bank. As such, depletion in 13C is related to changes in water chemistry driven by evaporation, freshwater discharge, and CaCO3 withdrawal. Deviation of modern platform seawater δ13C values away from those of surface seawater suggests that δ13C values of ancient cratonic carbonate must be cautiously interpreted. Initial depositional environment, as well as alteration during diagenesis, must be considered in extracting valid secular trends for oceanic δ13C variation.

Genetic and temporal relations between formation waters and biogenic methane: Upper Devonian Antrim Shale, Michigan Basin, USA

Abstract Controversy remains regarding how well geochemical criteria can distinguish microbial from thermogenic methane. Natural gas in most conventional deposits has migrated from a source rock to a reservoir, rarely remaining associated with the original or cogenetic formation waters. We investigated an unusual gas reservoir, the Late Devonian Antrim Shale, in which large volumes of variably saline water are coproduced with gas. The Antrim Shale is organic-rich, of relatively low thermal maturity, extensively fractured, and is both source and reservoir for methane that is generated dominantly by microbial activity. This hydrogeologic setting permits integration of chemical and isotopic compositions of coproduced water and gas, providing a unique opportunity to characterize methane generating mechanisms. The well-developed fracture network provides a conduit for gas and water mass transport within the Antrim Shale and allows invasion of meteoric water from overlying aquifers in the glacial drift. Steep regional concentration gradients in chemical and isotopic data are observed for formation waters and gases; dilute waters grade into dense brines (300,000 ppm) over lateral distances of less than 30 km. Radiogenic (14C and 3H) and stable isotope (18O and D) analyses of shallow Antrim Shale formation waters and glacial drift groundwaters indicate recharge times from modern to 20,000 yr bp . Carbon isotope compositions of methane from Antrim Shale wells are typical of the established range for thermogenic or mixed gas (δ13C = −47 to −56‰). However, the unusually high δ13C values of CO2 coproduced with methane (∼+22‰) and dissolved inorganic carbon (DIC) in formation waters (∼+28‰) require bacterial mediation. The δD values of methane and coproduced formation water provide the strongest evidence of bacterial methanogenesis. Methane/[ethane + propane] ratios and δ13C values for ethane indicate: (1) the presence of a thermogenic gas component that increases basinward and (2) progressive bacterial oxidation of ethane as the Antrim Shale subcrop is approached. Multiple episodes of Pleistocene glaciation over northern Michigan appear critical to the development of these gas deposits. Loading of thick ice sheets may have provided hydraulic head that enhanced dilation of preexisting fractures and influx of meteoric water. The physical erosion cycle of repeated glacial advances and retreats exhumed the Antrim Shale around the northern margin of the Michigan Basin, subjecting it to near-surface physiochemical and biochemical processes. The chemical and hydrologic relations demonstrated in the Antrim Shale reservoir suggest a dynamic connection between Pleistocene glacial history of the midcontinent region and development of recoverable, microbially generated natural gas reserves.

Origin and evolution of formation waters, Alberta Basin, Western Canada sedimentary Basin. I. Chemistry

Inorganic chemical analyses and short-chain aliphatic acid content are used to interpret the origin and compositional evolution of formation waters in the Alberta portion of the Western Canada Sedimentary Basin. Forty-three formation water samples were obtained covering a stratigraphic interval from Devonian to Cretaceous. The data show that: (1) there is a subaerially evaporated brine component that shows no apparent contribution of waters derived from evaporite dissolution; and (2) formation waters have maintained characteristics indicative of subaerially evaporated waters, despite subsequent flushing by gravity-driven meteoric waters in the basin. Formation waters are predominantly Na-CI brines that contain 4-235 g/1 total dissolved solids (TDS). Short-chain aliphatic acids (SCA) range up to 932 mg/l, with the following abundance: acetate >> propionate > butyrate. Their number varies randomly with subsurface temperature, depth, geological age and salinity. Instead, SCA distributions appear related to proximity to Jurassic and Mississippian source rocks and to zones of active bacterial SO4 reduction. Based on chemical composition, the formation waters can be divided into three groups. Group I waters arc from dominantly carbonate reservoirs and Group II from elastics. Groups 1 and II are differentiated from Group II1 in that they are composed of a brine end member, formed by evaporation of sea water beyond the point of halite saturation, that has been subsequently diluted 50-80% by a meteoric water end member. Group III waters are from elastic reservoirs and are dilute, meteoric waters that are decoupled from the more saline, stratigraphically lower, waters of Groups I and II. Group I waters have been influenced by clay mineral transformations in shales surrounding the carbonate reservoirs, ankeritization reactions of reservoir dolomites and calcites, and possible decarboxy- lation reactions. Group II waters indicate significant leaching reactions, particularly of feldspar and clay minerals. Group I and Group I1 waters both indicate ion exchange reactions were also possible. The waters are near equilibrium with respect to quartz, calcite, dolomite and barite, but are undcrsaturatcd with respect to evaporite minerals (halite, anhydrite). Occurrence of feldspar (predominantly albite) and kaolinite seems to control the population of the water cations. Post-Laramide invasion of meteoric waters provided an impetus for many of the diagenetic reactions in both carbonate, but especially in elastic reservoirs. Subsequent hydrochemical isolation of Group I and I1 waters from further meteoric influences occurred, resulting in pronounced mixing relations and eross-formational fluid flow replacing the once dominant lateral flow.

Coupling between sulfur recycling and syndepositional carbonate dissolution: evidence from oxygen and sulfur isotope composition of pore water sulfate, South Florida Platform, U.S.A.

Sulfur cycling in Fe-poor, organic-rich shelf carbonates, known to have rapid rates of SO4−2 reduction, remains poorly studied despite the volumetric significance of shelf deposits in modern and ancient carbon budgets. We investigated sulfur cycling in modern carbonates of the Florida Platform from end-member depositional environments (muddy sands from the Atlantic reef tract and finer-grained mudbank and island flank deposits from Florida Bay). Relations between pore water chemistry (SO4−2, ΣCO2, Ca−2/Cl−) and oxygen and sulfur stable isotope compositions of SO4−2 require direct coupling between sulfur redox cycling and syndepositional carbonate dissolution. Oxygen isotope compositions of pore water sulfate were remarkably shifted away from the established value for marine SO4−2 (+9.5‰), despite near normal SO4−2/Cl− ratios. Chemical evolution was least in reef tract pore waters and greatest in Florida Bay. Relative to overlying seawater, mudbank sediments exhibited sulfate depletion, with δ18OSO4 and δ34SSO4 values both increasing by about 7‰. More bioturbated island flank sediments, colonized by Thalassia grass, had a 5‰ increase in δ18OSO4, variable δ34SSO4 values (+17.7 to +23.3‰) and exceptionally high Ca+2/Cl− ratios. The large excess of Ca+2 (up to 1.7 mM) requires a much larger acid source than the amounts derived from utilization of dissolved O2 (∼0.3 mM) and small degrees of net SO4−2 reduction (<0.5 mM reduced). A conceptual model was constructed using chemical and isotopic data on natural pore waters and on sulfate isotope fractionation factors obtained from sediment incubation experiments. The model outputs show that pore water compositions can be explained by a redox cycle where microbial SO4−2 reduction is followed by very efficient H2S oxidation, thus maintaining virtually invariant SO4−2/Cl− ratios. The enhanced O2 transport may be driven by associated marine grass rhizome systems and microbial communities established in bioturbated sediments. The net result of the cycle is that the rate of sulfide oxidation, which is largely balanced by the rate of microbial sulfate reduction, is stoichiometrically related to the rate of carbonate dissolution. This is consistent with previously reported rates of carbonate dissolution (∼400 μmol/cm2-yr) and average rates of sulfate reduction (∼200 μmol/cm2-yr) from the Florida Platform and a 2:1 stoichiometry.

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.

Reconciling the elemental and Sr isotope composition of Himalayan weathering fluxes: insights from the carbonate geochemistry of stream waters

Determining the relative proportions of silicate vs. carbonate weathering in the Himalaya is important for understanding atmospheric CO2 consumption rates and the temporal evolution of seawater Sr. However, recent studies have shown that major element mass-balance equations attribute less CO2 consumption to silicate weathering than methods utilizing Ca/Sr and 87Sr/86Sr mixing equations. To investigate this problem, we compiled literature data providing elemental and 87Sr/86Sr analyses for stream waters and bedrock from tributary watersheds throughout the Himalaya Mountains. In addition, carbonate system parameters (PCO2, mineral saturation states) were evaluated for a selected suite of stream waters. The apparent discrepancy between the dominant weathering source of dissolved major elements vs. Sr can be reconciled in terms of carbonate mineral equilibria. Himalayan streams are predominantly Ca2+-Mg2+-HCO3− waters derived from calcite and dolomite dissolution, and mass-balance calculations demonstrate that carbonate weathering contributes ∼87% and ∼76% of the dissolved Ca2+ and Sr2+, respectively. However, calculated Ca/Sr ratios for the carbonate weathering flux are much lower than values observed in carbonate bedrock, suggesting that these divalent cations do not behave conservatively during stream mixing over large temperature and PCO2 gradients in the Himalaya. The state of calcite and dolomite saturation was evaluated across these gradients, and the data show that upon descending through the Himalaya, ∼50% of the streams evaluated become highly supersaturated with respect to calcite as waters warm and degas CO2. Stream water Ca/Mg and Ca/Sr ratios decrease as the degree of supersaturation with respect to calcite increases, and Mg2+, Ca2+, and HCO3− mass balances support interpretations of preferential Ca2+ removal by calcite precipitation. On the basis of patterns of saturation state and PCO2 changes, calcite precipitation was estimated to remove up to ∼70% of the Ca2+ originally derived from carbonate weathering. Accounting for the nonconservative behavior of Ca2+ during riverine transport brings the Ca/Sr and 87Sr/86Sr composition of the carbonate weathering flux into agreement with the composition of carbonate bedrock, thereby permitting consistency between elemental and Sr isotope approaches to partitioning stream water solute sources. These results resolve the dissolved Sr2+ budget and suggest that the conventional application of two-component Ca/Sr and 87Sr/86Sr mixing equations has overestimated silicate-derived Sr2+ and HCO3− fluxes from the Himalaya. In addition, these findings demonstrate that integrating stream water carbonate mineral equilibria, divalent cation compositional trends, and Sr isotope inventories provides a powerful approach for examining weathering fluxes.

δ18O values, 87Sr86Sr and Sr/Mg ratios of Late Devonian abiotic marine calcite: Implications for the composition of ancient seawater

Abstract Late Devonian (Frasnian) abiotic marine calcite has been microsampled and analyzed for 87 Sr 86 Sr ratios, δ18O and δ13C values, and minor element concentrations. Portions of marine cement crystals from the Alberta and Canning Basins have escaped diagenetic alteration and preserve original marine δ18O values (−4.8%. ± 0.5, PDB), δ13C values (+2.0 to +3.0%., PDB), 87 Sr 86 Sr ratios (0.70805 ± 3), and Sr/Mg weight ratios (0.04 to 0.05). Marine 87 Sr 86 Sr ratios are globally consistent and can be correlated within the Alberta Basin, and among the Alberta, Canning, and Williston Basins. Correlation of isotopic and chemical data strengthen the conclusion that marine cements from the Leduc Formation preserve original marine δ18O values which are 3 to 4%. lower than those of modern marine cements. These low δ18O values are best explained by precipitation from 18O-depleted seawater and not by elevated seawater temperature or diagenetic alteration. For comparison with Devonian data, analogous data were collected from Holocene Mg-calcite and aragonite marine cements from Enewetak Atoll, Marshall Islands. Mg-calcite and aragonite marine cements are in isotopic equilibrium with ambient seawater, and Mg-calcite cements are homogeneous with respect to Sr and Mg contents. Empirically derived homogeneous distribution coefficients for Mg and Sr in modern, abiotic Mg-calcite from Enewetak Atoll are 0.034 and 0.15, respectively. An equation describing the dependence of DSr on Mg content was based on a compilation of Sr and Mg data from Holocene abiotic marine calcite (DSr = 3.52 × 10−6 (ppm Mg) + 6.20 × 10−3). Unlike that derived from experimental data, this Sr-Mg relation is consistent over a range of 4 to 20 mol% MgCO3 and may represent precipitation phenomena which are minimally controlled by kinetic effects. Comparison of Sr and Mg contents of analogous Devonian and Holocene marine cements suggests that the Mg/Ca ratio of Late Devonian seawater was significantly lower and that the Sr/Ca ratio was significantly higher than that of modern seawater.

Origin and chemical evolution of formation waters from Silurian-Devonian strata in the Illinois basin, USA

Abstract A suite of formation-water samples from Silurian-Devonian reservoirs in the Illinois basin has been analyzed for major, minor and trace element concentrations and for H, O and Sr isotopic compositions in order to interpret origin of salinity and geochemical evolution of brine compositions in this evaporite- and shale-poor cratonic basin. Although chloride concentrations range from 2000 to 137,000 mg/L, Cl Br ratios (291 ± 18) are consistent with those of seawater or seawater evaporated short of halite saturation (Cl/Br = 292). Thus, during Silurian-Devonian time, subaerially evaporated, penesaline brine entered the subsurface where it was chemically modified through brine-rock interactions. Cation Br ratios and mineralogy of associated strata indicate that Na and K were depleted through interaction with clay minerals, Ca was enriched and Mg depleted by dolomitization and Sr was enriched as a result of CaCO3 recrystallization and dolomitization. Although significant dilution of the modified brine with meteoric water is supported by δD-δ18O covariance, original marine waters have not been completely expelled from Silurian-Devonian strata. Hydrogen and oxygen isotopes exhibit covariant relations with cation and anion concentrations, implying that isotopic exchange between H2O and minerals has not greatly influenced the δD − δ18O trend. Brine 87 Sr 86 Sr ratios range from 0.7092 to 0.7108; when these ratios are plotted versus 1/Sr, a two-component mixing trend is suggested, although Sr concentrations have experienced local diagenetic modification. A 87Sr-enriched fluid may have accompanied petroleum migration from New Albany shales into adjacent Silurian-Devonian carbonates where it mixed with remnant evaporated seawater. This event probably preceded the influx of meteoric water, as /gdD and δ18O are not correlated with Sr isotopic compositions of formation waters.

Dissolution and Recrystallization in Modern Shelf Carbonates: Evidence from Pore Water and Solid Phase Chemistry [and Discussion]

We present an overview of geochemical data from pore waters and solid phases that clarify earliest diagenetic processes affecting modern, shallow marine carbonate sediments. Acids produced by organic matter decomposition react rapidly with metastable carbonate minerals in pore waters to produce extensive syndepositional dissolution and recrystallization. Stoichiometric relations among pore water solutes suggest that dissolution is related to oxidation of H2S which can accumulate in these low-Fe sediments. Sulphide oxidation likely occurs by enhanced diffusion of O2 mediated by sulphide-oxidizing bacteria which colonize oxic/anoxic interfaces invaginating these intensely bioturbated sediments. Buffering of pore water stable isotopic compositions towards values of bulk sediment and rapid 45Ca exchange rates during sediment incubations demonstrate that carbonate recrystallization is a significant process. Comparison of average biogenic carbonate production rates with estimated rates of dissolution and recrystallization suggests that over half the gross production is dissolved and/or recrystallized. Thus isotopic and elemental composition of carbonate minerals can experience significant alteration during earliest burial driven by chemical exchange among carbonate minerals and decomposing organic matter. Temporal shifts in palaeo-ocean carbon isotope composition inferred from bulk-rocks may be seriously compromised by facies-dependent differences in dissolution and recrystallization rates.

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.