Measuring and predicting reservoir heterogeneity in complex deposystems: the Late Cambrian Rose Run sandstone of Eastern Ohio and Western Pennsylvania

A cooperative two-year multidisciplinary research program, conducted by the Ohio Division of Geological Survey (ODGS) and the Pennsylvania Bureau of Topographic and Geologic Survey (PTGS), designed to measure and predict reservoir heterogeneity in the Upper Cambrian Rose Run sandstone in those two states.257 pages, 125 figures (including numerous maps, cross sections, seismic lines, and photographs of rock thin sections), 6 tables, and five case studies of Rose Run oil and gas fields.Prepared for U.S. Department of Energy, Assistant Secretary for Fossil Energy. Work performed under Contract No. DE-AC22-90BC14657.This two-year investigation of the Upper Cambrian Rose Run sandstone in Eastern Ohio and Western Pennsylvania was conducted by the Ohio and Pennsylvania Geological Surveys in a cost-sharing agreement with the U.S. Department of Energy under the auspices of the Appalachian Oil and Natural Gas Research Consortium, which consists of West Virginia University and the state geological surveys of Kentucky, Ohio, Pennsylvania, and West Virginia

Mapping the internal recognition surface of an octanuclear coordination cage using guest libraries

Size and shape criteria for guest binding inside the cavity of an octanuclear cubic coordination cage in water have been established using a new fluorescence displacement assay to quantify guest binding. For aliphatic cyclic ketones of increasing size (from C5 to C11), there is a linear relationship between ΔG for guest binding and the guest’s surface area: the change in ΔG for binding is 0.3 kJ mol–1 Å–2, corresponding to 5 kJ mol–1 for each additional CH2 group in the guest, in good agreement with expectations based on hydrophobic desolvation. The highest association constant is K = 1.2 × 106 M–1 for cycloundecanone, whose volume is approximately 50% of the cavity volume; for larger C12 and C13 cyclic ketones, the association constant progressively decreases as the guests become too large. For a series of C10 aliphatic ketones differing in shape but not size, ΔG for guest binding showed no correlation with surface area. These guests are close to the volume limit of the cavity (cf. Rebek’s 55% rule), so the association constant is sensitive to shape complementarity, with small changes in guest structure resulting in large changes in binding affinity. The most flexible members of this series (linear aliphatic ketones) did not bind, whereas the more preorganized cyclic ketones all have association constants of 104–105 M–1. A crystal structure of the cage·cycloundecanone complex shows that the guest carbonyl oxygen is directed into a binding pocket defined by a convergent set of CH groups, which act as weak hydrogen-bond donors, and also shows close contacts between the exterior surface of the disc-shaped guest and the interior surface of the pseudospherical cage cavity despite the slight mismatch in shape

An Interconverting Family of Coordination Cages and a meso-Helicate; Effects of Temperature, Concentration, and Solvent on the Product Distribution of a Self-Assembly Process

The self-assembly between a water-soluble bis-bidentate ligand L^18w and Co­(II) salts in water affords three high-spin Co­(II) products: a dinuclear <i>meso</i>-helicate [Co₂(L^18w)₃]­X₄; a tetrahedral cage [Co₄(L^18w)₆]­X₈; and a dodecanuclear truncated-tetrahedral cage [Co₁₂(L^18w)₁₈]­X₂₄ (X = BF₄ or ClO₄). All three products were crystallized under different conditions and structurally characterized. In [Co₂(L^18w)₃]­X₄ all three bridging ligands span a pair of metal ions; in the two larger products, there is a metal ion at each vertex of the Co₄ or Co₁₂ polyhedral cage array with a bridging ligand spanning a pair of metal ions along every edge. All three structural types are known: what is unusual here is the presence of all three from the same reaction. The assemblies <b>Co</b>_<b>2</b>, <b>Co</b>_<b>4</b>, and <b>Co</b>_<b>12</b> are in slow equilibrium (hours/days) in aqueous solution, and this can be conveniently monitored by ¹H NMR spectroscopy because (i) the paramagnetism of Co­(II) disperses the signals over a range of ca. 200 ppm and (ii) the different symmetries of the three species give characteristically different numbers of independent ¹H NMR signals, which makes identification easy. From temperature- and concentration-dependent ¹H NMR studies it is clear that increasing temperature and increasing dilution favors fragmentation to give a larger proportion of the smaller assemblies for entropic reasons. High concentrations and low temperature favor the larger assembly despite the unfavorable entropic and electrostatic factors associated with its formation. We suggest that this arises from the hydrophobic effect: reorganization of several smaller complexes into one larger one results in a smaller proportion of the hydrophobic ligand surface being exposed to water, with a larger proportion of the ligand surface protected in the interior of the assembly. In agreement with this, ¹H NMR spectra in a nonaqueous solvent (MeNO₂) show formation of only [Co₂(L^18w)₃]­X₄ because the driving force for reorganization into larger assemblies is now absent. Thus, we can identify the contributions of temperature, concentration, and solvent on the result of the metal/ligand self-assembly process and have determined the speciation behavior of the <b>Co</b>_<b>2</b>/<b>Co</b>_<b>4</b>/<b>Co</b>_<b>12</b> system in aqueous solution

Produced Gas and Condensate Geochemistry of the Marcellus Formation in the Appalachian Basin: Insights into Petroleum Maturity, Migration, and Alteration in an Unconventional Shale Reservoir

The Middle Devonian Marcellus Formation of North America is the most prolific hydrocarbon play in the Appalachian basin, the second largest producer of natural gas in the United States, and one of the most productive gas fields in the world. Regional differences in Marcellus fluid chemistry reflect variations in thermal maturity, migration, and hydrocarbon alteration. These differences define specific wet gas/condensate and dry gas production in the basin. Marcellus gases co-produced with condensate in southwest Pennsylvania and northwest West Virginia are mixtures of residual primary-associated gases generated in the late oil window and postmature secondary hydrocarbons generated from oil cracking in the wet gas window. Correlation of API gravity and C7 expulsion temperatures, high heptane and isoheptane ratios, and the gas geochemical data confirm that the Marcellus condensates formed through oil cracking. Respective low toluene/nC7 and high nC7/methylcyclohexane ratios indicate selective depletion of low-boiling point aromatics and cyclic light saturates in all samples, suggesting that water washing and gas stripping altered the fluids. These alterations may be related to deep migration of hot basinal brines. Dry Marcellus gases produced in northeast Pennsylvania and northcentral West Virginia are mixtures of overmature methane largely cracked from refractory kerogen and ethane and propane cracked from light oil and wet gas. Carbon and hydrogen isotope distributions are interpreted to indicate (1) mixing of hydrocarbons of different thermal maturities, (2) high temperature Rayleigh fractionation of wet gas during redox reactions with transition metals and formation water, (3) isotope exchange between methane and water, and, possibly, (4) thermodynamic equilibrium conditions within the reservoirs. Evidence for thermodynamic equilibrium in the dry gases includes measured molecular proportions (C1/(C1 − C5) = 0.96 to 0.985) and δ13C1 values significantly greater than δ13CKEROGEN. Noble gas systematics support the interpretation of hydrocarbon–formation water interactions, constrain the high thermal maturity of the hydrocarbon fluids, and provide a method of quantifying gas retention versus expulsion in the reservoirs

CREATING A GEOLOGIC PLAY BOOK FOR TRENTON-BLACK RIVER APPALACHIAN BASIN EXPLORATION

The Trenton-Black River Appalachian Basin Research Consortium has made significant progress toward their goal of producing a geologic play book for the Trenton-Black River gas play. The final product will include a resource assessment model of Trenton-Black River reservoirs; possible fairways within which to concentrate further studies and seismic programs; and a model for the origin of Trenton-Black River hydrothermal dolomite reservoirs. All seismic data available to the consortium have been examined. Synthetic seismograms constructed for specific wells have enabled researchers to correlate the tops of 15 stratigraphic units determined from well logs to seismic profiles in New York, Pennsylvania, Ohio, West Virginia and Kentucky. In addition, three surfaces for the area have been depth converted, gridded and mapped. A 16-layer velocity model has been developed to help constrain time-to-depth conversions. Considerable progress was made in fault trend delineation and seismic-stratigraphic correlation within the project area. Isopach maps and a network of gamma-ray cross sections supplemented with core descriptions allowed researchers to more clearly define the architecture of the basin during Middle and Late Ordovician time, the control of basin architecture on carbonate and shale deposition and eventually, the location of reservoirs in Trenton Limestone and Black River Group carbonates. The basin architecture itself may be structurally controlled, and this fault-related structural control along platform margins influenced the formation of hydrothermal dolomite reservoirs in original limestone facies deposited in high energy environments. This resulted in productive trends along the northwest margin of the Trenton platform in Ohio. The continuation of this platform margin into New York should provide further areas with good exploration potential. The focus of the petrographic study shifted from cataloging a broad spectrum of carbonate rocks that occur in the Trenton-Black River interval to delineation of regional limestone diagenesis in the basin. A consistent basin-wide pattern of marine and burial diagenesis that resulted in relatively low porosity and permeability in the subtidal facies of these rocks has been documented across the study area. Six diagenetic stages have been recognized: four marine diagenesis stages and two burial diagenesis stages. This dominance of extensive marine and burial diagenesis yielded rocks with low reservoir potential, with the exception of fractured limestone and dolostone reservoirs. Commercial amounts of porosity, permeability and petroleum accumulation appear to be restricted to areas where secondary porosity developed in association with hydrothermal fluid flow along faults and fractures related to basement tectonics. A broad range of geochemical and fluid inclusion analyses have aided in a better understanding of the origin of the dolomites in the Trenton and Black River Groups over the study area. The results of these analyses support a hydrothermal origin for all of the various dolomite types found to date. The fluid inclusion data suggest that all of the dolomite types analyzed formed from hot saline brines. The dolomite is enriched in iron and manganese, which supports a subsurface origin for the dolomitizing brine. Strontium isotope data suggest that the fluids passed through basement rocks or immature siliciclastic rocks prior to forming the dolomites. All of these data suggest a hot, subsurface origin for the dolomites. The project database continued to be redesigned, developed and deployed. Production data are being reformatted for standard relational database management system requirements. Use of the project intranet by industry partners essentially doubled during the reporting period

A Geologic Play Book for Trenton-Black River Appalachian Basin Exploration

Appalachian basin architecture during Middle Ordovician time was dominated by a Black River ramp to the northwest flanked by the central Appalachian basin along its southeast margin, with the deeper Sevier basin still farther to the east and southeast. The ramp margin, which marked the western edge of the central Appalachian basin, was in the approximate location of the western edge of the Rome trough. Black River carbonate rocks were deposited on this broad, stable, shallow-water ramp as epeiric seas transgressed much of what is now the Appalachian region, while thick, shaley carbonates were being deposited within the trough-influenced foredeep and clastic sediments were being deposited in the Sevier basin. The elongate, north-northeast-trending depocenter that developed during early Black River time would continue to exist and even expand throughout the remainder of the Ordovician Period

Shape-, size-, and functional group-selective binding of small organic guests in a paramagnetic coordination cage

A cubic coordination cage acts in MeCN as a host for neutral organic guests which contain an H-bond-accepting group that interacts with the internal surface of the cage. The different thermodynamic contributions to guest recognition and the kinetics of both guest binding and reorganization inside the cavity have been analyzed in detail by 1H NMR spectroscopy, which is facilitated by the paramagnetism of the host cage