Appalachian Basin Research Articles

Regional Scale Assessment of Shallow Groundwater Vulnerability to Contamination from Unconventional Hydrocarbon Extraction.

Concerns over unconventional oil and gas (UOG) development persist, especially in rural communities that rely on shallow groundwater for drinking and other domestic purposes. Given the continued expansion of the industry, regional (vs local scale) models are needed to characterize groundwater contamination risks faced by the increasing proportion of the population residing in areas that accommodate UOG extraction. In this paper, we evaluate groundwater vulnerability to contamination from surface spills and shallow subsurface leakage of UOG wells within a 104,000 km2 region in the Appalachian Basin, northeastern USA. We test a computationally efficient ensemble approach for simulating groundwater flow and contaminant transport processes to quantify vulnerability with high resolution. We also examine metamodels, or machine learning models trained to emulate physically based models, and investigate their spatial transferability. We identify predictors describing proximity to UOG, hydrology, and topography that are important for metamodels to make accurate vulnerability predictions outside their training regions. Using our approach, we estimate that 21,000-30,000 individuals in our study area are dependent on domestic water wells that are vulnerable to contamination from UOG activities. Our novel modeling framework could be used to guide groundwater monitoring, provide information for public health studies, and assess environmental justice issues.

Devonian smooth-walled tasmanids and new insights of life-cycle descriptions through fluorescence microscopy

Fossil microspherules suspected to be marine algal cysts of varying mineralogy are abundant in Paleozoic deposits worldwide. Positive identification of remineralized microspherule fossils is problematic and long debated, particularly for tasmanid species. Several hundred silica-rich microspherules were retrieved through complete maceration of black shale samples from the Givetian Oatka Creek Formation of the Appalachian Basin. Microspherules were analyzed visually through transmitted, incident light, and fluorescence microscopy. The structural features of these microspherules are evident and are interpreted to be Tasmanites sinuous. The images presented herein are the first fluorescence images showing in detail the life cycle stages of the genus Tasmanites. This work also confirms that this tasmanid species does extend into the Givetian as suspected from prior research.

Analysis of Regulatory Framework for Produced Water Management and Reuse in Major Oil- and Gas-Producing Regions in the United States

The rapid development of unconventional oil and gas (O&G) extraction around the world produces a significant amount of wastewater that requires appropriate management and disposal. Produced water (PW) is primarily disposed of through saltwater disposal wells, and other reuse/disposal methods include using PW for hydraulic fracturing, enhanced oil recovery, well drilling, evaporation ponds or seepage pits within the O&G field, and transferring PW offsite for management or reuse. Currently, 1–2% of PW in the U.S. is used outside the O&G field after treatment. With the considerable interest in PW reuse to reduce environmental implications and alleviate regional water scarcity, it is imperative to analyze the current regulatory framework for PW management and reuse. In the U.S., PW is subject to a complex set of federal, state, and sometimes local regulations to address the wide range of PW management, construction, and operation practices. Under the supervision of the U.S. Environment Protection Agency (U.S. EPA), different states have their own regulatory agencies and requirements based on state-specific practices and laws. This study analyzed the regulatory framework in major O&G-producing regions surrounding the management of PW, including relevant laws and jurisdictional illustrations of water rules and responsibilities, water quality standards, and PW disposal and current/potential beneficial reuse up to early 2022. The selected eastern states (based on the 98th meridian designated by the U.S. EPA as a tool to separate discharge permitting) include the Appalachian Basin (Marcellus and Utica shale areas of Pennsylvania, Ohio, and West Virginia), Oklahoma, and Texas; and the western states include California, Colorado, New Mexico, and Wyoming. These regions represent different regulations; climates; water quantities; quality diversities; and geologic, geographic, and hydrologic conditions. This review is particularly focused on the water quality standards, reuse practices and scenarios, risks assessment, knowledge gaps, and research needs for the potential reuse of treated PW outside of O&G fields. Given the complexity surrounding PW regulations and rules, this study is intended as preliminary guidance for PW management, and for identifying the knowledge gaps and research needs to reduce the potential impacts of treated PW reuse on the environment and public health. The regulations and experiences learned from these case studies would significantly benefit other states and countries with O&G sources for the protection of their environment and public health.

Sedimentological and Geochemical Analysis of the Eocene Tallahatta Formation in Northern Mississippi, USA

The Eocene Tallahatta Formation forms part of the Tallahatta-Winona aquifer, which is part of the lower Claiborne confining unit of the Mississippi Embayment. A thorough understanding of the distribution of natural resources within the Tallahatta is limited by a lack of detailed studies at the outcrop and pore scales. In this study, we integrate particle size, petrographic, lithofacies, and geochemical analyses to interpret depositional environments, sequence stratigraphy, provenance, and diagenetic history from outcrops in Grenada County, Mississippi. Lithofacies include unprotected sand flat, tidal channel, open tidal mudflat, protected tidal flat, lower and middle shoreface, offshore transition, and offshore shelf settings. Lithofacies associations indicate that the Tallahatta consists of at least two parasequences within a falling stage systems tract (FSST). This is the first report on FSST strata from the Tallahatta Formation. Petrographic and geochemical results show that sediments were sourced from Precambrian Laurentian basement, recycled Appalachian basin sediment, and the Appalachian hinterland. Upsection changes in geochemistry represent an increase in contributions from recycled Appalachian basin sediment and progressive weathering of Acadian orogeny elements. Geochemistry also suggests that potentially economically important Ti-rich minerals are concentrated in tidal flat facies and scarce in shoreface facies. Primary porosity and bioturbation exert the greatest influence on the high porosity within many lithofacies. Early diagenesis also included detrital clay coating of framework grains, deposition of fecal pellets, minor chemical weathering, and hematite precipitation. Fecal pellets were altered to glauconite and opal cement was precipitated shortly after deposition or during early burial. Shrinkage of fecal pellets during glauconitization introduced minor moldic porosity. Limited burial produced minor physical compaction and only slightly reduced porosity. Abundant hematite precipitation during exhumation greatly decreased porosity locally.

Basement structure of the Appalachian Basin in Pennsylvania

Basement structure beneath the Pennsylvanian portion of the Appalachian basin, where some of the deepest basement in the basin is found, is investigated by constructing a map of the Precambrian unconformity using 3939 new point estimates of basement depth determined from seismic reflection profiles and P-wave receiver functions, combined with geophysical and well log data used in other published basement maps. The map shows a gradual and uniform deepening of the basement from depths of ~1500 m in the northwest to ~6000 m in the southeast, consistent with a foreland basin plate flexure model. However, basement depths in two regions, when compared to depths predicted by a plate flexure model, show basin over-deepening. One to two km of over-deepening coincides with the Neoproterozoic-early Paleozoic Rome Trough in southwestern Pennsylvania, and the Northumberland Deep Basement Zone (NDBZ) in east-central Pennsylvania shows two to two and a half km of over-deepening. Basin over-deepening in the Rome Trough does not extend into northern Pennsylvania, pointing to a termination of the trough within central Pennsylvania. The origin of basin over-deepening in the NDBZ is less certain but overlaps spatially with the southern portion of the Neoproterozoic Scranton Rift. The preservation of one or more failed Neoproterozoic-early Paleozoic rifts within the basement structure of the Appalachian Basin suggests crystalline basement was not significantly deformed by the Paleozoic orogenic events associated with basin formation. It also supports models placing the locus of Laurentian rifting from Rodinia well to the east of the Appalachian Basin.

Dissolved organic matter within oil and gas associated wastewaters from U.S. unconventional petroleum plays: Comparisons and consequences for disposal and reuse

Wastewater generated during petroleum extraction (produced water) may contain high concentrations of dissolved organics due to their intimate association with organic-rich source rocks, expelled petroleum, and organic additives to fluids used for hydraulic fracturing of unconventional (e.g., shale) reservoirs. Dissolved organic matter (DOM) within produced water represents a challenge for treatment prior to beneficial reuse. High salinities characteristic of produced water, often 10× greater than seawater, coupled to the complex DOM ensemble create analytical obstacles with typical methods. Excitation-emission matrix spectroscopy (EEMS) can rapidly characterize the fluorescent component of DOM with little impact from matrix effects. We applied EEMS to evaluate DOM composition in 18 produced water samples from six North American unconventional petroleum plays. Represented reservoirs include the Eagle Ford Shale (Gulf Coast Basin), Wolfcamp/Cline Shales (Permian Basin), Marcellus Shale and Utica/Point Pleasant (Appalachian Basin), Niobrara Chalk (Denver-Julesburg Basin), and the Bakken Formation (Williston Basin). Results indicate that the relative chromophoric DOM composition in unconventional produced water may distinguish different lithologies, thermal maturity of resource types (e.g., heavy oil vs. dry gas), and fracturing fluid compositions, but is generally insensitive to salinity and DOM concentration. These results are discussed with perspective toward DOM influence on geochemical processes and the potential for targeted organic compound treatment for the reuse of produced water.

Deep-basin gas generation via organic–inorganic interactions: New insights from redox-controlled hydrothermal experiments at elevated temperature

Under hot, deep-basin conditions, hydrogen-to-carbon ratios of residual kerogen are low. Whether ubiquitous water in sedimentary environments contributes hydrogen directly to hydrocarbon gas formation through organic-inorganic interactions is, therefore, critical for natural gas generation. Accordingly, we conducted laboratory experiments on immature to overmature kerogens at 300–600°C and 700 bar to examine the chemical interactions between kerogens and fluid under varying redox states and hydrothermal conditions. Mineral buffers, comprised of magnetite-hematite, nickel‑nickel oxide, cobalt‑cobalt oxide, and molybdenum‑molybdenum trioxide, were added to the experiments to control the redox state of the fluid from geologically reasonable to generally excessive values. The kerogens and mineral buffers were spatially isolated using double-capsule techniques to prevent contact catalysis.Our results indicated that chemical interactions between kerogens and water depended strongly on the kerogen thermal maturity and fluid redox state. The chemical interactions of overmature kerogens with reducing water were stronger than those of immature kerogens, which could be ascribed to the weaker competitive transfer of hydrogen from organics to organics than from water to organics. Unexpectedly high amounts of hydrocarbon gas were generated by incorporating water-derived hydrogen in the pyrolysis of overmature kerogens, and the yields increased under low to high reducing fluid conditions for a given temperature. Along with the increasing thermal maturity, residual kerogen eventually became ineffective for hydrocarbon gas generation through reduction reactions. Demethylation, bridge bond cleavage reaction, aromatic structure ring opening reactions in residual kerogen and subsequent redox reaction of intermediate products with reducing fluids is evidenced as the possible reaction mechanisms. The produced hydrocarbon gas under fH2 level of oilfield water is characterized by high dryness (99 mol%) and more-enriched 13C in CH4 compared with precursors. Natural gas deep within the Sichuan and Appalachian basins with similar characteristics suggests that our simulated organic–inorganic interactions could occur widely under natural conditions. Consequently, a potentially prolific source of natural gas may be formed by the overmature source rocks in the deep basin and fluid redox should be considered for gas potential evaluation of overmature source rocks.

Timing and evolution of the Mississippian sedimentary system on southeastern Laurussia: Evidence from the Appalachian area, U.S.A.

This paper is a synthesis of Mississippian sedimentation on the southeastern, Appalachian margin of Laurussia. The Mississippian stratigraphic framework in the Appalachian area shows a large-scale, three-part, wedge-like, clastic‑carbonate-clastic sequence, which has been interpreted to be a likely flexural response to coeval Neoacadian Orogeny. Using an already established flexural framework and biostratigraphy, we have interpreted the approximate timing of flexural events based on biostratigraphy. These flexural events begin with active deformational loading that initiated rapid subsidence in the Appalachian foreland basin, during which the deeper-water, black Sunbury Shale and equivalents were deposited throughout the basin. Subsequent relaxational loading contributed to basin infilling through the deposition of a deeper-water, clastic succession, manifest as the extensive Cuyahoga-Logan-Borden-Grainger-Price-Rockwell-Pocono deltaic clastic wedge. By the time this clastic wedge had filled the foreland basin, clastic source areas in the orogen had apparently been lowered to the point that shallow seas migrated far eastward across former source areas. This brief period of equilibrium between the basin and source areas resulted in reduced clastic influx at a time when the basin entered subtropical latitudes, setting the stage for widespread carbonate deposition, represented by units like the Newman, Greenbrier, and Slade Limestones. Ensuing, rebound-related uplift, perhaps abetted by incipient, subsurface, Alleghanian thrusting, generated new sediment source areas and accompanying wedges of prograding marginal-marine and terrestrial sediment represented by the Pennington, Mauch Chunk and equivalent units. Marginal-marine sedimentation continued into Early Pennsylvanian time, when a combination of Alleghanian uplift and LPIA lowstand conditions generated a period of widespread, deep erosion that in many places across the Appalachian Basin destroyed substantial parts of the underlying Mississippian succession along the sub-Absaroka or “Mississippian-Pennsylvanian” unconformity. Although the basic Mississippian stratigraphic framework described above for the Appalachian Basin largely appears to be a consequence of Neoacadian flexural responses, major details regarding processes, timing and lithology were apparently controlled by concomitant interactions involving paleoclimate, eustasy, coeval Ouachita tectonism, and possibly early Alleghanian tectonism.

Appalachian Basin–Pennsylvania, West Virginia, and Ohio–Oil and Gas Law Developments

This article addresses oil and gas case law developments that have occurred within the Appalachian Basin’s primary oil and gas producing states of Pennsylvania, West Virginia, and Ohio during 2021 by reviewing opinions issued by the highest appellate courts within each of these three states. The oil and gas law topics addressed by these state supreme courts during 2021 have ranged from those occurring upstream, such as leasing, to those occurring downstream, such as approval of a utility rate increase for the extension of a natural gas pipeline.

Multi-proxy provenance of the lower Pennsylvanian Pottsville sandstone of the northern Appalachian basin in Pennsylvania, U.S.A: Paleodrainage, sources, and detrital history

ABSTRACT The lower Pennsylvanian Pottsville Formation, in the Appalachian foreland basin, constitutes a late Paleozoic clastic wedge formed close to the Appalachian orogenic belt. In this study, we analyzed Pottsville sandstone from the western bituminous and eastern anthracite fields in Pennsylvania to evaluate the detrital history of the sediments. Petrographic modal analyses show that sandstone in the western bituminous field ranges from quartzarenite to sublitharenite, with mean composition of Qt84F1L15; sampled sandstone from the eastern anthracite field is dominated by sublitharenite to litharenite with mean composition of Qt70F2L29. Heavy-mineral assemblages from both fields are dominated by ultrastable minerals (zircon, rutile, and tourmaline), apatite, sphene, spinel, siderite, and abundant opaques. Almost all the studied sandstone samples are garnet-depleted except one from the eastern anthracite field. The chemical composition of chromium- and zinc-rich spinel in samples from both fields might suggest exhumation of an arc terrane and ophiolitic belt with ultramafic igneous rocks. Particularly, the ternary plot of Fe3+–Cr3+–Al3+ end members for the chrome spinels possibly suggest a derivation from an alpine-type peridotite complex. Laser 40Ar/39Ar analyses of detrital muscovite from eastern anthracite fields and western bituminous fields record separate ages, with the former characterized by prominent Middle to Late Ordovician Taconic and Middle Devonian Acadian ages with two discrete modes at 463 and 369 Ma, and the latter dominated by Late Ordovician Taconic, Middle Devonian Acadian, and Late Devonian Neoacadian ages with discrete modes at 445, 397, 360, and 351 Ma. The new data suggest that early Pennsylvanian sedimentation in the Appalachian foreland basin was controlled by southward, southwestward, and westward drainage systems that originated in the Appalachian orogenic belt to the east and northeast.

Boron proxies record paleosalinity variation in the North American Midcontinent Sea in response to Carboniferous glacio-eustasy

Abstract Salinity variation in ancient epicontinental seas has long been challenging to reconstruct. We determined salinity variation in the Late Pennsylvanian North American Midcontinent Sea based on normalized boron concentrations (B/Ga) and isotopic compositions (δ11B) of bulk shale. We analyzed the Stark Shale Member of the Missourian Stage Dennis Limestone cyclothem in the Charleston core (CC) from the Illinois Basin (eastward, more proximal) and the Iowa Riverton core (IRC) from the Midcontinent Shelf (westward, more distal). Both cores exhibited the same pattern of secular variation, with lower B/Ga and δ11B values at their base and top, recording less saline conditions during lower sea-level stands, and higher values in their middle part, recording more saline conditions at highstands—a pattern that conforms to conventional sequence stratigraphic and glacio-eustatic interpretations of Midcontinent cyclothems. At equivalent stratigraphic levels, B/Ga and δ11B values are systematically lower at CC relative to IRC, reflecting the generally lower salinity conditions of the Illinois Basin relative to the Midcontinent shelf, which is consistent with greater freshwater influence from the east due to heavy river runoff into the Appalachian foreland basin. Our findings serve to demonstrate the utility of paired B concentration and isotope data for paleosalinity analysis of deep-time shale formations.

Sequence stratigraphic reconstruction of the late Middle Devonian Geneseo Formation of NY, USA: Developing a genetic model for “Upper Devonian” unconventional targets in the Northern Appalachian Basin

The late Middle Devonian Geneseo Formation and its lateral equivalents in the northern Appalachian Basin are significant secondary targets to the extensively explored Marcellus Sub-group. Surface to sub-surface characterization of the mudstone-dominated Geneseo Formation combines detailed observations of facies, facies associations, stratal architecture, stratal geometry, and stratal terminations, in combination with geochemical proxies to assess proximal to distal trends and enable prediction of hydrocarbon play element quality and distribution. Correlations within this mudstone-rich succession are conducted at the parasequence-scale, and incorporate detailed descriptions of four drill cores, >100 outcrops, and mapping of >500 wireline logs.The Geneseo Formation herein has been subdivided into two depositional sequences comprising three lithostratigraphic units (i.e., Lower Geneseo, Fir Tree, and Upper Geneseo members respectively). The Lower and Upper Geneseo members show systematic aggradational to progradational parasequence stacking patterns, as well as downlap‒onlap stratal terminations with underlying strata; these members represent highstand systems tracts. The Fir Tree Member occurs between the Lower and Upper Geneseo members, truncates the underlying Lower Geneseo, shows progradational‒aggradational‒retrogradational parasequence stacking patterns, and spans two systems tracts: lowstand and transgressive.Isopach maps were constructed within the high-resolution sequence-stratigraphic framework to better understand thickness trends at the landing-zone scale. Thickness variation across the basin suggests reactivation of basement structures and syndepositional faulting strongly influenced accommodation. Specifically, the N–S trending Clarendon-Linden Fault System appears to have been a western sediment barrier during Geneseo time and the primary depocenter of fine-grained clastics occurs in south-central NY in a structural low. As the Geneseo system advanced, the succession sequentially filled topographic lows from east to west (proximal to distal). Understanding the controls on reservoir quality and distribution of secondary and tertiary targets to the Marcellus can facilitate ranking and prioritization of landing-zones, as well as optimization of well placement for completion design.

Assessing Unconventional Oil and Gas Exposure in the Appalachian Basin: Comparison of Exposure Surrogates and Residential Drinking Water Measurements.

Health studies report associations between metrics of residential proximity to unconventional oil and gas (UOG) development and adverse health endpoints. We investigated whether exposure through household groundwater is captured by existing metrics and a newly developed metric incorporating groundwater flow paths. We compared metrics with detection frequencies/concentrations of 64 organic and inorganic UOG-related chemicals/groups in residential groundwater from 255 homes (Pennsylvania n = 94 and Ohio n = 161). Twenty-seven chemicals were detected in ≥20% of water samples at concentrations generally below U.S. Environmental Protection Agency standards. In Pennsylvania, two organic chemicals/groups had reduced odds of detection with increasing distance to the nearest well: 1,2-dichloroethene and benzene (Odds Ratio [OR]: 0.46, 95% confidence interval [CI]: 0.23-0.93) and m- and p-xylene (OR: 0.28, 95% CI: 0.10-0.80); results were consistent across metrics. In Ohio, the odds of detecting toluene increased with increasing distance to the nearest well (OR: 1.48, 95% CI: 1.12-1.95), also consistent across metrics. Correlations between inorganic chemicals and metrics were limited (all |ρ| ≤ 0.28). Limited associations between metrics and chemicals may indicate that UOG-related water contamination occurs rarely/episodically, more complex metrics may be needed to capture drinking water exposure, and/or spatial metrics in health studies may better reflect exposure to other stressors.

Structural, Depositional, and Diagenetic Controls on Anomalous Lower Pennsylvanian Oil Play, Pottsville Group, Appalachian Basin

Structural, Depositional, and Diagenetic Controls on Anomalous Lower Pennsylvanian Oil Play, Pottsville Group, Appalachian Basin

The pre-Taghanic (Givetian, Middle Devonian) ecosystems of Miłoszów (Holy Cross Mts, Poland)

The middle and upper parts of the Skały Fm, Early to Middle Givetian in age, were investigated in four sections at Miłoszów Wood in the Łysogóry Region (northern region of the Holy Cross Mountains, central Poland). The dating is based on conodonts ( Polygnathus timorensis Zone to the later part of the Polygnathus varcus / Polygnathus rhenanus Zone; early Polygnathus ansatus Zone cannot be excluded) and spores (Ex1–2 subzones) and, coupled with cartographic analysis and geophysical investigation, allows correlation within the strongly faulted succession. Significant lateral facies variations within the carbonate ramp depositional system in comparison with the better studied Grzegorzowice–Skały section, about 3 km distant, are documented, thanks to conodont-based correlation of both successions. Foraminifers, fungi, sponges, rugose and tabulate corals, medusozoans, microconchids and cornulitids, polychaetes (scolecodonts), molluscs (bivalves, rostroconchs, and gastropods), arthropods (trilobites and ostracods), bryozoans, hederelloids, ascodictyids, brachiopods, echinoderms (mostly crinoids, rare echinoids, holuthurians, and ophiocistoids), conodonts, fish, plants (prasinophytes, chlorophycophytes, and land plant spores), and acritarchs are present. Brachiopods are the most diverse phylum present (68 species), other richly represented groups are bryozoans and echinoderms; in contrast, cephalopods and trilobites are low in diversity and abundance. The muddy, middle to outer ramp biota (200 marine taxa, including 170 species of marine animals, 22 photoautotrophs, 6 forams) represents a mixture of allochthonous shallower-water communities (upper BA3), including storm- and possibly tsunami-affected coral mounds, and autochthonous deep-water soft-bottom brachiopod (e.g., Bifida–Echinocoelia ) communities (BA 4–5). The richness and diversity of the Miłoszów biota is relatively high, comparable with other approximately coeval pre-Taghanic ecosystems during the Devonian climatic deterioration (cooling). Preliminary data indicate that in the Holy Cross Mountains, no large-scale replacement of brachiopod (and probably many other benthic ones, like crinoids) communities took place between the Early–Middle Givetian and the Early Frasnian, in contrast to the demise of the Hamilton/Upper Tully fauna in the Appalachian Basin. Such a similarity of pre- and post-Taghanic faunas does not exclude the occurrence of environmental perturbations and transient community turnovers, caused by immigrations during the Taghanic Biocrisis, but evidences the successful recovery of the indigenous biota.

Black Shale—Gray Shale Transitions in a Late Devonian Shale Succession, Central Appalachian Basin (Northern Ohio): Sedimentary and Geochemical Evidence for Terrestrial Organic Matter Driving Anoxia Events

Black Shale—Gray Shale Transitions in a Late Devonian Shale Succession, Central Appalachian Basin (Northern Ohio): Sedimentary and Geochemical Evidence for Terrestrial Organic Matter Driving Anoxia Events

Temporal changes in domestic water well methane reflect shifting sources of groundwater: Implications for evaluating contamination attributed to shale gas development

Regulatory agencies routinely assess the presence of stray gas release from unconventional gas wells by sampling for methane in nearby groundwater after the well is drilled or if citizens complain about methane in their water. We studied whether methane concentrations in groundwater naturally vary through time in a shale gas basin where unconventional development and hydraulic fracturing has not yet occurred, to test the assumption that pre-drilling observations of well water quality can be reliable measures for assessing impacts of later gas drilling. We collected groundwater samples from 11 domestic wells in New York monthly for 13 months for methane and ion concentrations in a highly gas productive part of the Appalachian basin where fracking has been banned. Changing methane concentrations correlated with changes in chloride and bromide, indicating changing mixtures of shallow freshwater and deeper formation brine extracted by the wells through time. The hydrogeologic setting of a water well can cause variability in methane concentrations that may mimic stray gas but cannot be attributable to gas drilling. For this reason, before and after testing has limited utility to distinguish impacts of gas drilling from other causes of changing methane concentrations unless that testing includes sampling a comprehensive set of ions multiple times prior to drilling.

Carbon cycle dynamics and ecology revealed by the carbon isotopic composition of single organic microfossils during the Late Devonian Biotic Crisis.

We apply a new approach for the δ13 C analysis of single organic-walled microfossils (OWM) to three sites in the Appalachian Basin of New York (AB) that span the Late Devonian Biotic Crisis (LDBC). Our data provide new insights into the nature of the Frasnian-Famennian carbon cycle in the AB and also provide possible constraints on the paleoecology of enigmatic OWM ubiquitous in Paleozoic shale successions. The carbon isotope compositions of OWM are consistent with normal marine organic matter of autochthonous origins and range from -32 to -17‰, but average -25‰ across all samples and are consistently 13 C-enriched compared to bulk sediments (δ13 Cbulk ) by ~0-10‰. We observe no difference between the δ13 COWM of leiospheres (smooth-walled) and acanthomorphic (spinose) acritarch OWM, indicating that our data are driven by ecological rather than taxonomic signals. We hypothesize that the offset between δ13 COWM and δ13 Cbulk is in part due to a large δ13 C gradient in the AB water column where OWM utilized relatively 13 C-enriched dissolved inorganic carbon near the surface. Thus, the organisms producing the balance of the total organic carbon were assimilating 13 C-depleted C sources, including but not limited to respired organic carbon or byproducts of fermentation. We also observe a systematic decrease in both δ13 COWM and δ13 Cbulk of 3‰ from shoreward to open-ocean facies that may reflect the effect of 13 C-enriched dissolved inorganic carbon (DIC) derived from riverine sources in the relatively enclosed AB. The hypothesized steep carbon isotope gradient in the AB could be due to a strong biological pump; this in turn may have contributed to low oxygen bottom water conditions during the LDBC. This is the first time single-microfossil δ13 Corg analyses of eukaryotes have been directly compared to bulk δ13 Corg in the deep-time fossil record.

Appalachian coal bed palynofloras: changes in composition through time and comparison with other areas

Abstract This paper presents a summary of palynological data for Pennsylvanian age coal beds in the Appalachian Basin, discussed primarily from a biostratigraphic perspective. Coal bed palynofloras of Lower Pennsylvanian through early Permian age are compared and correlated with miospore assemblage zones established for western Europe, and the Eastern Interior (Illinois) and Western Interior Basins of the mid-continent USA. Lower Pennsylvanian palynofloras, which are dominated by lycopsid spores, are correlative with the Langsettian of western Europe and the Morrowan of the Eastern and Western Interior mid-continent USA Basins. Stratigraphically useful palynotaxa include Dictyotriletes bireticulatus , Radiizonates striatus , Schulzospora rara , Granasporites medius , Laevigatosporites minor and Endosporites globiformis . Middle Pennsylvanian palynofloras change through time, being lycopsid dominant in the lower part and more heterogeneous in the middle and upper parts with increased contributions from other Pennsylvanian plant groups. They are correlative with the Duckmantian, Bolsovian and Asturian of western Europe and the Atokan and Desmoinesian of the Eastern and Western Interior mid-continent USA Basins. Stratigraphically useful palynotaxa include Secarisporites remotus , Microreticulatisporites sulcatus , Vestispora fenestrata , Triquitrites sculptilis , Laevigatosporites globosus , Radiizonates difformis , Torispora securis , Triquitrites minutus , Mooreisporites inusitatus , Murospora kosankei , Thymospora pseudothiessenii and Schopfites dimorphus . Upper Pennsylvanian and lower Permian coal beds in the Appalachian Basin, in contrast to their Lower and Middle Pennsylvanian counterparts, are strongly dominated by tree fern spore palynotaxa. Palynofloras correlate with the Stephanian and Autunian of western Europe and the Missourian, Virgilian and Wolcampian of the Eastern and Western Interior mid-continent USA Basins.

Groundwater Methane in Northeastern Pennsylvania Attributable to Thermogenic Sources and Hydrogeomorphologic Migration Pathways.

Conflicting evidence exists as to whether or not unconventional oil and gas (UOG) development has enhanced methane transport into groundwater aquifers over the past 15 years. In this study, recent groundwater samples were collected from 90 domestic wells and 4 springs in Northeastern Pennsylvania located above the Marcellus Shale after more than a decade of UOG development. No statistically significant correlations were observed between the groundwater methane level and various UOG geospatial metrics, including proximity to UOG wells and well violations, as well as the number of UOG wells and violations within particular radii. The δ13C and methane-to-higher chain hydrocarbon signatures suggested that the elevated methane levels were not attributable to UOG development nor could they be explained by using simple biogenic-thermogenic end-member mixing models. Instead, groundwater methane levels were significantly correlated with geochemical water type and topographical location. Comparing a subset of contemporary methane measurements to their co-located pre-drilling records (n = 64 at 49 distinct locations) did not indicate systematic increases in methane concentration but did reveal several cases of elevated concentration (n = 12) across a spectrum of topographies. Multiple lines of evidence suggested that the high-concentration groundwater methane could have originated from shallow thermogenic methane that migrated upward into groundwater aquifers with Appalachian Basin brine.