Cathodoluminescence differentiates sedimentary organic matter types.

High-resolution scanning electron microscopy (SEM) visualization of sedimentary organic matter is widely utilized in the geosciences for evaluating microscale rock properties relevant to depositional environment, diagenesis, and the processes of fluid generation, transport, and storage. However, despite thousands of studies which have incorporated SEM methods, the inability of SEM to differentiate sedimentary organic matter types has hampered the pace of scientific advancement. In this study, we show that SEM-cathodoluminescence (CL) properties can be used to identify and characterize sedimentary organic matter at low thermal maturity conditions. Eleven varied mudstone samples with a broad array of sedimentary organic matter types, ranging from the Paleoproterozoic to Eocene in age, were investigated. Sedimentary organic matter fluorescence intensity and CL intensity showed an almost one-to-one correspondence, with certain exceptions in three samples potentially related to radiolytic alteration. Therefore, because CL emission can be used as a proxy for fluorescence emission from sedimentary organic matter, CL emission during SEM visualization can be used to differentiate fluorescent from non-fluorescent sedimentary organic matter. This result will allow CL to be used as a visual means to quickly differentiate sedimentary organic matter types without employing correlative optical microscopy and could be widely and rapidly adapted for SEM-based studies in the geosciences.

Geologic sources and well integrity impact methane emissions from orphaned and abandoned oil and gas wells.

The 160-year history of oil and gas drilling in the United States has left a legacy of unplugged orphaned and abandoned wells, some of which are leaking methane and other hazardous chemicals into the environment. The locations of around 120,000 documented orphaned wells are currently known with the number of undocumented orphaned wells possibly ranging towards a million. The bulk of methane emissions originate from only 10 % of orphaned and abandoned wells, while the remaining wells have undetectable emissions. Understanding the sources of methane emissions from orphaned wells is key to estimating emission rates and prioritizing plugging. In this article, we identify key studies reporting methane emission measurements from orphaned and abandoned wells in the published literature and analyze previously published isotopic methane data to categorize the sources of methane emissions. Three primary geologic sources provide methane to a leaking well that can migrate from geologic formations into or along the wellbore to contaminate groundwater, the surface environment, and the atmosphere. These geologic sources of methane are petroleum (oil and gas) sourced reservoirs, coal seams, and methanogenesis occurring in and around the wellbore. Thermogenic petroleum gas reservoirs are associated with the highest emission rates measured to date. The next highest rates are from coalbed methane sources, while biogenic sources are the lowest based on the publicly available measured emissions data. Well conditions that could potentially enable methane transport include decay of the wellhead and surface infrastructure, wellbore deterioration from corrosive fluids in the subsurface, delamination of the casing and cement, damage from seismicity, and new fracture networks created by hydraulic fracturing of newly drilled neighboring wells. With an understanding of these geologic sources and well conditions, we can (1) better identify areas where high-emitting wells are likely to be present, (2) improve emission rate estimates from orphaned and abandoned wells, and (3) better prioritize wells for plugging. SYNOPSIS: Understanding the geologic sources of methane emissions from orphaned and abandoned wells and wellbore conditions that lead to methane release can significantly improve emissions estimates and aid in prioritizing which wells to plug.

Water-rock interaction and the concentrations of major, trace, and rare earth elements in hydrocarbon-associated produced waters of the United States.

Studies of co-produced waters from hydrocarbon extraction across multiple energy-producing basins have generally focused on major ions or a few select tracers, and studies that examine trace elements and involve laboratory experiments have generally been basin specific. Here, new perspective is sought through a broad analysis of concentration data for 26 elements from three hydrocarbon well types using the U.S. Geological Survey National Produced Waters Geochemical Database (v2.3). Those data are compared to leachates (water, hydrochloric acid, and artificial brine) from 12 energy-resource related shales from across the United States. Both lower pH and higher ionic strength were associated with greater concentrations of many trace elements in produced waters. However, individual effects were difficult to distinguish because higher ionic strengths drive decreases in pH. Water-rock interactions in the leaching experiments generally replicated produced water concentrations for trace elements including Al, As, Cd, Co, Cu, Mo, Ni, Pb, Sb, Si, and Zn. Enhanced middle rare earth element (REE) mobilization relative to shale REE content occurred with low pH leachates. Produced water concentrations of Li, Sr, and Ba were not replicated by the leaching experiments. Patterns of high Li, Sr, and Ba concentrations and ratios relative to other elements across produced waters types indicate controls on these elements in many settings related to pore space pools of salts, brines, and ion-exchange sites affected by diagenetic processes. The size of those pools is diluted and masked by other water-rock interaction processes at the water-rock ratios necessitated by laboratory experiments. The results broadly link water-rock interaction processes and environmental patterns across a wide variety of produced waters and host formations and thus provide context for trace element data from other environmental and laboratory studies of such waters.

Simultaneous Gaussian and exponential inversion for improved analysis of shales by NMR relaxometry.

Nuclear magnetic resonance (NMR) relaxometry is commonly used to provide lithology-independent porosity and pore-size estimates for petroleum resource evaluation based on fluid-phase signals. However in shales, substantial hydrogen content is associated with solid and fluid signals and both may be detected. Depending on the motional regime, the signal from the solids may be best described using either exponential or Gaussian decay functions. When the inverse Laplace transform, the standard method for analysis of NMR relaxometry results, is applied to data containing Gaussian decays, this can lead to physically unrealistic responses such as signal or porosity overcall and relaxation times that are too short to be determined using the applied instrument settings. We apply a new simultaneous Gaussian-Exponential (SGE) inversion method to simulated data and measured results obtained on a variety of oil shale samples. The SGE inversion produces more physically realistic results than the inverse Laplace transform and displays more consistent relaxation behavior at high magnetic field strengths. Residuals for the SGE inversion are consistently lower than for the inverse Laplace method and signal overcall at short T2 times is mitigated. Beyond geological samples, the method can also be applied in other fields where the sample relaxation consists of both Gaussian and exponential decays, for example in material, medical and food sciences.

Application of binomial-edited CPMG to shale characterization.

Unconventional shale resources may contain a significant amount of hydrogen in organic solids such as kerogen, but it is not possible to directly detect these solids with many NMR systems. Binomial-edited pulse sequences capitalize on magnetization transfer between solids, semi-solids, and liquids to provide an indirect method of detecting solid organic materials in shales. When the organic solids can be directly measured, binomial-editing helps distinguish between different phases. We applied a binomial-edited CPMG pulse sequence to a range of natural and experimentally-altered shale samples. The most substantial signal loss is seen in shales rich in organic solids while fluids associated with inorganic pores seem essentially unaffected. This suggests that binomial-editing is a potential method for determining fluid locations, solid organic content, and kerogen-bitumen discrimination.

Updated methodology for nuclear magnetic resonance characterization of shales.

Unconventional petroleum resources, particularly in shales, are expected to play an increasingly important role in the world's energy portfolio in the coming years. Nuclear magnetic resonance (NMR), particularly at low-field, provides important information in the evaluation of shale resources. Most of the low-field NMR analyses performed on shale samples rely heavily on standard T1 and T2 measurements. We present a new approach using solid echoes in the measurement of T1 and T1-T2 correlations that addresses some of the challenges encountered when making NMR measurements on shale samples compared to conventional reservoir rocks. Combining these techniques with standard T1 and T2 measurements provides a more complete assessment of the hydrogen-bearing constituents (e.g., bitumen, kerogen, clay-bound water) in shale samples. These methods are applied to immature and pyrolyzed oil shale samples to examine the solid and highly viscous organic phases present during the petroleum generation process. The solid echo measurements produce additional signal in the oil shale samples compared to the standard methodologies, indicating the presence of components undergoing homonuclear dipolar coupling. The results presented here include the first low-field NMR measurements performed on kerogen as well as detailed NMR analysis of highly viscous thermally generated bitumen present in pyrolyzed oil shale.

PAH repartitioning in field-contaminated sediment following removal of the labile chemical fraction.

The effect of removing the labile chemical fraction associated with sediment particles followed by internal chemical redistribution was examined in a field-contaminated sediment. Using data from desorption equilibrium (organic carbon-water partition coefficients, K(OC)) and kinetic (rate of release) experiments, estimates of polynuclear aromatic hydrocarbon biphasic partitioning and desorption rates for both the labile and nonlabile chemical fractions or organic matter compartments were obtained. Sediment K(OC) values increased between 50 and 150% after removal of the labile chemical fraction. Following depletion of the labile chemical fraction during desorption experiments, sediment was stored 30 and 90 days to allow for chemical redistribution between the labile and nonlabile compartments. The subsequent desorption data indicated repartitioning had occurred with the nonlabile chemical fraction recharging the labile compartment. The results provide evidence that chemical transfer between organic matter compartments, either through interparticle porewater or via direct intraparticle compartmental exchange, is a real phenomenon that occurs over relatively short times (weeks to months). This calls into question the idea that hydrophobic organic pollutants in the nonlabile chemical fraction are sequestered or less bioavailable over the long-term and has implications for water quality impacts during contaminated sediment resuspension events, risk assessment of polluted sites, and selection of sediment remediation strategies.

The pseudophase approach to assessing chemical partitioning in air-water-cyclodextrin systems.

Henry's Law constants (HLCs) of several common, subsurface hydrophobic organic pollutants (HOPs) including trichloroethylene (TCE), perchloroethylene (PCE) and benzene, toluene, ethylbenzene, and o-xylene (BTEX), were measured using a static headspace phase ratio (SHPR) method over a range of temperatures (35, 45, 55, and 65 degrees C) and experimentally and operationally relevant cyclodextrin (CD) concentrations (0, 10, 20, 50, and 100 g L(-1)). In aqueous CD solutions, HLC values decrease according to a power law relationship with increasing CD concentration due to an apparent solubility enhancement caused by HOP partitioning to the hydrophobic cavity of CD molecules. The temperature dependence of air-water partitioning under the influence of CD was well described by the van't Hoff equation for all HOPs tested. A three-phase equilibrium model was used to interpret air-water-CD partitioning data, treating CD as a pseudophase. Our results show that HOP CD-water partition coefficients decrease linearly with increasing temperature. CD-water partition coefficients were generally independent of CD concentration, with a few exceptions. Comparison of our results for hydroxypropyl-beta-CD and TCE to those from another study showed several major discrepancies, which were attributed to differences in the experimental methods employed. Our attempt to correlate CD-water partition coefficients with HOP chemical properties indicates that correlations based on individual chemical descriptors (e.g., aqueous solubility, octanol-water partition coefficient, molecular volume or ET (30) polarity index) will not be sufficient to obtain accurate estimates of HOP CD-water partition coefficients for other compounds with differing chemical structures.

A multi-method comparison of Atchafalaya Basin surface water organic matter samples.

Surface water organic matter (OM) was isolated from two distinct sites within the Atchafalaya Basin using a combination of XAD-8 and XAD-4 non-ionic macroporous resins and characterized by a suite of analytical methods, including elemental analysis, (13)C cross polarization magic angle spinning nuclear magnetic resonance, attenuated total reflectance Fourier transform infrared, luminescence spectroscopy including parallel factor analysis, and ultraviolet-visible spectroscopy. The major findings of the study are (i) despite the large differences in hydrology, optical properties, iron content, dissolved oxygen, and degree of human exploitation, the spectral and elemental signatures of the hydrophobic acids and transphilic acids fractions of the isolated OM for the different sites were remarkably similar; (ii) the luminescence characteristics of the four studied fractions provided information on the relative contributions from terrestrial and microbial input sources, as well as the degree of humification; and (iii) a detailed analysis of the total luminescence data led to a new dual excitation model based on quinone exciplexes for long wavelength emissions.