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A new laboratory approach to shale analysis using NMR relaxometry

Low-field nuclear magnetic resonance (LF-NMR) relaxometry is a non-invasive technique commonly used to assess hydrogen-bearing fluids in petroleum reservoir rocks. Measurements made using LF-NMR provide information on rock porosity, pore-size distributions, and in some cases, fluid types and saturations (Timur, 1967; Kenyon et al., 1986; Straley et al., 1994; Brown, 2001; Jackson, 2001; Kleinberg, 2001; Hurlimann et al., 2002). Recent improvements in LF-NMR instrument electronics have made it possible to apply methods used to measure pore fluids to assess highly viscous and even solid organic phases within reservoir rocks. T 1 and T 2 relaxation responses behave very differently in solids and liquids; therefore the relationship between these two modes of relaxation can be used to differentiate organic phases in rock samples or to characterize extracted organic materials. Using T 1 -T 2 correlation data, organic components present in shales, such as kerogen and bitumen, can be examined in laboratory relaxometry measurements. In addition, implementation of a solid-echo pulse sequence to refocus T 2 relaxation caused by homonuclear dipolar coupling during correlation measurements allows for improved resolution of solid-phase protons. LF-NMR measurements of T 1 and T 2 relaxation time distributions were carried out on raw oil shale samples from the Eocene Green River Formation and pyrolyzed samples of these shales processed by hydrous pyrolysis and techniques meant to mimic surface and in-situ retorting. Samples processed using the In Situ Simulator approach ranged from bitumen and early oil generation through to depletion of petroleum generating potential. The standard T 1 -T 2 correlation plots revealed distinct peaks representative of solid- and liquid-like organic phases; results on the pyrolyzed shales reflect changes that occurred during thermal processing. The solid-echo T 1 and T 2 measurements were used to improve assessment of the solid organic phases, specifically kerogen, thermally degraded kerogen, and char. Integrated peak areas from the LF-NMR results representative of kerogen and bitumen were found to be well correlated with S1 and S2 parameters from Rock-Eval programmed pyrolysis. This study demonstrates that LFNMR relaxometry can provide a wide range of information on shales and other reservoir rocks that goes well beyond porosity and pore-fluid analysis.

Conference Paper↗

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.

Journal of Magnetic Resonance↗

Field experiment provides ground truth for surface nuclear magnetic resonance measurement

The need for sustainable management of fresh water resources is one of the great challenges of the 21st century. Since most of the planet's liquid fresh water exists as groundwater, it is essential to develop non-invasive geophysical techniques to characterize groundwater aquifers. A field experiment was conducted in the High Plains Aquifer, central United States, to explore the mechanisms governing the non-invasive Surface NMR (SNMR) technology. We acquired both SNMR data and logging NMR data at a field site, along with lithology information from drill cuttings. This allowed us to directly compare the NMR relaxation parameter measured during logging, T 2 , to the relaxation parameter T 2 * measured using the SNMR method. The latter can be affected by inhomogeneity in the magnetic field, thus obscuring the link between the NMR relaxation parameter and the hydraulic conductivity of the geologic material. When the logging T 2 data were transformed to pseudo- T 2 * data, by accounting for inhomogeneity in the magnetic field and instrument dead time, we found good agreement with T 2 * obtained from the SNMR measurement. These results, combined with the additional information about lithology at the site, allowed us to delineate the physical mechanisms governing the SNMR measurement. Such understanding is a critical step in developing SNMR as a reliable geophysical method for the assessment of groundwater resources.

Geophysical Research Letters↗

EAST93: Geophysical traverse from the Transantarctic Mountains to the Wilkes Basin, East Antarctica

The East Antarctic Seismic Traverse (EAST93) was a geophysical traverse designed to image the bedrock under the East Antarctic ice cap. The traverse started 10 km west of the Taylor Dome drill site and 25 km west of the exposed bedrock of the Transantarctic Mountains at Lashly Mt. and ended 323 km west of the drill site over the Wilkes subglacial basin (Fig. 1). The traverse was located subparallel to latitude 78° S starting 30-50 km north of the Victoria Land Traverse (1958-1959). It was carried out jointly by the U.S. Geological Survey and Stanford University, U.S.A., together with the Institute of Geological and Nuclear Sciences, and Victoria University, New Zealand, during December 1993 and January 1994. The geophysical traverse included 236 km of multichannel seismic reflection data at 150 m shot intervals, 312.5 km of gravity data collected at intervals of 2.1 km, 312.5 km of magnetic data (total field intensity) collected at average intervals of 0.5 km, and 205 km of ground penetrating radar at intervals of 77 m. Relative locations and elevations of the entire traverse were measured at intervals of 150 m by traditional surveying methods, and tied to three absolute locations measured by the Global Positioning System (GPS). EAST93 is the first large-scale geophysical traverse on the polar plateau to our knowledge since the early 1960s. As such, the experiment presented several logistical challenges: (1) how to collect regional seismic profiles during the short Antarctic summer; (2) how to keep the scientific instruments running with minimal protection in harsh conditions; and (3) how to combine daily moves of camp with full days of work. The scientific and logistical aspects of the project proceeded, in general, according to plan despite the harsh conditions and our lack of previous experience on the polar plateau. Two unanticipated problems affected the progress of the work: the strong wind which slowed seismic acquisition, and the break-down of one of the large traverse vehicles. The major operational lessons of this project are. (1) Primacord laid close to the surface is not an adequate seismic source for imaging under the thick East Antarctic ice sheet, despite positive prior tests on the Ross Ice Shelf. (2) It is necessary to reduce the 6-7 hours spent daily on camp move and other chores by integrating the living quarters into the working teams, and by improving vehicle warming methods and generator housing. The following report details the operational and logistical aspects of the work, the weather and ground conditions, the technical aspects of acquisition of geophysical data, and lessons and recommendations for future geophysical traverses.

Open-File Report↗

Management of fluid mud in estuaries, bays, and lakes. II: Measurement, modeling, and management

Techniques for measurement, modeling, and management of fluid mud are available, but research is needed to improve them. Fluid mud can be difficult to detect, measure, or sample, which has led to new instruments and new ways of using existing instruments. Multifrequency acoustic fathometers sense neither density nor viscosity and are, therefore, unreliable in measuring fluid mud. Nuclear density probes, towed sleds, seismic, and drop probes equipped with density meters offer the potential for accurate measurements. Numerical modeling of fluid mud requires solving governing equations for flow velocity, density, pressure, salinity, water surface, plus sediment submodels. A number of such models exist in one-, two-, and three-dimensional form, but they rely on empirical relationships that require substantial site-specific validation to observations. Management of fluid mud techniques can be classified as those that accomplish: Source control, formation control, and removal. Nautical depth, a fourth category, defines the channel bottom as a specific fluid mud density or alternative parameter as safe for navigation. Source control includes watershed management measures to keep fine sediment out of waterways and in-water measures such as structures and traps. Formation control methods include streamlined channels and structures plus other measures to reduce flocculation and structures that train currents. Removal methods include the traditional dredging and transport of dredged material plus agitation that contributes to formation control and/or nautical depth. Conditioning of fluid mud by dredging and aerating offers the possibility of improved navigability. Two examples—the Atchafalaya Bar Channel and Savannah Harbor—illustrate the use of measurements and management of fluid mud.

Journal of Hydraulic Engineering↗

Three new calcium formate reference materials for δ13C measurements and a redetermination of the R(13C/12C) ratio for VPDB based on proton nuclear magnetic resonance measurements

Rationale Isotope ratio mass spectrometry (IRMS) and proton nuclear magnetic resonance ( 1 H NMR) spectroscopy are independent techniques for determining the isotope ratio R ( 13 C/ 12 C) in organic compounds. However, the lack of suitable reference materials has limited intercalibration of results from these methods. Methods Three high-purity calcium formate isotopic reference materials were developed, each ideal for accurate isotope ratio measurements by both 1 H NMR and isotope-ratio mass spectrometry (IRMS). For each material, R ( 13 C/ 12 C) was determined by 1 H NMR, and the relative isotope abundance ( δ 13 C VPDB-LSVEC ) by IRMS. The combined IRMS and NMR results were used to determine the R ( 13 C/ 12 C) value of Vienna Peedee belemnite (VPDB). Results The combined datasets yield a value for R ( 13 C/ 12 C) of 0.0111050 ± 0.0000047 ( k = 2) for VPDB, which is 6.7‰ lower than the commonly cited value of 0.011180, but similar to other recent determinations. These three calcium formate reference materials exhibit high accuracy across both analytical methods and provide robust tools for instrument calibration, method validation, and inter-laboratory comparison in carbon stable isotope ratio analysis. Conclusions An accurate R ( 13 C/ 12 C) value for VPDB strengthens the link between relative ( δ 13 C VPDB-LSVEC ) values from IRMS and R ( 13 C/ 12 C) isotope ratios from NMR and other techniques. These three calcium formate isotopic reference materials (USGS106, USGS107, and USGS108) are available from the US Geological Survey and provide reference materials for calibration, method validation, and inter-laboratory comparison in carbon isotope ratio analysis.

Rapid Communications in Mass Spectrometry↗

Neutron activation determination of iridium, gold, platinum, and silver in geologic samples

Low-level methods for the determination of iridium and other noble metals have become increasingly important in recent years due to interest in locating abundance anomalies associated with the Cretaceous and Tertiary (K-T) boundary. Typical iridium anomalies are in the range of 1 to 100 ??g/kg (ppb). Thus methods with detection limits near 0.1 ??g/kg should be adequate to detect K-T boundary anomalies. Radiochemical neutron activation analysis methods continue to be required although instrumental neutron activation analysis techniques employing elaborate gamma-counters are under development. In the procedure developed in this study samples irradiated in the epithermal neutron facility of the U. S. Geological Survey TRIGA Reactor (Denver, Colorado) are treated with a mini-fire assay technique. The iridium, gold, and silver are collected in a 1-gram metallic lead button. Primary contaminants at this stage are arsenic and antimony. These can be removed by heating the button with a mixture of sodium perioxide and sodium hydroxide. The resulting 0.2-gram lead bead is counted in a Compton suppression spectrometer. Carrier yields are determined by reirradiation of the lead beads. This procedure has been applied to the U.S.G.S. Standard Rock PCC-1 and samples from K-T boundary sites in the Western Interior of North America. ?? 1987 Akade??miai Kiado??.

Journal of Radioanalytical and Nuclear Chemistry A↗

Decomposition techniques

Sample decomposition is a fundamental and integral step in the procedure of geochemical analysis. It is often the limiting factor to sample throughput, especially with the recent application of the fast and modern multi-element measurement instrumentation. The complexity of geological materials makes it necessary to choose the sample decomposition technique that is compatible with the specific objective of the analysis. When selecting a decomposition technique, consideration should be given to the chemical and mineralogical characteristics of the sample, elements to be determined, precision and accuracy requirements, sample throughput, technical capability of personnel, and time constraints. This paper addresses these concerns and discusses the attributes and limitations of many techniques of sample decomposition along with examples of their application to geochemical analysis. The chemical properties of reagents as to their function as decomposition agents are also reviewed. The section on acid dissolution techniques addresses the various inorganic acids that are used individually or in combination in both open and closed systems. Fluxes used in sample fusion are discussed. The promising microwave-oven technology and the emerging field of automation are also examined. A section on applications highlights the use of decomposition techniques for the determination of Au, platinum group elements (PGEs), Hg, U, hydride-forming elements, rare earth elements (REEs), and multi-elements in geological materials. Partial dissolution techniques used for geochemical exploration which have been treated in detail elsewhere are not discussed here; nor are fire-assaying for noble metals and decomposition techniques for X-ray fluorescence or nuclear methods be discussed.

Journal of Geochemical Exploration↗

Determination of beta activity in water

Many elements have one or more naturally radioactive isotopes, and several hundred other radionuclides have been produced artificially. Radioactive substances may be present in natural water as a result of geochemical processes or the release of radioactive waste and other nuclear debris to the environment. The Geological Survey has developed methods for measuring certain of these .radioactive substances in water. Radioactive substances often are present in water samples in microgram quantities or less. Therefore, precautions must be taken to prevent loss of material and to assure that the sample truly represents its source at the time of collection. Addition of acids, complexing agents, or stable isotopes often aids in preventing loss of radioactivity on container walls, on sediment, or on other solid materials in contact with the sample. The disintegration of radioactive atoms is a random process subject to established methods of statistical analysis. Because many water samples contain small amounts of radioactivity, low-level counting techniques must be used. The usual assumption that counting data follow a Gaussian distribution is invalid under these conditions, and statistical analyses must be based on the Poisson distribution. The gross beta activity in water samples is determined from the residue left after evaporation of the sample to dryness. Evaporation is accomplished first in a teflon dish, then the residue is transferred with distilled water to a counting planchet and again is reduced to dryness. The radioactivity on the planchet is measured with an anticoincidence-shielded, low-background, beta counter and is compared with measurements of a strontium-90-yttrium-90 standard prepared and measured in the same manner. Control charts are used to assure consistent operation of the counting instrument.

Water Supply Paper↗