Kelsey Kehoe | USGS Science

USGS2018

Development of Raman spectroscopy as a thermal maturity proxy in unconventional resource assessment

The objective of this study was to correlate shale hydrous pyrolysis with thermal maturity measurements based on solid bitumen reflectance (BRo) at the U.S. Geological Survey (USGS) and Raman microscopy (RM) at WellDog. In semi-blind Phase I, BRo values of the initial set of 8 samples were withheld prior to RM analysis. As reported previously, a strong correlation was observed between BRo and Raman parameters. For Phase-II, BRo values for the second set of 8 samples were shared before RM. Observations from Phase-II are reported here as well as the ability of RM to correctly order the semi-blind Phase I samples. Immature shale samples from the Bakken (Phase-I) and Duvernay (Phase-II) formations were subjected to hydrous pyrolysis for 72 hours at temperatures from 280°C to 360°C. Rock residues from both series were mounted and polished (ASTM D2797) for analysis of BRo (ASTM D7708) and confocal laser-scanning Raman microscopy. For RM, multiple hyperspectral maps were collected from each sample, resulting in tens of thousands of spectra per sample. Map areas were ~5,000 μm2, with a spectrum collected from every square micrometer. The organic carbon G- (Graphitic-) and D- (Disordered) bands in each Raman spectrum were fit algorithmically to a multi-peak model, yielding a number of diagnostic parameters that correlate with changes occurring in samples as a result of thermal maturation and pyrolysis. Parameters extracted from analysis of Raman spectra were plotted against the previously determined BRo values to determine which Raman parameters best correlate with thermal maturity. Plotting two of the sample-averaged anonymized spectral parameters versus BRo in the Bakken series indicated an exponential trend with strong correlations (R2>0.8) as reported at URTeC in 2017 (MS-2671253). Similar strong relationships occurred in the Duvernay samples with respect to increasing maturity when using Partial Least-Squares analysis.

Conference Paper↗

USGS2017

Analysis of artificially matured shales with confocal laser scanning raman microscopy: Applications to organic matter characterization

Raman spectroscopy has been suggested as a method for characterizing the thermal maturity of rocks. The literature contains many empirical correlations between thermal maturity proxies, such as vitrinite reflectance (V Ro ) and pyrolysis-T max , with spectral metrics such as Raman peak-widths, peak-center positions, peak-areas and all manner of differences and ratios of these parameters. However, while these correlations may be convincing for small data sets from limited sample series, broader application of these metrics to disparate and heterogeneous samples proves difficult and there remains no consensus. In this extended abstract, Raman spectroscopy is introduced and the history of Raman analysis of carbonaceous material is briefly outlined, highlighting some of the latent difficulties and potential sources of bias. We suggest the organization of a community working group to establish terminology, guidelines, procedures and standards necessary for the successful development of this technique to characterize organic matter in an accessible, unbiased, and reproducible manner. For the present multi-phase study, immature shale samples from the Bakken and Duvernay formations were subjected to hydrous pyrolysis for 72 hours at temperatures from 280°C to 360°C. Rock residues were mounted and polished for analysis via confocal laser-scanning Raman microscopy and reflectance. The maturation series from the Bakken was randomized for the Phase-I single-blind study to be presented at this conference. For the Phase-II study, solid bitumen reflectance (B Ro ) values for the Duvernay series will be known. Multiple hyperspectral maps were collected from each Bakken sample, with each map consisting of a single diffraction-limited spot-size spectrum per 1 µm 2 in rectangular areas several hundred micrometers on a side. Initial attempts at using basic spectral metrics on small numbers of hand-selected spectra to sort the blind series produced inconclusive results: any number of possible correlations could be found. In an improved approach, the statistics of the full spectral datasets were leveraged to: 1) objectively identify organic carbon types (OCTs) in a given map based on Raman and fluorescence spectral characteristics, 2) identify those OCTs in other maps from the same sample and determine if the heterogeneity of the sample has been adequately characterized, and 3) identify the same OCTs in maps from other samples in the maturation series. In ongoing work, our goals are to: 1) use these analyses of the blind series to develop a hypothesis for a correlation to maturation, 2) test the hypothesis by applying the same analyses to the known Duvernay series (in Phase-II), 3) if necessary refine the hypothesis based on observations from the Duvernay analysis, and 4) finally reveal the true order of the Bakken series to verify if the hypothesized correlation accurately predicts the maturity order of the samples. In this document, we share progress to date. The analysis of one area of interest is detailed showing the differentiation of two OCTs based on Raman and fluorescence spectral features, including the use of 2-factor histograms, Principle Components Analysis (PCA), and Nonlinear Iterative Peak Fitting (NIPF).

Conference Paper↗