Maturation grade of coals as revealed by Raman spectroscopy: progress and problems.

The present study questions the sensitivity and the accuracy of Raman spectroscopy as a tool for determining the maturity of natural organic matter (NOM). It focuses on the definition of optimized experimental parameters in order to maximize the quality of the Raman signal and control the accuracy and reproducibility of measurements. A series of 11 coals has been investigated, sampling a wide maturity range (2-7% vitrinite reflectance VR). The role of experimental parameters is first investigated. An excitation wavelength of 514.5 nm gives better results than 457.9 and 632.8 nm, minimizing the fluorescence background observed in the spectra of low-rank coals. Both Raman and fluorescence spectra were investigated with time-resolved experiments in air and argon. These data show that fluorescence and Raman spectra are sensitive to acquisition time and laser power parameters, and reveal a physicochemical instability of the samples under laser irradiation, mostly due to photo-oxidation processes. These data clearly show that the experiments, especially in air, should be performed with strictly constant acquisition parameters. In addition, the results of a whole series of coal measurements performed in air under constant experimental conditions show that Raman spectroscopy is definitely sensitive to the maturity of coal samples with VR> approximately 1%. The most sensitive spectral maturity tracers are the width of the D-band (FWHM-D), the ratio of the peak intensities of the D- and G-bands (I(D)/I(G)), the normalized ratio of the band integrated intensities A(D)/[A(D)+A(G)] for the maturity range VR=3-7% and the width of the G-band (FWHM-G) for VR=1-5%. However, the accuracy and reproducibility are definitely weaker in such measurements compared to the standard VR. Future work must solve the problem of sample stability under laser irradiation, and greatly increase the number of samples to improve the statistical significance of the results.