Multi-elemental surface mapping and analysis of carbonaceous shale by laser-induced breakdown spectroscopy

• Multi-elemental surface mapping and analysis of shale by LIBS were carried out.
• Redox sensitive elements of V, Cr and Ni were detected in shale by LIBS.
• Surface distribution for Si, Al, Fe, Ca, Mg, Na and K was constructed.

Gas shale is one of the important unconventional hydrocarbon source rocks, whose composition, such as mineral components and redox sensitive trace elements, has been proved as important geochemical proxies playing essential roles in indicating the gas potential and gas productivity in recent geological researches. Fast and accurate measurements for the shale composition, especially those with spatial resolution, will reveal rich information for the understanding and evaluation of gas shale reservoirs. In this paper, we demonstrated the potentiality as well as feasibility of laser-induced breakdown spectroscopy as an effective technique to perform spectrochemical analysis for shale samples. In case of the bulk analysis of pressed shale pellet, spectral analysis of the plasma emission revealed high sensitivity of LIBS for major, minor and even trace elements. More than 356 lines emitted by 19 different elements can be found. Among these species, redox sensitive trace elements such as V, Cr, and Ni were detected with high signal-to-ratios. Two-dimensional surface micro-analysis for the concerned major or minor elements with strong emissions was then applied to the smoothed shale slab. Local thermodynamic equilibrium for the plasma was first verified with a line profile point-by-point on the sample surface, the matrix effect was then assessed as negligible by the extracted electron density and temperature of the plasmas induced at each position on the same profile. Concentration mappings for the major elements of Si, Al, Fe, Ca, Mg, Na and K were finally constructed with their measured relative variations of line emission intensities. The distribution and correlations of these elements in concentration may reflect changes of shale mineral components with respected to the variations of the depositional environments and provide an important clue in identifying sedimentary processes when combined with other geological or geochemical evidences. These results well demonstrated the potential of LIBS technique for shale studies.