The record of ductile strain by Raman spectroscopy of carbonaceous material – deformation experiments and applications to the brittle-ductile régime

Raman spectroscopy on carbonaceous material (RSCM) is a method widely used to infer the temperature of metamorphism in metasediments. Furthermore, anomalies in the Raman signature of carbonaceous particles contained in fault zones have been interpreted as reflecting short-lived heating events due to friction during earthquakes. These applications of RSCM rely all on the assumption that temperature is the main factor controlling the reorganization of carbonaceous material (CM) and its expression by Raman spectroscopy. Nonetheless, few examples of natural fault zones and shear zones recently raised questions about the possible role of strain in such reorganization.In this work, we studied the influence of deformation on the Raman spectra of CM. We carried out experiments of deformation on low-grade shales in the Paterson and Griggs-type rigs, corresponding to low and high pressure conditions, for variable conditions of temperature and strain rates, simulating deformation at the brittle-ductile transition. In parallel, we examined in these experiments the evolution of CM using the intensity ratio (IR), defined as the intensity ratio of the Defect band over the Graphite band of the Raman spectrum.Deformation proceeded as a combination of slip on discrete planes, corresponding to macroscopic stick-slip events, and of ductile shear in few hundreds of µm’s-thick zones. The effect of stick-slip events on RSCM signal is unclear, principally because the deformed layers are too thin to contain CM to be analyzed. In contrast, in zones of distributed strain we observed a systematic and significant increase in IR compared to undeformed domains, reflecting an enhancement in the structural organization of CM. On the basis of additional experiments of static heating we carried out in parallel, we show that the IR increase cannot be connected to local and transient increase in temperature during the experiment, and has therefore to be connected to strain itself.The zones of concentrated ductile strain are characterized by comminution of the clasts of quartz and feldspar initially present, accompanied by the development of a porosity at the submicron-scale. Chemical analysis revealed that along with intense grain-size reduction, the chemical composition of the feldspar was modified. On the basis of these microstructural and chemical evidence, it appears that the elementary processes behind ductile deformation include intense mechanical fracturing and mass transfer along the grain boundaries.As a conclusion, it appears that strain has an undisputable effect to increase IR of . When applied to nature, the relevant temperature and mechanical realm of these experiments is the brittle-ductile transition, for temperature of the order or below 300°C. These conditions are also the ones corresponding to seismic deformation. Therefore we show here that Raman spectra in fault zones reflect not only the temperature history (including coseismic flash-heating), but also, and to a large extent, the strain history of the rock.