Diagenetic history of calcite fractures in Vaca Muerta shales (Argentina) inferred from paired Δ₄₇ and fluid inclusion geothermometry

Many low-permeability, hydrocarbon-bearing rocks are productive for petroleum because natural fractures enhance hydrocarbon delivery to wellbores. Exploration and development decisions often must be made in the face of uncertainty about the presence and properties of natural fractures at scales of beds, field and plays, and how they contribute to production. Fractures patterns in subsurface rocks are challenging to predict or characterize owing to the difficulty in obtaining representative samples of fractures and the sparse set of tools for reconstructing how and when fractures grow during sedimentary basin evolution. In this study, we investigate bed-parallel fracture diagenesis in the Vaca Muerta shales (Argentina) based on a set of calcite vein collected from core across a thermal maturity sequence that ranges from the oil to dry gas window. We characterize these samples using secondary ions mass spectrometry (SIMS) measurements of stable isotope ratios, carbonate clumped isotope geothermometry and fluid inclusion analysis. These measurements precisely reconstruct the evolution of fluid geochemistry, temperature and pore fluid pressure during fracture opening. Here we show that within each studied site, all bedding parallel fibrous veins calcite formed at similar ranges of temperature. The fracture mineralization temperature increases substantially at the basin scale, from 90 °C to 120 °C, correlated with host-rock thermal maturity. We compare our constraints on carbonate and fluid temperature with apatite fission track thermal models and find that most of the fractures of the Vaca Muerta shales have formed in a relatively early stage of subsidence of the basin (c.a. 90 to 70 Ma). These ages estimations are consistent with recently published U–Pb ages on calcite veins from the outcropping area (117–61 Ma). The presence of petroleum inclusions (oil, condensate, and gas) in most of the vein's calcite fibers from cores also provides clear evidence that fracture formation was contemporaneous or posterior with petroleum generation, constraining the timing of catagenesis in the Vaca Muerta. Reconstructed paleo pressures conditions of veins formation from fluid inclusion analysis highlight significant fluid overpressure in the shale interval, which likely contributed to fracture initiation and growth. Preserved apparent Δ₄₇ temperatures in fibrous veins carbonates mineralization evolves gradually from 130 °C to 175 °C with increasing host rock thermal maturity. These clumped-isotope-based temperatures are systematically higher than trapping temperatures of associated fluid inclusions; one interpretation of this observation is that carbonate clumped isotope compositions re-equilibrated to near maximum burial conditions by solid-state isotopic re-ordering, yielding a record of the maximum burial temperature the shale unit experienced. The combination of paleothermometry techniques used in this study illustrates the importance of simultaneously exploring several independent geothermometers, particularly the informative combination of fluid inclusion and clumped isotope constraints, which provides a means of understanding the complex diagenesis of old sedimentary rocks that have experienced burial temperatures in the oil and gas thermal windows.