The research team made the following advancements towards completing the INHERIT objectives:
-Tracking the evolution of D/H through time requires understanding the processes that govern H isotopic modification in the mantle. Samples from different localities, ages and depths have therefore been chosen for spectroscopic, petrographic, compositional and isotopic analysis. We are developing a new protocol for reliable H isotope analyses of diamonds that addresses the challenges associated with isotopic analyses using EA IRMS. Thus far, extensive testing has been done to effectively remove contaminant H on the surface of samples. After achieving optimal working conditions, the validity of the isotopic data has been tested using mantle minerals, before analysing diamonds. We are also developing a protocol to quantify H which may result in more accurate H contents compared to other techniques.
-Identification of mineral inclusions in diamonds via Raman spectroscopy is a crucial part of the sample analysis, allowing determination of diamond paragenesis and the P/T conditions of formation. To this end, a new program, RamanCrystalHunter, was developed which contains many useful tools for Earth Scientists but also material scientists, chemists and the cultural heritage community.
A large-scale FTIR study of the H2O contents of inclusions in diamonds was completed showing that inclusions reflect the H2O content of the diamond-forming media. Our results revealed that significant H loss from the inclusion is unlikely and that the trapping of H by N defects mitigates diffusive loss of H from the inclusion and the diamond to the mantle, reinforcing our findings (see below).
-To ensure that the D/H of diamond reflects a primordial source, the atomistic behaviour of H in diamond, from the moment of incorporation to the end of mantle residence, must be understood. A comprehensive literature review of FTIR data from diamonds revealed that H-defects form earlier on during diamond formation than previously thought. We showed that once trapped by N, H cannot disassociate from N-defects and instead aggregates to form different N/H- defects with continued mantle residence.
To understand how N- and H-defects form, we investigated rare Type Ib diamonds and indentified a new type of N-defect (Y-center) that forms during early N-aggregation and three previously unobserved, IR peaks that correspond to new N/H-defects. Using novel ab initio and molecular dynamics calculations, we show that these new defects are the first to form in diamond and act to “lock-in” hydrogen such that the D/H ratio of diamonds reflects that of the parental fluid.