Diamond formation — Where, when and how?

• Diamonds grow in harzburgitic and lherzolitic/eclogitic substrates under subsolidus and supersolidus conditions, respectively
• The redox buffering capacity of cratonic peridotites is extremely limited
• Cratonic peridotites generally record fO2 below EMOD, i.e. they last interacted with a reducing fluid/melt
• Diamond can precipitate directly from cooling/ascending CHO fluids without redox interaction with the surrounding mantle

Geothermobarometric calculations for a worldwide database of inclusions in diamond indicate that formation of the dominant harzburgitic diamond association occurred predominantly (90%) under subsolidus conditions. Diamonds in eclogitic and lherzolitic lithologies grew in the presence of a melt, unless their formation is related to strongly reducing CHO fluids that would increase the solidus temperature or occurred at pressure–temperature conditions below about 5 GPa and 1050 °C. Three quarters of peridotitic garnet inclusions in diamond classify as “depleted” due to their low Y and Zr contents but, based on LREEN–HREEN ratios invariably near or greater than one, they nevertheless reflect re-enrichment through either highly fractionated fluids or small amounts of melt. The trace element signatures of harzburgitic and lherzolitic garnet inclusions are broadly consistent with formation under subsolidus and supersolidus conditions, respectively. Diamond formation may be followed by cooling in the range of ~ 60–180 °C as a consequence of slow thermal relaxation or, in the case of the Kimberley area in South Africa, possibly uplift due to extension in the lithospheric mantle. In other cases, diamond formation and final residence took place at comparable temperatures or even associated with small temperature increases over time.Diamond formation in peridotitic substrates can only occur at conditions at least as reducing as the EMOD buffer. Evaluation of the redox state of 225 garnet peridotite xenoliths from cratons worldwide indicates that the vast majority of samples deriving from within the diamond stability field represent fO2 conditions below EMOD. Modeling reveals that less than 50 ppm fluid are required to completely reset the redox state of depleted cratonic peridotite to that of the fluid. Consequently, the overall reduced state of diamond stable peridotites implies that the last fluids to interact with the deep cratonic lithosphere were generally reducing in character. A further consequence of the extremely limited redox buffering capacity of cratonic peridotites is that redox reactions with infiltrating fluid/melt likely cannot produce large diamonds or high diamond grades. Evaluating the shift in maximum carbon content in CHO fluids during either isobaric cooling or ascent along a cratonic geotherm, however, reveals that isochemical precipitation of carbon from CHO fluids provides an efficient mode of diamond crystallization. Since subsolidus fluids are permissible in harzburgites only, and supersolidus melts in lherzolite we suggest that CHO fluid metasomatism may explain the long observed close association between diamonds and harzburgitic garnets. In the absence of thermodynamic data we cannot evaluate if supersolidus carbonate-bearing melts, stable at fO2 conditions below EMOD, would experience a similar decrease in maximum carbon solubility during cooling or ascent along a geotherm. The absence of a clear association between diamond and lherzolitic garnets, however, suggests that this is not the case. A very strong association between diamond and eclogite likely relates to the fact that the transition from carbonate to diamond stable conditions occurs at redox conditions that are at least about 1 log unit more oxidizing than EMOD. At this time we cannot quantitatively evaluate the redox buffering capacity of cratonic eclogites but given their much higher Fe contents it has to be significantly higher than for peridotites. Alternatively, diamond in eclogite may precipitate directly from cooling carbonate-bearing melts that may be too oxidizing to crystallize diamond in olivine-bearing lithologies.