Deep carbon through time: Earth's diamond record and its implications for carbon cycling and fluid speciation in the mantle

Diamonds are unrivalled in their ability to record the mantle carbon cycle and mantle fO(2) over a vast portion of Earth's history. Diamonds' inertness and antiquity means their carbon isotopic characteristics directly reflect their growth environment within the mantle as far back as similar to 3.5 Ga. This paper reports the results of a thorough secondary ion mass spectrometry (SIMS) carbon isotope and nitrogen concentration study, carried out on fragments of 144 diamond samples from various locations, from similar to 3.5 to 1.4 Ga for P [peridotitic]-type diamonds and 3.0 to 1.0 Ga for E [eclogitic]-type diamonds. The majority of the studied samples were from diamonds used to establish formation ages and thus provide a direct connection between the carbon isotope values, nitrogen contents and the formation ages. In total, 908 carbon isotope and nitrogen concentration measurements were obtained. The total delta C-13 data range from -17.1 to -1.9 parts per thousand (P = -8.4 to -1.9 parts per thousand; E = -17.1 to -2.1 parts per thousand) and N contents range from 0 to 3073 at. ppm (P 0 to 3073 at. ppm; E = 1 to 2661 at. ppm). In general, there is no systematic variation with time in the mantle carbon isotope record since > 3 Ga. The mode in delta C-13 of peridotitic diamonds has been at similar to 5 (+/- 2) parts per thousand since the earliest diamond growth similar to 3.5 Ga, and this mode is also observed in the eclogitic diamond record since similar to 3 Ga. The skewness of eclogitic diamonds' delta C-13 distributions to more negative values, which the data establishes began around 3 Ga, is also consistent through time, with no global trends apparent. No isotopic and concentration trends were recorded within individual samples, indicating that, firstly, closed system fractionation trends are rare. This implies that diamonds typically grow in systems with high excess of carbon in the fluid (i.e. relative to the mass of the growing diamond). Any minerals included into diamond during the growth process are more likely to be isotopically reset at the time of diamond formation, meaning inclusion ages would be representative of the diamond growth event irrespective of whether they are syngenetic or protogenetic. Secondly, the lack of significant variation seen in the peridotitic diamonds studied is in keeping with modeling of Rayleigh isotopic fractionation in multicomponent systems (RIFMS) during isochemical diamond precipitation in harzburgitic mantle. The RIFMS model not only showed that in water-maximum fluids at constant depths along a geotherm, fractionation can only account for variations of <1 parts per thousand, but also that the principal delta C-13 mode of similar to 5 +/- 1 parts per thousand in the global harzburgitic diamond record occurs if the variation in fO(2) is only 0.4 log units. Due to the wide age distribution of P-type diamonds, this leads to the conclusion that the speciation and oxygen fugacity of diamond forming fluids has been relatively consistent. The deep mantle has therefore generated fluids with near constant carbon speciation for 3.5 Ga. (C) 2020 Published by Elsevier Ltd.