Constraining the internal variability of the stable isotopes of carbon and nitrogen within mantle diamonds

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The carbon and nitrogen isotope values of mantle xenoliths and xenocrysts are used to trace the cycling of volatiles in the deep Earth, for example, to place empirical constraints on the origin of diamond-forming carbon in the mantle. The global database for diamond shows that the δ13C value of peridotitic diamonds is very narrow, typically around −5‰, whereas eclogitic diamonds can show positive and very negative δ13C values resembling crustal carbonates and crustal organic carbon (<−40 to >+2‰); commonly interpreted to reflect a relationship between eclogitic diamond formation and subduction zone planet tectonics. Curiously, diamonds from both parageneses can show positive (crust-like) and negative (mantle-like) δ15N values (from <−40 to >+20‰). Most of these data are derived from single stage combustion gas sourced mass spectrometry, which produces simplistic datasets. By fragmenting single diamonds or using in-situ ion-beam techniques it is known that single diamonds can show large-scale heterogeneity for their carbon isotope values and nitrogen abundances, sometimes as large as entire populations of diamond across a few hundred micrometres. What is less well known is the scale of nitrogen isotope heterogeneity within single diamonds, and if the nitrogen isotope heterogeneity of single diamonds can provide an insight into why diamonds that show very restricted δ13C values show a much large range of δ15N values.To investigate the scale, and to determine the origin of the nitrogen isotope heterogeneity (source vs. fractionation during diamond-formation) shown for populations of mantle diamonds we have determined multiple δ13C–δ15N values and nitrogen abundances from 14 monocrystalline (MCDs) and 25 polycrystalline diamonds (PCDs) using step-wise oxidation gas sourced mass spectrometry. These data show that the heterogeneity shown for carbon and nitrogen isotope values from single diamond samples presented here is typically <5‰ and <8‰ respectively, both of which are comparable to the standard deviation for the mean mantle δ13C and δ15N values (±3 and ±4‰). However, there are samples that show much larger heterogeneities for δ13C and δ15N values (≤23‰ and ≤33‰ respectively), which cannot be generated by equilibrium stable isotope fractionation during, or prior to diamond-formation. These data suggest that isotopic heterogeneity may be present within the diamond-forming fluid on sub-mm scale, or that these diamonds formed during multiple diamond-formation events from isotopically distinct sources. From these 39 samples there are only 5 PCDs that show a larger range of carbon isotopes relative to nitrogen isotopes, but of these 5 samples only 2 show a range of δ13C values outside of analytical uncertainty. The remaining 34 samples show a greater isotopic heterogeneity for δ15N relative to δ13C values. The samples with the largest carbon and nitrogen isotopic heterogeneity are also the samples with low-bulk δ13C values (<−10‰), whilst there is no relationship between the ranges of nitrogen isotope values for a given sample and the corresponding bulk δ15N value or nitrogen content.These data show that δ15N values recorded in mantle diamonds are relatively heterogeneous, and can show both mantle-like (negative) and crustal (sedimentary)-like (positive) δ15N values within the same sample. We conclude that the large range of nitrogen isotope values seen within individual diamonds means that the observation of negative, mantle-like, nitrogen in mantle diamonds acquired by single-stage bulk combustion isotope ratio mass spectrometry cannot be used as a conclusive indicator for a mantle origin for the entirety of the diamond-forming carbon, and vice versa. Also, the behaviour of 15N/14N is not coupled with the behaviour of 14N/12C during diamond-formation. Instead, it appears that diamond-forming fluids can have positive and negative δ15N values, irrespective of their δ13C value(s). These data suggest that subduction induced nitrogen isotope heterogeneity may not be coupled with subduction induced carbon isotope heterogeneity in diamond-forming fluids.