Nitrogen in peridotite xenoliths: Lithophile behavior and magmatic isotope fractionation

In order to document the origin and speciation of nitrogen in mantle-derived rocks and minerals, the N and Ar contents and isotopic compositions were investigated for hydrous and anhydrous peridotite xenoliths from Ataq, Yemen, from Eifel, Germany, and from Massif Central, France. Nitrogen and Ar were extracted by stepwise combustion with a fine temperature resolution, followed by fusion in a platinum crucible. A large isotopic disequilibrium of up to 25.4‰ is observed within single peridotite xenoliths, with δ¹⁵N values as low as −17.3‰ in phlogopite whereas clinopyroxene and olivine show positive δ¹⁵N values. Identical Sr isotopic ratios of phlogopite, clinopyroxene and whole rock in this wehrlite sample are consistent with crystallization from a common reservoir, suggesting that the light N signature of phlogopite might be the result of isotopic fractionation during N uptake from the host magma. The nitrogen concentration is systematically high in phlogopite, (7.6-25.7 ppm), whereas that of bulk peridotite xenoliths is between 0.1 and 0.8 ppm. The high N content of phlogopite is at least partly due to host magma-mineral interaction, and may also suggest the occurrence of N as that substituted for K⁺ during mineral growth in mafic magmas. Such speciation is consistent with the fact that N and Rb contents correlate well for a set of samples from mantle regions that were affected by subduction-related metasomatism and magmatism. The N/Rb ratios of these samples are comparable with values estimated for subduction zone magmas, but are one order of magnitude lower than the N/Rb ratios characterizing subducting slabs. This difference suggests preferential release of N relative to alkalis in the forearc region. N/⁴⁰Ar^∗ ratios of minerals from analyzed mantle xenoliths are much higher than those of vesicles in MORBs and OIBs, requiring either the occurrence of nitrogen speciation in the mantle more compatible than Ar, significant loss of fluid phase during entrainment, or long residence time of volatile elements in the mantle source(s) of fluids to increase drastically the ⁴⁰Ar^∗ budget of the latter.