Indigenous nitrogen in the Moon: Constraints from coupled nitrogen–noble gas analyses of mare basalts

Abstract

Nitrogen and noble gas (Ne–Ar) abundances and isotope ratios, determined by step-wise CO2 laser-extraction, static-mass spectrometry analysis, are reported for bulk fragments and mineral separates of ten lunar mare basalts (10020, 10057, 12008, 14053, 15555, 70255, 71557, 71576, 74255, 74275), one highland breccia (14321), and one ferroan anorthosite (15414). The mare basalt sub-samples 10057,183 and 71576,12 contain a large amount of solar noble gases, whereas neon and argon in all other samples are purely cosmogenic, as shown by their 21Ne/22Ne ratios of ≈0.85 and 36Ar/38Ar ratios of ≈0.65. The solar-gas-free basalts contain a two-component mixture of cosmogenic 15N and indigenous nitrogen (<0.5 ppm). Mare basalt 74255 and the olivine fraction of 15555,876 record the smallest proportion of 15Ncosm; therefore, their δ15N values of −0.2 to +26.7‰ (observed at the low-temperature steps) are thought to well represent the isotopic composition of indigenous lunar nitrogen. However, δ15N values ≤−30‰ are found in several basalts, overlapping with the isotopic signature of Earth's primordial mantle or an enstatite chondrite-like impactor. While the lowest δ15N values allow for nitrogen trapped in the Moon's interior to be inherited from the proto-Earth and/or the impactor, the more 15N-enriched compositions require that carbonaceous chondrites provided nitrogen to the lunar magma ocean prior to the solidification of the crust. Since nitrogen can efficiently be incorporated into mafic minerals (olivine, pyroxene) under oxygen fugacities close to or below the iron-wustite buffer (Li et al., 2013), the mare basalt source region is likely characterized by a high nitrogen storage capacity. In contrast, anorthosite 15414 shows no traces of indigenous nitrogen, suggesting that nitrogen was not efficiently incorporated into the lunar crust during magma ocean differentiation.