Nitrogen in the Orgueil meteorite: Abundant ammonium among other reservoirs of variable isotopic compositions

Nitrogen, because of its abundance and variety of carrier phases, is a unique tracer of physico-chemical processes occurring throughout star and planet formations. The refractory organic matter is commonly considered as the main carrier of nitrogen in the most primitive objects of our Solar System. However, nitrogen in the form of ammonium (NH 4 + ) was observed in the Ivuna-type carbonaceous (CI) chondrites Alais in 1834, and Orgueil just after its fall in 1864, as well as more recently on Ceres, comet 67P/Churyumov-Gerasimenko, and possibly on some asteroids. In the present study, we have measured the nitrogen content and isotopic composition in various nitrogen-bearing phases of several samples of the Orgueil meteorite, with different degrees of terrestrial weathering. Water-soluble NH 4 + is present in Orgueil at a mean concentration of 0.07 ± 0.01 wt%, with a mean isotopic composition of δ 15 N = +72 ± 9 ‰ ( 14 N/ 15 N = 254 ± 2), confirming its extra-terrestrial origin. In the most terrestrially altered sample of Orgueil that we analysed, the isotopic composition is δ 15 N = +50 ± 12 ‰ ( 14 N/ 15 N = 259 ± 3). NH 4 + is in species that are thermally stable up to 383 K, possibly ammonium inorganic/organic salts and ammoniated phyllosilicates. We also show that the nitrogen in Orgueil is distributed among the insoluble organic matter (IOM) (35 ± 5 %), ammonium (27 ± 5 %), and other minor water-soluble species (e.g., nitrate, amines etc.: < 6 %). The remaining nitrogen (34 ± 14 %) is mainly in an unidentified organic matter (UOM), which may be IOM lost during its extraction and/or acid hydrolysable functional groups bounded to the IOM and/or organic nitrogen trapped within minerals. The three main carriers of nitrogen in Orgueil have δ 15 N (and 14 N/ 15 N) values of + 32 ± 1 ‰ (264 ± 0.3) for IOM, +39 ± 16 ‰ (262 ± 4) for UOM, and + 72 ± 9 ‰ (254 ± 2) for NH 4 + . Although IOM and NH 4 + have significantly different δ 15 N, we cannot exclude that these phases could be compositionally related because IOM is heterogeneous in 15 N. Ammonium could have been produced via heating and/or aqueous alteration processes of organic matter in the CI parent body. Alternatively, or additionnally, ammonium could be a tracer of the accretion and/or later deposit of NH 3 ice, NH 3 hydrates, and/or NH 4 + salts on the CI parent body. As shown by previous studies, Ryugu grains sampled by the Hayabusa2 mission (JAXA) have heterogeneous compositions at the millimeter scale, with nitrogen concentrations and δ 15 N similar or lower than Orgueil, possibly because of different parent body processing. The present study suggests that the lack or loss of 15 N-rich NH 4 + in some Ryugu grains may explain some of these differences with Orgueil.