A reinterpretation of the crustal N-isotope record: Evidence for a ¹⁵N-enriched Archean atmosphere?

A new compilation of N-isotope and abundance data for metasedimentary rocks, and hyrdothermal micas that proxy for bulk crust, show systematic patterns. (1) δ¹⁵N values of kerogen in Precambrian cherts are more negative relative to siliciclastic counterparts, probably due to a mantle hydrothermal component. (2) There is a secular trend from average δ¹⁵N 15.3 ± 1.8‰ in Archean shales, through intermediate values in the Proterozoic, to Phanerozoic counterparts where δ¹⁵N averages +3.5‰. (3) Hydrothermal micas in metamorphic hydrothermal systems of Palaeozoic and Mesozoic age that proxy for crust have δ¹⁵N within the range of contemporaneous sedimentary rocks. (4) Hydrothermal micas track the secular trend of δ¹⁵N for kerogen from 2.7 Ga to the Phanerozoic. (5) Within Precambrian datasets δ¹⁵N does not increase with decreasing N content; accordingly, high δ¹⁵N values cannot stem either from metamorphism or form Rayleigh fractionation. (6) Previous studies show isotopic shifts during metamorphism are only +1 to +3‰ up to amphibolite facies. Values of 10-24‰ are attributed to a high δ¹⁵N Archean atmosphere, a residual signature of Cl carbonaceous chondrites where δ¹⁵N is +30‰ to + 42‰.