Nitrogen in biogenic and abiogenic minerals from Paleozoic black shales: an NRA study

Nuclear reaction analyses were performed on feldspars, quartz, abiogenic and biogenic sulfides and phosphates in organic matter-rich black shales. The goal was to study N-fractionation in black shales during diagenesis and contemporaneous hydrothermalism. Light elements (N, C) together with heavier ones (K, Ca, Ni, Fe, Zn) were analyzed by PIXE. Due to the heterogeneous sample composition, a scanning mode was used. Each phase was identified before extracting the corresponding spectra for quantification. Six phases, carrying nitrogen (and C), have been identified. K-feldspars are the richest in N (1.0-2.4 wt.%), followed by organic carbon (0.67 wt.%). Quartz, biogenic and abiogenic sulfides and phosphates contain N in the range of 0.56-1.08 wt.%. The present N-distribution in the black shales is explained by a two-step nitrogen release: (1) organic matter decay produces N, P, S nutriments for the development of a hydrothermal vent fauna and (2) biomineralization of this vent fauna liberates nitrogen to early diagenetic fluids. The extreme N enrichment of feldspars is related to its crystal structure, favoring the potassium substitution by NH4+, and the N-uptake during organic matter replacement