Nitrogen geochemistry as a tracer of fluid flow in a hydrothermal vent complex in the Karoo Basin, South Africa

We have investigated the N geochemistry of minerals and rocks from contact metamorphic aureoles and hydrothermal vent complexes (HVC) in the Karoo Basin in South Africa. The HVC formed during phreatic eruptions associated with rapid devolatilization and pressure build-up in contact aureoles around early Jurassic sill intrusions. By combining outcrop data from a HVC and core data from contact aureoles, we investigate the relationship between light element release during metamorphism and vertical fluid migration. Sandstone and breccia from the HVC contain early-diagenetic ammonium -bearing feldspar (buddingtonite) and illite. Ammonium occupies up to 95% of the A site in feldspar, corresponding to concentrations up to 5.2 wt% N. Bulk-rock N isotope data for rocks from inside and outside the hydrothermal vent complex fall into two distinct groups. Background samples have δ¹⁵N_air between +1.5‰ and +4.9‰, whereas minerals from the vent complex have δ¹⁵N in the range +7.5 to +10.6‰. The N geochemistry of contact metamorphic shale from the lower stratigraphic units of the Karoo Basin shows that the vitrinite reflectance and δ¹⁵N values are positively correlated. Shale with reflectivity values >4%Ro are enriched in ¹⁵N, with δ¹⁵N values between +6‰ and +14‰, implying the release of isotopically light N into metamorphic fluids (probably as N₂). We suggest that the relatively high δ¹⁵N values of the early-diagenetic buddingtonite in the HVC reflect exchange of buddingtonite with N-bearing fluids ascending from greater depth after their release during contact metamorphism and dehydration. We present a qualitative model whereby hydrothermal vent complexes represent fluid flow structures after their formation, focusing N-bearing metamorphic fluids sourced in deeper levels of the basin. The release of organic N from sediments at depth in volcanic basins could play a role in the geochemical cycle of N, becoming particularly important during periods of intense volcanic activity.