Nitrogen enrichment in the altered upper oceanic crust: A new perspective on constraining the global subducting nitrogen budget and implications for subduction-zone nitrogen recycling

Abstract

Studies of alteration enrichment of nitrogen (N) in seafloor basalts clearly indicate that the upper oceanic crust is an important reservoir to transfer crustal N into Earth's interior. However, since previous studies have focused on relatively few DSDP/ODP/IODP drill cores, the factors controlling N enrichment in the altered upper oceanic crust at a global scale have not been revealed. Here we report N concentrations and isotope compositions of altered basalts from four additional DSDP/ODP Holes (556, 1224F, 417A and 543A). These new data, together with the published data from Holes 801C, 1149D, 1256D and 504B, enable systematic assessment of the potential affecting factors such as alteration degree, crustal age, spreading rate and sediment type, on N enrichment in the upper oceanic crust. The new data demonstrate ubiquitous N enrichment (1.3 – 48.4 ppm) in global seafloor basalts. The results indicate that, (i) the secondary N (in the form of ammonium) in altered basalts was sourced from sediment/seawater with δ15N values of 0‰ to +8‰, with a minor source from abiotic N2 reduction with δ15N values of -12‰ to -21‰; (ii) N enrichments in the upper oceanic crust do not correlate with crustal age, suggesting that the N uptake should mainly occur over early ages (likely within ∼20 Myr of crustal formation); (iii) the magnitude of N enrichment in the upper oceanic crust is primarily controlled by the N availability in the surrounding environment, which is ultimately related to the N abundance of basal sediments and/or seawater. The highest degree of N enrichment occurs in the upper oceanic crust overlain by N-rich basal sediments (claystone), i.e., at Hole 543A (N = 24.9±8.3 ppm; 1σ). In contrast, the lowest degree of N enrichment occurs in the upper oceanic crust overlain by N-poor basal sediments (chert), i.e., at Hole 1149D (N = 2.0±0.5 ppm; 1σ). With the consideration of this primary controlling factor, a global N input flux of 3.7±0.3 ×109 mol⋅yr−1 for the 300 – 600 m upper oceanic crust is calculated. These new data also demonstrate that N concentrations are relatively low in global altered basalts (average: 10.1±7.8 pm; 1σ). In comparison to their metamorphic equivalents, blueschists have much higher N concentrations (up to ∼122 ppm) whereas eclogites have N concentrations comparable to altered basalts. This implies further N enrichment in basaltic oceanic crust during early subduction and N devolatilization during deep subduction (by eclogite facies).