Nitrogen isotopes in ophiolitic metagabbros: A re-evaluation of modern nitrogen fluxes in subduction zones and implication for the early Earth atmosphere

Abstract

Nitrogen contents and isotope compositions together with major and trace element concentrations were determined in a sequence of metagabbros from the western Alps (Europe) in order to constrain the evolution and behavior of N during hydrothermal alteration on the seafloor and progressive dehydration during subduction in a cold slab environment (8 °C/km). The rocks investigated include: (i) low-strain metagabbros that equilibrated under greenschist to amphibolite facies (Chenaillet Massif), blueschist facies (Queyras region) and eclogite facies (Monviso massif) conditions and (ii) highly-strained mylonites and associated eclogitic veins from the Monviso Massif. In all samples, nitrogen (2.6–55 ppm) occurs as bound ammonium ( NH 4 + ) substituting for K or Na–Ca in minerals. Cu concentrations show a large variation, from 73.2 to 6.4 ppm, and are used as an index of hydrothermal alteration on the seafloor because of Cu fluid-mobility at relatively high temperature (>300 °C). In low-strain metagabbros, δ 15N values of +0.8‰ to +8.1‰ are negatively correlated with Cu concentrations. Eclogitic mylonites and veins display Cu concentrations lower than 11 ppm and show a δ 15N–Cu relationship that does not match the δ 15N–Cu correlation found in low-strain rocks. This δ 15N–Cu correlation preserved in low-strain rocks is best interpreted by leaching of Cu–N compounds, possibly of the form Cu(NH 3) 2 2+, during hydrothermal alteration. Recognition that the different types of low-strain metagabbros show the same δ 15N–Cu correlation indicates that fluid release during subduction zone metamorphism did not modify the original N and Cu contents of the parent hydrothermally-altered metagabbros. In contrast, the low Cu content present in eclogitic veins and mylonites implies that ductile deformation and veining were accompanied either by a loss of copper or that externally-derived nitrogen was added to the system. We estimate the global annual flux of N subducted by metagabbros as 4.2 (±2.0) × 10 11 g/yr. This value is about half that of sedimentary rocks, which suggests that gabbros carry a significant portion of the subducted nitrogen. The net budget between subducted N and that outgassed at volcanic arcs indicates that ∼80% of the subducted N is not recycled to the surface. On a global scale, the total amount of N buried to the mantle via subduction zones is estimated to be three times higher than that released from the mantle via mid-ocean ridges, arc and intraplate volcanoes and back-arc basins. This implies that N contained in Earth surface reservoirs, mainly in the atmosphere, is progressively transferred and sequestered into the mantle, with a net flux of ∼9.6 × 10 11 g/yr. Assuming a constant flux of subducted N over the Earth’s history indicates that an amount equivalent to the present atmospheric N may have been sequestered into the silicate Earth over a period of 4 billion years.