Iron mineral structure, reactivity, and isotopic composition in a South Pacific Gyre ferromanganese nodule over 4 Ma

Deep-sea ferromanganese nodules accumulate trace elements from seawater and underlying sediment porewaters during the growth of concentric mineral layers over millions of years. These trace elements have the potential to record past ocean geochemical conditions. The goal of this study was to determine whether Fe mineral alteration occurs and how the speciation of trace elements responds to alteration over ∼3.7 Ma of marine ferromanganese nodule (MFN) formation, a timeline constrained by estimates from 9Be/10Be concentrations in the nodule material. We determined Fe-bearing phases and Fe isotope composition in a South Pacific Gyre (SPG) nodule. Specifically, the distribution patterns and speciation of trace element uptake by these Fe phases were investigated. The time interval covered by the growth of our sample of the nodule was derived from 9Be/10Be accelerator mass spectrometry (AMS). The composition and distribution of major and trace elements were mapped at various spatial scales, using micro-X-ray fluorescence (μXRF), electron microprobe analysis (EMPA), and inductively coupled plasma mass spectrometry (ICP-MS). Fe phases were characterized by micro-extended X-ray absorption fine structure (μEXAFS) spectroscopy and micro-X-ray diffraction (μXRD). Speciation of Ti and V, associated with Fe, was measured using micro-X-ray absorption near edge structure (μXANES) spectroscopy. Iron isotope composition (δ56/54Fe) in subsamples of 1-3 mm increments along the radius of the nodule was determined with multiple-collector ICP-MS (MC-ICP-MS). The SPG nodule formed through primarily hydrogeneous inputs at a rate of 4.0 ± 0.4 mm/Ma. The nodule exhibited a high diversity of Fe mineral phases: feroxyhite (δ-FeOOH), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and poorly ordered ferrihydrite-like phases. These findings provide evidence that Fe oxyhydroxides within the nodule undergo alteration to more stable phases over millions of years. Trace Ti and V were spatially correlated with Fe and found to be adsorbed to Fe-bearing minerals. Ti/Fe and V/Fe ratios, and Ti and V speciation, did not vary along the nodule radius. The δ56/54Fe values, when averaged over sample increments representing 0.25 to 0.75 Ma, were homogeneous within uncertainty along the nodule radius, at -0.12 ± 0.07 ‰ (2sd, n=10). Our results indicate that the Fe isotope composition of the nodule remained constant during nodule growth and that mineral alteration did not affect the primary Fe isotope composition of the nodule. Furthermore, the average δ56/54Fe value of -0.12 ‰ we find is consistent with Fe sourced from continental eolian particles (dust). Despite mineral alteration, the trace element partitioning of Ti and V, and Fe isotope composition, do not appear to change within the sensitivity of our measurements. These findings suggest that Fe oxyhydroxides within hydrogenetic ferromanganese nodules are out of geochemical contact with seawater once they are covered by subsequent concentric mineral layers. Even though Fe-bearing minerals are altered, trace element ratios, speciation and Fe isotope composition are preserved within the nodule.

VESPA cruise report. Volcanic Evolution of South Pacific Arcs. n/o L’Atalante, Nouméa – Nouméa, 22 May - 17 June 2015

VESPA was a successful 25 day research cruise on R/V l'Atalante that took place in May and June 2015. The main aim was to acquire new rock samples from extinct volcanoes on the Norfolk, Loyalty and Three Kings ridges, which connect New Caledonia and New Zealand. This was in order to test various hypotheses of Late Cretaceous-Miocene SW Pacific tectonic development relating to (i) nature and duration of magmatism on the ridges; (ii) timing of subduction initiation east of northern Zealandia; (iii) postulated subduction polarity changes. A total of 3400 km of 'sismique rapide' shallow reflection seismic data were acquired and processed onboard. The seismic lines provided a very useful structural-stratigraphic framework for the rock dredging. Combined with multibeam bathymetry data they allowed intelligent targeting of acoustic basement (lavas) and specific seismic reflectors (sedimentary strata) on rocky slopes and fault scarps. Different stratigraphic levels of the Loyalty and Three Kings Ridge volcanic piles were sampled by dredging at different water depths on the Cook Fracture Zone and Cagou Trough fault scarps. By the end of the cruise, 43 dredges had been attempted and 36 of them yielded igneous or sedimentary rocks potentially useful to the VESPA project. Onboard use of a portable X-ray fluorescence unit confirmed the presence of intraplate (but no arc) volcanoes on the Norfolk Ridge and presence of arc, intraplate and shoshonitic volcanoes on the Loyalty and Three Kings Ridges. A total of 770 kg of rock was retained for post-cruise analysis in New Caledonia, France and New Zealand. Future work will include micropaleontological dating of sedimentary rocks, U-Pb and Ar-Ar isotopic dating of igneous rocks, and whole rock geochemical and tracer isotope analyses. We are optimistic that many of the initial research hypotheses will be able to be tested.