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.

The Southeast Indian Ridge between 88°E and 118°E: Variations in crustal accretion at constant spreading rate

The temperature of the mantle and the rate of melt production are parameters which play important roles in controlling the style of crustal accretion along mid-ocean ridges. To investigate the variability in crustal accretion that develops in response to variations in mantle temperature, we have conducted a geophysical investigation of the Southeast Indian Ridge (SEIR) between the Amsterdam hotspot and the Australian-Antarctic Discordance (88 degrees E-118 degrees E). The spreading center deepens by 2100 m from west to east within the study area. Despite a uniform, intermediate spreading rate (69-75 mm yr-l), the SEIR exhibits the range in axial morphology displayed by the East Pacific Rise and the Mid-Atlantic Ridge (MAR) and usually associated with variations in spreading rate. The spreading center is characterized by an axial high west of 102 degrees 45'E, whereas an axial valley is prevalent east of this longitude. Both the deepening of the ridge axis and the general evolution of axial morphology from an axial high to a rift valley are not uniform. A region of intermediate morphology separates axial highs and MAR-like rift valleys. Local transitions in axial morphology occur in three areas along the ridge axis. The increase in axial depth toward the Australian-Antarctic Discordance may be explained by the thinning of the oceanic crust by similar to 4 km and the change in axial topography. The long-wavelength changes observed along the SEIR can be attributed to a gradient in mantle temperature between regions influenced by the Amsterdam and Kerguelen hot spots and the Australian-Antarctic Discordance. However, local processes, perhaps associated with an heterogeneous mantle or along-axis asthenospheric flow, may give rise to local transitions in axial topography and depth anomalies.