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.

Temporal variation of delta C-13 in particulate organic matter and oyster Crassostrea gigas in Marennes-Oleron Bay (France): Effect of freshwater inflow

The temporal variability of delta(13)C in suspended particulate organic matter (POM) and oyster Crassostrea gigas along a salinity gradient was investigated from May 1992 to September 1993 within the estuarine bay of Marennes-Oleron (France). During this period the mean daily discharge of the Charente River exhibited large seasonal variation, with a high discharge from November 1992 to January 1993. Contrary to that at the river mouth and the marine littoral, delta(13)C in POM and in oysters at mid-estuary was affected by the high flood period. The delta(13)C values of POM decreased in mid-estuary and remained at low levels during the high discharge period, indicating an increasing contribution of terrestrial inputs to the estuarine POM pool. At the same site, a remarkable decrease of delta(13)C in oysters occurred between December 1992 and March 1993 (after a time lag compared to the ambient POM), indicating incorporation of terrestrial organic matter in oyster tissues during the high flood discharge. The lag between the delta(13)C decrease in POM and oysters is attributed to the time needed for oyster tissues to incorporate enough newly terrestrial light carbon to be recognized by the delta(13)C measure (about 1 to 2 mo). This time interval depends on tissue turnover time. The delta(13)C POM decrease (i.e. 1.3 parts per thousand) cannot explain entirely the decrease observed in oysters (i.e. 2.3 parts per thousand). In fact, the pattern exhibited by mid-estuarine oysters can be explained by the increasing contribution of terrestrial organic matter to their feeding, and the inability to preferentially utilize specific components of the estuarine POM that are C-13-enriched.